iPA-450/3-74-031
IUNE 1974
                    AIR POLLUTION
          CONTROL ENGINEERING
                  AND  COST STUDY
                     OF  THE  PAINT
         AND VARNISH INDUSTRY
       U.S. ENVIRONMENTAL PROTECTION AGENCY
           Office of Air and Water Programs
       Office of Air Quality Planning and Standards
       Research Triangle Park, North Carolina 27711

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                                        FOREWARD


This air pollution control engineering and cost study of the paint and varnish industry was conducted
under  Contract  No.  68-02-0259 for the  office of Air  Quality Planning and  Standards,  Emission
Standards  and Engineering Division,  Industrial Studies Branch. The study  is being conducted  by
the EPA under public law No. 91604, Clean Air Amendments of 1970. This law permits that industry
studies be conducted to obtain information as outlined below.
Section 111
This section of the law requires that future growth of industry should contribute  a minimum impact
on the  quality of air.  It  provides that  the Federal Government will review the capabilities for con-
trolling  air  pollution  in industry and that  certain  designed source categories will be  required  to
install the best emission control systems.
One source of information used to develop performance standards required to ensure best emission
control  evolves from the type of  industry  study provided herein. Trade  associations of the industry
are consulted during the establishment of proposed standards. Plants which utilize the best control
techniques  are examined  and source tested. Test data and economics of  control are considered
in the  setting of standards.  Proposed standards are then  reviewed  at  open meetings by industry,
governmental agencies and other interested parties.
Section 114
This section of the law provides to the Environmental Protection Agency the right to such infor-
mation  as  it  deems necessary  for establishing  standards. Industry cannot  withhold  information
from the EPA on the grounds that it is  considered confidential.  In accordance with title  18  of
Section 1905 in the United States  Code, if  the  EPA  requires information  which in  a company's
opinion  is a trade secret then the  company  may submit, along with  the  information, a request
that  the data  be maintained  confidential.  This  request must include reasons why  the data  is
confidential. EPA Legal  Council will review the request and will  render a decision as to whether
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it should be held confidential  and will so notify the company.  If the decision is made that  it will
not be held confidential, the company has 30 days to consider legal action.
The three general categories of information requested of industry are:
       a.  Emission data
       b.  Economic information
       c.  Process information
The Clean Air Act clearly states that emission data is public information and will be made available
upon  request. Process data may be  held confidential only if the  information  can be shown  to
constitute a trade secret. The  Office of General Council must rule on any process data considered
to be  confidential by a company based on the reasons submitted with the request for confidentiality.
With a determination  that certain information is a trade secret, such information will  be used for
setting performance standards, but  the data will not  be released to the general public. Such infor-
mation may be  used in summaries or in legal  action if required  by the Federal Government for
carrying out the purpose of the act.

Section 113 — Federal Enforcement Powers
Most  state agencies  will  in all likelihood enforce new source performance standards; however,
the federal agency has the  right to  intervene  under this section of the law.  Where a state  is
not prepared to enforce the standards, the Federal Government  will have the responsibility.
The paint and varnish industry shall be considered to consist of all  phases of operations normally
found located  in plants engaged in the manufacture of paints,  lacquers,  varnishes, etc. (Standard
Industrial  Classification  2851).  The study shall include  the storing, packaging, shipping, handling,
mixing, thinning, grinding, cooking,  and other  processing  necessary in the  manufacturing of paint
and varnish  products from raw materials through finished products.  The manufacture  of resins  by
both paint manufacturers and  raw material suppliers  shall be included.  The manufacture and
processing of  a  number of pigments will  also be included in this study. The study of the pigments
will not be as detailed as the  paint and varnish  study and it will be  limited to those manufacturing
processes which contribute  significantly to  environmental air pollution. The study will  develop the
following information  on the paint and varnish industry:
       1.  An industry description  which incorporates all industry  information relevant to emission
problems, including comprehensive  industry statistics, emission  sources, types of emissions as well
as emission quantities as related to  operational factors.
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        2.  A study of technical and economic information on the best control systems. An assess-
 ment of the  economic impact on  the  entire  industry if these best controls were  applied to new
 and existing plants.
        3.  Identification of technological and economic deficiencies in air pollution control technology
 within the paint and varnish  industry. Analysis of those  deficiencies that restrict additional reduction
 of  emissions along  with  recommendations of  R&D Programs that would  produce the greatest
 improvement in control technology.
 Resulting reports will include  past and projected production data,  geographical location of paint
 plants, types and  amounts  of air  pollutant emissions,  control techniques, performance and costs
 of existing and best control  technology, impact of emissions on air quality,  inspection procedures
 to determine compliance with  air pollution control regulations, and areas of needed research and
 development.

 Techniques used in the study  included literature searches, plant visits, source testing and compre-
 hensive industry questionnaires.  Two subcontractors were also employed. These subcontracts are
 discussed below.

 The Industrial Gas Cleaning Institute (IGCI)  was subcontracted to  supply  detailed capital, instal-
 lation and operating cost information for air pollution equipment used  by the coating industry.

The Sherwin-Williams Company was subcontracted to supply capital  and operating cost information
for  the model plant developed  for this study. These  two subcontracts are  discussed in more detail
in Chapter 7,  "ECONOMICS  OF EMISSION CONTROL".

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                                 ACKNOWLEDGEMENTS

The work reported herein has been reviewed by an Industry Advisory Committee comprised of the
members listed below.  The authors wish to gratefully  acknowledge the technical review, advice
and assistance they provided throughout the period of this contract.

                                Committee  Representatives
Ashland Chemical Company                              J. Blegen
Conchemco, Incorporated                                R. Radford
E. I. duPont de Nemours                                 W. Zimmt
Eagle-Picher Industries, Inc.                              H. Stephenson
IGCI                                                   G. Brewer
Los Angeles County APCD                               W. Krentz
                                                       N. Schaeffer (alternate)
N. J. Department of Environmental Protection               M. Polakovic
NL Industries                                           G. Rodman
National Paint & Coatings Association                      R. Brown
                                                       R. Connor (alternate)
PPG Industries                                          D. Bridge
                                                       T. Duvall  (alternate)
Reichhold Chemicals, Incorporated                        S. Hewett
Sherwin-Williams                                        F. Gaugush
                                                       A. Thomas (alternate)
Stresen-Reuter International/Lawter Chemical, Inc.           A. Stresen-Reuter
                                                       R. Voedisch  (alternate)
Union Carbide                                          B. Duzy

                              Environmental Protection Agency
Chief, Industrial Studies Branch                           S. Cuffe
Industrial Survey Section                                 J. Dale
Chief, Industrial Survey Section                           J. Sableski
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                            National Paint and Coating Association
Executive Vice President                                   R. Roland
Manufacturing Management Committee                     W. Bartelt
"The Design and Construction of a Modern Paint             R. Brewster
    Manufacturing Facility"

                  Air Correction Division of U.O.P. — Equipment Manufacturer

                     Hirt Combustion Engineers — Equipment Manufacturer

The assistance of other  organizations and companies who supplied assistance in  completion  of
this study are too numerous to  list and are also gratefully acknowledged,  particularly  those who
filled out questionnaires, supplied data, provided time for visits, and permitted source testing.
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                                        SUMMARY
       Activity in  this program was directed  to  an analysis of  the  technical and economic
aspects of emission controls in the paint and varnish manufacturing industry. The main objective
of the study was to provide an improved technical and economic basis which the Environmental
Protection Agency could  use to evaluate emissions and  control technology in the paint  and
varnish  industry. Industry structure and statistics, the nature and sources of emissions, technical
problems associated  with  emission controls, cost  of  emission  control equipment  and the overall
economic impact of air pollution control were among the major  topics investigated in the program.
The salient results of the program are highlighted in the following sections.

Process and Emissions
       Significant  air  pollution problems associated with this industry are localized odor nuisance
complaints and fugitive solvent vapors. The odor  complaints result primarily  from open  kettles,
varnish  cooks, closed reactor resin  cooks and handling operations of low odor threshold  raw
materials. The quantity of this type  of  emission is  very small but,  nevertheless, contains a wide
variety of highly odorous substances.  Fugitive and non-fugitive  solvent losses represent the
major quantity of emissions from the manufacturing operations but  these amount to only a small
percent of the solvent losses which occur during the  application and drying of coatings.
       A brief history and description of the  paint and varnish  industry is presented in  this
chapter. The various  production processes and manufacturing steps are discussed. The chemistry
of varnishes and  resin cooking is presented in some detail with the  production of alkyd  resins
given major emphasis. Other resins discussed are vinyl,  acrylic, epoxy, urethane, cellulosic,
amino, hydrocarbon, phenolic and silicone.
       Process information gathered from an industry questionnaire  is summarized. A total of
452 questionnaires were  mailed  to  382 different  paint  companies. Of  these, 338 or about 75
percent  were used in  the process information summaries presented. Included in these summaries
is a listing of major products, raw materials and production equipment.
       The  design basis and material balance of the  model plant  developed to evaluate the
economics of the  industry are presented  in detail.  The design of the plant was based on a
study made  by the Management Committee of the National Paint and Coating Association  and
presented at the  1972 NPCA annual meeting in a paper by Mr. R. F.  Brewster.  The model
plant  was modified in capacity to  more  closely  approach the  average size plant  reported in
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the industry questionnaire. On-site resin production facilities were also added.
       A description of the type, source  and quantity of emissions that are  encountered in
the production of paints  and varnishes is discussed  along with the influence  of  various process
operations on these emissions.  Emission data  from  the industry questionnaire,  source  tests by
afterburner equipment manufacturers and source  tests conducted by the Federal EPA are
summarized and presented. Primary  emphasis was placed  on emissions from varnish and  resin
cooking. A detailed source by  source calculation of  emissions from the model plant is also
presented. Finally, there is a brief discussion of liquid and solid wastes.
       Primary sources  of  gaseous  emissions are: varnish cooking, resin cooking and  thinning.
Secondary sources  of gaseous emissions are: handling and storage, milling operations,  blending
and finishing, and  filling. The primary source  of particulate emissions is the pigment dusting
encountered in the milling operation.
       As a  part of this study,  the  Federal EPA conducted 10  source  tests  on emissions from
the production of four  types of resins in  four different  resin reactors. The work was carried
out by Scott Research  Laboratories under the direction  of  the EPA source test group.  Flow
rates, total hydrocarbons and  gas chromatography data were obtained and are summarized
and presented.

Industry Statistics
       The Paint and Allied Product Industry  (SIC  2851) is  made up of approximately 1,727
establishments operated by  some 1,365 companies. In this chapter, the type, size and geographical
distribution of these plants are  presented  and analyzed.  Past,  present and projected  industry
trends to the year  1985 are also presented and discussed.  Data is presented on production
and production capacity relations,  number of plants, size of plants, and typical  plant  and
equipment ages.  A discussion of the  influence  on the future of this industry due to technical
innovation and other outside effects is also presented.
Measurements of Emissions
       As yet, there is no  tried and proven method for source  measurements of  hydrocarbons.
This problem  is even further complicated  by the large variety  and highly cyclic  nature of the
emissions emitted  from paint  and  varnish kettles. In this chapter, these  problems  and the
current state-of-the-art for both source and continuous monitoring are discussed. Detailed descriptions
of the methods currently used by industry  and  regulatory agencies are  discussed. A description
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of the method used  by the Federal EPA during the source testing conducted  for this  study
is also presented.

Inventory of Emissions
       In this  chapter, emission factors are developed for this industry as a function of production
capacity  and type of product. Solvent emission factors were developed for three types of plants.

       Plants  Producing Resins Only          13,700 Ib/MM Ib Resin
       Plants  Producing Resins & Paints       45,000 Ib/MM gal Solvent Based Paint,
                                             5,460 Ib/MM Ib Resin
       Plants  Producing Paints Only           56,000 Ib/MM gal Solvent Based Paint
Data  collected from  the  industry questionnaire was used  as the  basis for the above  emission
factors. The emission factors for plants  producing both paint and resins  compare well in total
with those calculated  for the study's model plant.  As might be expected,  these emission factors
represent averages of widely differing individual plant emissions and care should be exercised
in applying them arbitrarily to specific plants.
       By using an  average gaseous emission  factor of 50,000 pounds  per million gallons
of solvent based paint produced  and paint  production for 1972,  potential  gaseous emissions
in  the U.S.A. from paint production are estimated to be 17,900 tons for the  year 1972. A
geographical distribution of organic emissions is presented in Figure 41 on page 198.
Emission Control Technology
       In this chapter, a  detailed discussion of the existing  state-of-the-art of air  pollution
control for the paint  and  varnish  industry is  presented. The discussion  includes a  description
of the best control  techniques for each  emission  source, alternate control techniques, methods
of control other than  add-on equipment, performance of currently used systems  and capability
of best control  systems to  meet more  stringent standards. Potential  water and solid waste
disposal  systems are also  reviewed. Best control for pigment  particulate emissions  are fabric
filters.  Best control for gaseous emissions including odors are catalytic and thermal afterburners.
Considerable  discussion  is  devoted to  the  design and application  of  afterburner systems to
resin  and varnish kettles. A discussion of the use of a refrigerated  condenser as an alternate
control device  is also included.

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Inspection Procedures
       This section of the report was written  for enforcement officers to assist them when
entering  and inspecting paint, varnish and  resin facilities and details the type  and location of
emission problems and control equipment.  It was written to  provide the compliance  inspector
with an understanding of the industry sufficient to conduct a proper inspection.

Economics of Emission Control
       Specific among  the goals of  this study was the determination of the financial  impact of
air  pollution control on the paint and coating industry. To  accomplish this, the investigation
was divided into the three following parts:
       Cost of Best Control Equipment
       Model Plant Economic Study
       Projections of Present and Future Industry-wide Costs
       Costs of best control equipment were obtained from  equipment manufacturers through
the Industrial Gas Cleaning Institute which was retained as a subcontractor. These were obtained
in response to detailed process, operating and bid specifications  prepared by Air  Resources,  Inc.
This information was then summarized  and is graphically  presented within  this section. The
capital cost and total annual operating cost for turnkey systems, catalytic  and thermal afterburners
plus auxiliaries and  afterburners  only are presented. These costs are plotted  against size  as
measured  by gas flow. Separate plots are  presented for afterburners with  and without heat
exchange.
       Model  plant costs were developed by the Sherwin-Williams Company who acted as a
subcontractor for this specific purpose. A detailed capital cost of the  model plant was made
by their engineering department. Balance sheets  and  operating statements for both the  controlled
and uncontrolled plants were developed by  their accounting department. Present total  cost and
fifteen-year projected cost of the  use of best control  by the  industry were  also developed and
are  summarized below:
                            Total Cost to Industry for Best Control
                          Capital Investment Cost       $16,200,000
                          Annual Operating Cost          4,500,000
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                          Projected Cost of Control (15-year period)
                          Capital Investment Cost      $30,600,000
                          Annual Operating Cost         8,500,000

       The  application  of best control technology  to the model plant will result  in a loss of
income ranging  between $0.006  and $0.008 per gallon of paint produced. This is equivalent
to a decrease in stockholder equity of between 1.73 and 3.25 per cent.
       Please  note that all  costs presented in this chapter  are based  on 1972 monetary
values and do not provide escalation factors for current requirements.

Pigment Industry
       For purposes of this study,  the  pigment industry was  included as  part of the paint
and varnish industry. General statistics  for the industry are presented  followed by  a review
of the pigments judged  to have  the  most potential  for significant air pollution emissions.  Major
pigments studied were the cadmium  pigments, zinc  oxide, the chrome pigments,  iron oxide  and
titanium  dioxide.  Of these, the  manufacture of titanium dioxide by both the sulfate  process
and the chloride process was studied in  further detail. A study  of emission control technology
was  also conducted  and includes type  and performance of currently used emission control
systems and other potential methods of control.
       An industry  questionnaire  similar  in  content  to the paint  and varnish questionnaire was
prepared specifically  for the  titanium dioxide manufacturers. The results of  the questionnaire
are  summarized and  presented. Estimated emission factors for various  operations utilized by
both the sulfate and chloride process were  developed and are also presented.
Recommended Research and Development Programs
       The  deficiencies in both  pollution control technology and emission measurements  are
treated in detail  and recommendations are made for research and development programs  which
can lead to improvements in these areas.
       Recommended programs for improvement in air pollution control technology are as follows:
       1. Design of a closed reactor for resin and varnish cooking.
       2. Development of liquid handling  of resin cook raw materials.
       3. Development of inexpensive solvent scavenging system.
       4. Development of transfer system for direct flame incinerator.
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5.   Determination of  best existing control technology currently applied to the  manufacture
    of TiO2 by the sulfate process.
Recommended program for improvement in emission measurements is as follows:
1.   Development of a simple and inexpensive instrument to detect hydrocarbon  emission
    and measure flow from kettle  cooking operations.
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                                 TABLE OF CONTENTS
LIST OF FIGURES   	    xjx
LIST OF TABLES  	   xxij
CHAPTER 1.  PROCESS AND EMISSION  	    1
       I.  PROCESS  	  1
           A.  Detailed Process Description  	    1
              1.  History  	    1
              2.  Description of Manufacturing Process 	    2
           B.  Process Data from Questionnaires  	   42
              1.  Raw Materials 	   45
              2.  Products and Production  	   56
              3.  Process Equipment  	   58
                 a.  Dispersion and Grinding Equipment  	   58
                 b.  Solvent Storage Tanks  	   60
                 c.  Resin  Reactor Usage  	   60
           C.  Material Balance for Model Plant  	  63
              1.  Design Basis 	   63
              2.  Production and Inventory  	   65
              3.  Equipment Requirement  	   68
                 a.  Paint Plant  	   68
                 b.  Resin Plant	   73
                 c.  Tankage Requirements  	   77
              4.  Raw Materials 	   77
              5.  Labor Requirements  	   81
              6.  Plant Layout and Flow Sheet  	   81
       II.   EMISSIONS  	  81
           A.  Description of Emissions  	   81
              1.  Fugitive  	   90
              2.  Non-Fugitive  	   91
              3.  Chemical and Physical Properties  	   91
           B.  Sources of Emissions  	   92
              1.  Major  	   92
              2.  Minor  	  100
           C.  Quantities of Emission from Uncontrolled Plants 	  100
              1.  Model Plant 	  100
                 a.  Solvent Emissions from Tanks  	  101
                 b.  Manufacturing Area  	  101
                 c.  Resin Production  	  106
                 d.  Thin Tanks and Filter  Presses  	  115
                 e.  Summary  	  118
              2.  Varnish and Resins Production  	  118
           D.  Process Operations Influencing Emissions  	  133
              1.  Equipment and/or Process Characteristics  	  133
                 a.  Handling and  Storage  	 133
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                 b.  Paint Operations  	  134
                 c.  Resin Production  	  134
             2.  Raw Materials 	  135
                 a.  Paniculate  	  135
                 b.  Gaseous  Emissions 	  135
             3.  Start-up and Shut Down 	  136
             4.  Operation Above and  Below Capacity  	  136
             5.  Process Operation Upsets  	  136
          E.  Raw Data Tabulated  	  138
             1.  Questionnaires  	  138
          F. By-Products   	  138
             1.  Liquid Wastes 	  143
             2.  Solid Waste 	  143
          G.  EPA Source Test Data 	  143
CHAPTER 2.  INDUSTRY STATISTICS  	  151
       I.  TYPE, SIZE AND LOCATION OF PRESENT DAY PLANTS  	  151
       II.  PAST, PRESENT AND PROJECTED INDUSTRY TRENDS TO 1985 	  156
          A.  Production 	  156
          B.  Number of Plants  	  161
          C.  Size of Plants 	  163
          D.  Capacity — Production Relations  	  166
          E. Typical Plant and Equipment Ages  	  166
          F. Technological Revolutions and Outside Influences Causing Changes
             in the Industry  	  168
             1.  Application Techniques 	  168
             2.  Pigment Industry  	  170
             3.  Environmental and Health Considerations  	  171
       III.   DISTRIBUTION OF CAPITAL EXPENDITURES  	  172
CHAPTER 3.  MEASUREMENTS OF EMISSIONS  	  175
       I.  SAMPLING AND ANALYTICAL PROCEDURES  	  175
          A. General Requirements for Source Testing  	  175
          B. Description of Source Sampling and Analytical Procedures  	  178
             1.  Flow Measurement  	  178
             2.  Paniculate Measurements  	  179
                 a.  General Considerations 	  179
                 b.  Collection and Analysis Techniques 	  180
             3.  Hydrocarbon Analysis  	  181
                 a.  Discontinuous Sampling  	  181
             4.  Analytical Techniques  	  184
                 a.  Infrared Analyzers 	  184
                 b.  Combustion Analyzers  	  184
                 c.   Flame lonization Detection  	  185
                 d.  Gas Chromatography  	  185
          C. EPA Test Methods 	  185
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      II. CONTINUOUS SOURCE MONITORING TECHNIQUES USED BY INDUSTRY  ..  191
CHAPTER 4.  INVENTORY OF EMISSIONS  	  193
      I.  EMISSION FACTORS FOR EACH SOURCE  	  193
      II. EMISSION INVENTORY FOR THE INDUSTRY 	  197
CHAPTER 5.  EMISSION CONTROL TECHNOLOGY 	  199
      I.  DESCRIPTION OF BEST CONTROL SYSTEMS 	  199
         A.  Control of Participate Emissions 	  199
         B.  Control of Gaseous Emissions 	  202
             1.  Flame Incineration 	  202
             2.  Thermal Combustion 	  204
             3.  Catalytic Afterburners 	  215
      II. DESCRIPTION OF EMISSION CONTROL OTHER THAN BEST CONTROL	  224
         A.  Scrubbers  	  224
         B.  Vapor Condensation  	  224
      III.  METHODS OF CONTROL OTHER THAN ADD ON EQUIPMENT  	  233
         A.  Raw Material Substitution 	  233
             1.  Solvents  	  234
             2.  Pigments and Other Solids  	  235
         B.  Changes in Process or Operating Conditions 	  235
      IV.   PERFORMANCE  OF  CURRENTLY   USED  METHODS   OF   EMISSION
         REDUCTION 	  235
         A.  Performance Data  	  235
             1.  Scrubbers 	  236
             2.  Afterburners  	  236
             3.  Fabric Filters 	  242
         B.  Operating Life and Maintenance Experience for Control Systems  	  242
      V. CAPABILITY TO MEET MORE STRINGENT STANDARDS  	  244
         A.  Fabric Filters  	  249
         B.  Afterburners  	  249
         C.  Scrubbers  	  249
         D.  Refrigerated Condensers 	  250
      VI.  WATER AND SOLID WASTE PROBLEMS ASSOCIATED WITH
         BEST CONTROL  	  250
CHAPTER 6.  INSPECTION PROCEDURES  	  251
      I.  NATURE OF SOURCE PROBLEMS  	  251
      II. PROCESS DESCRIPTION 	  252
         A.  Paint Manufacturing  	  252
         B.  Varnish Cooking  	  254
         C.  Resin Manufacturing  	  257
             1.  Oils or Fatty Acid  	  259
             2.  Polyols  	  259
             3.  Acids and Anhydrides 	  261
         D.  Air Pollution Control Techniques 	  265
      III.  INSPECTION POINTS 	  272
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          A.  Raw Material Handling and Storage  	  275
          B.  Manufacturing  	  275
          C.  Filling and Packaging   	  279
CHAPTER 7.  ECONOMICS OF EMISSION CONTROL  	  281
       I.  COST OF BEST CONTROL EQUIPMENT  	  281
          A.  Thermal Afterburners 	  283
          B.  Catalytic Afterburners   	  284
          C.  Fabric Collectors  	  284
       II.  MODEL PLANT STUDY 	  285
          A.  Capital Cost of Plant 	  285
          B.  Balance Sheet and Operating Statement   	  285
          C.  Balance Sheet and Operating Statement for Controlled Plant  	  288
          D.  Cost of Control Other Than Add-on Equipment  	  289
              1.  Raw Material Substitution 	  289
              2.  Process Modification 	  290
          E.  Varying Types and Levels of Control  	  291
          F.  Impact on Income, Cash Flow and Investment  	  291
       III.  INDUSTRY WIDE STUDIES 	  294
          A.  Present Total Cost to Industry to Meet Best Control Requirements  	  294
          B.  Fifteen Year Projection of the Cost of Control   	  295
          C.  Sources of Capital for Pollution  Control  	  296
          D.  Industry Structure  	  296
          E.  Product Elasticity — Production Substitution   	  297
CHAPTER 8.  PIGMENT INDUSTRY 	  361
       I.  INTRODUCTION 	  361
          A.  Classification and Statistics  	  361
          B.  Purpose and Scope 	  365
       II.  REVIEW OF MAJOR PIGMENTS 	  366
          A.  Cadmium Pigments  	  366
          B.  Zinc  Oxide  	  369
          C.  Chrome Pigments 	  376
              1.  Lead Chromes  	  376
              2.  Zinc Chromes 	  377
              3.  Chrome Green  	  377
              4.  Chromium Oxide Greens  	  377
              5.  Molybdate Orange   	  377
          D.  Iron Oxides  	  378
          E.  Titanium Dioxide Pigments 	  381
              1.  Sulfate Process  	  383
              2.  Chloride Process 	  393
              3.  Industry Statistics — Questionnaires  	  397
                 a.  Products and Raw Materials  	  397
                 b.  Process Equipment  	  399
       III.  EMISSIONS  	  399
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          A.   Description of Emission 	  399
          B.   Source of Emissions   	  404
              1.   Sulfate Process 	  404
              2.   Chloride Process	  406
          C.   Measurement of Emissions  	  406
          D.   Raw Data Tabulated   	  407
              1.   Questionnaires 	  407
                 a.  Digestors  	  407
                 b.  Sulfate Calciners 	  408
                 c.  Drying and Milling 	  408
                 d.  Chlorinators  	  408
                 e.  Summary of Emission Factors  	  415
              2.   Other Sources  	  415
       IV.  EMISSION CONTROL TECHNOLOGY  	  421
          A.   Description of Currently Used Control Systems  	  421
          B.   Other Methods of Control 	  421
          C.   Performance of Currently Used Control Systems  	  421
CHAPTER 9.  RECOMMENDED RESEARCH AND DEVELOPMENT PROGRAMS  	  425
       I.  EMISSION CONTROL TECHNOLOGY  	  425
          A.   Technical Developments for Reduced Levels of Emission  	  425
              1.   Process Chemistry and Kinetics  	  425
              2.   Process Equipment and/or Operations  	  426
              3.   Control Equipment and/or Operations 	  426
          B.   Economic Deficiencies Preventing Reduced Levels of Emissions  	  427
          C.   R&D Priorities to Improve Control Technology 	  427
          D.   Recommended Programs for Achieving R&D Requirements  	  428
              1.   Closed Reactor Design Program 	  428
              2.   Investigation of Methods for Handling Liquid Resin Compounds  	  429
              3.   Development of Inexpensive Solvent Scavenging Systems  	  430
              4.   Development of Transfer System for Direct Flame Incineration  	  431
       II.  MEASUREMENT OF EMISSIONS 	  431
          A.   Deficiencies in Manual Methods of Source Sample Collection and Analysis ..  432
          B.   Deficiencies in Techniques and/or Equipment for Continuous Monitoring
              of Source Emissions  	  432
          C.   R&D Priorities to Improve Measurement Techniques  	  432
          D.   Recommended Programs for Achieving R&D Requirements  	  433
       III.  PIGMENT INDUSTRY 	  435
REFERENCES 	  439
LIST OF STANDARD ABBREVIATIONS  	  442
APPENDICES
BIBLIOGRAPHIC DATA SHEET AND ABSTRACT
                                         XVIII

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                                     LIST OF FIGURES
                                                                                   Page No.

Figure 1     Paint Manufacturing Using Sand Mill for Grinding Operation  	     3
Figure 2    Typical Varnish Cooking Room  	     9
Figure 3    Modern Resin Production System of Solvent and Fusion Cooks  	    25
Figure 4    Materials Flow Sheet for Paint Manufacturing  	    41
Figure 5    Flow Sheet for Solvent Through a Paint-Resin Plant  	    62
Figure 6    Typical Sales and Production Curves — Trade Sales Products  	    69
Figure 7    Typical Inventory Curve — Trade Sales Products  	    70
Figure 8    Grinding Capacity — Ball and Pebble Mills 	    74
Figure 9    Modern Resin Production System  	    78
Figure 10   Model Plant — Factory Manning Chart  	    85
Figure 11   Materials Flow Sheet for Model Paint Plant  	    86
Figure 12   Model Paint Plant  	    87
Figure 13   Model Paint Plant  	    88
Figure 14   Model Plant — Area Plot Plan 	    89
Figure 15   Emission Points  from Raw Material Storage Tanks of Model  Plant 	   102
Figure 16   Emission Points  from Production Areas of Model Plant  	   103
Figure 17   Emission Characteristics — Short Oil Fusion Cook 	   110
Figure 18   Emission Characteristics — Long Oil Solvent Cook  	   113
Figure 19   Hydrocarbon Emission for 500 Gallon, Closed Kettle  	   122
Figure 20   Hydrocarbon Emission for 500 Gallon, Closed Kettle  	   123
Figure 21   Hydrocarbon Emission for 1,000 Gallon, Closed Kettle  	   124
Figure 22   Hydrocarbon Emission for 1,000 Gallon, Closed Kettle  	   125
Figure 23   Hydrocarbon Emission — 2 Batches Monitored  	   126
Figure 24   Hydrocarbon Emission for 2,500 Gallon, Closed Kettle  	   127
Figure 25   Emissions from 100 Gallon Epoxy Reactor Solvent Pressure Cook
              — 30 psig  	   129
Figure 26   Emission from 2,000 Gallon Reactor  	   130
Figure 27   Emission from 1,500 Gallon Polyester Reactor Fusion Cook  	   131
Figure 28   Emission from Two-1,000 Gallon Reactors 	   132
Figure 29   U.S. Paint & Varnish Industry Distribution  by Product Class  	   152
Figure 30   U.S. Paint & Varnish Industry Distribution  by Production Value Size Class 	   154
Figure 31   U.S. Paint & Varnish Industry 1971  Distribution of Plants & Employees by
              Plant Size  	   155
Figure 32   U.S. Paint & Varnish Industry Distribution  by State Estimated 1972
              Production  	   158
Figure 33   U.S. Paint & Varnish Industry Shipments (Actual & Forecast) —
              Million Gallons  	   159
Figure 34   U.S. Paint & Varnish Industry Shipments (Actual & Forecast) —
              Million Dollars   	   160
Figure 35   U.S. Paint & Varnish Industry Distribution  by State (Actual &  Projected)  	   162
Figure 36   U.S. Paint & Varnish Industry Distribution of Plants by Size —
              Number of Employees  	   164
                                            XIX

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                                                                                 Page No.

Figure 37    U.S. Paint & Varnish Industry Capital Expenditures — Million Dollars  	    167
Figure 38    Particulate — Sampling Train	    182
Figure 39    Schematic Flow Diagram of Flame lonization Detector  	    186
Figure 40    Hydrocarbon Monitoring System  	    187
Figure 41    Geographical Distribution of Organic Emissions from Paint Production 1972  ...    198
Figure 42    Pigment Emission Control System  	    200
Figure 43    Schematic Diagram of a Flame Incineration Unit 	    203
Figure 44    Schematic of Typical Thermal Afterburner and Control System  	    205
Figure 45    Residence Time vs. Temperature at 95% Conversion and 2 Btu/SCF  	    208
Figure 46    Conversion vs. Temperature at 0.6 sec Residence Time and 2 Btu/SCF 	    209
Figure 47    Conversion vs. Inlet Concentration at 0.6 sec Residence Time
              and 1350ฐF Outlet	    211
Figure 48    Schematic of Typical Thermal Afterburner and Control System  	    213
Figure 49    Schematic Diagram of a Catalytic Oxidation System for Varnish Kettles  	    216
Figure 50    Catalytic Oxidation Rates for Solvents  	    218
Figure 51    Reaction  Rate Constants for Low,  Intermediate, and High Temperatures  	    222
Figure 52    Comparison of Thermal and Catalytic Reaction Rates for Maleic Anhydride  ....    223
Figure 53    Refrigerated Condenser System for Control of Resin Kettles  	    225
Figure 54    Refrigeration System  	    227
Figure 55    Two Stage Condenser System  	    228
Figure 56    Emission Characteristics — Kettle D  	    232
Figure 57    Paint Manufacturing Using Sand Mill for Grinding Operation 	    253
Figure 58    Materials Flow Sheet for Paint Manufacturing  	    255
Figure 59    Typical Varnish Cooking Room  	    258
Figure 60    Modern Resin Production System  	    266
Figure 61    Pigment Emission Control System  	    268
Figure 62    Thermal Afterburner System for Resin Reactor or Closed Kettle  	    270
Figure 63    Schematic Diagram of a Catalytic Afterburner System for Varnish Kettles 	    271
Figure 64    Capital Costs for Catalytic Afterburners Without Heat Exchange  	    327
Figure 65    Capital Costs for Catalytic Afterburners With (23% Efficient) Heat Exchange ...    328
Figure 66    Capital Costs for Thermal Afterburners Without Heat Exchange  	    329
Figure 67    Capital Costs for Thermal Afterburner With (42% Efficient) Heat Exchange  	    330
Figure 68    Total Installed Costs for Thermal and Catalytic Afterburners 	    331
Figure 69    Direct Annual Operating Costs for Thermal and Catalytic Afterburners
              Without Heat Exchange 	    332
Figure 70    Total Annual Operating Cost for Thermal and Catalytic Afterburners
              Without Heat Exchange 	    333
Figure 71    Direct Annual Operating Cost for Thermal and Catalytic Afterburners
              With Heat Exchange  	    334
Figure 72    Total Annual Operating Cost for Thermal and Catalytic Afterburners
              With Heat Exchange  	    335
Figure 73    Model Plant Factory Manning Chart   	    350
                                            xx

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                                                                                 Page No.

Figure 74    Flow Diagram for Cadmium Sulfide Production  	   368
Figure 75    Flow Sheet for French Process  	   371
Figure 76    Flow Sheet for American Process  	   372
Figure 77A  TiO2 Manufacture Sulfate Process  	   386
Figure 77B  TiO2 Manufacture Sulfate Process  	   387
Figure 78    TiO2 Manufacture Chloride Process  	   394
Figure 79    Exhaust Rate from Sulfate Process Digestion Tanks  	   418
Figure 80    Calciner Emission Control System  	   419
                                         XXI

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                                    LIST OF TABLES
                                                                                Page No.

Table 1      Varnish Raw Materials  	     8
Table 2      Questionnaire Distribution  	    44
Table 3      Geographical Distribution of Questionnaires 	    46
Table 4      Percentage Distribution of Questionnaires, Paint Plants, and Value of
              Shipments  	    47
Table 5      Industry Questionnaire — Tabulation Summary 	    48
Table 6      Industry Questionnaire — Tabulation Summary 	    49
Table 7      Solvent Usage 	    54
Table 8      Drying Agents and Mercury Compounds  	    57
Table 9      Mills, Mixers, Etc	    59
Table 10    Solvent Tanks Over 5,000  Gallons  	    61
Table 11     Filling Losses for Selected  Solvents @ 20ฐC  	    61
Table 12    Reactor Usage, Gallons of Kettle Volume  	    64
Table 13    Resin Processing,  Number of Plants  	    64
Table 14    Model Plant — Product Mix 	    66
Table 15    Model Plant — Trade Sales Color Distribution  	    66
Table 16    Model Plant — Product Type  	    67
Table 17    Model Plant — Finished Goods Inventory — Maximum Projection  	    71
Table 18    Model Plant — Equipment  Specifications   	    72
Table 19    Model Plant — Paint Formulations for Alkyd Type Coatings  	    75
Table 20    Model Plant — Summary of Tankage Requirements   	    79
Table 21     Model Plant — Annual Raw Material Consumption 	    82
Table 22    Model Plant — Annual Package and Package Material Requirements  	    83
Table 23    Model Plant — Labor Requirements  	    84
Table 24    Composition of Oil and Varnish Emissions 	    93
Table 25    Odor and Composition (by  Functional Groups) of Oil and Varnish Emissions  ...    94
Table 26    Solvent Characteristics  	    96
Table 27    Maximum OSHA Allowable Concentration Limits 	    97
Table 28    Odor Thresholds of Some Organic Vapors 	    98
Table 29    Particle Size Range of Various Pigments and Extenders 	    99
Table 30    Operating Parameters for Model Plant Storage Tank Emission Sources  	   104
Table 31     Emissions During Filling for Model Plant Storage Tanks  	   105
Table 32    Contaminant Levels in Various Parts of Model Paint Plant  	   107
Table 33    Emissions from Model Plant Production Area Exhaust 	   108
Table 34    Summary of Emissions from Model  Plant  500 Gallon  Fusion Reactor
              and 1,500 Gallon Solvent Reactor  	   114
Table 35    Emission  Data Summary 	   116
Table 36    Emission  Summary for Gaseous Contaminants — Model Plant  	   117
Table 37    Source Test Summary for Paint Plant  	   121
Table 38    Emission  Data from Questionnaires — Paint and Resin Plants  	   139
Table 39    Emission  Data from Questionnaires — Paint Plants  	   140
Table 40    Emission  Data from Questionnaires — Resin Plants   	   141
                                           XXII

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                                                                                   Page No.

Table 41    Questionnaire Summary of Waste Material Disposal — Odor Complaints
              from Questionnaires  	   142
Table 42    Summary of Tested Batches  	   145
Table 43    U.S. Paint & Varnish Industry Distribution of Plants by Employee Size Class  ...   165
Table 44    U.S. Paint, Varnish and Inorganic Pigments Industry 1967 Labor and
              Finance Summary 	   173
Table 45    Common Raw Materials and Solvents Used in the Manufacture of Resins  	   176
Table 46    Solvent Boiling Ranges  	   177
Table 47    Emission Factors from Selected Paint Plants  	•	   194
Table 48    Emission Factors from Selected Resin  Plants  	   195
Table 49    Emission Factors from Selected Plants Producing Coatings and  Resins   	   196
Table 50    Kettle A — Alkyd Cook  	   230
Table 51    Kettle D — Polyester  	   231
Table 52    Type 1 Plants — Air Pollution Control — Loading Mills, Etc. — Fabric
              Filters — Scrubbers 	   237
Table 53    Type 1 Plants — Air Pollution Control — Reactors and Kettles — Scrubbers  ...   239
Table 54    Type 3 Plants — Air Pollution Control — Reactors and Kettles —
              Afterburners Scrubbers  	   240
Table 55    Air  Pollution Control — Reactors and Kettles — Thermal Afterburners —
              Catalytic Afterburners  	   241
Table 56    Type 2 Plants — Air Pollution Control — Loading, Mills, Etc. — Fabric
              Filters  	   243
Table 57    Type 3 Plants — Air Pollution Control — Loading, Mills, Etc. — Mechanical
              Fabric Filters	   245
Table 58    Test Result of Control Equipment Efficiencies  	   246
Table 59    Thermal Afterburner Test Data  	   247
Table 60    Operating Life and Maintenance Requirement for Air Pollution Control
              Equipment  	   248
Table 61    Varnish Raw Materials 	   256
Table 62    Classification of Typical Solvents  	   276
Table 63    Filling Losses for Selected Solvents @ 20ฐC  	   277
Table 64    Specifications for Abatement Equipment  	   299
Table 65    Instructions for Submitting Cost Data  	   302
Table 66    Thermal Afterburner Process Description for Resin Reactor Specification 	   304
Table 67    Thermal Afterburner Operating Conditions for Resin Reactor Specification
              (Without Heat  Exchange)  	   306
Table 68    Thermal Afterburner Operating Conditions for Resin Reactor Specification
              (Without Heat  Exchange)  	   307
Table 69    Thermal Afterburner Operating Conditions for Resin Reactor Specification
              (With Heat Exchange)  	   308
Table 70    Thermal Afterburner Operating Conditions for Resin Reactor Specification
              (With Heat Exchange)  	   309
                                            XXIII

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                                                                                  Page No.
Table 71     Thermal Afterburner Process Description for Open Kettle Specification 	  310
Table 72     Thermal Afterburner Operating Conditions for Open Kettle Specification
              (Without Heat Exchange)   	  312
Table 73     Thermal Afterburner Operating Conditions for Open Kettle Specification
              (Without Heat Exchange)   	  313
Table 74     Catalytic Afterburner Process Description for Resin Reactor Specification 	  314
Table 75     Catalytic Afterburner Operating Conditions for Resin Reactor Specification
              (Without Heat Exchange)   	  316
Table 76     Catalytic Afterburner Operating Conditions for Resin Reactor Specification
              (Without Heat Exchange)   	  317
Table 77     Catalytic Afterburner Operating Conditions for Resin Reactor Specification
              (With Heat Exchange) 	  318
Table 78     Catalytic Afterburner Operating Conditions for Resin Reactor Specification
              (With Heat Exchange) 	  319
Table 79     Catalytic Afterburner Process Description for Open Kettle Specification 	  320
Table 80     Catalytic Afterburner Operating Conditions for Open Kettle Specification
              (Without Heat Exchange)   	  322
Table 81     Catalytic Afterburner Operating Conditions for Open Kettle Specification
              (Without Heat Exchange)   	  323
Table 82     City Cost Indices  	  324
Table 83     Average Hourly Labor Rates by Trade 	  325
Table 84     Installation and Operating Cost for Baghouse  	  326
Table 85     Model  Plant Annual Raw Material Costs  	  336
Table 86     Model  Plant Annual Package &  Package Material Costs 	  338
Table 87     Model  Plant Annual Wage & Salary Cost of Plant 	  339
Table 88     Model  Plant Depreciation Schedule   	  341
Table 89     Model  Plant Income Statement   	  342
Table 90     Model  Plant Production  Schedule 1.9 Million Gallons Output  	  344
Table 91     Model  Plant Balance Sheet   	  346
Table 92     Model  Plant Cash Flow  Statement 	  347
Table 93     Model  Plant Return on Investment 	  348
Table 94     Model  Plant 1.9 Million Gallon Finished Output  	  349
Table 95     Model  Paint Plant Cost, Dollars  	  351
Table 96     Model  Paint Plant Cost, Dollars  	  352
Table 97     Model  Controlled Plant Depreciation Schedule 	  353
Table 98     Model  Controlled Plant Income Statement   	  354
Table 99     Model  Controlled Plant Balance Sheet 	  356
Table 100   Model  Controlled Plant Cash Flow Statement  	  357
Table 101   Model  Controlled Plant Return on Investment  	  358
Table 102   Model  Controlled Plant Air Emission Control Devices 	  359
Table 103   Pigment Production by Major Type 	  363
                                            XXIV

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                                                                                  Page No.
Table 104   Major White Pigments  	   363
Table 105   Production of Organic Pigments   	   364
Table 106   Production of Major Inorganic Color Pigments  	   364
Table 107   Zinc Oxide Producers  	   375
Table 108   Analysis of llmenite Ores   	   384
Table 109   TiO2 Industry Questionnaire Tabulation Summary 1972  	   398
Table 110   TiO2 Industry Questionnaire Production — Raw Materials Inventory
              Five TiO2 Plants 	   400
Table 111   TiO2 Industry Questionnaire Sulfate Process Equipment  	   401
Table 112   TiO2 Industry Questionnaire Chloride Process Equipment  	   402
Table 113   TiO2 Industry Questionnaire Mills, Etc	   403
Table 114   Sulfate Process Emissions — Drying and Milling  	   409
Table 115   Chloride Process Emissions — Drying and Milling  	   410
Table 116   Chlorinator Emissions After Control  	   412
Table 117   Chlorinator Emissions Before Control  	   413
Table 118   Plant 6 — Emission Inventory  	   414
Table 119   Estimate of Emission  Factors for Uncontrolled Processes  	   416
Table 120   TiO2 Industry Questionnaire Particulate Control Devices  	   422
Table 121   TiO2 Industry Questionnaire Emission Control Devices   	   423
                                          xxv

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                                        CHAPTER 1
                                 PROCESS AND EMISSION

        In this chapter a discussion  of the process operations used in the manufacture of paint,
varnishes and resins will be presented. The type, quantity and source of emissions evolved from
these processes will also be presented.

I.       PROCESS
        This section will cover process operations only. The discussion will include a brief history of
the industry, a description of the various manufacturing processes, the influence of process operation
on emissions and detailed material balances. The material balance will be based on the model plant
developed for the industry.

A.	Detailed Process Description
J^	History — The paint and varnish industry is one of the oldest manufacturing industries in the
United States. The industry is made up of about 1,500 companies operating about 1,700 plants.1 The
industry is well distributed geographically throughout the country and production volume is definitely
related to density  of population. Even though about 36 companies account for about 64% of the
total sales, the industry is one of the few remaining which  contains numerous small companies that
specialize in a limited product line to be marketed within a geographical region. There are fewer than
20 companies that sell paint nationwide.
       The industry is now emerging as a scientific business from its beginning as an art, 50 years
ago. Even with rapid growth in technology, the industry process techniques still are not well  defined
and not only vary from one producer to another but there is also variation in the techniques used by a
single producer.  To add further complication, the industry is technically one of the  most complex of
the chemical  industry. A plant that produces a broad line of products might utilize over 600 different
raw materials and purchased intermediates. These materials can be generally classified in the following
categories: oils,  metallic driers, resins, pigments,  extenders, plasticizers, solvents, dyes, bleaching
agents, organic monomers for resins, and additives of many kinds.

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       The industry produces an equally large  number of finished products which are generally
classified as trade sale finishes, maintenance finishes, and industrial finishes.
       Trade sale products  are  stock-type  paints generally distributed  through wholesale-retail
channels and packaged in sizes ranging from 1/2 pint to 1 gallon. A subdivision of trade sale products
are maintenance finishes  which are  used for the protection and upkeep of factories, buildings, and
structures such as bridges and storage tanks. Since they are usually stock type,  they come under
the Department of Commerce definition of trade sales.
       The other major type of paint products are industrial finishes which are generally defined as
those applied to manufactured  products.  These  finishes, such as  automotive,  aircraft, furniture,
and electrical finishes are usually  specifically formulated  for the using industry. Within these major
product lines there are  literally thousands  of different products  for many different applications and
types of customers. Trade sale finishes and industrial finishes are  produced in almost equal volume
with the production for 1972 estimated at 465 million gallons for trade sales and 485 million gallons
for industrial finishes. Trade sales, however, are estimated to account for 55% of the dollar sales or
about $1,715 million dollars.1
2.	Description of Manufacturing Process — Starting with all purchased raw material, the manu-
facturing process for pigmented products appears simple from  a  schematic  viewpoint. Basically,  it
consists of  mixing or  dispersing  pigment and vehicle to give the final product. This  process is
schematically illustrated in Figure 1.
       The paint vehicle  is  defined as the liquid portion  of the paint and consists  of volatile solvent
or dispersing medium  and non-volatile binder such as oils and resins. The non-volatile portion is
also called the vehicle solid or film former. The pigment portion of the paint consists of hiding pigments
such as titanium dioxide (TiO2), extenders such as talc or barium sulfate, colorants, and any mineral
matter used for flatting or  other purposes.
       Also included in the  non-volatile portion of the coatings are various additives present in small
quantities for a variety of reasons.  From an environmental standpoint the most important of these are
the preservatives and the  driers. The preservatives are fungicides and mildewcides which sometimes
contain mercury  compounds. While they are  present in small  quantities, they have  nevertheless
become of interest to health and regulatory  agencies. It  is anticipated  that the use  of mercury will
be substantially eliminated in the next few years.
       The driers are catalysts whose purpose is to promote the oxidative cross-linking of the resins
and/or oils used in coatings. Without such catalysts many of the coatings in use today  would not be

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possible since they would never dry completely, or at least would dry too slowly to be of practical value.
The common driers  are organic acid salts of lead, cobalt, calcium, zinc, manganese, or zirconium.
Lead naphthenates have historically been the most often used but recent regulations limiting lead to
0.5% of the dried film and possibly more stringent future regulations have prompted  some degree of
reformulation of the drier systems.
        The incorporation of the pigment  in the paint vehicle is  accomplished by a combination of
grinding and dispersion or dispersion alone. When it is necessary to further grind the raw pigment,
pebble or steel ball  mills are normally used. With the advent of fine particle grades of pigment and
extenders, as well as the wide spread use of wetting agents, the trend  is toward milling methods
that are based on dispersion  without grinding. Dispersion consists of breaking up of the pigment
clusters and agglomerates, followed by wetting of the individual particles  with the binder or vehicle.
Some of the more popular methods currently being used are high-speed  disc impellers, high speed
impingement mills and the sand mill.
        Some typical paint formulas, both  simple and complex, are listed below and on the following
page.

                             WHITE ACRYLIC BAKING ENAMEL*
                                                                  Ib         gal
         Rutile TiC-2                                              220.3         6.64
         Thermosetting acrylic resins (50% NVM)                    444.1        54.20
         Melamine  resin (100% NVM)                               95.2         9.52
         Catalyst for melamine                                     6.63         0.87
         Xylol                                                    184.0        25.51
         Ethylene glycol monoethyl ether  acetate                     26.4         3.26
                                                                 976.3       100.00
 'Formulas courtesy of Ashland Chemical Company.

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                           WHITE GLOSS INTERIOR ENAMEL*
                                                               Ib         gal
        Rutile TiO2                                            300.0        9.02
        Suspension and flow agent                                8.0        1.15
        Long-oil, tall oil alkyd (70% NVM)                         536.0        67.0
        Mineral spirits                                          150.0       23.08
        6% Co naphthenate                                      4.4        0.56
        4% Ca naphthenate                                      9.4        1.25
        6% Zr drier catalyst                                     12.5        1.75
        Antiskinning agent                                        1.0        0.13
                                                            1,021.3      103.94
                      POLYVINYL ACETATE EMULSION WALL PAINT*
       Grind (high speed mill)                                    Ib          gal
       Water                                                275.0       33.05
       KTPP, dispersant                                         2.0        0.10
       R&R-551 soya lecithin dispersant                           8.0        0.92
       Tergitolฎ NPX, dispersant                                 2.0        0.23
       Nopcoฎ NOW,  anti-foamer                                 0.5        0.07
       Rutile titanium dioxide                                   200.0        5.94
       Diatomaceous silica                                      45.0        2.34
       Clay                                                  130.0        6.05
       Calcium carbonate                                     100.0        4.43
              Sub-total                                       762.5       53.13
       Reduction
       Methocelฎ 65HG (31/2%  solution)                         120.0       14.42
       Carbitolฎ acetate,  coalescing agent                        25.0        2.98
       Nopcoฎ NOW, anti-foamer                                 0.5        0.07
       PVAc emulsion                                         224.0       24.62
       Water                                                 10.0        1.20
              Pre-mix
       PMS-30, mildewcide                                      0.3        —
       Water                                                 30.0        3.61
              Total                                          1,172.3      100.03
'Formulas courtesy of Ashland Chemical Company.
                                         5

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       Aside from the dispersion step, pigment paint manufacturing involves handling of raw material
as well as handling and packaging of finished product.
       Air pollutant emissions are primarily the fugitive type and consist of evaporation losses of
the volatile portion of the vehicle from the milling operation and from various product holding tanks
and packing stations.  There are also some fugitive paniculate emissions that  result from handling
and emptying  of pigment  or extender bags into the  grinding and dispersion mills.  In  some plants
these loading  areas are  hooded  and bags and pigment dusts are passed to  a central collection
station. At this station bags are removed for refuse disposal and the pigment dust is collected in a
fabric filter and recycled into primer or other dark paint mixes.
       Some  of the larger and a few  of  the  medium manufacturers make a  significant  amount
of their formulation ingredients, such as pigments, resins, and  modified oils. Some manufacturers
produce these ingredients in an amount exceeding their requirements and  sell the excess to other
manufacturers. A  significant number also  make only  a portion of their resins  and purchase  the
remainder from their competitors or suppliers who specialize  in resin manufacturing.
       The manufacturing of resins  and varnishes is  by far the most complex  process in a paint
plant, primarily as  the  result of the large variety of  different raw materials, products and cooking
formulas  utilized. One manufacturer has reported that  he has over 9,300 active resin formulas. Of
these 600 to 700  are in general monthly use while the remainder are produced on an  intermittent
basis. Furthermore, new formulas are added at the rate of 5  to 10 per month. While this  plant is not
typical since it produces a more diverse product line than most, it  nonetheless  serves to illustrate
the wide diversity found in  the industry. This diversity is the source of the difficulty that is encountered
in attempting to characterize the industry or in making generalized statements about emissions, control
technology, or any other subject for that  matter.
       The complexity begins with  the nomenclature used in classification of the final product.
Originally, varnishes were  all made from naturally occurring material  and they were easily defined as
a homogeneous solution of drying oils and  resins in organic  solvents. As new synthetic resins were
developed, the resulting   binders or varnishes were classified on the basis  of the  resins used.
Examples of this are alkyd, epoxy, and polyurethane resins. In an attempt to simplify nomenclature
the industry is attempting to adopt the  term "clear coating" to cover some varnishes,  resins and
lacquers.
       There  are  two basic types of varnishes,  spirit varnishes and oleoresinous varnishes.2 Spirit
varnishes are formed by dissolving a resin  in a solvent and  they dry by evaporation of the solvent.

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The dry film formed undergoes no substantial change in the process of drying and is classified as
non-convertible. A good example  of this type of varnish is shellac which is a mixture of a natural
resin and  alcohol.
        Materials that might fall in the general category of spirit varnishes, that use nitro-cellulose
or similar compounds for their basic film former, have by common practice been termed lacquer. These
are defined as a colloidal dispersion or solutions of nitro-cellulose, or of similar film-forming compounds,
with resins and plasticizers in solvents and diluents which dry primarily by solvent evaporation. One
of the advantages  and general characteristics  of spirit  varnishes  is that  upon recoating, the film
will soften and partially redissolve so that patched areas show no sharp line of demarcation.
        Oleoresinous varnishes, as the name implies, are  solutions of both oils and resins.  These
varnishes dry  by solvent evaporation and by reaction of the non-volatile liquid portion with oxygen in
the air to  form a solid film. They are classified as oxygen convertible varnishes and the film formed
on drying  is insoluble in the original solvent. A summary of the various types of material used in the
production of classical Oleoresinous varnishes is given  in Table  1.
        Varnish is cooked in both portable kettles and large reactors.  Kettles are used only to a
limited extent and primarily by the smaller manufacturers. The very old, coke fired, 30 gallon capacity
copper kettles are no longer used.  The varnish kettles which are used, have capacities of  150 to 375
gallons. These are  fabricated of stainless steel,  have straight sides and are equipped with three or
four-wheel trucks.  Heating is done with natural gas or fuel oil for  better temperature control. The
kettles are fitted with retractable hoods and exhaust pipes, some of which may incorporate solvent
condensers. Cooling and thinning  is normally done in special  rooms.  A typical varnish  production
operation  is  illustrated in Figure 2.
       All of the resin manufacturers and most of the large and medium size paint manufacturers
utilize large indirectly heated closed reactors for varnish production. These reactors will be described
in more detail  in later report sections covering modern resin manufacturing.
       The manufacturing of Oleoresinous varnishes is somewhat more complex than for spirit
varnishes. Manufacture  of this product consists  of the  heating or cooking of oil and resins together
for the purpose of obtaining compatability of resin and oil and solubility of the mixture in  solvent as
well  as for development of higher molecular weight molecules or polymers.
       The time and temperature of the cook are the operating variables used to develop the desired
end  product polymerization or "body".  The chemical reactions that  occur are  not well defined. The
resin is a  polymer before cooking  and  may or may not increase in  molecular size during the cook.

-------


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The resin may react with the oil to produce copolymers of oil and resin, or it may exist as a homogeneous
mixture or solution of oil homopolymers and resin homopolymers.
       In special cases it is possible to produce oleoresinous varnish without the application of heat
by simply dissolving or "cold  cutting" the  resin and heat bodied oil in the solvent. Heat bodying or
polymerization of an  oil  is done to increase its viscosity and is carried out in  a kettle  in a fashion
similar to varnish cooking. The fundamental reaction that occurs is polymerization of the oil monomers
to form dinners with a small portion of trimers.
       It is possible to  blend resins and  heat bodied oil and obtain the same varnish that can be
produced  by cooking the resin  and the unbodied oils.  This  indicates  that copolymerization is  not
the fundamental reaction in varnish cooking.
       A fundamental variable that determines  the final property of a varnish is the proportion of
oil to resin. It is expressed as gallons of oil to 100 pounds of resin. On this basis, varnish is generally
classified as follows:
               Short oil:     5 to 15 gallons (28 to 54% oil*)
               Medium  oil:   16 to 30 gallons (54 to 70% oil*)
               Long oil:      30 to 60 gallons (70 to 86% oil*)
'Percentages based on an oil of approximately 7.8 Ib/gal.
       A myriad of formulations are used in varnish manufacture. Typical varnish cooking formulations
are given below:2
                  20 GALLON CAN COATING VARNISH — STRAIGHT COOK
                                                                  Ib          gal
        Amberol M-88 modified phenolic resin*                      100        11.24
        Castungฎ 403 Z3 dehydrated castor oil**                     160        20.00
        Kadoxฎ 25, ultra-fine zinc oxide***                            3         —
        Manganese naphthenate (6% Mn)                            2         0.25
        Mineral spirits                                             235        36.70
               Theoretical yield                                   500        68.19
  * Rohm and Haas Co.
 ** Baker Castor Oil Co.
 *** New Jersey Zinc Co.
                                          10

-------
                                         Procedure
       Heat resin and oil to 580ฐF (304ฐC) in 45 minutes. Add zinc oxide and hold 580ฐF about 30
minutes to body (50 seconds Ford No.  4 Cup at 52% solids in mineral  spirits). Cool quickly by
water spray to 450ฐF (232ฐC) add thinner and drier and filter carefully.
                                         Constants
              Solids  	52% minimum
              Viscosity  	50 to 60 sec. in Ford No. 4 Cup (about G-l)
              Color, Gardner 1933  	14 to 18
              wt/gal  	7.4 Ib
       The above formula  is made in portable kettles.  High  temperature  is necessary to develop
maximum resistance, yet cooling must be fast to avoid overpolymerization. It is probably impossible
to handle batches larger than 300 gallons safely.
                PHENOLIC RESIN SPAR VARNISH* — DISPERSION METHOD
                                                                 Ib          gal
       Phenolic resin CKM 5254                                 100.0        10.0
       Alkali refined linseed oil                                    85.0        11.0
       Tung oil                                                 164.0        21.0
       Refined castor oil                                          8.0        1.0
       Mineral spirits                                           202.0        31.0
       Dipentene                                                26.9        3.8
       Turpentine                                               26.9        3.8
       n-Butyl alcohol                                           13.45        2.0
              Theoretical yield                                 626.25        83.6
                                         Procedure
       Heat the resin and linseed oil to 560ฐF (293ฐC) for 30  minutes for body. Check with tung oil.
(Reduces to about 350ฐF.) Reheat to 450ฐF (232ฐC) in 15  minutes for body, add castor oil, thin and
filter.
                                         Properties
              Viscosity  	C to D
              Solids  	57%
              Color, Gardner 1933  	11
              wt/gal  	7.57 Ib
'Formula courtesy of Union Carbide Corporation, Chemicals and Plastics
                                          11

-------
                                       Driers (on oil)
               Lead  	0.1 %
               Cobalt  	0.01%
               Manganese  	0.005%

               INSITU GENERAL PURPOSE VARNISH — UNIPHASE METHOD2
                                                                 Ib          gal
       Alkali refined soya oil                                                  23.7
       Hydrated lime paste*                                grams 32
       Pentaerythritol                                             19
       Glycerol                                                  21
       Tall oil rosin                                              135
       Maleic anhydride                                           38
       Mineral spirits                                             372         58.0
       Activ 8**                                            fl oz   2      	
               Calculated net yield, allowing for
                  loss in processing                                         100.0
                                         Procedure
       Maintain CO2  over  batch throughout the cook.  Heat soya oil to 400ฐF (204ฐC),  add lime
paste, gain 450ฐF (232ฐC). Add the pentaerythritol slowly, keeping the temperature at 425 to 450ฐF
for 45 minutes.  Open condenser, close stack, and heat to 470ฐF (243ฐC). Hold at 460 to 470ฐF. Add
the glycerol through the  funnel, keeping  the temperature above 425ฐF.  Heat to  460ฐF,  and hold
460 to 470ฐF for solubility of at least 2:1  in methanol. Cool  to 400ฐF by circulating cold Dowtherm
through the jacket. Open  stack and close  the condenser. Add the rosin. After the rosin has  melted,
add the maleic anhydride. Heat to 520ฐF and hold for a reduced viscosity of  I-J  at 50% solids in
mineral spirits. Drop to 480ฐF (249ฐC) and hold for a reduced viscosity of T-U. Cool, thin and filter.
       The major problem in varnish cooking is control of  cooking time and  temperature to yield
 * Hydrolysis catalyst, a paste of hydrated lime in soya oil.
** An  organic  drying catalyst —  R.  T.  Vanderbilt Co. It supplements metallic driers; does not
  replace them.
                                          12

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the desired product and prevention of over bodying or gelation. This is done by a variety of cooking
methods and control techniques. The main methods for cooking modern oleoresinous varnishes are
listed below and the technique used is primarily a function of the type of ingredients employed.
        (1)  Regular or straight cook.
        (2)  Oil-checked method.
        (3)  Resin-checked method.
        (4)  Dispersion method of split-cook.
        (5)  Insitu or uniphase method.
These various  methods are used  to prevent gelation and/or improper dispersion.  Methods (1) and
(4) apply when cooking varnishes from the material listed in Table  1. They are suitable for cooking
in the small portable kettles discussed earlier. Control of these cooks is done by  examination of a
cold pill on glass. The criteria  used are the clarity and the tack and string of the pill when touched.
        The fifth method,  listed above, for insitu cooking is  carried  out primarily in  large set kettles
or reactors. As indicated  in the  insitu  formula listed earlier, the principle of this type of cooking is
simultaneous reaction of  basic raw material to form resin or both resin and  oil which further react
to form the desired varnish in one continuous operation. This is a  much more  complicated cook
and more  sophisticated  control  is required. The  end point of the cook is  controlled  by periodic
viscosity measurements or using a remote viscosity instrument. The reaction is carried out in a closed
kettle blanketed with an inert atmosphere. An inert gas  is bubbled through the mixture to aid in the
removal of water formed from esterification of the organic and/or rosin acids and polyols. The reactions
involved are illustrated on the  following page.

        Resins, along with drying  oils,  make up  the backbone of surface coatings since  they are
responsible for the formation  of  a film with  physical integrity and adhesion. It is the ability to form
this film that differentiates paint from a mere mixture of  pigment and vehicle.  Film formers  are such
a critical component of  the finish  product that the  latter is generally classified by the predominant
resin associated with it (e.g. epoxy and polyurethane).
        In their original usage resins were various  natural solid and semi-solid organic substances
(such as rosin  and shellac) exuded from certain plants  and trees,  however,  since the mid 1920's
natural resins have been supplanted by synthetically manufactured chemicals. Manufactured phenolics
first became commercially available in 1924, alkyd vehicles in 1925, and alkyd resins modified by
urea-formaldehyde in  1925. Each  of these  introductions  represented a major breakthrough  in the
                                           13

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                 FATTY ACID TO  OIL


      CH2OH                     CH2OOCR '

      CHOH + 3RCOOH 	>  CHOOCR + 3H20

      CH2OH                     CH2OOCR

    Plyol (Glycerol)   +   3 Fatty Acid      ->•   Triglyceride    + 3 water
                    MALEIC RESIN


R-CH2-CH=CH-CHa-R + HC = CH	> R~CH=CH-CH-R
                      I    I                   I
                                           HC - (

   OIL OR RESIN     0   0   0

                                          C
                 MALEIC ANHYDRIDE
                                        OIL OR RESIN
                                          ADDUCT
                                R1   R1
                                I     I
      R  MA   +   G  	>  -G-MA-G-MA-G-
                              1,1     I
      ADDUCT   GLYCEROL       0 R -MA   OH
                              H     I
                                   G-OH

                                R'-MA


                             MALEIC RESIN
                      14

-------
production  and application  of surface coatings. In  1970 resins  accounted for approximately 18%
by weight and 40% by production value of all chemical raw materials consumed  by the paint and
varnish  industry (this was equivalent to about $0.32/lb for synthetic resins as opposed to  $0.15/lb
for total raw materials). By  comparison natural  resins comprised less than 2% of  total film formers
in 1970 where prior to World War II they had contributed more than 50%.3
        There  is a large variety of synthetic resins produced for  use in the manufacture of surface
coatings. A listing of  the more popular resins is given below.  They  are listed by order  of 1970
consumption by the coatings industry.3
                                                   Consumption — 1970
                        	Resin	           (million pounds)
                        Alkyd                              680
                        Vinyl                              300
                        Acrylic                             220
                        Epoxy                              80
                        Cellulosic                           65
                        Amino                              60
                        Urethane                            55
                        Rosin ester                         50
                        Styrene                             40
                        Phenolic                            35
                        Hydrocarbon                        30
                        Other synthetic                      45
        By  far the most widely used resins are the alkyds whose  consumption is twice that of its
nearest rival, the vinyls. Oil  free polyesters, included in the "other" group in 1970, are enjoying rapid
growth.  Based on the questionnaire sample obtained for this study, 1972 production was at least
91 million pounds.
        Resins are polymer molecules built up from simpler units, or building blocks. The union of
these building blocks  is  generally brought about by the action of heat and catalyst.  When  the
polymer molecule is a simple repetition of the  same unit  it  is a homopolymer; when two  or more
different type units are present a copolymer results. To be capable of polymerizing,  a monomer must
contain chemical groups that have  potential chemical reactivity. The major monomers used are those
containing one ethylene double bond which permits very long chain polymers.
       There  are two types of polymers  used in coatings: condensation polymers and  addition
                                          15

-------
polymers. A condensation polymer is a polymer formed from the reaction of two (or more) different
types of molecules with the splitting out of some product,  usually water.  Addition polymers are
formed from the "addition" of molecules, or monomers, to form the larger molecule without any other
reaction product.
       Examples of condensation polymers include  polyesters, amino resins, and alkyds.  Alkyds
are really oil modified  polyesters and constitute the most important groups. Polyester type resins
are formed from acid-alcohol reactions. Polymer formation requires the use of polyfunctional reactants.
Difunctional  reactants produce linear polymers while the use of trifunctional, or higher, constituents
permits branching and cross linking to take place.
       Examples of addition polymers  include the acrylics and vinyls. These proceed via a free
radical mechanism in the presence of a catalyst to produce  linear polymers.  Modifiers can be intro-
duced to produce cross linking where desired.
       In addition to the kind of building blocks used, the average number units in (or total molecular
weight of) the product molecule determines properties of the resin. In general, increasing molecular
weight improves film hardness, strength, resistance to water, chemicals  and solvents but also results
in reduced solubility and higher viscosity. Of course, ultimate film properties can also be determined
by appropriate combinations of two, or more, resin types.  In fact, a significant portion of coating
formulations utilize such combinations.
Alkyd Resin — Alkyds are widely used for a variety of reasons. They are ideal vehicles for pigmented
coatings and exhibit good wetting and dispersing properties. They use low cost solvents with minimum
odor and  produce coatings  having excellent durability, flexibility and gloss retention. Coatings can
be formulated with good solvent resistance, toughness, heat resistance, and  color retention.
       Alkyds can be combined with any of the following materials.5
       Nitrocellulose                         Polyisocyanates
       Urea-formaldehyde resins              Silicone resins
       Melamine-formaldehyde resins         Polyamides
       Phenolic resins                        Natural resins
       Ethyl cellulose                         Cellulose acetatebutyrate
       Chlorinated rubber                     Monomers (styrene, vinyl toluene, methyl methacrylate)
       Chlorinated paraffin                    Synthetic latices (styrene-butadiene,
       Epoxy resins                            polyvinyl acetate, acrylic)
       Alkyd resins comprise a group of synthetic resins  which can be described as oil-modified
                                            16

-------
polyester resins. They are produced from  the reaction of polyols or  polyhydric alcohols, polybasic
acids and oils or fatty monobasic acids. A listing of commonly used raw material is given below:
       Oils or fatty acids2
       Linseed                               Castor
       Soybean                              Coconut
       Safflower                             Cottonseed
       Tall oil fatty acid                      Laurie acid
       Tall oil                               Pelargonic acid
       Fish                                  Isodecanoic acid
       Tung (minor)                          Isooctanoic acid
       Oiticica (minor)
       Dehydrated castor (minor)
       The materials in the first column are oxidizing or drying types. The materials in the second
column are non-oxidizing and yield soft non-drying alkyds which  are used primarily as plasticizers
with hard resins. The acids shown in the last column are the only materials that are strictly synthetic
in origin.
       Oils or fatty acids impart flexibility and drying to an alkyd. In general, the greater the unsatur-
ation (measured  by iodine  value), the  greater the drying  or  hardening properties. The use and
characteristics of these  oils was discussed  earlier under varnish manufacturing.
       Glycerol or glycerine was  the  first polyol used for alkyds. This  material was  first obtained
as a byproduct of the splitting of fat and oils in soap manufacturing. Also, glycerine is now produced
synthetically from petroleum sources and is supplied  at a purity of 99+%.  Glycerine has historically
been the most widely used polyol for alkyds.
       At  the present time,  however,  the  leading polyol, based on usage, is pentaerythritol (PE),
which came into common use in the 1940's. PE is supplied as "technical grade" material and contains
mono, di, tri and  polypentaerythritol. The  material consists primarily of the  mono form  which  is
illustrated on page 20.
       The choice of which polyol to  use is based  on both technical  and economic factors. For
some applications glycerine based  alkyds are more suitable,  while for others,  pentaerythritol  is
better. In many cases, however, a suitable alkyd can be formulated from either and for these a choice
can be made on the basis of cost or availability.  Present economics favor pentaerythritol.
       The important distinguishing feature of the various polyols is the number of potentially reactive
                                            17

-------
hydroxyl groups in the molecule, known as functionality. The glycols with a functionality of two produce
only straight chain polymers and their alkyd resins are soft and flexible. The resultant products are
used primarily as plasticizers for hard resins. They are the least expensive polyols and are blended
with more reactive polyols such as PE. Glycerine has a functionality of three and is used primarily in
short and medium  oil  alkyds.  Pentaerythritol, with a functionality  of four,  cross links to  a greater
extent, forming harder polymers. It is ideal for use in long oil alkyds. However, due to its high reactivity,
it presents problems of end point control in processing of short or medium oil  alkyds. Dilution with
ethylene glycol, as discussed earlier, reduces this latter problem and increases  solubility in the
oils.
Acids and Anhydrides
          Name
Formula
Form
Phthalic
anhydride
(ortho)
 Isophthalic
 acid (meta)
 Terephthalic
 acid (para)
 Benzoic
 acid
                          White solid
                           White needles
                           White crystals
                           White solid
                                             18

-------
        Name
                                    Formula
                                                                  Form
Maleic anhydride
  H-C  = C-H


  C/VS
                                                          White solid
Maleic acid

                                   c
                               ^
                                             OH
                                                           White solid
Ethylene glycol
Diethylene glycol
Propylene glycol
Glycerine
  CP-95% glycerine
  Super-98%
         H
         I
      H-C-OH
         I
      H-C-OH
         I
         H

    H H    H  H
    II     I  I
HO-C-C-0-C-C-OH
    I  I     II
    H H    H  H

      H  H H
      I  i   I
    H-C-C-C-OH
      I  I   I
      H  0 H
         H

         H
         I
      H-C-OH
         I
      H-C-OH
         I
      H-C-OH
         I
         H
Liquid
Liquid
Liquid
Liquid
                                     19

-------
         Name
             Formula
                                                                            Form

Trimethylolepropane




Pentaerythritol

CH2OH
1 White solid
rie>-'-5 w L* ri -^ vJ r"i i
3 ฃ. ฃL. '
, 1
1 CH2OH
wni-i r ru nui
nurioL.\. xuri->i'n
\ /
r White solid
/ \
unu r ^^LJ r\u
nUn2^ LrlpUn
Sorbitol
        H  H  H H H H
        I   I   I   I   I   I
    HO-C-C-C-C-C-C-OH
        I   I   I   I   I   I
        H  0  0 0  OH
           H  H H  H
             0
White solid
Fumaric acid
       HC —C —OH
         II
HO-C-CH
White solid
                                  0
       The acidic material may be used in the form of an acid or an anhydride. An acid anhydride is
formed from the elimination of one molecule of water from two carboxylic acid groups and is pre-
ferred since it reacts faster and yields less water to be removed from the cook.
       For many years, phthalic anhydride  (ortho) was the only polybasic acid used in substantial
proportions in alkyds.  It still remains the  predominant dibasic  acid. PA is  produced from  the
catalytic  oxidation of  naphthalene or ortho-xylene.  Some resin manufacturers  produce their
own PA.  However,  this process will not be studied  here  since it is more  properly part of  the
petrochemical industry.
       Some  of the  acids  listed above,  such as  benzole  acid,  are monobasic or  mono-
functional,  and cannot  be used as the  sole organic acid. They are  used to  terminate alkyd
polymers  and to modify the  properties  of resins.  Benzoic acid is substituted  for part  of  the
fatty acids. It makes the resin harder and less flexible as well as enhancing the gloss.
                                           20

-------
       The chemistry of alkyd resin systems  is  very complex.  So much  so that theoretical
considerations offer  only a  good starting  point.  Final  formulae  and variations  are developed
by trial  and error changes, based on performance requirements and shortcomings  of  previous
batches.
       Condensation  is  the  reaction  basic  to  all  polyester  resins,   including alkyds.  This
reaction follows the elementary equation for esterification as shown below:
                         .0                                  JQ
                  RC            +    R, OH    J     RC
                         OH                                  OR,
                                                                 I
                     Acid         +    Alcohol   J     Ester

                                           For Alkyd Resins
                  PA       +      Glycerine    J     Glycerol phthalate + H2 0
                                                                     H20
       The ester  monomer formed is very complex and  further reacts to form  large polymers
called  resins.  The  polymers formed are  low  in  molecular  weight  by  comparison to  other
resins. For  example, alkyd resins have  molecular  weights  ranging  from  1,000  to 7,000  while
some vinyl  and acrylic  resins have average  molecular weights in  excess  of  100,000  and  in
some cases as high as 500,000.
       The alkyd  polymers also  react with oil or fatty acid and  are  generally classified by the
amount of oil or PA used in the formulation, as described below:
                                                             % Oil    _% PA
        Short Oil
        Medium Oil
        Long Oil
        Very Long Oil
       The resulting reactants of  the PA, polyol  and oil may be  represented  in part  as follows:
                               PA         +         G(OH)3
                        Phthalic Anhydride             Glycerine
                 HQ-G-PA-G-PA-G-PA-G-PA-    +
33 to 45
46 to 55
56 to 70
71 up
> 35
30 to 35
20 to 30
< 20
                                                                 H20
                      OH       PA      PA
                           Glyceryl phthalate
                                                OH
                                                               water
                                           21

-------
       This then will react  with  the  long  chain  oil  raw glyceride  or fatty  acid (~FA) to yield:
                 HO-G-PA-G-PA-G-PA-G-PA-

                              PA      PA
                      FA                        FA

       Alkyds can be  manufactured directly  from  a  fatty acid,  polyol,  and  acid  or  from the
fatty acid  oil, polyol, and acid. The second combination (oil,  glycerine  & PA)  produces glyceryl
phthalate  which  is insoluble in the oil and precipitates. This  problem can be  overcome  by first
converting  the oil  to a monoglyceride by  heating with a  polyol in the presence of a  catalyst.
This process is called "alcoholysis" of the oil. The basic reaction is shown below:
                         CH-OOCR         CH2OH         CH2OH
                         I                   I               '
                         C-HOOCR     + 2CHOH     +  3CHOH
                         I                   I               I
                         C-H2OOCR         C-H2OH        CH2OOCR
                         Triglyceride          Glycerine       Monoglyceride
        This is an  ester interchange reaction with no loss of water.
        When fatty acid rather than oil is  used as  the starting material,  this is called  the "one-
 stage" process.  In this process, the fatty acid  and glycerine are added to the kettle, the agitator is
 started and heat is introduced. Sparge gas is turned  on to develop an inert atmosphere before the
 temperature of the batch reaches 300ฐF where the reaction starts. When the batch reaches 400ฐF,
 the  PA is slowly added and cooking continued for another 3 to 4 hours  until the desired body and
 acid number are reached.
        If the fusion  process is being used,  a continuous purge of inert gas is maintained to remove
 the water formed in  the reaction. This water may also be removed by what is known as the  solvent
 process. This latter process may also be referred  to as the solution  process or the azeotropic
 process. It is similar to the fusion process except that about 10% aromatic solvent (usually  xylene)
 is added at the start. The vaporized solvent is  passed into a condenser. The condensate then flows
 to a decant receiver for separation of reaction water. Recovered solvent is returned to the reactor.
 Most manufacturers  maintain small inert gas flows throughout a solvent cook to  prevent air leakage
 into the reactor system.
        A typical manufacturing formula for a  50% oil  modified glyceryl phthalate alkyd using the
                                           22

-------
one stage process is given below:5
                                                        Actual, Ibs   Theoretical, Ibs
         Phthalic anhydride                                 39.3           38.7
         Glycerol (95% pure)                                25.1           21.3
         Linseed oil fatty acids                              48.5           47.9
         Catalyst
         Methyl p-toluene sulfonate                           0.2            0.2
                                                          113.2          108.1
                   Approx. loss                             13.2            8.1
                   Yield                                   100.0          100.0
        The above formulation is based on  a 10% excess of glycerol and a manufacturing loss
of 5% more than theoretical.
        As discussed earlier, when oil is used rather  than fatty  acid,  the alkyds  are  produced in
a  two  stage process.  In the first stage  monoglyceride is first produced  from the linseed oil and
glycerol. Part  or all of the polyol is loaded into the reactor.  The reactor is purged with  inert gas
and the agitator and heat turned on. Before the  catalyst and oil are added, the reactor is heated
to vaporize some polyol so  that it can  esterify  any uncombined PA  from the previous batch.  If
this is  not done, the uncombined PA will  react with the catalyst and  destroy its usefulness. The
catalyst and oil are then  added and the alcoholysis of the polyol and oil is  carried out between
450 and 500ฐF until the desired end point  is reached.  This end point is determined by solubility of
the batch in methanol. The  solubility requirements vary  with the type  of  alkyd  being  produced.
When the alcoholysis is completed,  any additional polyol needed is added.
        Following this,  the  required amounts of PA and esterification catalyst are slowly  added.  If
solvent cooling is to be used, the solvent is also added at this time. Cooking then proceeds as before.
        A typical manufacturing formula  for a 50% oil modified  glyceryl  phthalate alkyd using the
two stage process is given below:4
         First stage                                         Ib
             Linseed oil                                    51.3
             Glycerol (95%)                                 12.8
             Catalyst,  Ca(OH)2                              0.026
                                           23

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         Second stage
             Glycerol (95%)                                  6.2
             Phthalic anhydride                             39.7
             Catalyst
             Methyl p-toluene sulfonate                       0.2
                                                          110.2
                   Approx. loss                             10.2
                   Solids yield                             100.0
       Alkyd  and other  resins are cooked  in closed kettles more properly called  reactors.  They
vary in size in commercial production from 500 to 10,000 gallons. A typical reactor system is shown in
Figure 3.
       They are generally fabricated of Type 304 or 316 stainless steel with well polished surfaces
to assure easy cleaning. Design pressure is usually 50 psig. These reactors may be heated electrically,
direct fired with gas or oil, or indirectly heated using a  heat transfer media such as Dowthermฎ.
Reactors are  equipped with  a porthole sightglass, charging and sample  line,  condenser system,
weigh tanks, temperature measuring devices, and agitator. The porthole is used both for charging
solid material and for access to the kettle for cleaning and repair.
       Good  agitation is required for intimate mixing of  the reactants  and proper heat transfer. A
variety of different type blades are used but most are controlled  with a variable speed drive. Too
rapid an  agitation may cause discoloration and too slow  an agitation can cause poor heat transfer
that will increase heat  up time and  may cause excessive polymerization due to localized hot  spots
at the metal-liquid interfaces.
       The reactor may be  equipped with  a variety of  different  condenser systems. The system
shown in Figure 3 includes a packed fractionating column, a reflux condenser and a main condenser.
The  condensers are water  cooled shell and tube type and  may be either  horizontally or vertically
inclined. Vapors are processed and condensed on the tube  side and drain  to a decant receiver for
separation and possible return of solvent to the reactor.  A dual function aspirator Venturi scrubber
is often added to the system. It is used to ventilate the kettle during addition of solid materials and
may also remove entrained unreacted or vaporized solids and liquids from the venting gases.
       It is not clear  from the literature what kind of production rates,  as a function of nominal
kettle volume, can be expected from an alkyd reactor. Rather than assume some maximum theoretical
production capacity, it  was  decided to rely on industry experience as determined from some of the

                                           24

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            - SPRAV  TOWER
                                              REFLUX
                                             CONIDEMSER
                                                          VENT
                          FRACTIONATING
                           DISTILLATION
                            COLUN/IN
                                                  PORTHOLE
                                                  FOR SOLIDS
                                                DIREdT  FIRED  OR
                                                JACKETED FOR  HIC3H
                                                TEMPERATURE VAPOR
                                                    LIQUID
                       FIGURE
MODERN  REISIN   PRODUCTION   SYSTEM
                           OF
         SOLVENT  AND  FUSION  COOKS
                             25

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questionnaires that were sent out as part of this study.
       Questionnaire data from 18 alkyd resin producing plants with 45 alkyd kettles was analyzed
in  an attempt to determine the effective production  capacity of  an alkyd resin reactor as a function
of  kettle  volume. Reactor volumes of  400 to 7,800 gallons were  reported, with the majority of
kettles in the 500 to 2,000 gallon range. Cooking times from 61/2 to 29 hours were reported. In the
500 to 2,000 gallon  size range, cooking  times were well distributed in the 8 to 16 hour range.
       In this same size  range,  production per batch worked  out to about 5,000 pounds of alkyd
solids per 1,000 gallons of  reactor volume. This number possessed a surprising degree of consistency,
within  reasonable limits, from  plant to  plant. Assuming a typical density  of about 9 pounds per
gallon  for alkyds, this means that  a  1,000 gallon  kettle will produce about 550 gallons  of alkyd
resin in each batch. The larger kettles tended to be filled to  a larger fraction of their nominal volume.
       Thinning tanks are always included as part of the reactor system. They are normally water
cooled and equipped with  a condenser and agitator. The partially cooled finished alkyd is transferred
from the reactor to the partially filled thinning tank. Since most alkyd resins  are  thinned to 50%
solids, the  capacities of these tanks  are normally  twice the capacity of the reactor.  These tanks
are also frequently mounted on scales so that thinning solvents  may be accurately added.
       The final step in a reactor system is  filtering of the thinned resin prior to final storage. This
is  normally  done while  it  is still hot.  Filter presses are the most commonly used filtering device.
Centrifuges are also used. One manufacturer is currently using a continuous "in-line" blending and
filtering system for the majority of its  resin production. It is not used in all cases, however, due to
limitations of the filters.
       The manufacturing procedures and equipment used for the production of other resins listed
at  the  beginning of this  discussion are quite similar. The major  differences are the raw material and
process steps utilized. A  brief discussion of  the other important  resin types follows.  The technical
information  contained in these discussions was obtained from Martens' book4  and the Federation
Series on  Coating  Technology.2 Economic and production information is from  the SRI  Chemical
Economics Handbook.3
Vinyl Resins — Vinyl polymers and copolymers were among the first of the synthetic polymers to gain
acceptance as binders  for organic coatings. They  are  available in  solution with organic solvents,
as high solids dispersions ("organosols" or "plastisols"), as dry powders or as  water-borne latexes.
Discussion here is restricted to vinyl chloride, vinyl acetate, their related copolymers, and modified
types.  Following conventional practice  other  materials  like polyethylene, polystyrene etc. are not

                                            26

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included although these also contain the basic vinyl building-block group R-CH=CHX.
       In 1966 approximately 200 million pounds of vinyl resins were produced for use in surface
coatings. Four years later, in 1970 this number had increased by 50% to 300 million pounds. This
group of resins is highly versatile and  relatively inexpensive.  Next to the alkyds it enjoys the largest
surface coating use based on volume and sales value. One of the factors responsible for widespread
use of these resins is that manufacturers with  alkyd kettles were  able to adapt these for making
vinyl acetate latexes.
       Vinyl  resins are  long  molecular  chains  formed by  the addition  of  vinyl chloride or vinyl
acetate monomers. No water or other reaction by-product is formed. The manufacturing chemistry
is outlined below.
  CH2 = CMC                                                                 CH2 = CHOOCCH3
  Vinyl chloride 	ป>            i	•*	Vinyl acetate

  Polymerize                            Copolymerize                          Polymerize

      J                                                                         1
  Polyvinyl Chloride       Polycovinyl-Vinyl Chloride Acetate                          Polyvinyl  acetate
  -ChL-CH-          -CH, -CH-CH9-CH-                             - CH,  - CH -
       2   |                     II                                        I
          Cl                    Cl         O-C-CH3                             0-C-CH3
                                               O                                       0
       Monomers comprising the final polymer retain their identity except for the  double  bonds
which  largely  disappear. The chain length, determined by the number of monomers, is controlled
by chain stopping agents or a combination of time, temperature and pressure. The polymerization
reaction is highly exothermic and,  consequently, heat  removal rather than addition is often the
problem once the reaction gets started.
       There  are basically  four commercially available manufacturing processes for vinyl resins.
Combinations  of more than one process,  depending upon the end properties desired, is  also viable.
These  are:
       1.  Bulk polymerization — The monomers  are  polymerized by themselves  (analogous to
       the fusion process  for alkyds).  Due to poor  heat  transfer properties and difficulties in
       controlling the reaction, this process has lost popularity.
       2.  Solution polymerization — Vinyl monomers are diluted  in solvents containing catalysts.
       Under  controlled conditions this mixture is stirred  in  an  autoclave  until  the increasing
                                           27

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       viscosity (by virtue of molecular size) reaches  a predetermined level. When  the  desired
       molecular weight range is attained the reaction is stopped. The polymer solution may be
       used as is,  or can  be transferred to precipitation tanks where  non-solvents precipitate the
       resin. The several steps involved make this a costly, but nevertheless competitive, method.
       3.  Suspension  polymerization — Small  droplets of vinyl monomers  containing catalysts
       are  suspended  in  water  and polymerized.  Polymerization is  initiated within  the  droplet.
       This method is  used for  the manufacture of a  greater tonnage of vinyl  resin than either
       of the processes mentioned above. It has largely replaced the first and competes favorably
       with the second  in producing a less costly resin  at some expense of quality. The autoclave
       emulsion product is a suspension of submicron  polymer particles and  may be  marketed in
       the latex form or the  dry resin may be recovered and sold as a powder. The separation of
       water from submicron particles poses a difficult problem and invariably results in dusting and
       loss of powder to the  atmosphere as fugitive emissions. Resins sold as dry powder are used
       to prepare organic coating dispersions ("plastisols" and "organosols").
       4.  Emulsion polymerization —  This process  differs from the preceding one in  that an
       emulsifier or surfactant is used causing the formation  of a very stable fine dispersion  of
       monomer (and  consequently of  polymer)  particles  in water.  The catalyst is dissolved  in
       the water phase and  initiation takes place  it the droplet interface. While suspension resins
       are frequently filtered and dried prior to sale, emulsion polymers are rarely so treated.
       Combination methods may employ one of the above  processes followed by further chemical
treatment to impart additional desirable qualities such as alkyd compatability.
       Solvent based vinyl systems require the  use of relatively strong, polar solvents. Ketones,
nitroparaffins, esters, and some  chlorinated solvents can be used. Aromatic hydrocarbons tend to
swell the resins but can successfully be used as diluents to reduce  costs.  Alcohols  and aliphatic
hydrocarbons are not used.
Acrylic resins — Acrylic  resins form a group of transparent thermoplastic (or thermosetting if suitably
modified)  resins formed by  polymerizing monomeric esters of  acrylic  acid  or  methacrylic acid.
Acrylic resins are addition polymers and produce no water or other reaction by-product.
       Usage  of the term "acrylic resins" is restricted  here to  resins having  the following typical
acrylic or methacrylic structures:
                                           28

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                   H

           - CH2 ^C - CH2 - C -
             COOC2H5
COOC2H5
                 or
CH,
1
r^ui /"" C1
— V_ปrlrt """>*-' — ^
COOCH3
CH,
1
H2?C-
COOCH3
                                                                            -1 N
            (Poly) ethyl acrylate
                              (Poly) methyl methacrylate
       Acrylic resins, available in several  physical forms,  are  used in  finishes  for metal,  wood,
leather, ceramic and plastic surfaces. Their  coatings are characterized by resistance to degradation
by  UV light,  hydrolysis  and corrosive chemicals,  resistance to  mechanical damage and a high
quality appearance with aesthetic appeal. Copolymerization with functional monomers  is used to
control hardness  and slip properties, adhesion, solvent  resistance and to provide a  means  for
subsequent  cross-linking if required.  Acrylic polymerization is  exothermic and  presents a heat
removal problem.
       The two basic types of acrylic emulsions available are thermoplastic and  modified thermo-
setting. The former is comprised  of copolymers of methyl  methacrylate with varying amounts of
acrylate esters; these are for use in latex paints and in lacquer type finishes. Cross-linking reagents,
which react with the functional groups when  the film is baked, can be added to produce a thermoset
polymer.  Films formed in this manner display  increased resistance to  solvents, chemicals,  and
greatly improved toughness and hardness at high temperatures.
       Manufacturing processes for acrylic  resins closely parallel those employed for vinyl resins.
These are:
       1.  Bulk polymerization — Polymerization of undiluted monomer.
       2.  Solution  polymerization  — Makes use of a  solvent reaction  medium in which both
       monomer  and polymer are soluble.  This process is  used for producing  medium-molecular
       weight resins.
       3.  Suspension polymerization — The liquid monomer is suspended as droplets in a water
       medium by vigorous stirring. This technique is restricted almost exclusively to the manufacture
       of a few powder resins for  use in lacquers.
       4.  Emulsion polymerization  — Liquid  monomers  and surfactant or  emulsifying agents
       are added directly to water. The rate of monomer addition (during the process), the pH  and
       the temperature  of the  emulsion determine final  properties. Water acts  as heat transfer
       medium and a very  high  molecular weight polymer results. This  method is  used mostly
       for water-base  acrylic  coating  resins.  In  handling  by  consumers the hazard,  odor  and
                                          29

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       expense of flammable solvents are eliminated.
       Monomers used in acrylic resin  production include the methyl, ethyl,  and n-butyl esters of
the acrylates and the methacrylates. These substances are  characterized by  a low to medium
boiling range and by  very low odor thresholds. Indeed, odor nuisance is  probably the primary air
pollution problem associated with acrylic  resin production.
       Solvent based acrylic  systems utilize a variety of solvents.  Thermoplastic solution  resins
are supplied in  solvents  such as MEK, toluene, or mineral  spirits  depending on  the  particular
polymer and the intended application. Thermosetting  acrylic  resins are supplied as solutions in
solvents such as xylene, butanol, and ethylene glycol monoethyl ether acetate.
       The following items of statistical interest3 concerning the market for acrylic resins, are offered:
       1.   In 1970, 220 million Ibs of acrylic resins were produced for a value of  $85  million.
       2.   In  1970,  these resins accounted for about  13.3%  by weight and 16% by value of all
       synthetic resins, placing them third after  alkyds and vinyls.
       3.   Rohm and Haas Company  is the largest  producer  of acrylics for latex  paints  (65 to
       70% of this market in 1971).
       4.   Of the 14 other producers of acrylics for latex  paints,  only Union  Carbide,  Celanese
       Resins, and Thibaut & Walker enjoy any  significant  sales volume.  Most other suppliers in
       the  latex paint industry  concentrate  their efforts on vinyl resins  (polyvinyl  chlorides  and
       acetates).
       5.  Ten  paint companies  produce  acrylic emulsions  for captive use  (including DuPont,
       Celanese, Glidden, DeSoto, NL Industries, and Sherwin-Williams).
       6.   In  1971,   over 60%  of all acrylic lacquer  was  used by  General Motors as topcoats
       for automobiles (other domestic auto makers use thermosetting acrylic enamels).
       7.   More than 24 companies produce acrylic enamel resins (thermosetting solution polymers).
       The major markets are served by Celanese, Cook Paint & Varnish,  DeSoto,  DuPont, Ford
       Motor, Glidden, Inmont,  Mobil,  PPG,  and  Sherwin-Williams. These major markets are
       almost entirely in captive use.

Epoxy resins — Industrial  finishes make extensive use of epoxy surface coatings. This popularity is
is ascribed to  their  high  resistance to corrosion,  strong  chemicals,  physical abuse,  and their
adhesion properties.
       Disadvantages of epoxy coatings,  which  have curtailed their use in trade sales,  are:
                                            30

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              1.  The need for strong, toxic and/or pungent solvents
                      4
              2.  High cost (although cost per pound, per year of service can be lower than for other resins)
              3.  Tendency to chalk (loss of gloss) and
              4.  Appearance
              The term "epoxy resin" refers broadly to polymers containing epoxide or oxirane groups:
                                               H
         H
                                    R - C  - C -  R'
                                         \/
                                           O
       The most commonly used epoxy resins in surface coatings are the diglycidyl ether type
derived from epichlorohydrin and bisphenol A. Manufacturing chemistry is outlined below:
                                       CH3
                              fV-c
                                       CH,
CH2 - CH - CH2 - Cl
     0
                          alkaline
                          conditions
Epichlorohydrin
CH2  - CH  - CH2  - O
     0
     '3
Bisphenol A
            0 -  CH,, -  CH - CH,, - O
             Epichlorohydrin is charged as a liquid to the reactor. The bisphenol A is a dry powder and
      as such presents a possible dusting  problem. The reaction is carried out at moderate temperatures
      (up to 250ฐF) and produces HCI as a by-product.
             The molecular weight of this entire group of resins is often too low to permit use without a
      curing  process (usually conducted at 140 to 400ฐF). This results in a two-package, "amine-cured"
      coating, so named because the curing agents depend on the reaction between the terminal epoxide
      groups of the epoxy resin and the amine hydrogen atoms of primary or secondary amines.
             Among the first curing agents to be used for this application were the aliphatic polyamines
      DTA (diethylenetriamine) and TETA (triethylenetetramine). These aliphatic  amines  can lead to
      dermatitic  or respiratory problems where proper precautions and  housekeeping practices are not
      followed during application.
             Polyamine adducts provide  comparable physical  and chemical resistance  properties  and
      exhibit lower dermatitic  potential and lower vapor  pressure  than  the parent aliphatic polyamine.
             Amine terminated polyamide resins form another  major group of curing agents with lower
                                                31

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irritation  potential.  These resins  produce a more  flexible film with  lower chemical resistance than
amine-cured films.
       Solvents for most unmodified epoxy resins are ketones and esters. Aromatic hydrocarbons are
used as diluents. Solvent selection is based on method of application required: brush application requires
slow evaporating solvents (e.g. diacetone alcohol,  methyl isobutyl ketone) and diluents (e.g. xylene),
while spray application calls for faster evaporating solvents (e.g. methyl ethyl ketone) and diluents
(e.g. toluene).
       In 1970, epoxy coating resin consumption was approximately 80 million pounds; production
growth has exceeded a 12%  average  annual  rate compared  to a  2 to 3%  average for total
surface coatings (based on data reported  to the  U.S.  Department of Commerce, Bureau  of  the
Census).  Classified as  either  unmodified or modified (by fatty acids), production can be broken
down as:
       1.  Unmodified
           a.  Shell — approximately 50%
           b.  Dow, Ciba and Celanese, jointly — approximately 40 to 45%
           c.  Union Carbide, Reichhold and Resyn — the remainder
       2.  Modified
           a. For sale only — 21 companies  produce modified  epoxies for sale,  this accounts
               for 15% of total epoxy  resin demand on weight basis.
           b.  For captive use  —  Celanese  is the  largest producer.  Other  companies  with
               significant  captive  consumption include  Cook Paint & Varnish,  DeSoto, duPont,
               Inmont Chemical, Mobil,  PPG, and Glidden Division  of SCM.
Urethane resins — Unlike vinyls and  acrylics, urethanes are not polymers made up of monomeric
urethane molecules or groups. They are reaction products of isocyanates  with hydroxyl-containing
materials:

                  R-N=C =  O   +    R'OH    ->   R-N-C-O-R'
                                                         I   II
                     isocyanate           hydroxyl          H   0

       The term "urethane" is used for protective finishes that incorporate a resin containing any
of the isocyanate-derived linkages as shown on  the following page.
                                           32

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                         0
                         II
                  -  N - C - 0 -
                     C = 0
                  -  N - H
                     allophanate
       fi    Y
- N  - C -  N
  i    O
  C  =  O
- N  - H
  biuret
                        A
                   o=c    c.o
                       N    N
                        Y
                          y
                     isocyanurate
H    O
H
fl  _ C -  N -
   urea
  H    0
-L'c'-o
  urethane
       Polymer formation  is accomplished  by the use of polyfunctional  isocyanates and  poly-
hydroxyl  compounds.  The primary raw  material used for production  of  urethane  coatings are
isocyanates, particularly TDI (toluene diisocyanate).
       The commercial grade of TDI is usually a 80:20 mixture of the 2, 4 and 2, 6 isomers:
                               CH-
                                    NCO
                                                              CH3
                               NCO
                               80%
               20%
       Handling of TDI poses special problems because it has a significant vapor pressure and
an  irritant effect on the mucous membrane.  It has been found4 that if the unreacted TDI in any
prepolymer is kept below 1% of the total product then the amount of TDI vapor released to the air
will be at a level considered "safe." Manufacturers  are attempting to maintain the free or unreacted
isocyanate monomers below this safe  level.
       Another diisocyanate of commercial importance is 4, 4 — diphenyl-methane-diisocyanate
(MDI):
                      OCN
      NCO
                                          33

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MDI is a solid at ordinary temperatures.
        Polyols commonly used  included glycerine,  glycols,  IMP,  PE, phenols, and polyethers.
Polyesters, alkyds, and castor oil can  also be used to supply the hydroxyl groups. A drying oil
modified urethane (sometimes called "uralkyds") can be made in a manner similar to alkyds. In
this variation the diisocyanate performs the acid function of the phthalic anhydride  in linking two
monoglycerides. Oil modified urethanes are finding increasing use, especially in trade sales products.
These avoid  the  elaborate  curing mechanisms required for the moisture cure, blocked, and two-
package formulation types of urethanes.
        These materials require strong solvents such  as ketones, esters, and aromatics particularly
for  reactive urethane  resins. Adequate  ventilation must be  provided where these materials  are to
be handled. Possible  alternatives under investigation are coatings  without solvents, water emulsion
systems and the  use of  less  toxic  aliphatic solvents  in place of aromatics. This substitution by
aliphatics is practical only when total isocyanate content of the resin is below 25%. The oil modified
urethanes can utilize mineral spirits and  naphtha type solvents.
        In comparison to  other resins (e.g. alkyds, epoxies, vinyls) urethanes  can be formulated
to offer a  better combination  of curing rates, abrasion resistance  and water  resistance.  For an
equivalent hardness they are more flexible. Their major  drawbacks are cost,  yellowing (of urethanes
based on aromatic isocyanates),  need for strong solvents,  and toxicity of some raw materials (as
previously discussed).
        In the U.S. over 600 companies produce urethane coatings and about 80 companies  manu-
facture urethane resins. Of these, only 22 produce and  sell the resins but not the coatings — these
account for half of the resin produced.  The largest single  application for the coatings is in clear
wood finishes.

Cellulosic resin — Cellulosic resins are used in the production of about 57%  of total lacquers  which,
by definition,  are surface coatings that dry solely by evaporation of an organic solvent (rather than
by reaction, such  as  oxidation or cross-linking, of  resin components). Nitrocellulose  accounts for
75% of this entire group and is used chiefly as a wood finish. It is easy to apply, low in cost, has
excellent intercoat adhesion  and solvent release  properties. It  is also,  however,  flammable,  it
yellows and has low chemical  resistance.
        Cellulosic  lacquer  resins  are manufactured  by the esterification  of cellulose, a  hydrolyl
containing  compound. For example,  nitrocellulose  is prepared  by nitration  of cellulose with nitric
acid in the presence of sulfuric acid which removes  water formed during the  reaction. Manufacturing

                                            34

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chemistry is:
                 Cellulose + HNO3 + H2SO4 -ป Nitrocellulose + H2SO4 + H2O
        Cellulose, in the form of cotton linters, is boiled and washed then treated with nitric acid.
The reaction product is then treated with ethyl, isopropyl or butyl alcohol (30% alcohol to 70% cellulose),
resulting in  a highly  flammable mixture.  Even the  recent use  of  water  instead of alcohol as a
dampener does not  appreciably  reduce  the  hazard potential  of  handling  nitrocellulose. Various
safeguards  regarding this  material are listed in "Handling of Nitrocellulose  Manual  Sheet N-1"
available from the  Manufacturers  Chemist Association. It may be  pointed out that  initial interest
in nitrocellulose was in the field of explosives.
        This group of surface coatings represents a fair vapor emission potential since it is normally
used  with several volatile  materials such as ketones,  esters, glycol  ethers,  alcohols, and other
hydrocarbon solvents.
        Cellulosic lacquer resins are produced for sale only by Dow Chemical, duPont, Eastman
and Hercules. The lacquers themselves  call  for conventional grinding and mixing  operations so
most coating producers  are capable of manufacturing them.
        Cellulosic lacquers can be reformulated  with solvent systems considered exempt in  many
states to accommodate their air pollution laws.
        Markets  for nitrocellulose  lacquers are not  expected to  show substantial growth due to
competition  from other  coating systems.  Cellulose acetate  butyrate (CAB) is,  however, expected
to display moderate  growth  because of  its  use in  thermosetting  acrylic automotive  enamels to
improve their performance. CAB  is produced by reaction  of acetic  and butyric acids and their
anhydrides with cellulose followed by partial hydrolysis.
Amino resins — Amino resins are used as a binding or cross-linking agent in the preparation of baking
or thermosetting coatings.  They can  be  used in  conjunction with  alkyds, epoxies,  thermosetting
acrylics, phenolics and other heat reactive  resins. When  used in this manner, these resins comprise
up to 30% of the total vehicle binding agents. Their use  serves to improve  baking speed, hardness,
solvent  and  chemical  resistance of the film. Reaction occurs primarily with hydroxyl groups present
in the polymers to form a cross-linked, thermosetting polymer.
        The  most widely used resins in this group are condensation products of urea or melamine
with formaldehyde. Reaction with urea to form dimethylol urea (DMU) is illustrated:
                     NFL                        H - N  - CH,OH
                     I  ?                              I
                     C    = 0  +  2 H CHO   ->       C  =  0
                     I                                 I
                     NH2                        H - N  - CH2OH
                     urea         formaldehyde         dimethylol urea
                                           35

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Reaction of formaldehyde with melamine
                                           NH
                                              2
                                           c
                                                 N
                                                 II
                                NH2  - C         C -  NH,
                                         ^^ซ~ *
                                            N
proceeds such that the three —NHa groups convert to —N(CH2OH)2 groups to form hexamethylol
melamine. Recently methyl ethers of methylol melamine have received much attention with respect
to the elimination of organic solvents from baking finishes.
       DMU and  hexamethylol  melamine  undergo self-condensation reactions to form  polymers
with the splitting out of water. The condensation  is via methylol  groups to yield on ether linkage
under alkaline conditions and via interaction between methylol and amide groups to  form methylene
linkages under acid conditions. For use as coating  resins, this self-condensation tendency is blocked
by etherification with reactive alcohols such  as  n-butanol:

                     H                               H   H
                     I                                I    I
                 R_N-CH2OH   +  C4HgOH   -> R - N - C - 0 - C4Hg  +  H2O
                                                         H
                      methylol     +  n-butanol   ->   n-butyl ether         +  water

Some condensation takes place during etherification. The  butylated aminoplast can also undergo
further polymerization  but only  at elevated temperatures. This is the  basis  for its use  in baking
systems. The butylated  amino  resin will also cross-link with hydroxyl  containing  polymers when
acid catalyzed  at  elevated temperatures. This explains its use as a binding agent in conjunction
with other resins in baking finishes. The degree of polymerization  allowed during etherification and
the amount  of combined  formaldehyde  can  be  controlled to produce the desired properties.
       An  example of the preparation of  a  butylated  ether of urea-formaldehyde is outlined by
Martens4 as follows:
       "Heat one mole  of urea with 2 to 3 moles of  slightly  alkaline aqueous formalin (pH 8 to 9)
to form the  methylol derivatives. Add 2 to 3 moles of butanol and adjust with acid to a pH of 3 to 6.
Remove  the bulk of the  water by continuous  azeotropic distillation and  proceed to an atmospheric
distillation for removal of the final traces of water." Amino resins are usually supplied in butanol-xylene
solvent systems.
                                           36

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Hydrocarbon resins5 — This group is loosely named and includes:
       1.  Coumarone — Indene Resins
       2.  Petroleum Resins
       3.  Styrene — Butadiene Resins
       4.  Terpene Resins
Together these materials account for a production value roughly equivalent to that of amino resins
($15 million in  1970). Discussion of individual resins is restricted  to a brief description.
       This group, broadly,  covers low molecular weight  (under 20,000), thermoplastic  resins.
Their use is justified by ease of processing, by their neutral hydrocarbon nature, acid-alkali resistance,
solubility, and low cost.
       1.  Coumarone —  Indene Resins:  these were  first  produced commercially in the  1920's
       by polymerization of the fraction  of coal tar distillates containing  coumarone  and indene.
       Polymerization is conducted in the presence  of  sulfuric  acid  (or sometimes aluminum,
       stannic or antimony chloride) as catalyst.  These  resins are soluble  in aromatic solvents
       and  moderately soluble in petroleum solvents.  Structures of coumarone and  indene are
       illustrated:
                                                     H  H
                                                     Indene
       2.   Petroleum resins:  are  derived  from unsaturated hydrocarbons  made available  from
       the cracking of petroleum.  Because of a strong tendency to form gummy polymers, these
       resins are undesirable in gasoline and are removed. This ease of polymerization is, however,
       taken advantage of in the production of resins at low cost.  They can be dissolved in solvents
       and  blended with  bodied  oils  for aluminum paints.  Monomers for these resins include
       ethylene, acetylene, butylene, isobutylene, isoprene, and cyclopentadiene.
       3.   Styrene-butadiene  resins: are copolymers containing  at least 85%  styrene. They are
       soluble in aromatic  hydrocarbons, ketones, and esters. They are not  generally compatible
       with  alkyd resins or drying oils; but are compatible with  rosin materials and coumarone-
       indene resins.
       4.   Terpene resins  are produced from  compounds derived from the resin of the pine  tree.
                                           37

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       The most important of these compounds in coating resins is /3-pinene:
                                           CH,
                                                      CH,
       These resins are soluble in aliphatic hydrocarbons.
       All  of the monomers  used  in the various types  of  hydrocarbon resins are considered
photochemically reactive. They contain olefinic and/or cyclo-olefinic types of unsaturation.

Phenolic  resins — Among the oldest of synthetic resins, phenolics have been  in use since 1910.
Although their use in coatings ranks them lower in consumption volume than other groups discussed
so far, their total production as a plastic exceeds  a billion pounds annually.
       Phenolics are condensation polymers obtained by the reaction of a phenol or a substituted
phenol with an aldehyde — usually formaldehyde.  Depending upon ingredients used, their proportions,
catalysts employed,  and on reaction conditions,  the final form can be a viscous  liquid or a brittle
solid. Further, these may or may not be heat-reactive.
       Phenolics formed in alkaline  systems have a  high ratio of  formaldehyde to phenol ranging
from 1.0  to 3.0. In acid systems the ratio lies between 0.7 and 0.9, and the product consists of a
thermoplastic or "novalak" (or heat-reactive and non-heat reactive, respectively).  A high ratio alkaline
catalyst system produces thermosetting resins.
       Resins prepared in alkali are of low molecular weight and their coatings on metal tend to
eyehole and  crawl; phenolics formed in acid medium require the  addition  of curing  agents which
limit their shelf life. Ammonia or amine catalyzed  phenolics become the normal choice. These, when
cured, have an attractive gold color found in  can linings.  Most phenolic resin  coatings comply with
Food and Drug Administration regulations concerning safe linings of food containers.
       Manufacture of phenolics  calls for ordinary stainless steel  kettles designed  to  withstand
                                           38

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both vacuum  and moderate pressure and equipped with  reflux  condenser and dumping hatch.
       The chemistry of phenolic resin production is illustrated below:
               OH             H                                            OH
                         +    C - 0   ->       f\T-—CH2ฐH    +       L   U
                              H                ^^                     CH2OH
             phenol         formalciehyde
The —CH2OH groups can react with available ortho or para hydrogens on phenolic rings or with
other —CH2OH groups. Either way, a molecule of water is formed.
       Most of the commercial phenolics  use formaldehyde as the source of the aldehyde groups
even though, in  theory,  many aldehydes are suitable. Formaldehyde is  a gas  at ordinary temper-
atures  but is usually supplied commercially in 37 to 50% aqueous solutions.
       Besides phenol, a few substituted phenols are used. These  include p-cresol, p-phenylphenol,
p-tert-butylphenol,  and bisphenol A. Only the para  forms of the above compounds  are used since
the ortho and mefa forms produce polymers of poorer quality.
       Solvents used for phenolics include alcohols, ketones, esters, and glycol ethers.
Silicone resins — Silicone resins are generally supplied as solutions  in aromatic hydrocarbon solvents
which  are included in manufacture to improve control of  hydrolysis and  prevent gelation. Aliphatic
hydrocarbons and alcohols may also be used; ketones and esters are seldom required.
       Silicone  resins  exhibit excellent color  and  gloss retention even at 500ฐF. They can be
copolymerized to improve properties of other resins at elevated  temperatures. They also  exhibit
excellent external durability. These two properties are responsible  for their position  in the coatings
industry.
       The manufacture  of silicone resins begins with the production of chloro-substituted silanes.
Several methods are available, all of which produce mixtures of various alkyl-chloro substituted
products (such as  (CH3)4Si, (CH3)3SiCI,  (CH3)2SiCI2, CHsSiCU). These are separated by fractional
distillation.
       The next step is the preparation of  silanols as, for example,
       RsSiCI + H2O -ป  R3SiOH + HCI
       R2SiCI2 + 2H2O -ป R2Si(OH)2 +  2HCI
       RSiCI3 + 3H2O -ป RSi(OH)3 + 3HCI
This is  followed by  the polymerization of the polyfunctional silanols:
                                           39

-------
R
1
HO-Si-0-
i
1
R
R
1
Si-0-
1
1
R
R
I
Si
1
R
              nR2Si(OH)2
                                                    n-2        +(n-1)H20
Monofunctional silanols are used to terminate the chain while trifunctional silanols can be used as
cross linking agents.
       Silicone resins can be used as such but are often combined with other vehicles either as a
blend, or, better, as  a copolymer. A  commonly used  copolymer  is that  made with  alkyds. The
alkyd can either be  cooked separately and then copolymerized with  a methoxy or hydroxy functional
silicone intermediate; or the alkyd raw  materials and  the silicone intermediate can  be charged
together and cooked in a single step.
       Another important copolymer group is the  silicone-acrylic copolymer  emulsions. These are
used mainly for exterior house paint and maintenance  coatings.  This  concludes the discussion of
the resin types.
       As may be surmised from the preceding discussions, paint manufacturing can be summarized
as  a raw material  and finished  products handling problem with a variety  of intermediate batch
operations. The inter-relationship of all  these operations  is schematically illustrated  in Figure 4.
As  paint  manufacturing has developed into a specialized  branch  of the chemical process industry,
the quantity and number of raw materials and finished products  have increased significantly. The
industry,  however, has been able to  maintain the price of finished product by increased batch size,
by  more  efficient  use  of labor,  and,  most  importantly,  through improved  material  and  product
handling.
       Usually, plants that produce many of  their  own resins and manufacture  a  variety of trade
and industrial products are divided  into the  general  areas indicated  on  Figure  4.  This simplifies
handling  of solid materials and solvents which vary for each type of operation. This is  also true for
packaging of the finished products.
       The early paint plants were normally built in four story buildings to allow for gravity process
flow.  Vehicles and  solid were stored on the  top floor in tanks and bags.  Mixing of pigments  and
vehicles took place on the third floor; the grinding or  dispersion occurred on the second floor;  and
the filling, packaging, warehousing, and shipping took  place on the first  floor.
       New paint plants are now designed differently from earlier  facilities.  They can be a single
story open building with or without a mezzanine or a three story plant laid  out  on a  hillside. The
                                            40

-------
tn

I
V)
cr
u
           *
           o
!
           1
                                         41

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major impetus for this change was handling and warehousing of raw material as well as finished
stock. This is done entirely on the ground floor using fork trucks,  conveyors and storage racks. The
hillside three story building meets  these requirements, since the top story is also a ground floor.
Processing is then done on the second floor and filling and warehousing on the lower level. Material
flow is also conducted by gravity  and this arrangement is probably the best.

B.     Process Data From Questionnaires
       A primary source of information for this study will be the Paint and Varnish Industry Question-
naire which  has been distributed to a sampling of the industry. The questionnaires were distributed
under authority granted the  U.S.   Environmental  Protection Agency  by  Section  114 (a) of the
Clean Air Act.
       Several criteria were considered in selecting those plants which would receive a questionnaire.
These included:
       1.  Geographical location
       2.  Type of products
       3.  Plant size
       4.  Presence of air pollution control equipment
       5.  Total output
       6.  Number of plants
       The list of plants which were chosen represents  a compromise with respect to the above-
mentioned criteria. The  nature of the coatings industry is such that it is difficult, if not impossible,
to obtain  a sample  population which  is representative of the  industry according to all of these
criteria.  If, for instance, one  were  to obtain a representative sample  according to plant size, the
result would be a very poor sample with respect to production volume. The aim, then, was to obtain
a list  of  plants which would  provide the desired information and yet provide at least "adequate"
representation with respect to the guidelines set forth above.
       Table  2 contains a breakdown of the  way  the questionnaires were distributed.  This table
reflects the groups as they were sent out.
       The "Resin  List" was taken from  the  NPCA  Raw Materials Index - Resin Section.6 The
Index listed 59 companies which produced  paint resins for sale.  It includes some companies which
produce finished coatings as  well as resins but  does not include companies which produce resins
for  internal use only. Of the 59 companies,  32 were chosen on the basis of diversity of product and
                                           42

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amount of output.  Plant locations were obtained from the companies themselves  or, for  those
companies which  would not release that information, from the Chemical Economics Handbook
of the Stanford  Research Institute3 or the Paint  Red Book.7 A total  of 55  plants were selected.
Where a company had more than a single plant, about half its plants were chosen.
       A list and description of  the 200  largest paint companies is contained in Kline's Marketing
Guide to the Paint Industry.1 These 200 companies account for about 88% of the industry output.
From this list 139  large companies were selected. These were  further subdivided into single plant
companies and 31 multi-plant companies. As before, each of the 31 companies that had more than
one plant had questionnaires sent to about one half  of its plants resulting in a total of 75 questionnaires.
Many of the plants in this group produce resin as well as paint.
       The "small" plant list was obtained from a list of its "A" members supplied by the National
Paint and  Coating  Association.  The companies  were classified by the NPCA into  very  general
categories  according to size, percent trade or industrial, and product type.  This list  was used to
obtain a sample of small producers. In the  NPCA  classification accompanying the  membership
list, "small" was defined as having sales of less than 5 million dollars.  A sample of  198 companies
classified as  small  was selected. Only two of these companies were included in the 200 largest
companies described  in Kline's. The smallest of these two had sales of 1 to 2 million  dollars.
Because of the nature of the  paint industry, it is likely that these 198 companies average considerably
less  than one million  dollars in  sales. As far as  could be determined  at the time, none of  these
plants produced  resins. This  has been substantiated by the questionnaires received.
       Finally,  another 16 plants  from  13 companies were selected.  They  were included on  the
basis of reports  that they contained air pollution control devices. Since  one of the purposes of  the
questionnaires was to obtain cost effectiveness   information on  such devices, effort was  made
throughout  to locate plants with  control  equipment. For this reason, a  somewhat disproportionate
share of those plants in geographical areas  known to have a history  of vigorous pollution control
legislation received questionnaires.
       Table 3 contains a geographical breakdown of the categories as listed in Table 2. Table 4
presents a percentage distribution by geographical  regions for the entire  questionnaire  sample
compared to the distribution of all plants and of value of shipments for the entire industry.
       Examination of Table 4 indicates that the mid-Atlantic region is somewhat under-represented.
A large  part of  this under-representation can be traced to the "small"  plant list. It is felt that this
will not materially affect any conclusions  which  might be drawn from the questionnaires as a group.
                                          43

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                              TABLE 2
                   QUESTIONNAIRE DISTRIBUTION

               Type                  Companies        Plants
Resin                                    32             55*
Marketing Guide
    (a)  Multi-plant                        31              75
    (b)  Single plant                       108             108
Small                                    198             198
Other                                    13             16
Total                                     382             452
"Ten of these plants also manufacture coatings.
                             44

-------
Questionnaire Returns
       A total of 338 questionnaires have been returned in time to be used in this study. As each
one was received, it was placed into one of the three categories outlined below.
                  Plant Type            Production               Questionnaire Received
                      1                 Coating and Resin                 76
                      2                 Coatings only                     223
                      3                 Resins only                       39
In addition 22 questionnaires  have been withheld by the Environmental Protection  Agency  due
to requests for confidentiality and  are  not  included  in the above. Another 13 plants,  by  mutual
agreement, were not required  to return the questionnaire since it did  not properly apply to their
situations. The 338 returns used amount to 75% of the total mailed.
1.     Raw Materials
        Table 6 lists raw  materials used  by the respondent  plants.  All quantities are  in million
pounds per year. Broad categories covered  are oils, polyols, acids, monomers,  purchased resins,
pigments and extenders. Solvents, due to their importance in  air pollution, are covered in a separate
table.
        Among the oils,  usage of linseed exceeded that of soybean oil, for responding plants, by
a much smaller margin than in industry-wide figures. Linseed is a drying oil but it yellows whereas
soybean oil is semi-drying and resists yellowing. Usage of these two oils, for the 338 plants  was
about 95 million pounds and 82  million  pounds respectively. Approximately one-fourth of the total
oil was used in production of resins by type  3  plants. Sixteen percent is used by type 2  plants for
production  of  coatings. The remaining 56% is used  by type  1 plants for both resin production  and
coating production.
        The primary usage  of polyhydric alcohols, or polyols, is in the production of resins by the
esterification reaction with an acid.  Glycerol or glycerine, first obtained as  a by-product of soap
manufacture, is used in  short and medium oil alkyds. Pentaerythritol,  with four hydroxyl groups, is
used primarily  in long oil alkyds.  These two polyols  are used in quantities  of 22.7 and 36.1 million
pounds, respectively. Ethylene and propylene glycols are the lowest cost  polyols available  and
their use in type 2 plants (which do not produce resins) is largely as an "anti-freeze" agent. "Other"
polyols listed include trimethylolethane and sorbitol.
                                           45

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                                        TABLE 3

                  GEOGRAPHICAL DISTRIBUTION OF QUESTIONNAIRES

                                      Multi-     Single
         Location           Resin      Plant      Plant      Small      Other      Total
New England                   3          2          3         15          2        25
  Me., Vt., N.H.,
  Mass., R.I.,  Conn.

Mid Atlantic                   11         13        24         23          5        76
  N.Y., Pa., N.J.

East No. Central               14         20        33         54          4       125
  Wis., Mich., III.,
  Ind., Ohio

West No. Central               1          3        13         13          0        30
  N.D., S.D., Neb.,
  Kan., Minn., la., Mo.

South Atlantic                  3          8        12         22          0        45
  Md., Del., W.Va.,
  Va., N.C., S.C., Ga.

East So. Central                8          4          6         12          0        30
  Ky., Tenn., Miss.,
  Ala.

West So. Central               4          6          5         15          1        31
  Tex., Okla., Ark.,
  La.

Mountain                      0          1          2          7          1        11
  Mont., Id., Wyo.,
  Nov., Utah,  Colo.,
  Ariz., N.Mex.

Pacific                        11         18        10         37          3        79
  Wash., Ore., Cal.          	     	    	     	    	     	

                             55         75        108        198         16       452
                                        46

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      Region
                                     TABLE 4
                  PERCENTAGE DISTRIBUTION OF QUESTIONNAIRES,
                     PAINT PLANTS, AND VALUE OF SHIPMENTS
New England
Mid Atlantic
East No. Central
West No. Central
So. Atlantic
East So. Central
West So. Central
Mountain
Pacific
Questionnaires
5.5
16.8
27.7
6.6
10.0
6.6
6.9
2.4
17.5
Number of
Plants*
5.8
26.1
23.6
6.3
10.3
3.2
6.6
1.5
16.6
Value of
Shipments*
2.8
23.4
35.0
6.5
7.5
4.6
6.2
0.6
13.4
                                   100.0
100.0
100.0
'Source:  1967 Census of Manufacturers
                                      47

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                                       TABLE 5

                 INDUSTRY QUESTIONNAIRE — TABULATION SUMMARY
Number of Plants in Sample

Products & Production

Major Products (MM gal)

Paints — oil/solvent base
Paints water base
Varnishes
Lacquers

Total


Trade sales
% of total sales

Major Resins and Varnishes
Produced (MM Ib)

Alkyd
Acrylic
Polyester
PVA
PVC
Epoxy
Urethane
Cellulosic
Ami no
Rosin
Styrene
Phenolic
HC
Other

Total

Varnish Total

Separately packaged solvents


Type 1 Type 2
76 223
98.32 77.01
49.28 43.86
21.43 1.10
12.07 23.16
181.10 145.13
108.66 77.45
60 53
299.15
51.07
28.76
48.72
0.03
49.88
4.21
2.18
19.42
0.65
15.79
3.16
0.08
29.67
552.77
18.68
17.07 8.41


Type 3
39




—


191.32
114.03
67.50
27.93
63.50
12.84
1.79
14.76
24.03
24.68
0.60
—
38.00
40.89
621.87
37.74
—

All
Types
338
175.33
93.14
22.53
35.23
326.23
186.11
57
490.47
165.10
96.26
76.65
63.53
62.72
6.00
16.94
43.45
25.33
16.39
3.16
38.08
70.56
1,174.64
56.42
25.48
1970
Industry
Total3





83
43
5














166


                                        48

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                                       TABLE 6

                 INDUSTRY QUESTIONNAIRE — TABULATION SUMMARY

Raw Materials Used (MM Ib)
Oils

Type 1
5.71
0.02
47.37
6.01
56.05
5.51
27.72
0.81
0.60
8.87

Type 2
2.15
0+
29.43
1.44
1.99
0.93
0.02
1.73
—
7.54

Type 3
0.85
0+
18.12
5.02
23.55
1.37
18.68
0.56
0.83
8.41
All
Types
8.71
0.02
94.92
12.47
81.59
7.81
46.42
3.10
1.43
24.82
Castor
Cotton Seed
Linseed
Safflower
Soya
Tung
Tall
Fish
Coconut
Other

Total                                       158.67        45.23        77.39       281.29

Polyols	

Glycerol
Ethylene glycol
PE
TMP
PG
Other

Total                                        76.82        11.88        43.00       131.70

Acids

PA                                          61.69                     42.86       104.55
IPA                                          7.38                      4.82         12.20
MA                                           4.47                      6.25         10.72
Benzoic                                       2.37                      0.11          2.48
Adipic                                        0.77                      0.49          1.26
Other                                        7.02   	        10.56         17.58

Total                                        83.70         —          65.09       148.79
16.07
12.53
21.80
2.20
9.38
14.84
0.02
7.95
0.04
—
2.52
1.35
6.64
4.54
14.22
0.57
12.87
4.16
22.73
25.02
36.06
2.77
24.77
20.35
                                        49

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Type 1 Type 2
24.85
2.89
51.96
13.42
—
13.91

Type 3
43.68
10.66
21.63
16.23
60.39
95.21
All
Types
68.53
13.55
73.59
29.65
60.39
109.12
                                   TABLE 6 (continued)



Monomers

Styrene
Vinyl Toluene
Acrylic Esters
Vinyl Acetate
Vinyl Chloride
Other

Total                                        107.03         —         247.80       354.83

Resins Purchased
Alkyd
Acrylic
Polyester
PVA
PVC
Epoxy
Epoxy
Urethane
Cellulosic
Amino
Rosin
Styrene
Phenolic
HC
Other

Total                                        235.76       360.52        24.86       621.14

Pigments

TiO2
Iron Oxide
Zinc Oxide
Zinc Chromate
Chromium
Metallic
Lead  Chromate
Other Lead
Cadmium
Iron Blue
Other Inorganic

Total  Inorganic                               235.26       207.89         —         443.15
                                          50
46.25
46.00
5.20
27.15
11.34
27.66
27.66
0.89
6.43
13.15
1.70
10.01
2.25
1.72
36.01
163.93
44.67
10.30
54.06
12.25
12.74
12.74
0.83
15.36
10.19
1.05
0.92
0.88
1.49
31.85
3.46
—
0.06
0.02
11.25
1.54
1.54
—
—
1.00
1.59
0.04
2.95
1.51
1.44
213.64
90.67
15.56
81.23
34.84
41.94
41.94
1.72
21.79
24.34
4.34
10.97
6.08
4.72
69.30
168.77
16.18
17.06
2.54
1.64
5.11
10.60
6.93
0.07
0.06
6.30
137.24
14.34
10.13
3.19
1.55
19.56
8.37
7.75
0.12
0.08
5.56
306.01
30.52
27.19
5.73
3.19
24.67
18.97
14.68
0.19
0.14
11.86

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                                   TABLE 6 (continued)
                                                                                       All
                                            Type 1       Type 2       Type 3        Types
Carbon blacks total                              1.08          1.02          —           2.10

Organic total                                    7.42          2.58          —          10.00

Extenders total                               247.36       245.88          —         493.24
                                          51

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       Acids  are  used in conjunction  with  polyols for resin production and are,  therefore,  not
purchased  by type 2 plants.  Phthalic anhydride is  used in alkyd production, because being an
acid anhydride it has a fast reaction rate and produces  minimum water. It accounts for 70% of the
usage or 104.5 million pounds. Isophthalic acid and maleic anhydride add another 10 to 12 million
pounds each. "Other" acids include fumaric and succinic acids.
       Monomers provide individual molecules,  acting  as  basic "building blocks", for polymers
which form  unmodified  resins. Significant quantities of monomers, other than those listed in  the
questionnaire, were tabulated —  the list has been expanded to include  vinyl acetate and vinyl
chloride.  In addition, "other" monomers  are comprised mainly of the group indene, cyclopentadiene
and  methyl cyclopentadiene.  Usage of  all monomers by type 3 plants is substantially higher than
for type  1  plants.  This  relationship is also reflected in  the  production of vinyl and  acrylic  resins,
in Table 5.
       Approximately 34% of all  purchased resin quantities are alkyds.  This quantity obviously
does not represent the total  consumption  of alkyds by these plants. Since type 1  plants  satisfy
some of  their own needs for resins, while marketing other quantities and purchasing still others,
it is  impossible to  correlate production  and consumption by resin types  between Tables 5  and 6.
Quantities purchased by  type 3 plants are  intended  for reformulation  or  merely to  complete a
product  line in resale. These purchases are  small, with the exception of polyvinyl chloride which
accounts for better than  half of their purchases.
       Of  the 31.8  million pounds "other" resins purchased by type  2 plants, almost 3  million
pounds were  reported  as asphalt,  another 1.3 million pounds as chlorinated rubber and  paraffin
and  about  1  million pounds of vinyl acrylic. Similarly, 4 million pounds of vinyl acrylic contribute to
the 36.0 million pounds "other" resins purchased by type 1 plants.
       The purposes of hiding, protection,  and decorating a surface is served by pigments. Hiding
can be accomplished by white, opaque, pigments which reflect all wavelengths of incident light and
decorating  by non-hiding pigments which impart  a color to  the coating by reflecting only a select
portion of the  spectrum. In other cases, the color pigment has sufficient hiding power alone. It can
be seen  from Table  6  that almost 71% of the inorganic pigments are titanium dioxide which has
an extremely  high refractive  index.  Despite its higher cost per pound  it is more economical  per
unit hiding power.
       Use of lead pigments, which at  one time  enjoyed great popularity, has been  declining sub-
stantially due to the availability of higher hiding pigments such as TiO2. Recent legislation has also
                                           52

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affected usage in  trade sale finishes.  A fair number of  responding plants commented pertaining
to their use of these  pigments. These comments included "... discontinued  use. , .", "Other lead
... to be discontinued . . .", ". . . in traffic paint only.", and ". .. have phased out. ..". In all, planned
and implemented discontinuations in use of lead pigments accounted for 3%  of this group; current
usage in traffic paints  for 7.7%.
       Raw materials listed under "extenders" include such items as talc, ground calcium carbonate,
silica,  kaolin, barytes  and mica. These materials, generally, have low refractive indices and little
hiding power  by themselves but used in  combination they provide important properties at  low
cost. Extenders also permit the use of smaller quantities of higher cost pigments. Table 6 indicates
that usage of extenders actually exceeds that of pigments, by a small margin.
       Table  7 presents  a summary of solvent consumption by plant type as determined from
the questionnaire responses. Respondents were asked to report their solvents by group as follows:
       1)  Ethers                                2)  Olefinic ethers
       3)  Esters                                4)  Olefinic esters
       5)  Alcohol                               6)  Olefinic alcohol
       7)  Aromatic (Toluene & Xylene)            8)  Branch chain ketone
       9)  Straight chain  ketone                  10)  Olefinic ketone
       11) Solvents containing a combination  of hydrocarbons, alcohol, esters, ethers, or ketones
           having an Olefinic or cyclo-olefinic type of unsaturation of 5%  or more.
       12) Solvent containing a combination of aromatic compounds with 8 or more carbon atoms
           to the molecule, except ethylbenzene, of 8% or more.
       13) Solvent containing  a combination  of ethylbenzene,  ketones having branched hydro-
           carbon structures, trichloroethylene, or toluene of 20% or more.
       Grouped solvents  which  make  up less than 5% of the total solvents coufd  be lumped
together under  "Other Solvents".
       These classifications were based  on the Los  Angeles County  Rule  66 type definition of
photochemically reactive solvents. Under  this definition  groups  2,  4, 6 to 8,  and 10  to 13  are
considered photochemically reactive.  This  classification  is used in  a modified form in Table 7.
Groups 2, 4,  6, and  10  were reported  in such minimal quantities that they  have been simply
included  in a  separate category  "Other  Photochemical".  Difference between "Rule 66"  and  the
classification system used  here are found in categories 11, 12, and 13. Rule 66 considers solvents
to be reactive if they contain more than 5%, 8%, or 20%, respectively, of the objectionable substances.
                                           53

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                                       TABLE 7
                              SOLVENT USAGE, (MM Ib/yr)
                                  (Questionnaire Data)
Ether
Ester
Alcohol
Aromatic
Ketone (Branch Chain)
Ketone (St. Chain)
Group 11
Group 12
Group 13
Mineral Spirits — Naphtha
Other Non-photochemical
Other Photochemical
Other

Photochemical
Non-photochemical
Unknown
Total
Summary:
  Photochemical
  Non-photochemical
  Unknown
    Total                                    1,268.31       100.0
Type 1
4.28
25.60
35.32
221.99
15.27
50.04
0.94
89.94
2.66
70.11
72.83
4.28
117.83
335.08
188.07
187.94
711.09
MMIb
583.11
400.83
284.37
4.59
23.29
25.59
105.72
9.53
28.38
11.36
27.60
6.23
49.25
39.73
0.95
19.38
161.39
121.58
68.63
351.60
%
46.0
31.6
22.4
Type 3
1.11
8.63
51.10
63.05
3.10
7.83
7.50
5.68
0.75
17.04
22.51
6.56
10.76
86.64
91.18
27.80
205.62




Industry
Total3

350
550
800
1 800









3390




                                        54

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The present system includes the 5%, 8%, and 20% levels, respectively, in the reactive category.
       The mineral spirits — naphtha group was added to accommodate the large quantities of
solvents  reported as  such. A qualification applies,  however.  If a solvent was  reported as simply
mineral spirits it is  included  in this group. However,  if a solvent is defined  as "exempt" mineral
spirits  (or  naphtha,  VMP,  etc.) it is included  in  the  category "Other Non-photochemical".  The
category "Mineral Spirits — Naphtha" no  doubt contains material which could be classified photo-
chemical according  to the above definition  as well as material which is non-photochemical.
       Some  companies reported solvents as simply "aliphatic".  These were also included  in the
group "Other Non-photochemical".
       The "Cellosolveฎ" type solvents present some difficulty in classification. A series of glycol
ethers and esters of glycol ethers find extensive use as solvents. These are commonly known as
"Cellosolvesฎ" due to their use as solvents for Celluloseฎ derivatives. One such compound, ethylene
glycol monoethylether has the following structure:
                                      H  H
                                      I     I
                                HO  - C - C  - 0 -  C9H,
                                      II           2  5
                                      H   H
       An ester derivative of this, ethylene glycol monoethylether acetate has  the structure:
                                      H   H
                                      I   I
                               CH.COOC - C -  0 - C9H,
                                 3    I   I          2 5
                                      H   H
       The first of these compounds, Cellosolveฎ, could be classified as either an alcohol or as an
ether. For the  purpose of this study Cellosolveฎ and its  related compounds (e.g. methyl Cellosolveฎ,
butyl Cellosolveฎ, etc.) are classed as ethers.
       The second of the above structure, Cellosolveฎ acetate, could be classed as an ether or as
an ester. For this study,  Cellosolveฎ acetate and related compounds  (e.g. butyl Cellosolveฎ acetate,
etc.) are considered esters.
       Table  7 also contains  totals with respect  to  photochemical properties. The "unknown"
group includes the  "other" category as well as the mineral spirits — naphtha.  Solvents that  can
definitely be classed in  photochemical groups make up 46% of the  total. The largest single  group
of solvents is the aromatics (toluene and xylene) which make up 31% of all solvents used.
       It was  often necessary to convert from data reported in  gallons to a weight basis. Where a
specific compound was  reported it was possible to use an actual density from the literature. Where
                                            55

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mixtures or general classes were listed, an  average value for solvents of the particular type was
used. Some representative conversion factors for mixtures and general classes are listed as follows:
                            Solvent                    Pounds/Gallon
                        Alcohols                           6.7
                        Ketones                           6.7
                        Esters                             7.3
                        Aromatic                           7.24
                        VMP Naphtha                      6.3
                        Mineral Spirits                      6.5
        For solvents listed under "other" a value of 7.0 pounds/gallon was used.
        Two other categories  of  material  that  have been listed in  the questionnaire are drying
agents and mercury compounds. These are used in relatively small quantities, but may be important
from an environmental standpoint.
        Drying agents  are  usually organic acid salts of  lead,  cobalt,  zirconium,  manganese, or
calcium. Lead based driers have historically been the most common. However, this is in the process
of changing due to increasingly stringent regulations on lead content.  The questionnaire responses,
unfortunately do not list separate drier categories.
        Mercury  compounds, usually phenyl mercury based, are used as preservatives and fungicide.
Limitations on  mercury  content in paint  are presently  under  consideration  by various groups.
Usage of mercury compounds  and drying agents as reported in  the questionnaire is summarized
in Table 8.
2.     Products  and Production
        In the Industry Questionnaire, production of coatings was broken down by oil/solvent base
paints,  water base paints,  varnishes and lacquers.  Similarly  resin  production  was reported by
fourteen major types. Production of coatings is in million gallons and that of resins in million pounds.
A summary of the production data tabulated is presented in Table 5. As described earlier, type 1
plants produce  both coatings  and resin,  type 2 plants produce coatings  only, and  type 3 plants
produce resins only.
        Total coatings  production for  the plants included  in the table amounts to somewhat over
30% of the industry's 1972  production — total production  estimated to be 930 million gallons based
on Current Industrial Reports (and estimates  for December 1972). This 30+% of the total represents
a broad sample of plants since the emphasis in selecting was on diversity of plant type and size.
                                           56

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                     TABLE 8
    DRYING AGENTS AND MERCURY COMPOUNDS
                (Questionnaire Data)
                            Drying Agents          Hg Compounds
Type of Plant                    (Ib/yr)                  (Ib/yr)
      1                       6,427,484               695,977
      2                       4,399,769               637,878
      3                          46.892                 1.898
   Total                      10,874,145              1,335,853
                        57

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Emphasis, in this sample, on plants with emission control devices skewed the distribution towards
larger plants which resulted in a sample  consisting of 18% of  all  plants but 30% of all coatings
production. More than half of the coatings for type 1  and type 2 plants are oil/solvent base which
is fairly typical of the industry.
       While trade sale finishes accounted for 49% of U.S. production in 1972, plants in Table 6
indicate that  57% of their  products fall into this category. This results from including in the sample
a few very large type 1 plants specializing  in sales to the consumer rather than to industry.
       Table 5 also shows products and production under the category of resins and varnishes.
Although alkyd resins  are facing increasing competition from  acrylics, epoxies, polyvinyl acetate
and  polyurethanes  they still account  for about 50%  of all  resins produced and consumed. Less
than 10% of the alkyds produced find uses in areas other than coatings. Production of alkyd resins
is distributed about equally in the industry between  plants making resins only and those that produce
both resins  and coatings. In  our sample,  however, distribution of alkyd production is  weighted
towards those making both. Type 3  plants, on the other hand, produce substantially larger quantities
of acrylic, polyester, polyvinyl chloride, amino and hydrocarbon resins than do type 1 plants.
       The largest single component  in the "Other" resins category is vinyl acrylic  amounting to
20 million pounds  or almost one-third of the production listed under this subtitle. The remainder is
comprised of small volume resins such as chlorinated rubber, asphalt, silicones, and natural resins.

3.     Process Equipment
a.  Dispersion and Grinding Equipment — The principle manufacturing  steps involved in producing
a finished  coating  from  raw  materials consist of  various  types of milling and dispersion  steps.
Milling consists of a reduction in the size of the primary pigment particle. Dispersion consists of a
deagglomeration or separation of aggregates of individual particles, wetting of particles and agglom-
erates, and  a  uniform distributing of particles throughout  the  liquid phase. Pebble  and ball mills
accomplish size reduction as well as dispersion. Roll and sand mills are primarily used for dispersion.
Various types of high speed dispersers, disc impellers, etc. are used for dispersing easily dispersed
pigments. A final category of simple mixers  or blenders is employed for such purposes as thinning,
shading, and other finishing operations.
       A portion  of the  questionnaire was devoted to a listing of such devices. A summary of
this  information is presented in  Table 9.  A problem exists  here of terminology. The  terms "mills",
"mixers", "dispersers", etc. often have imprecise meanings as far as every day usage in the paint
                                            58

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                               TABLE 9
                         MILLS, MIXERS, ETC.
                          (Questionnaire Data)
                        	Number	
                  Type 1                Type 2                Type 3
Roll                 126                  152                     5
Pebble               336                  506                     0
Sand                299                  289                     5
Ball                 382                  282                     1
Other               2741                 2043                   128
                              59

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industry is concerned. The roll, pebble, sand and ball mills have a definite meaning to most people
and  it  is felt that  these  have been reported  in an  unambiguous manner.  The "other" category
apparently  includes an undetermined,  but  perhaps large, degree  of  duplication. In many cases,
the same unit is apparently  listed as, for instance, a "mixer" in one part of  the questionnaire  and
as some other type of device in another part. The numbers reported in the "other" category are
probably too high for reasons outlined above.
b.   Solvent Storage Tanks — The  questionnaires  requested data  on  all solvent tanks over 5,000
gallons covering size, turnover, type  of solvent, vapor pressure, and type of control if any. A summary
of total number of tanks, number of uncontrolled tanks, and turnover is given in  Table 10. Uncontrolled
tanks comprise 41% of the  total. Total  quantity  of solvent handled in 5,000 gallon or larger tank
can  be  calculated  to equal  1,130 million pounds a year using a density of  7 pounds/gallon. This
represents  89% of the total consumption of 1,268 million  pounds reported earlier in Section 1.
       Controlled vents, as  reported in the questionnaires, consisted almost entirely of conservation
vents.  In general,  tanks  containing high vapor pressure solvents  were  more likely to have con-
servation vents  though this was  by no means  universally  observed. Filling losses are relatively
unaffected  by use of conservation  vents. Vapor losses  during filling  operations are proportional,
on a weight basis, to  the product of vapor  pressure and molecular weight. Some theoretical filling
losses have been calculated for some selected solvents and are given in Table 11. The calculation
assumes that the gas displaced from the tank being filled is saturated with the solvent in question
at a temperature of 20ฐC. A pumping rate in excess of 144 gal/min for toluene will give an instantaneous
emission rate in excess  of  the 8  Ib/hr limit often invoked  for photochemically  reactive solvents.
Whether this is in  violation  depends on local interpretation of local regulations and is beyond the
scope of this section. It can be pointed out that these losses represent a very small percentage
of  the  solvent being handled. On the  other hand, a given  quantity of solvent undergoes  several
fill-empty cycles as it travels through a plant. These are  shown schematically  in Figure 5. A given
plant may have some or  all  of these cycles. Each  is associated with a vapor loss due to pure dis-
placement of the gas above the container as it fills. The amount actually lost in each step will vary
as the vapor pressure varies due to temperature,  solutes, and degree of saturation of the gas in
the vapor space.
c.   Resin Reactor Usage — The amount of  resin reactor volume attributable to various types of
operations is given in Table 12. A total of 371 kettles were reported by type 1 plants and 218 by
type 3. The average kettle volume is considerably higher for type 3 than for type 1. This is partly due
                                           60

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                                    TABLE 10
                       SOLVENT TANKS OVER 5,000 GALLONS
                                (Questionnaire Data)
    Number of Tanks
    Number Uncontrolled
    Turnover (MM gal/yr)
Type 1
681
185
57.06
Type 2
497
278
44.01
Type 3
205
106
60.84
Total
1,383
569
161.91
                                  TABLE 11
                FILLING LOSSES FOR SELECTED SOLVENTS @ 20ฐC
                              (Questionnaire Data)
       Solvent
Acetone
Ethyl Acetate
Toluene
Mineral Spirits
V.P.




@ 20ฐC, mm
186
74
22
2 (est.)
Molec. Wt.
58
88
92
160 (est.)
Filling Loss,
lb/100gal
0.494
0.299
0.0927
0.0147
                                     61

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to the fact that type  1  plants  have a large number of  varnish kettles and  these are generally
rather small.
       Table 13 gives the number of plants which operate a particular type of reactor. The alkyd
kettles are divided  into those which are used  primarily  for fusion cooking and  those which are
primarily for solvent processing. Examination of the data indicates that, in terms of gallons, solvent
processing is strongly favored by type 1  plants while the opposite is true for type 3 plants. In terms of
numbers of plants, however, the preferences  are much less pronounced.
       The production of water based emulsions tends  to be concentrated in the type 3 plants.
Varnishes, on the other hand, tend to be produced by type 1 plants.  Varnishes in this context are
whatever the plants responding chose to call varnishes. Most of the time they consisted of the
classic oleoresinous type.
       The tendency to operate on a 24 hour basis increased as the size of the resin plant increased.
Two shift operation was most common in the  small to medium size plants. The large producers were
almost always 24 hour operations. A few of the small producers reported a single 8 to 10 hour shift.

C.     Material Balance For Model Plant
       One of  the  purposes of this industry study is  to determine the financial impact of air pol-
lution control on the paint industry. To accomplish this purpose a model plant was developed and
has been used  to:
       1.  Develop an operating statement for the uncontrolled plant.
       2.  Develop an operating statement for the plant using best control equipment and compare
           with above.
       3.  Develop plant balance sheet  to  show the effect of capital investment for  air  pollution
           control equipment upon assets, liabilities and equity.
       Sherwin-Williams has been retained as the subcontractor to develop the model plant economics.
1.     Design Basis
       The major features for  the  model paint  plant were based on the design  contained in a
paper presented by Mr. R. F. Brewster at the National Paint and Coating  Association meeting on
October 31, 1972.9 This design  resulted from a study  by the Management Committee of the NPCA.
By using this information, it was possible to take advantage of the expertise  of those in the  industry,
as well as provide a common ground with the industry. Copies of some of the slides and calculation
sheets on which the paper was based were provided by Mr. Brewster.
                                          63

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                                       TABLE 12
                    REACTOR USAGE, GALLONS OF KETTLE VOLUME
                                   (Questionnaire Data)
                                Type 1                Type 3                Total
Alkyd
Fusion
Solvent
Varnish
Water Emulsion
Other Resin*
Other or Unspecified**
45,955
143,900
64,788
47,977
116,450
33,325
82,080
47,000
10,070
154,000
243,325
45,820
128,035
1 90,900
74,858
201 ,977
359,775
79,145
Total                           452,395              582,295              1,034,690

*Such as polyester, epoxy, solvent based acrylic, etc.
"Includes heat bodying oils.

TABLE 13

RESIN PROCESSING, NUMBER OF PLANTS
(Questionnaire Data)


or Solvent)





3d**
Type 1
76
45
23
33
34
20
15
22
Type 3
39
16
10
9
9
9
13
8
       Total
       Alkyd (Fusion ai
         Fusion
         Solvent
       Varnish
       Water Emulsion
       Other Resin*
       Other or Unspecified**

 *Such as polyester, epoxy, solvent based acrylic, etc.
"Includes heat bodying oils.
                                          64

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       The model plant developed for this  study  differs from the  NPCA plant in  two important
respects: (1) a resin plant has been added to produce trade sales and industrial alkyds; and (2) the
plant was modified to operate on a two-shift rather than single-shift basis. The first of these changes
necessitates additional facilities for handling the resin raw material as well  as space and equipment
for resin  production itself. The second  change  requires additional space  for  raw material  and
finished product storage and handling as well as increased labor requirements.  The paint manufactur-
ing equipment itself (mixers, dispersers, filling equipment, etc.) remains unchanged.
       The NPCA plant was designed to  produce one million gallons per year on a  single-shift
basis.  In projecting to  two shifts, one should take  into account the fact that some of  the ball or
pebble milling processes require more than eight hours. Thus, going to two  shifts will not necessarily
double the  output  of these  operations.  These, however,  represent a small percentage of  total
production. Of more importance is the question of labor efficiency. Industry personnel have indicated
that the efficiency of the second shift tends to be less than that of the first  shift. Efficiency drops
even further if a  third  shift is used. Based  on their comments, it will  be assumed that the plant
produces  at 90%  efficiency on the second  shift. The  plant, then, will produce  1,900,000 gallons
per year.  It  is  assumed that the product  distribution is the same as  that for  the NPCA  plant.  This
distribution, with the revised gallon  production, is given  in Tables 14, 15, and 16. Table 16 contains,
in addition, the resin plant output, which will be discussed later.
       It may be noted that the industrial coatings  listed as "Other Solvent  Based" were specified
to include the following:
                              Gallons                            Type
                              95,000     Monomer  modified alkyd for fast  dry coatings
                              95,000     Acrylic  baking enamel
                              190,000     Alkyd urea baking enamel
In selecting these particular types, the size  and  expected level of technical sophistication  of the
model plant were  taken  into consideration. These resins are to  be purchased from outside suppliers
rather than manufactured in the plant.
2.     Production and Inventory
       The design of the NPCA  plant  is based on  certain  assumptions  concerning  production
rates and inventory. For consistency, these  assumptions have been retained for this study.  The
objective is to turn trade sales inventory six times a year and industrial inventory 18 times. That is,
the average inventory  levels  are  162/3% of  annual trade  sales shipments  and 55/9% of annual
                                           65

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                                     TABLE 14
                                   MODEL PLANT
                                   PRODUCT MIX
                      60% Trade
                          70% Latex
                          30% Alkyd
                      40% Industrial
                          50% Alkyd
                          50% Other

                      Total
                   1,140,000 Gallons
                           800,000 Gallons
                           340,000 Gallons
                     760,000 Gallons
                           380,000 Gallons
                           380,000 Gallons

                   1,900,000 Gallons
                                      TABLE 15
                                   MODEL PLANT
                         TRADE SALES COLOR DISTRIBUTION
Whites and tint bases
Tints (12 shades)
Solid colors (7 colors)
Total
                           Latex
800,000
               Alkyd
340,000
               Total
673,000
94,000
33,000
283,000
33,000
24,000
956,000
127,000
57,000
1,140,000
                                        66

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                                        TABLE 16
                                     MODEL PLANT
                                    PRODUCT TYPE
                            Latex
                       Alkyd
Total
Trade sales
Outside H.P.
Outside trim
Inside flat
Inside semi-gloss
Inside gloss
Sub-total
% gal
14.4 275,000

27.6 525,000


42.0 800,000
%

0.83

11.78
5.39
18.00
gal

15,800

224,000
100,200
340,000
%
14.4
0.83
27.6
11.78
5.39
60.00
gal
275,000
15,800
525,000
225,000
100,200
1,140,000
   Industrial sales       %          gal
Alkyd                20       380,000
Other solvent based     20       380,000
   Sub-total           40       760,000
  Alkyd resin
Long oil trade sales
Medium oil industrial
Short oil industrial
  Total
Pounds (NVM)
1,025,000
  285,000
  856,000
2,166,000
                                         67

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industrial shipments. It is further assumed that production rates are held uniform throughout the year.
Shipments  of trade sales products will fluctuate through the year as shown in Figure 6.  Industrial
shipments are uniform.
       The consequences  of these assumptions  are that trade sales inventory must successively
increase  and decrease to accommodate the annual sales curve. The typical  trade sales  inventory
curve for this  plant is shown in Figure 7. Inventory peaks at 29% of annual sales in March  and
declines  to a low of 5% of annual sales in September. The finished goods inventory, including its
distribution by type of container, is shown in Table 17. Annual production and maximum  inventory
levels by various categories are presented in this table. The distribution is as given for the  NPCA
plant, whereas the actual numbers have been revised upwards to account for the increased  yearly
production assumed for the present plant.
       These assumptions may be  somewhat unrealistic  in some  respects.  First,  the uniform
production  rate may not be representative of the  way many plants operate. Second, the  minimum
trade sales  inventory of 5% of annual shipments may be somewhat low. Both these points were
discussed in the NPCA report and it was felt by the authors that the plant, nonetheless, provided a
useful base from which to relate other  situations.
3.      Equipment Requirement
a.   Paint Plant— Equipment requirements worked out for the NPCA plant are unchanged for this
study. The product distribution is the  same, while increased production  is accomplished  solely by
the addition of another working shift. The equipment summary is presented in Table 18.
       It is anticipated that high speed dispersion will be suitable for almost all the  latex paints,
as well as for a relatively  large  portion of the architectural  solvent finishes. The sand  mills will
process those items having an intermediate difficulty of dispersion. The  output of the sand mills is
assumed to be  at an hourly rate five to  ten  times the size designation. Neither the  high  speed
dispersers nor the sand mills reduce particle size (i.e. grind).
       The pebble mills  will be used primarily for bright colored industrial finishes and for certain
trade sales products. Ball mills will see relatively limited use — primarily hard to disperse dark colors.
       The ball and  pebble mills were selected to provide a continuous  capacity range rather than
to  provide a given output.  Mills of this type are assumed  to have  an effective working capacity  of
20% to 50% of actual capacity. Outside this range, they do not operate properly. Figure 8 illustrates,
on a logarithmic scale, the  grinding capacities  of the ball and pebble mills. Since the scale is loga-
rithmic, each mill is represented by a bar of equal length. This chart portrays the degree of overlap
                                           68

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                                 70

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                    TABLE 17
                  MODEL PLANT
FINISHED GOODS INVENTORY — MAXIMUM PROJECTION
                      Annual
Maximum Inventory
Trade
Gallons
Drums
5
1
1/4
1/8
Industrial
Gallons
Drums
5
Total
Gallons
Drums
5
1
1/4
1/8
Production Packages
(gal) (number) Gallons
1,140,000 330,000
0
22,800
912,000
420,000
91,200
760,000 42,000
10,400
38,000
1,900,000 372,200
10,400
60,800
912,000
420,000
91,200
Number

0
6,600
264,000
119,000
26,400

575
2,110

575
8,710
264,000
119,000
26,400
                      71

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Pebble mills

      1
      1
      1
      1
      1
      1

Ball mills

      1
      1

Sand mills

      1
      1
      1

High speed dispersers
                    TABLE 18

                 MODEL PLANT

          EQUIPMENT SPECIFICATIONS

                       Diameter

                          21 in.
                          24 in.
                          32 in.
                          42 in.
                          60 in.
                          72 in.
                          32 in.
                          48 in.
           10H.P.
           25H.P.
           50 H.P.
     -   100 H.P.
    28 in.
    36 in.
    36 in.
    48 in.
    72 in.
    96 in.
    32 in.
    60 in.
125
470
                                                                      3
                                                                      8
                                                                     16
Mixing tanks
Twin fillers
Associated filling equipment
1 — Labeller
1 - Bail-0-Matic
1 — Packing Station
1 - Case Sealer
                        Number

                          20
                          14
                           8
                           4

                       "Instantaneous" rate

                          24 one-gallon/min
                          40 quarts/min
                          60 pints/min
Size, gallons

    220, portable
    550
   1,100
   2,200
Filtering equipment

1 — Two cartridge
3 — Six cartridge
2 — Vibratory screens
                                          72

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which  exists between  successive pebble mills. In  this way, a continuous pebble  milling  capacity
ranging from 5.7 to 702 gallons is obtainable.
        Mixing  and finishing  tanks  are  of two  types, fixed  and portable. The  220 gallon  portable
tanks are to be  used in  conjunction with the high speed  dispersers. The  larger sizes are floor
mounted and equipped with belt driven turbine drives and electric motors.
        Two twin  filler machines are provided. A single unit  operating at an 80% utilization  rate can
theoretically handle all the filling operations, but it was felt that this represented a too narrow safety
factor. The filling machines can be moved back and forth under the tanks.
b.  Resin Plant — Since the  NPCA plant did not include resin production facilities, it was necessary
to start from scratch in designing this part.  It was  necessary to first estimate the amount  of alkyd
resin  required.  The size of the  resin plant and, finally, the  specific  equipment required were then
determined.
        It has been assumed that the plant will produce all of its own alkyd resins.  It will further be
assumed that one-half of the  industrial output consists of alkyd based coatings. For the NPCA plant,
this means that 180,000 (trade) + 1/2 x 400,000 (industrial) or 380,000 gallons of alkyd based paints
will be produced.  Scaling up to two shifts, we get 1.9 x 380,000 =  722,000 gallons.
        Several workable, up-to-date, paint formulations for alkyd type coatings have been  supplied
by Ashland  Chemical Company. Based on these formulations (two of which are given in Table 19)
an average  resin content  of about three pounds solids per  gallon  of paint is representative for the
type of products this plant would produce. The required alkyd production is 3 x 722,000 = 2,166,000
pounds of resin solids per year.
        The size  of the resin reactors  required for this amount of  production  was determined by
reference to material presented  earlier.  As discussed in Section A-2 of Chapter 1, industry practice
suggests that a medium size alkyd  kettle produces about 5,000 pounds of resin solids per batch
per 1,000 gallons of reactor volume.
        Even if the resin plant is operated on a two shift basis, only  a single batch can normally be
processed per day due to the cooking times (8 to 16 hours) required. Assuming  250 working days
per year, 1,730 gallons of kettle volume are required as a minimum to produce the  necessary resin
for the model plant.
        In determining  the exact configuration of  the resin plant, three aspects were kept  in mind;
efficiency, flexibility, and cooking times.  In order to obtain the efficiency  of large batches  and still
retain the flexibility to handle a broad product line,  it was decided  that two reactors be installed. A
                                            73

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                                        TABLE 19
                                     MODEL PLANT
                   PAINT FORMULATIONS FOR ALKYD TYPE COATINGS
                 "Exempt" Air Dry Gloss Interior-Exterior Architectural Enamel
                                                              Ib          gal
       Rutile titanium dioxide1                                 306.75        8.99
       Suspension and sag control agent2                        5.11        0.35
       Loss of dry inhibitor3                                     6.13        0.56
       6% Calcium naphthenate                                 3.27        0.42
       Long soya alkyd solution (70% NVM)4                    221.90       27.70
       "Exempt" mineral spirits                                 73.62       11.25
                    Disperse to 7+ Grind (Hegman)-Cowles or Pebble Mill
       Long soya alkyd solution (70% NVM in "exempt"
         mineral spirits)4                                      327.20       40.90
       6% Cobalt naphthenate drier                              3.07        0.39
       6% Zirconium drier                                     10.22        1.43
       Anti-skinning agent5                                     1.02        0.14
       "Exempt" mineral spirits                                 51.12        7.87
                                                          1,009.41      100.00
1Titanoxฎ 2060 Titanium Pigments Div. N.L.  Industries; or equal
2Bentoneฎ 38 Chemical Div. N.L. Industries; or equal
3LFDฎ Mooney Chemicals; or equal
"Aroplazฎ 1266-M-70 Ashland Chemical Co.; or equal
5Exkin No. 2ฎ Tenneco; or equal
                                        75

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                                 TABLE 19 (continued)
                       Air Dry Lead Free Yellow Enamel (Industrial)

                                                              Ib          gal
       Organic Yellow1                                        56.40        4.78
       (Short tall oil fatty acids alkyd-50% NVM in xylol)          141.00       16.99
       VM&P Naphtha                                        69.30       10.72
       Toluene/VM&P 1/1 blend                               100.00       14.58
                                Grind 24 hours porox balls
       (Short tall oil fatty acids alkyd-50% NVM in xylol)          313.00       37.71
       Butanol                                               32.60        4.82
       Toluene                                               44.00        6.08
       6% Cobalt octoate drier                                  1.52        0.21
       6% Calcium naphthenate drier                           30.63        3.94
       6% Manganese naphthenate drier                         0.76        0.11
       Anti-skinning agent2                                      0.51        0.06
                                                            795.39      100.00
1DuPont's Dalamar YT-808D; or equal
2Exkin  #2 Tenneco; or equal
                                          76

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degree of excess capacity was built in to compensate for equipment malfunctions, etc. and to allow
increased production over and above the minimum without incorporating a third working shift.
       In order  to insure that all  formulations can be processed in two working shifts,  the largest
kettle should be  less than 2,000 gallons in size. Data from the questionnaire sample indicates that,
as expected,  process times tend to increase with the size of the batch. Up to 1,500 gallons  kettle
size, processing  times were almost always less than 16 hours. For the larger kettles, times in excess
of 16 hours were sometimes reported.
       In view  of these considerations, two reactors were specified. Their capacities are  1,500
gallons and 500  gallons, respectively. In summary, the resin plant description is as follows:

       1.  1,500 Gallon Reactor — A reactor system similar to that shown in  Figure 9 will be provided.
This system can be operated as either a fusion  reactor or as a solvent process reactor.
       Material:         Stainless Steel
       Heat Source:     Dowthermฎ (Typical)
       Thin Tank:      3,000 Gallons Capacity
       2.  500 Gallon Reactor — Also similar to Figure 9 except that the condensers and decanter-
receiver are omitted. This system  operates only as a fusion reactor. The  material  of construction
and heat source are the same as for the larger reactor. The thin tank is 1,000 gallons capacity.
c.  Tankage Requirements — Tankage requirements are based on the assumption that the plant
should maintain  a minimum of one month's supply of raw materials.  It was further assumed that
liquid raw materials would be delivered in 5,000 gallon quantities.  The tank volume  necessary to
maintain  a minimum inventory of  30 days' supply can be  calculated, then, by dividing  the annual
requirements  by twelve and adding 5,000  gallons to  the result.  For instance, 216,000 gallons  per
year of odorless mineral spirits are required.  The tank required is 216,000 4- 12  + 5,000 = 18,000
+ 5,000 = 23,000. A summary of the tankage requirements (sometimes rounded off to a  convenient
size)  is presented  in Table 20.  Industry  sources have  suggested that  while  this total tankage
ought to be adequate, in practice it would probably consist of a larger number of smaller tanks
4.     Raw Materials
       Raw material requirements were determined by simply scaling up  the  NPCA raw materials
sheet by  a factor of 1.9 where appropriate. Additions and modifications have been made to accom-
modate the resin production. These changes and additions occur  in  the  solvents, miscellaneous
industrial resins,  oil, glycerine, and phthalic anhydride. The latter three quantities were not present
                                           77

-------
                                                             REFLUX
                                                            COINDEirxlSElR
                         SPRAY TOWER
                                                                          CONDENSER
                                      FRACTIONATING
                                        DISTILLATION!
                                         COLUMN
                                                                         DECAISITER
                                                                         RECEIVER
            SCRUBBER
                                               REACTOR
                                                                  PORTHOLE
                                                                  FOR  SOLIDS
OVERFLOW
        CONDENSER
                           TMINNINO
                              TANK
                                     DIRECT  FIRED  OR
                                     JACKETED  FOR HIC3H
                                     TEMPERATURE  VAPOR
                                      R  LIQUID
TO RESIN
STORAOE
                                    RC3URE  Q
          MODERN  RESIN   PRODUCTION   SYSTEM
                                            78

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               TABLE 20
             MODEL PLANT
SUMMARY OF TANKAGE REQUIREMENTS
Size
(gallons)
25,000
25,000
12,500
12,500
7,500
17,500
22,500
10,000
5,000
10,000
7,500
1,000
1,000
1,000
1,000
1,000
1,000
1,000
Contents
OMS
Xylene
Oil
Oil
Glycerine
Exterior latex
Interior latex
Trade alkyd
Trade alkyd
Industrial alkyd resin
Industrial alkyd resin
Industrial alkyd
Industrial alkyd
Industrial alkyd
Industrial alkyd
Waste solvent
Waste solvent
Aqueous waste
                                          Location
                                   Outside
                                   Outside
                                   Inside, lower level
                                   Inside, lower level
                                   Inside, lower level
                                   Inside, lower level
                                   Inside, lower level
                                   Inside, lower level
                                   Inside, lower level
                                   Inside, lower level
                                   Inside, lower level
                                   Inside, lower level
                                   Inside, lower level
                                   Inside, lower level
                                   Inside, lower level
                                   Outside
                                   Outside
                                   Inside, lower level
                 79

-------
at all in the NPCA plant.
       The raw materials requirements for resin production are based on the following assumptions:
       1.  Trade sales alkyds consist of long oil types at an average of 65% oil.
       2.  1/4 of the industrial alkyds are medium oil at an average of 50% oil.
       3.  3/4 of the industrial alkyds are short oil types at an average of 40% oil.
A weighted average can be calculated as follows:
       1.8/3.8 x 0.65 = 0.308
       0.5/3.8 x 0.50 = 0.066
       1.5/3.8 x 0.40 = 0.158
       The average alkyd contains 53% oil. Assume also that, on  the average, PA and glycerol
are present in a 2:1 weight ratio. This represents an excess hydroxy  content (based on PA and
glycerine only) of about 20%. Resin raw materials can be calculated as follows:
       Basis  1,140,000 pounds resin solids (one shift):
              1,140,000 x 0.53 = 616,000 pounds oil
       Correction for 5% loss (mostly water):  1.05 x 1,140,000 = 1,200,000 pounds
       Glycerol + PA = 1,200,000 - 616,000 = 584,000 pounds.
       Glycerol:  584,000 x  1/3 = 195,000 pounds
       PA:      584,000 x 2/3 = 390,000 pounds
       For two  shift  operation,  assuming 90% efficiency on  the second  shift, the approximate
requirements  are:
                                    1,170,000 pounds oil
                                  370,000 pounds glycerine
                                    740,000 pounds PA
       By volume the liquid requirements are:
       1,170,000/7.64 = 153,000 gallons oil (as Soya)
       370,000/10.5 = 35,000 gallons glycerine
       In addition to  these materials, solvent  requirements over and  above those in the  NPCA
plant must be met. Since the alkyds are  to be produced in the plant, the solvent that otherwise
would have been  a part of the purchased resin solution must be supplied  separately. For the trade
sales  alkyds, this solvent will be an odorless mineral spirit. The industrial alkyds  will require a
stronger  solvent such as xylene or an equivalent  exempt solvent system. These solvent require-
ments have been incorporated in  the raw  materials data sheet which is given in Table 21. This is
                                           80

-------
followed  by Table 22  which lists  packaging material  requirements. These tables contain some
revised entries prepared by Sherwin-Williams based on the NPCA report and on the resin require-
ment outlined earlier.
5.     Labor Requirements
       In revising and expanding the NPCA manning chart, the following assumptions were made:
       1.  The  numbers and types of personnel  in the factory and filling  areas are the same for
           the second shift as for the first shift.
       2.  All shipping and receiving is done on the first shift.
       3.  The resin plant requires two men on each shift.
       4.  Shipping and receiving  personnel need to be increased by 50% to handle the increased
           capacity.
       These and other changes have been incorporated into the revised manpower requirements
shown in Table 23. A manning chart for the plant is given in Figure 10.
6.     Plant Layout and Flow Sheet
       A flow sheet for the  plant is given  in Figure 11.  Prints of the plant layout incorporating
the design changes necessary to  accommodate  the resin  plant and increased capacity are  pre-
sented in Figures 12 and 13. In order to operate under the same storage and inventory assumptions
as the NPCA plant, it will be necessary to nearly  double warehouse,  raw material storage,  and
shipping  and receiving areas. This is in addition to  any plant expansion needed to accommodate
the resin production facilities. The  manufacturing  and filling areas are essentially unchanged from
the NPCA plant.  A site plan is given in Figure 14.
II.      EMISSIONS

        There  are two  major types of emissions  from  a paint plant. These are  confined  (or
non-fugitive) and fugitive. Non-fugitive emissions are  those  that are collected by and confined
within an  exhaust system with or without an  air pollution control device.  Fugitive emissions are
those that escape into the plant atmosphere from various operations  and  exit the plant buildings
through  the doors and windows in an unregulated fashion.
A.     Description of Emissions
       These  two types of emissions  can both be further subdivided into gaseous and particulate
emissions. Details of each type of fugitive and non-fugitive emissions  are discussed on the following
page.
                                          81

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                                          TABLE 21

                                       MODEL PLANT

                          ANNUAL RAW  MATERIAL CONSUMPTION
                       (FINISHED OUTPUT OF 1.9 MILLION GALLONS)
     Raw Material
Pigments & Extenders

     Titanium Dioxide
     Misc. Colors
     Silica
     Calcium Carbonate
     Talc
     Clay

Resins — Manufactured

     Soya Oil
     Phthalic Anhydride
     Glycerine

Resins — Purchased
     Exterior Latex (11.42 Ib/gal)
     Interior Latex (10.6 Ib/gal)
     Aropol 830-V-60
     Aroplaz 7435-XM-50ฎ
     Resimene V-920ฎ
     Acryloid AT-5  1 ฎ
     Epon 1001X75ฎ

Solvents & Miscellaneous
     Driers (9.8 Ib/gal)
     Misc. Solids
     Misc. Liquids (8 Ib/gal)
     Water
     Odorless Mineral Spirits
     Anti-Skin (7.72 Ib/gal)
     Toluene
     Xylene
     Aromatic 100 (Solvesso 100)
     Aromatic 150 (Solvesso 150)
     VM + P Naphtha
     Butanol (6.74 Ib/gal)
     Cellosolveฎ Acetate
     Triethyl Amine (6.07 Ib/gal)
     Trade Sales
   Industrial Finishes
                                           Pounds
2,039,000
   27,500
1,179,000
  893,500
  475,850
  199,700
  714,000
  276,000
  138,000


1,644,500
2,141,200
             Gallons
   55,890
   29,200
  241,600
   26,402
             272,300
             169,500
Pounds
760,000
380,000
232,750

522,500
492,000
470,000
247,000
400,000
870,000
152,000
510,000
 60,600


 81,340

 30,400


 22,774
Gallons
                                  20,894
                                  67,300
                                     577
                                               45,600
                                              221,400
                                               20,900
                                                6,975
                                               32,650
                                          82

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                                     TABLE 22

                                   MODEL PLANT

            ANNUAL PACKAGE & PACKAGE MATERIAL REQUIREMENTS
                   (FINISHED OUTPUT OF 1.9 MILLION GALLONS)

                                          Trade Sales                       Industrial Sales
     Package Type                           Quantity                          Quantity
Packages

     Drums (55 gal)                           --                              10,364

     Pails (5 gal)                             22,800                            12,350

     Pails (5 gal)  (Interior Coated)               --                              25,650

     Cans (gal)                             273,600                             	

     Cans (gal) (Interior Coated)              638,400                             	

     Cans (qts)                             205,200                             	

     Cans (qts) (Interior Coated)              205,200

     Cans (pts)                              91,200

Labels

     5 gallon size                            22,800                            38,000

     Gallon size                            912,000

     Quart size                             410,400                             	

     Pint size                                91,200

Cartons

     Gallon size (4 gals)                      228,000

     Quart size (6 qts)                        68,400                             	

     Pint size  (12 pts)                         7,600                             	

Pallets (30" x 42" Size)

     Drums                                  	                               5,182

     5 gal pails                               1,425                             2,375

     Gallons                                 9,500                             	

     Quarts                                    977

     Pints                                      136
                                          83

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                                        TABLE 23
                                      MODEL PLANT
                                 LABOR REQUIREMENTS
       No. People
        Salaried
            1
            1
            1
            1
            1
            1
            2
            3
            1
Hourly Paid  Employees
1st Shift Workers
           15
            2
            2
            2
            2
           12
2nd Shift Workers
           10
            2
            2
            2
            2
            5
 Job Title

Plant Manager
Secretary
Supervisor 1st Shift
Supervisor 2nd Shift
Supervisor Warehouse & Shipping
Quality Control Chemist
Quality Control Technician
Clerks 1st Shift
Clerk 2nd Shift
Various Classifications
Resin Plant Operators
Fillers — Industrial
Fillers — Trade
Caser & Palletizer
Stockman

Various Classifications
Resin Plant Operators
Fillers — Industrial
Fillers — Trade
Caser & Palletizer
Stockman
                                          84

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1.     Fugitive — In  today's typical paint plant there  are  two types of fugitive emissions. These
are pigment particulate and paint solvents. In a small percentage of the plants an attempt is made
to collect these emissions. The incentive for doing so is based on insurance requirements as well
as occupational, health  and safety rather than for air  pollution considerations or regulations. The
newly passed Occupational Safety and Health Act (OSHA) will have a dramatic effect on the paint
industry practice and necessitate the collection of fugitive emissions in the future.
       Fugitive  particulate emissions consist  primarily  of  the  various dry material  used such as
pigments and extender. Details of these pigments are  discussed in Chapter 8 of this report. As a
general rule, the pigments are received and stored in 25 to 50 pound paper sacks  or fiber drums.
Modern pigment manufacturers  have developed  finely  sized  pigments, 0.05 to 0.25 microns, for
ease of dispersion  into  the paint vehicle. Loading of these fine pigments into grinding equipment
results in  fugitive particulate  dust emissions  into the surrounding plant areas. This dust is either
collected by a ventilation and exhaust system or allowed to settle and later collected as part of the
general housekeeping requirements. The pigment particles tend to agglomerate during shipment
and storage and the  losses during loading are not as  significant as might be associated with  this
submicron particle size.
       A variety of resins are received as granular or flaked solids which are of large size and do
not result in  a  fugitive dust emission.  The manufacturer of  these  solid resins,  however, does
encounter fugitive emission problems in his flaking or grinding operations.
       Solvent emissions occur in almost every phase of  paint and  varnish manufacturing and in
numerous locations throughout individual plants. A listing of emission points is given  below:
        Location                 Operation            Temperature       Pressure, Atm
a.
b.
c.
d.
e.
f.
9-
h.
i.
j.
Resin Plant
Resin Plant
Resin Plant
Paint Plant
Paint Plant
Paint Plant
Paint Plant
Paint Plant
Paint Plant
Paint Plant
Thinning
Filtering
Storage Tanks
Blending Tanks
Grinding
Dispersion
Holding Tank
Filtering
Packaging
Storage Tanks
200 to SOOT
200 to 300ฐ F
100ฐF
Ambient
Ambient
Ambient
Ambient
Ambient
Ambient
Ambient
1
1
1
1
1
1
1
1
1
1
                                            90

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The extent of these emissions vary with  the type of operation and the effort extended to control
atmospheric  losses. The  high temperature thinning  and filtering  results in  the  largest emissions,
while packaging in drums and  cans contribute the smallest emission. Other operations contribute
intermediate  emissions which vary depending  on the degree of control exercised and the vapor
pressure of the solvent used. Simple good  housekeeping rules, such as keeping loading hatches
closed, will significantly reduce these emissions.
        In some cases,  efforts  are made to collect fugitive  emissions by  use of local exhaust
systems.  More  frequently,  however,  they are exhausted from the  building by general building
exhaust fans which ventilate areas having  the highest contaminant concentration.
        The  total  quantities  of  solvent losses as  fugitive emissions have  not  been  extensively
measured to date and are not well-known. As a percentage of the total solvent used, these losses
are  relatively small. As a percentage  of  total  solvent loss, they are quite  significant.  Details  are
presented in  Part D of this Section.
        The quantities of fugitive pigment emissions are also not well-known but represent a very
small  percentage  of  the  total pigments used  in paint manufacturing.  The  quantity  of emissions
cannot be easily  measured  directly but can  be estimated using weight balance  calculations on
plants with an efficient particulate collection system. This system will be described in  more  detail
in Chapter 5.

2.     Non-fugitive — The number of  regulated emissions emanating from a paint plant will vary
significantly with the type  of operation involved. Some trade sales plants that manufacture none of
their own resins and make no effort to confine solvent losses during  dispersion, filtering,  or storage,
will  have  no  non-fugitive emissions.  On  the  other  hand, resin plants or paint plants producing
resins and varnishes  are likely  to have a number of  non-fugitive  emissions.  These  emissions
consist primarily of organic vapors in air or inert gas streams.
3.     Chemical  and  Physical  Properties —  There  are  two  significant types  of  organic vapors
generated in paint manufacturing. These  are varnish and resin kettle emissions  which  usually fall
into  the non-fugitive category and solvent vapor emissions which  are usually  fugitive in nature.
The chemical and  physical properties of each type will be discussed  below.
        Considerable effort has  been expended to identify the various types of chemical compounds
emitted during a  varnish cook. The  majority of this  work was  done  in the 1950's and is well
summarized  by  R. L.  Stenburg  in the H.E.W.  Technical  Report A58-4. Copies of his  summaries
                                           91

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are included here as Tables 24 and 25.
       In general,  one or more of the following compounds  are  emitted, depending upon  the
ingredients in the cook and the cooking temperature; water vapor, fatty acids, glycerine, acrolein,
phenols,  aldehydes, ketones,  terpene oils, and terpene. These materials are mainly decomposition
products  of the varnish ingredients.
       Solvent vapors account for the majority of the gaseous emission from a paint plant. Some
of the relevant properties of the  more widely used solvents are given in Table 26. None of these
materials  are considered  exceptionally hazardous. Several,  however, have maximum allowable
concentration limits as set by OSHA. These are given in Table 27.
       Odor thresholds for some of the organic vapors encountered  in the  paint plants as well as
raw materials and trace products which are encountered in resin manufacturing are given in Table
28. They include solvents listed earlier as well as some which might be found in the miscellaneous
solvent category.
       The carrier  gas for all contaminated streams except the resin reactor  exhaust will be
essentially ambient  air. This will be true also for the kettles  during charging of reactants.  During
most of the reaction cycle for the fusion kettle, the carrier gas consists of the sparge gas passed
through the reactor.  This is produced in the inert gas generator and is approximately 10 to 12% CC>2
and 85 to 90% fxb,  on a dry  basis.  Small  quantities of CO may be present along with  other trace
components normally found in air (argon, etc.) and combustion products. Gas leaving the scrubber-
ejectors and the  solvent kettle condenser vent will be saturated in water vapor  at the operating
temperature of the condenser or scrubber.
       As discussed  earlier,  there  are a  variety of particulate emissions from paint and varnish
manufacturing. The major source  of these emissions are the pigments and extenders. Representative
particle size ranges for the  more widely used  pigments and extenders are given  in  Table  29.
Maximum allowable concentration limits for these  as set by OSHA are given in Table 27.
       It can be  noted that the thermal settling velocity of a 50 micron  diameter particle of specific
gravity 2.0 is about  18 cm/sec or 0.6 ft/sec. Particles and agglomerates in this size range or larger
should not escape  into the surrounding atmosphere during loading.  On the other hand, particles
smaller than this size that do escape during loading have the potential to be swept out of the building
by the ventilation  system.
B.     Sources of Emissions
1.     Major — The major sources of emission are listed on page 100.
                                            92

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                TABLE 24



COMPOSITION OF OIL AND VARNISH EMISSIONS
Bodying Oils
Water vapor
Fatty acids
Glycerine
Acrolein
Aldehydes
Ketones
Carbon dioxide



Manufacturing
Running Natural Oleo-Resinous
Gums Varnish
Water vapor Water vapor
Fatty acids Fatty acids
Terpenes Glycerine
Terpene oils Acrolein
Tar Phenols
Aldehydes
Ketones
Terpene oils
Terpenes
Carbon dioxide
Manufacturing
Alkyd Varnish
Water vapor
Fatty acids
Glycerine
Phthalic anhydride
Carbon dioxide





                 93

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                                           TABLE 25

                    ODOR AND COMPOSITION (BY FUNCTIONAL GROUPS)

                              OF OIL AND VARNISH EMISSIONS
 Process and Temperature      Kettle Ingredients
Heat Polymerization of
Linseed Oil
           575ฐF
3 Dark Linseed Oil
           580ฐ F
0-Pale Linseed Oil
           580ฐF
1-Pale Linseed Oil
00-Pale Linseed Oil
           580ฐ F
Linseed Oil
Admoline (a catalyzed
Linseed Oil)
Raw Linseed Oil
Alkali Refined
Linseed Oil
Alkali Refined
Linseed Oil
Alkali Refined
Linseed Oil
  Compounds Identified

Saturated and/or unsatur-
ated:
   Aliphatic Fatty acids
   Aldehydes
Aliphatic Esters
Paraffins
Olefins

Saturated and/or unsatur-
ated:
   Carboxylic Acids
Aliphatic Esters
Alkyl Aldehydes
Paraffins
Olefins
Unsatu rated:
   Acids
   Esters
   Aldehydes

Saturated and/or unsatur-
ated:
   Aliphatic Fatty acids
Olefins

Saturated and/or unsatur-
ated:
   Fatty Acids
Saturated Aldehydes
Olefins

Saturated and/or unsatur-
ated:
   Aliphatic carboxylic
   acids
Unsaturated Alkane Esters
Saturated Alkyl Aldehydes
Olefins
                                                           Odor
                                                                           Harsh pungent odor.
                                                                           Characteristic of short chain
                                                                           aldehydes. (Cause eye
                                                                           watering to varying degrees.)
Tall Oil Alkyd
           475ฐF
Tall Oil

Glycerine
Fumaric Acid
Saturated and/or unsatur-
ated:
    Carboxylic acids
Esters
Aldehydes
Alcohols
Paraffins
Olefins
Fumaric Acid
                                                                          Hydrogen Sulfide
                                                                          (Rotten egg odor).
                                           94

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                                    TABLE 25 (continued)

Process and Temperature     Kettle Ingredients       Compounds Identified
                                                       Odor
Tall Oil Alkyd
           560ฐF
Soybean Oil Alkyd
           475ฐF
Tall Oil
Glycerine
Pentaerythritol
Soybean Oil
Glycerine
Fumaric Acid
Rosin
Linseed Oil Alkyd
           475ฐF
Alkali Refined
linseed oil
Glycerine
Phthalic Anhydride
Litharge
                                                                         lemon-like odor.
                         Very Offensive
                         -Hydrogen Sulfide,
                         n-Butyl Mercaptan
                         (Skunk Odor).

Saturated and/or unsatur-
ated:
    Aliphatic carboxylic   Mild soapy and slightly
    acids
Aliphatic Alcohols
Alkyl Aldehydes
Alkane Esters
Paraffins
Olefins

Aromatic Acids
Aromatic Esters
Aromatic Aldehydes
Aliphatic Carboxylic
  acids
Aliphatic Aldehydes
Aliphatic Alcohols
Typical linseed oil
cooking odors
(harsh and stinging).
                                            95

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                                    TABLE 26



                           SOLVENT CHARACTERISTICS
Solvent
Mineral spirits
Xylene
Toluene
Methanol
Ethanol
n-Butanol
Acetone
MEK
Ethyl acetate
Molecular
weight
160(est.)
106
92
32
42
74
58
72
88
Vapor pressure
20ฐC
2 (est.)
7.1
22
92
43
4.3
186
80
56
, mm Hg
100ฐC
30 (est.)
250
580
-
-
400
-
-
—
Boiling poin
ฐC
—
-
-
64.7
78.4
-
56.5
79.6
77.1
*For solvents that boil below 100ฐC
                                       96

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                                      TABLE 27
                 MAXIMUM OSHA ALLOWABLE CONCENTRATION LIMITS
                                              Maximum allowable exposure
                               Material         (8 hour weighted average)
                       Ethyl Acrylate                     25 ppm
                       n-Butanol                       100 ppm
                       Phthalic Anhydride                12mg/m3
                       Toluene                         200 ppm*
                       Xylene                         100 ppm
                       Carbon black                     3.5 mg/m3
                       Talc (non-asbestos form)           20 particles/cm3
                       Talc (asbestos form —
                         Tremolyte)                      5 fibers/cm3**
                       Inert dust
                         Respirable                      5 mg/m3
                         Total                          15 mg/m3

 'Will change to 100 ppm in near future
"Will change to 2 fibers/cm3 in 1976

Source: Fed. Reg., Vol. 37,  No. 202, 1972.  Additional information available from this source.
                                      97

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                                      TABLE 28*
                   ODOR THRESHOLDS OF SOME ORGANIC VAPORS
                              Chemical
                       Acetaldehyde
                       Acetone
                       Acrolein
                       Benzene
                       Ethanol
                       Ethyl acrylate
                       Formaldehyde
                       MEK
                       Methanol
                       Methyl methacrylate
                       Methylene chloride
                       Phenol
                       p-Xylene
                       Styrene (inhibited)
                       Styrene (uninhibited)
                       Toluene
Odor threshold, ppm
        0.21
      100.0
        0.21
        4.68
       10.0
        0.00047
        1.0
       10.0
      100.0
        0.21
      214.0
        0.0470
        0.47
        0.10
        0.047
        2.14
*Air Pollution Control Assoc. Journal, Volume 19, Number 2, Feb. 1969, pages 91 to 95
                                          98

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                          TABLE 29
PARTICLE SIZE RANGE OF VARIOUS PIGMENTS AND EXTENDERS2,4
           Pigment                  Size range, microns
           TiO2                          0.1 to 1
           Extenders
             Silica                        0.1 to 20
             CaCO3                      0.03 to 8
             Talc                        0.2 to 10
             Clay                        0.5 to 10
           Iron oxides                     0.2 to 15
           Carbon blacks                 0.01 to 0.3
                             99

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       1.  Varnish cooking
       2.  Resin cooking
       3.  Thinning
They are all non-fugitive and consist primarily of organic vapors including phthalic anhydride, which
may or may not be in the  vapor  state. They are also normally the major source of potential odor
nuisance problems.
2.     Minor— Minor sources of emissions included are tabulated below:
             Location                      Fugitive               Non-Fugitive
           1. Handling & Storage    Hydrocarbons
           2. Milling Operation       Hydrocarbons, Pigments  Hydrocarbons, Pigments
           3. Blending & Finishing   Hydrocarbons
           4. Filling                 Hydrocarbons

On an  individual basis, each of these sources can be considered minor. If they were to be collected
and vented at a common point, they would constitute a major source. This is demonstrated in more
detail in the following section.
C.     Quantities of Emission from Uncontrolled Plants
       As indicated in Section I,  the manufacturing of paint is a very  non-standardized industry.
The type  and quantity of emission will  vary significantly from  plant to  plant. To provide  a better
representation of the  average situation,  the  model plant presented earlier will be used as a basis
for this discussion where applicable. Varnish and resin  manufacturing are  not well covered in the
model  plant and the quantity of emissions from these sources will be discussed separately.
1.     Model Plant — The model plant has been designed to reflect modern practices and technology
as generally applied,  rather than  the frontiers of technology as practiced by perhaps a few  plants.
       Likewise, the emissions calculations will assume commonly applied practice and observations.
It will further assume that equipment items, such as condensers, have been properly sized and are
properly maintained to insure good operation.
       Common practice in this context  is determined from questionnaire data, literature references,
information from equipment manufacturers,  and personal experience. Wherever possible,  data for
plants and equipment similar in size and function to that for the model plant will  be  used in preference
to overall industry averages. Where a system  is sufficiently well defined, a theoretical calculation
is used to estimate emissions.
                                           100

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       A schematic  diagram showing the  emission  points  for this model  plant  are given in
Figures 15 and 16. Some tanks are tied in to common vent points as shown.
a.  Solvent  Emissions From Tanks — This group comprises  emission points 1 through 7. It will
be assumed that the  outside storage tanks (5, 6, 7) are equipped with conservation vents. Since
the inside storage tanks (1  to 4) are  not subjected  to significant daily temperature  cycles, these
vents are left uncontrolled. Emissions, then, are confined  to losses during  filling  operations.  It
will further be assumed that xylene is the solvent  used for industrial alkyds. Finally an average
ambient temperature of 20ฐC both inside and outside will be specified.
       Table 30 summarizes the operating data for the storage tank emission sources. Table 31
lists  the  calculated  emissions for these sources.  For sources 1, 2 and  3 it is assumed that the
vapor pressure of the solvent over a resin solution  is  half that of the pure solvent.  Similarly, the
waste solvent is  assumed to be 50% xylene and the rest primarily mineral spirits. The vapor pressure
over this is taken as 50% that of pure xylene with the contribution of the mineral spirits  neglected.
The  emissions were calculated  by converting the turnover in gallons to cubic feet and determining
the amount of solvent present in that number of cubic feet of  gas saturated with solvent vapor at
the appropriate vapor  pressure. Table 31 also gives the instantaneous emission  rate assuming liquid
is pumped into the  tank at  100 gallons  per  minute. Total emissions  from these sources amount
to 184.8 pounds per  year. Emission  rates run as high as 2.06 pounds per hour at 100 gallons
per minute input filling rate.

b.  Manufacturing Area — The  manufacturing  area  emissions consist of sources 8  and 9. Upper
floor manufacturing area  includes the mills,  mixers, finishing  tanks, etc.  The  lower  floor  includes
the filling area as well as the ambient air around the resin plant and  indoor storage  tanks. It does
not include the thin  tank and resin reactor vents themselves  as these will be considered  separately.
The emissions from the manufacturing areas exit as part of the exhaust from the ventilation system.
        The ventilation system  for the model  plant was designed  to  produce  six air changes per
hour. This converts to an exhaust rate of 48,400  cfm for each  of points 8 and 9.  The Canadian
Paint Societies has discussed a model plant in which ventilation requirements were set at 2 cfm
per ft2 of floor area.10 The present situation compares well at 2.2 cfm  per ft2. In order to determine
the emission rate for these sources,  it  is necessary to  estimate the concentration of pollutants
in the exhaust gas stream.
       An examination  of the questionnaires reveals two  plants which present data  that is usable
                                          101

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                                    TABLE 30



                   OPERATING PARAMETERS FOR MODEL PLANT



                       STORAGE TANK EMISSION SOURCES



Emission point          Tankage                Material stored          Turnover (gal/yr)




     1                  4,000            Industrial alkyd (50% NVM)       53,000



     2                 17,500            Industrial alkyd (50% NVM)      232,000



     3                 15,000            Trade alkyd (50% NVM)          257,000



     4                 32,500            Oil, glycerine                   188,200



     5                 25,000            Mineral spirits                  216,000



     6                 25,000            Xylene                        234,000



     7                  2,000            Waste solvent (50% xylene)        30,900
                                      104

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105

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for  estimating  exhaust gas  contaminant levels. These  companies  reported  the solvent  vapor
concentrations in the air at various locations in their plants. The first plant (Plant A) produces almost
one million gallons per year of which 80% is solvent based.
       The second plant (Plant B) is a 2.5  million gallons a year facility with 55% solvent based.
The results from this questionnaire are also summarized in Table 32.
       Based on  this data,  an emission level of  15 ppm  in the exhaust  from  the  upper floor
production  area (Source 8)  should not be an  unreasonable estimate. This allows for averaging and
dilution from parts of the area which  show low solvent vapor levels. A level of 5 ppm will be used
to estimate the levels  from the  lower floor production area (Source 9). The calculated emissions
for those sources are given in Table 33. The total for these two sources is 63,500 pounds per year.
       Only one  plant reported sufficient data in the questionnaires  to provide a basis by which
the model  plant emissions  can be compared to existing  plant emissions. This  plant produces 2.7
million gallons  per year of coatings (all solvent based). The  production  areas corresponding to
points 8  and 9 of the  model plant have ventilation rates which together total 35,800 cfm (versus
96,800 cfm for  the model plant). This plant reported emissions from these areas of 62,660 pounds
per year. The emissions for the model plant, per million  gallons of paint produced, in  comparison
are higher. At least some of  this difference can be attributed to the considerably higher ventilation
rate in the model plant.
       No estimate  has been made  for particulate emissions from these sources.  The absence of
ducts and  hoods  specifically for the purpose  of dust collection  means that a large  part  of the
pigment  dust which  escapes into the  air will tend to settle out  inside the  plant.  The ventilation
system will not provide air velocities sufficiently high to capture any but a portion of the particulate.
It would  be very  difficult to estimate the pigment emission from the plant,  as presently  designed,
by comparing data reported for hooded and locally exhausted systems.

c.  Resin  Production — Emissions from the  500 gallon fusion reactor are  of two types:  (1) Those
that occur during sparging;  and (2) those that occur during loading  when  the hatch  is opened.
The ejector-scrubber is  in operation at all times during the cook.  The emission levels that will
be estimated for this reactor  are those at point 10, the reactor outlet vent and before the scrubber.
At the present time, insufficient information  is  available to  estimate  emissions downstream  from
the scrubber.
        It is expected that the  small reactor will  be used primarily  to process small  batches  of
                                            106

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                         TABLE 33
EMISSIONS FROM MODEL PLANT PRODUCTION AREA EXHAUST
                                   Source 8      Source 9
          Exhaust rate, cfm           48,400        48,400
          Principal contaminant        Xylene        Xylene
          Concentration, ppm             15             5
          Emissions, Ib/hr                 11.9           4.0
          Emissions, Ib/yr             47,500        16,000
                          108

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specialty industrial alkyds.  For illustrative purposes, a "typical" batch will be assumed to consist
of a short oil formulation charge to the reactor at 2,500  pounds of raw materials. A total run time
of 8 hours  is considered  representative with  3 hours  allowed  for  alcoholysis  and 5  hours for
esterification.
       A "typical" log for this process follows:
   Time, hr  Temperature, ฐF
    0           Ambient    Charge reactor  with  1,000  pounds  of  oil, 600 pounds of  glycerine.
                           Blanket with inert gas.  Agitator and heat on.
    1.5           450      Shut off agitator. Add Catalyst.
    1.55          430      Agitator on.
    1.75          450      Holdat450ฐF.
    3.00          450      Alcoholysis complete. Agitator off. Cool slightly.
    3.10          400      Add 900 pounds of phthalic anhydride. Agitator on. Sparge at 10 cfm.
    3.30          450      Hold at 450ฐF for esterification.
    5.10          450      Sparge at 5 cfm.
    6.10          450      Sparge at 2.5 cfm.
    7.50          450      Esterification complete. Cool.
    8.00          400      Agitator, sparge off. Drop to thin tank.
       This log is based on similar information contained in technical literature published by the
Brighton  Corporation11  and on information contained  in  Martens'  book.4 It  is  hypothetical  but
reflects the general features of resin plant operation.
       Figure 17  presents  emission levels, exhaust rates for  noncondensibles (air  and/or inerts),
and water evolved as a function of time. Again, these are hypothetical but are intended to represent
general trends and orders of magnitude.
       The emission curve is  adapted from  that presented  later in Figure 23 of this report. This
represents  hydrocarbon ppm (as methane) at the reactor vent for a fusion cook.  Concentration is
reported  on a dry  basis. Generally speaking,  the analytical method used to obtain this curve does
not measure phthalic anhydride, though small amounts may have entered the instrument and been
recorded. It represents  that portion of  the emissions which  is  virtually unaffected by the  scrubber
and so provides an estimate  of emissions from the scrubber exhaust.  It was  estimated by the
engineer who supervised the  source test which produced  Figure  23 that a  typical scrubber will
remove, at  most, 10% of these contaminants.
                                            109

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EMISSION CHARACTERISTICS — SHORT OIL FUSION COOK
                           110

-------
        Exhaust rates were based on 2 cfm inert gas blanket during alcoholysis, 0.04 cfm per gallon
 of charge during the first two hours of esterification,  0.02  during the third hour, and 0.01  for the
 remainder of the cook.  A peak of 100 cfm during charging was assumed based on questionnaire
 data. The water evolution curve is based on the Brighton11  information  and Martens.4 It was con-
 structed to reflect the characteristics of a short oil alkyd cook.
        The 1,500  gallon reactor  is set up  for either fusion  or solvent cooking.  It is expected,
 however, that solvent cooking will represent the normal mode of operation.  A "typical" batch for
 this  reactor will be assumed to be a  long oil alkyd formulation charged at 7,500 pounds of raw
 materials. A total run time of 12 hours, 5 hours for alcoholysis and 7 for esterification will be assumed.
 A "typical" log for this process is given on the following page.

        Figure  18  presents contaminant  levels,  exhaust  rates,  and water evolution as a  function
 of time. The contaminant  levels and  exhaust  rates  are presented for point 12,  the condenser
 vent. The exhaust  rates for  noncondensibles is based  on questionnaire data.  Only a few plants
 to date have reported exhaust rates  from  the condenser vent. Values  of 2.5 cfm to 7 cfm have
 been reported  for the noncondensibles from kettles of 300 to 3,000 gallons capacity. A value of
 0.25 cfm has been chosen to represent the inert gas blanket flow rate for this reactor.*
        Maximum emission levels were calculated by assuming  that the exhaust from the condenser
 vent is  saturated in xylene vapor at the  operating temperature of the condenser.  It was assumed
 that  the condenser  vent temperature is at 100ฐF during the peak reaction period and drops slightly
 towards the end of the cook. At 100ฐF the vapor pressure of xylene is taken as 18 mm Hg. At 1 atm
 total pressure, this is equivalent to 24,000 ppm xylene  (192,000 ppm  as Ci).
        The water evolution curve is representative of  the shape often observed for long oil alkyds.
 It reflects the  observation that  the  reaction rate for long oil alkyds is very high initially and  then
 drops off for the remainder of the cook. This can be compared  with the curve for the short oil alkyd
 which shows a  more moderate reaction rate which extends for a longer portion of the reaction time.
*For the two solvent cook source tests shown in Appendix D, noncondensible flow rates average
about 0.5 SCFM for one cook and about 0.25 SCFM for the other. These flows  were observed
after the solvent was added and the condenser was turned on. It does  not cover the loading and
heat-up phase during which the ejector was on.
                                           111

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              TYPICAL LOG OF 1,500 GALLON SOLVENT PROCESS REACTOR
                                 Long Oil Alkyd — 60% Oil
  Time, hr  Temperature, ฐF
    0           Ambient   Charge reactor with 4,500 pounds oil. Blanket with inert gas. Agitator
                          and heat on.
    2.0           500     Agitator off. Add 1,000 pounds glycerine. Add catalyst.
    2.10          450     Agitator on. Inert gas blanket.
    2.60          500     Hold at 500ฐF.
    4.50          500     Alcoholysis complete. Cool to 400ฐF.
    5.00          400     Start condenser. Add 350 pounds xylene, 2,000 pounds  PA. Agitator
                          on. Inert gas blanket.
    5.75          450     Hold at 450ฐF for esterification.
    11.50          450     Esterification complete. Cool.
    12.00          400     Agitator off. Drop to thin tank. Condenser off.
       As before, this is an adaption of information published by Brighton Corporation and Martens.
It reflects the general features for this type of cook.
       The  reverse  peaks in  the curves of  Figure 18 occur during loading. When the  hatch is
opened, the scrubber-ejector  is turned on.  This  draws all the exhaust to  the scrubber  vent and
prevents gas from escaping  through  the condenser. The flow rate to  the  scrubbers (Point  13)
will be expected to be in the 100  to 150 cfm range during loading. It is not  possible, with available
information,  to estimate the emission rates  during this time. The  rate will probably be rather high
for a short period of time and consist primarily of solvent vapors and phthalic anhydride.
       The  emissions, by weight, for each of the reactors can be determined from the information
given in Figures 17 and 18. For a given time period, the exhaust rate and the average hydrocarbon
concentration for that time period provides  the information  necessary  to calculate the emissions.
This has been done  for each reactor and the results summarized in Table 34.  It should  be noted
that  the  emissions during loading operations are not  included  since  insufficient  information is
available.  It  can be  expected  that the emission  rate will be  quite high for short periods of time
during charging.
       Several comments can  be made  at this time. The emissions from  the solvent reactor are
proportional  to  the assumed  inert gas flow and strongly dependent on the assumed condenser
vent temperature.  Source test  personnel from air pollution equipment manufacturers report that
it is not uncommon for condensers to be in very poor operating  condition  due to fouling or other
                                          112

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                                       TABLE 34
                     SUMMARY OF EMISSIONS FROM MODEL PLANT
         500 GALLON FUSION REACTOR AND 1,500 GALLON SOLVENT REACTOR*
                                         Fusion cook      Solvent cook**
            Time of cook, hr                     8                12
            Total emissions as methane,
              pounds                           1.15              0.7
            Max. emission rate, Ib/hr              0.41              0.12
            Emission per 1,000 pounds
              charged, pounds                   0.46              0.094
            Max. emission rate per 1,000
              pounds charged, Ib/hr              0.16              0.016
            Emission per year based on
              250 batches/year, pounds         288               175

*The emissions listed  here for both fusion and solvent  processes  are  for the  "noncondensible"
organics. It does not  include  phthalic anhydride, very heavy organics, etc. that are emitted during
the baking phases of operation. No reliable data has been located for estimating these latter quantities.

**An average inert gas flow of 0.25 SCFM was used in estimating the solvent process emissions.
Many plants operate  with essentially no inert gas flow while others may maintain several SCFM.
In the former case, emissions will be limited largely to a "breathing flow" situation and will be very
small. For the latter case emissions will be much higher than suggested in this table since emissions
are roughly proportional to inert gas flow rate.
                                        114

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causes.  If  the condenser vent in the present instance were operating at 120ฐF instead of  100ฐF,
the emissions from this source will double.
        The inert  gas flow  through  solvent process  reactors is  also the subject of considerable
variation. Among other things, it varies as a function of reactor size and formulation.  In some  cases,
no inert gas flow is used while in others flows as high as 7 cfm have been reported in the questionnaires
and 16 cfm in  data  supplied by one company.  Emissions, then, can range from essentially none
to several times that calculated for this case.
        Finally,  the emissions  from  these  kettles were determined for specific cooking  formulas
using  specific  process  cycles  and  parameters.  Consequently,  one  should  not attempt to draw
generalized conclusions  concerning  the  relative merits of solvent versus  fusion cooking  from the
results presented  here. They are  intended to be  specific to the model plant under consideration
and are  representative of the industry in general only to the extent that the  model plant  is  repre-
sentative. It may be noted that the  results fall within the range reported  by  one manufacturer as
listed in Table 3512.

d.    Thin Tanks  and Filter Presses —  Emission  source points 11, 14  and 15 (Figure  16) will be
covered  in  this  category.  It will  be assumed that each resin is to be thinned to 50%  NVM.  The thin
tanks are equipped with condensers.  It will  be assumed that the condenser outlet vent operates at
100ฐF and that the gas is saturated in xylene at that temperature. The gas vented from the thin tank
consists  of a noncondensible fraction which results  from that displaced  when  the tank  is filled.
The fusion  reactor batch is about 250 gallons while that for the solvent reactor is about 750 gallons.
The vapor  pressure of xylene at  100ฐF is  about 18 mm  Hg. A fairly  straightforward  calculation
gives emissions as xylene of 0.22 pounds per batch for point 11  and 0.65 pounds per batch for
point 14. Based on  250  batches per year,  yearly emissions will be 55 pounds/year for  point  11
and  163  pounds/year for point 14.
       The filter presses, taken collectively as source 15,  represent a significant source of  vapor
emissions.  It is  not possible with presently available information to estimate the quantities involved,
however. Vaporized  solvent escapes directly  into the room  air and  leaves  as  part  of the room
ventilation.  Its contribution to emissions is included in the emissions estimated for  the  lower floor
manufacturing area since, as the model plant is  conceived, the 48,400 cfm exhaust  system for the
lower floor area includes the room in which the filter presses and thin tanks are  located.
                                          115

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         EMISSION SUMMARY FOR
      Emission point*
    TABLE 36
GASEOUS CONTAMINANTS — MODEL PLANT
Number Description
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Indus, alkyd storage
Indus, alkyd storage
Trade alkyd storage
Oil, glycerine storage
Min. spirits storage
Xylene storage
Waste solvent storage
Upper floor vent
Lower floor vent
Fusion reactor
Thin tank
Solvent reactor
Solvent reactor
Thin tank
Principle emission
Xylene
Xylene
Mineral spirits
Oil, glycerine
Mineral spirits
Xylene
Xylene
Xylene
Xylene
Mixed organics
Xylene
Xylene
Xylene, PA
Xylene
Annual emissions
(Ib/yr)
9.1
39.8
18.7
nil
31.5
80.4
5.3
47,500
16,000
288
55
175
undetermined
163
*Refer to Figures 15 and 16 for locations of these points in model plant.
                                    117

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e.  Summary — Table 36 presents  yearly emissions by point  sources as defined in Figures 15
and 16. The total for these sources is 65,590 pounds per year.
      '  It should be realized, of course, that certain assumptions were made in calculating each of
the emissions. In order to understand the numbers,  one must have  a thorough  understanding of
the nature  of these assumptions and the  methods of calculation. The effects of  small changes
can sometimes be  rather dramatic. For instance, a few  ppm difference in the contaminant level
assumed for the manufacturing area exhaust systems (Point 8 and  9) can make  a  considerable
difference in the emissions from these sources.  Likewise, as discussed earlier, emissions from the
resin plant are sensitive to the exact operating conditions.
        The total  gaseous emissions consist almost solely  of solvents. They represent  1.7% of
total solvents consumed.
2.     Varnish and Resins Production —  No varnishes  and a relatively  small  portion of  resins
used in the model plant are produced in  the model. Production of these materials is  discussed in
more detail below.
        Varnishes and oils are cooked or bodied at temperatures from  200 to 650ฐF. At about 350ฐF
decomposition begins and continues throughout the cooking cycle which  normally runs between
8 and  12 hours.  The quantity, composition and rate of  emissions  depend upon the ingredients
in the cook as well as the maximum temperature, the length, the method of introducing additive,
the degree of stirring and  the use of inert gas blowing. In general the emissions will average between
one to three percent of the charge in oil bodying  and three to  six percent in varnish cooking17.
        The exact amount of non-fugitive  emissions for open kettle varnish  cooking is not of great
significance for two reasons. First, the amount of  varnish cooked  in  this fashion is quite  small
and is  declining.  Secondly,  modern  varnish reactors  are equipped with  reflux and water cooled
condensers which provide better control  of the extent of emission.  Of more  importance are the
characteristics of the emissions  related  to ease of removal  by  the applicable pollution control
devices.
        Modern resin reactors and varnish  cookers account for the majority of paint vehicle production
in the  paint and varnish  industry. As described earlier, these products are cooked in larger more
carefully controlled reactors  equipped with  product  recovery  devices which  also  help  reduce
atmospheric emission. As with the old varnish kettles, the amount of emissions vary with the type
of cook, the cooking time, the maximum temperature, the initial  ingredients as well as the type
and method of introducing additives.
                                          118

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       The basic methods of cooking used  are solvent cooking and fusion  cooking. The original
and  still widely  used method  is fusion cooking.2 In this  method  the ingredients  are heated
together without solvents at temperatures of 435 to 485ฐF.  This type of process has the maximum
emission level caused primarily by the blowing of inert gas through the reactor to remove the water
of reaction. Refluxing is required when volatile monomers  such as styrene are employed. Fusion
cooking is the fastest  method for the production of polyester resins other than the alkyd resins.
       Solvent cooking is  the  more modern and now popular cooking method. In this process a
small portion of aromatic solvent,  usually 4 to 10% is added with the charge  or after alcoholysis
in the two-stage procedure.  The solvent is condensed and refluxed to a decanter for water separation
and  then returned to  the reactor.  The main  advantages of solvent cooking are faster removal of
reaction water, shorter  cooking time for  alkyd resins,  better control  of temperature, as  well as
reduction of hydrocarbon emissions and phthalic sublimation. The condensers must be run warm
enough to  prevent fouling by condensed phthalic anhydride or phthalic  acid so some hydrocarbon
emissions are unavoidable.
       A considerable amount of emission source testing has recently been completed by suppliers
of air  pollution control devices  on closed kettles or reactors. These efforts  have been  directed
primarily towards quantifying the emissions rather than qualifying them. Recent nationwide hydrocarbon
emission surveys of  a  large  resin manufacturer  indicated that better than  85%  of  the reactor
emissions  were materials originally charged to the reactor.18 A similar conclusion without exact
percentages was indicated  by W. G. Skelly in his report  covering the analysis of potential sources
of odor and pollutants from  the Bensenville, Illinois plant of Stresen-Reuter International.19
       From an air pollution  control engineering design standpoint, the conclusions above are the
major significant result of the above tests. The rest is mainly of academic interest. Assuming thermal
or catalytic incineration  as the  best control  device, the type of information  required is  exhaust
rate, temperature, maximum  hydrocarbon concentration or  Btu loading, and particulate aerosol or
condensible hydrocarbon concentration. The hydrocarbon concentration  is required to calculate the
heat released  or  system  temperature  rise from incineration of the fumes.  This  is  required to
assure proper sizing of  the system, burner, heat exchanger, and residence chamber.  Particularly,
aerosol and condensible hydrocarbon concentrations are required to prevent condensation in the
connecting  ductwork and heat exchanger or unit inlet, which will eventually lead to plugging, loss of
adequate ventilation and/or  system fires or explosions.
       For solvent cooking the quantity of emission does not  vary  significantly with the size of
                                           119

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the reactor  but is rather more a function of the  volatility of the solvent being used and the  size
and/or efficiency of the condenser. Since there is  less sparge gas used in solvent cooking, exhaust
volumes are small (less than 1  SCFM) and consist primarily of noncondensibles. Emissions except
when charging will run from  0.1 to 0.5 pounds per hour and will be less cyclic in nature than for
fusion cooks.
       Emissions during fusion cooking run much higher and vary with size of the  reactor.  The
total exhaust  volume is dependent primarily on  the sparge rate of inert gas. Dean H. Parker5
indicated typical sparge rates of 0.04  cfm/gal of  charge during the first hour, 0.02 cfm/gal during
the second, and 0.01  cfm/gal  during  the remainder of  the cook. The exhaust rate  will average
from  2 cfm/100 gallons of capacity on small reactors to 1 cfm/100 gallons of capacity on  large
reactors. A summary of source test results from a  variety of resin reactors is presented in Table37.20
       Since  fusion  cooking is a cyclic batch process, the concentration of emission will  vary from
the start to  finish of  the cook.  Hydrocarbon  concentration will vary from 15,000 to 80,000 ppm as
methane equivalent,  depending on  the time of the cycle and the type  of cook. There  are at least
100 different emission curves that  could  be encountered if one tried  to cover all of the different
cooking formulas. Particulate phthalic anhydride (PA) is also emitted from the kettle and concentration
levels vary  depending on  cycle time, type of cook, method of  charging  and  type of  PA used.
Charging of liquid PA rather than dry solid PA significantly reduces the emission rate.  Maintaining
the linear velocity of the sparge gas below 150 ft/min will also reduce the carryover of PA.  Entrained
and sublimed  PA will run between  1  to 3 pounds  per hour over a period of 50 to 70 minutes during
and following  the charging period. When isophthalic acid is used these types of emissions are
reduced.
       Details of emission levels from varnish  and resin kettles  are  presented in Table 37 and
Figures 19 thru 24 and discussed below.
       The 500 gallon reactor shown in Figures 19  and 20 had no reflux  condenser and no
separate thinning tank. Thinning was done in the reactor. The combination of these two deviations
from  normal practice accounted for the high emission  rates. Corrective action  has been  taken.
       The 1,000 gallon reactor shown in Figures 21  and 22 is equipped  with a reflux condenser
and separate  thinning tank.  This  kettle is used  for both solvent  and fusion  cooks.  As indicated
on Figure 22 the kettle is run blocked-in during most of the solvent cook, and there are no significant
emissions until the vent is opened after the batch  has been dropped to the thin tank.
       The 1,500 gallon kettle shown in Figure  23  has no reflux condenser.  It is used  for fusion
                                           120

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cooks only.  Thinning  is done  in a  separate tank. Hydrocarbon  emissions from  the  fusion cook
shown on Figure 23 are lower than previously plotted fusion cooks and more in line with what
might be considered normal emissions.  It is felt that this  kettle  runs with lower emissions since
solvent is never added to the kettle or  conversely that the other fusion cooks have higher than
normal emissions since solvent cooks are interdispersed with the fusion cooks.
       The  2,500  gallon kettle shown in Figure 24 has a  reflux condenser  and thin down tank.
It is  used for both solvent and fusion cooking and as indicated  above has higher emission than
those shown on the kettle used for fusion cooking only.
       Measurements of emission from three 60 gallon open varnish kettles were also completed.
The  data is  reported at the  bottom  of Table 37. In general, concentrations were below 220 ppm
except during the addition of  lime to the 60 gallon lime cook.  At this time there was a peak emission
of 1,800 ppm for about a one minute period.
       It is also of interest that no increase in emission was measured during cooking of the wood
oil cook. Cooling was accomplished  by the addition of one gpm of water for a three minute  period.
       The hydrocarbon concentration reported was calculated on a dry basis. A modified M—S—A
Total Combustibles Analyzer was used in measuring the hydrocarbon  concentration. The instrument
was  preceeded by a filter to prevent the cells from becoming fouled. This would tend  to make the
readings  presented low by the amount of PA and other heavy  organics that might come out in the
filter. In clean applications and for  measurement  of low hydrocarbon concentrations, such as an
incinerator outlet, a portable Delphi  Model C Flame lonization  Detector was used. Vent flow rates
were measured with a precalibrated orifice and magnahelix gauge.
       Emission measurements from other closed kettles are  graphically presented in Figures 25,
26, 27 and 28. Figure 25 shows the emission from an epoxy cook. The  graph is fairly self-explanatory.
Note that the kettle is closed-in and operated at 30 psig pressure for four hours.
       Figure 26  shows emission rates from a 2,000 gallon resin  reactor processing an alkyd
cook by the  fusion method. Vent flow during cooking ran at a fairly steady rate of about 12 SCFM.
As indicated on the graph there was a decanter foam-over at hour seven when hot PA and solvent
were added  to the batch. Although this is not normal operation, it is  not an uncommon occurrence
in the industry.
       Figure 27  shows emissions from  a 1,500 gallon  polyester  fusion cook. The graph and
accompanying data are self-explanatory and show no unusual features.
       Figure 28 shows emissions from two 1,000 gallon closed kettles. One kettle was processing
                                          128

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   Time

   8:00 AM
   8:45 AM
   9:00 AM
   9:30 AM
  10:00 AM
  10:30 AM
  11:00 AM
  12:30PM
   2:45 PM
 Mrs

0
 3/4
1
1-1/2
2
2-1/2
3
4-1/2
6-3/4
          Hydrocarbon
           (% LEL)
             225
             270
             325
             340
             300
             275
                                      Liquid
                                   Temperature
100
450
450
440
450
440

305
260
            IG
           Flow
          (Meter)    Remarks
02
02
02
02
02
05
0 1
0 1
01
                                           Start heat up
                                           Exotherm
                                           Close vent — add solvent
                                           Pressure up to 24 psig
                                           Vent remained closed until about 2 45 PM
     450
     400
UJ
     300
     200
      IOO
I	v
'     EXOTHERM   \
                                   \
                                    *
                      1^
                                                            OPEN VENT
                                  VENT CLOSED
                                ADDING SOLVENT
                                            I
                                    I
                                                                 450
                                                                 400
                                                                 300
                                                                 200
                                                                                        UJ
                                                                                        or
                                                                          01
                                                                          UJ
                                                                          Q_
                                                                          S
                                                                          UJ
                                                                 100
                      456
                     TIME, HOURS
                     RGURE
                                                                 8
                   EMISSIONS  FROM  IOO GALLON  EIPOXY
                          SOLVENT  PRESSURE COQK— -3O PSIG
                                             129

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    Time

  10:20 AM
  10:30 AM
  10:45 AM
  11:00 AM
  11:30 AM
  11:45 AM
  12:00 noon
   1:00 PM
   1:30 PM
   2:00 PM
   2:30 PM
   3:00 PM
   3:20 PM
              Hydrocarbon
               (% LEL)

                  25
                 350
                 350
                 300
                 220
                 150
                 230
                 200
                 190
                 180
                 180
                 180
                 180
  IG*
 Flow
(SCFM)
  10
  20
  30
  30
  10
  30
  30
  60
  60
  60
  80
  80
Emissions
  (Ib/hr)
   4.4
   8.8
  11.3
   83
   1.9
   8.6
   7.5
  14.3
  13.5
  135
  18.0
  18.0
 Remarks

Prior to sparging
Start sparge
Increase sparge rate
Increase sparge rate

Make DPG correction addition
Sparge back to normal

Increase sparge rate
Increase sparge rate
*Flow rate based on rotometer reading.

'Emissions calculated as pounds/hour as methane (based on LEL measurements).
      400
UJ
^    30O

 I

I

-------
    300
                                              • DECANTER
                                              FOAM OVER
    250
           VENT FLOW - 12 SCFM
    200

     ISO
8
g
150
                                                              500
                                              INCREASE I.G.

                                               SPARGE
     5O
            HOLDING AT380ฐF

           FOR PA. ADDITION

            LINE PLUGGED
ADD RA. AND

  SOLVENT
                                                              400
                                                              300
200
                                                                         U
                                                                         cr
                                                                     UJ
                                                                     a.
                                                                     S
                                                                     UJ
                 100
                             I
                                   I
              2345678

                           TIME , HOURS


                         FIGURE 2-7


           EMISSION FROM  ISOO GALLON
                   R EACTOR FUSION  COOK
                                                             K)
                                   131

-------
                            -ADD CATALYST THRU
                             HATCH REACTOR #2
150
            -LOAD  P.E. IN
            THRU  HATCH
  125
IOO
X

 I
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u
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 50
                                                LOAD  RA. THRU HATCH

                                                IN  REACTOR #2


                                                   OPEN  REACTOR  #1
                                                   HATCH  SAMPLE  TAKEN
                                           U
                                                         2  REACTORS

                                                         I- POLYURETHANE
                                                           ALKYD

                                                         2-INTERMEDIATE
                                                           BASE  FISH OIL
                                                           ALKYD
 25
                                                SAMPLE  DILUTED  10 TO  I

                                                FLOW- 138 TO  149
                                 FIGURE
           EMISSION  FROM  TWO-IOOO GALLON  REIACTOF^S


                                    132

-------
a  polyurethane alkyd and  the other  kettle  was processing an  intermediate base  fish oil alkyd.
Measurements  were made on the inlet of a 500 SCFM thermal incinerator. The gases from  the
two kettles were  combined  and had  passed through one water scrubber  and one water curtain
prior to measurement. It was also diluted about 10 to 1 with air prior to measurement. Flow at  the
point  of measurement was about 150 SCFM as measured  by a pitot traverse. The exhaust was
further diluted prior to entry into the incinerator. Maximum  hydrocarbon emissions ran around 31
Ib/hr.  As indicated on the graph, there were a number of  peak emissions  throughout the period
of measurement. All were in excess of safe operating  limits for the thermal afterburner.
        In order to meet requirements  of 1/4  LEL (13  Btu/SCF) and thermal  incinerator inlet loading
requirements of 9 to 12  Btu/SCF emissions are diluted with air prior to  being  exhausted  or sent
to a pollution control device. In  most  cases the streams involved  are passed through some type
of crude water scrubber to remove heavy  oils, resins  and condensible phthalic anhydride.  The
scrubber is normally retained as  a pretreatment and safety device if an incinerator  has been added
for final pollution  control. Hydrocarbon concentration  after air dilution will run from 1,000 to 4,000
ppm after an adequate water scrubber. Exhaust rates will average around 1,000 SCFM for  a 2,500
gallon reactor capacity. This rate will vary significantly, however,  if other vent streams from thinning
tanks, filter press and the like are included  with the exhaust system.

D.      Process Operations Influencing Emissions
1.      Equipment and/or Process Characteristics
a.  Handling and Storage— Materials handling activities are of  two types: liquids and dry solids.
Bulk liquids are transferred wherever possible through pumps and meters. This confines emissions
in liquid transfer  operations primarily  to displacement of the atmosphere  in the  container being
filled.  For a covered container it should be  possible to estimate by engineering  calculation what
these losses will be. If the container is open (for instance, an uncovered tub), the amount of solvent
lost through evaporation  will  be  more  difficult to determine. Breathing  losses, due to changes in
temperature and atmospheric pressure, must also  be considered.  However, if the turnover of  the
storage tanks is high compared to the size  of the tanks and if the tank  is not  subject to large
short term temperature fluctuations, this breathing loss should be less than the filling losses.
       The finished product filling area represents another source.  Emissions from this area would
normally be part of the building  ventilation exhaust. Determination of the quantities  involved must
depend on operating experience and measurements.
                                          133

-------
        Liquids handled in drum size quantities are  subject to  evaporative losses during  dumping
operations. Again these would normally show up in the building ventilation. The potential for  emission
on  a per gallon basis  is higher for liquids handled in this form since the dumping tends  to cause
more agitation of the liquid and tends to be performed into open tanks.
        Dry solids handling is a source of particulate emissions.  Materials of this sort are usually
received in 50 pound  bags  or in fiberboard drums.  Until  the  bags are opened and dumped no
emissions  will occur from  this source. The bags are usually opened at the  station  at which they
will  be used. These include  mills,  mixers and  dispersers in the  case of pigments  and the  resin
reactors in the case of  acid  anhydrides. Particulate emissions will also be  part of the  building
ventilation system.
b.   Paint Operations — The production of paint products themselves consists of milling, dispersion
and mixing operations. Ball and pebble mills are free of gaseous emissions, except when loading
and unloading, since they are completely closed during operation. Sand mills often  discharge into
open portable tanks. Since such tanks are not equipped with  covers and vents, there exists  a source
of solvent evaporation  associated  with the operation of the  sand  mill. Sand mills can be set  up to
discharge  into  closed, vented containers.  This will reduce evaporative  losses. The high speed
dispersers  sometimes  operate in  open tanks and provide  a source of solvent emissions. Often,
however, finishing tanks are equipped with tops and top-mounted agitators. This should  serve to
reduce emissions from these sources.
        Most of the emissions from the paint manufacturing area will tend to  be carried  out with
the  ventilation  system. Hoods or local  ductwork  can be  used to  collect emissions from points
within the paint manufacturing area. In other cases,  no attempt is made to contain emissions and
evaporation is  directly to the plant ambient atmosphere. Particulate emissions from this  area  will
be  minimal except when loading dry pigment into the  equipment.
c.   Resin Production — Resin processing represents a major source of emissions for the coating
industry.
        Fusion  cooking is characterized  by a continuous sparge  of  inert gas. Intermittently during
the process, the hatch is opened for charging  raw materials. During this time the volumetric flow
rate,  and  associated  emissions,  are increased considerably. The flow rate can increase during
charging to better than 100 cfm.
        Since there is less inert gas used in solvent cooking, exhaust volumes are small and consist
primarily of noncondensibles. As in the fusion process, however, the  rates increase during  charging
                                           134

-------
of raw materials. Condensers are used on solvent reactors but must be kept warm enough to prevent
accumulations  of condensed  phthalic. It is common practice in the resin  industry to maintain  a
small  inert  gas flow throughout a solvent cook to  avoid  the  possibility of leaking  air into  the
system.
        Thinning is usually done in separate tanks. The  resin  batch is "dropped"  by  gravity feed
or pumped into a thin tank which is equipped with a  condenser to reduce solvent losses. In some
cases thinning  is done  in the resin kettle  itself. This usually results in a higher  solvent emission.
2.     Raw Materials
        The particular  raw materials  used  in a  given  plant influence  greatly both the type and
quantity of emissions produced. Emissions potential consists of two problem areas: (a) particulate
and (b) gaseous.
a.  Particulate  — Pigments and extenders  account for a major  portion of the particulate emissions.
The extenders, along with TiOz, represent the major groups of pigments.  Others  which find use
include iron oxides  and  carbon blacks. Representative particle size ranges for these products were
given earlier in Table 29. Particles outside these ranges are found,  but the majority of particles of
a particular pigment material,  as manufactured, fall within the ranges given.
        Some pigments  are now available already dispersed as a liquid slurry. The  use of this type
of raw material  will significantly reduce particulate emissions.
        The other source of particulate emission  consists of phthalic anhydride, PE, or other acids
and polyols. This is connected solely with the resin  production operation, particularly during, and
immediately after charging. This type of emission can  be  reduced by the  use  of liquid  phthalic
anhydride. Sublimed PA can  also result  in a particulate  emission in that the vapor may condense
into a fine fume as it  leaves the  high temperature sections of the equipment. Phthalic also has
the unfortunate tendency to plug and foul condensers and similar equipment.
b.  Gaseous Emissions  — The primary  source of gaseous emissions  is the solvents. These  are
potential air pollutants in all phases of the operations including  handling,  storage, resin production
and dispersion and mixing. Basic parameters influencing emissions of solvents include vapor pressure
and molecular  weight. The rate of evaporation  can also depend  on such things as  diffusivity,
surface tension and heat of vaporization. The influence  of these properties  is less, however, and
is  rather difficult to predict. Table 26 gives vapor pressures and molecular weights  for some of
the more common  types  of solvents encountered  in the industry. The molecular weight is important
in that it affects the  quantity of emissions  on a weight basis.
                                           135

-------
       Oils and glycerine are relatively non-volatile and so do not contribute significantly to quantities
emitted except at very high temperature. They can, however, be the source of reaction by-products
which can present odor problems even in small quantities, or the source of aerosol mists.
3.     Start-up and Shut Down
        Start-up operations should present no unusual problems provided the appropriate condensers,
fans, scrubbers,  etc., are turned on at or  near the beginning of the process.  If the process heat
and purge gas is allowed  to commence operation before these items are turned on, a significant
pollution problem could  exist during start-up.  It is assumed that  kettles, etc., would  be purged
with inert gas prior to addition of any volatile material.
        Shut down operations,  particularly if done under emergency conditions, offer  a greater
potential for  air pollution. Good practice would dictate purging lines and vessels with inert gas to
eliminate residual solvent and PA. These materials would in  all likelihood be vented to the atmos-
phere.  A  complete  shut  down might  also involve solvent  transfer operations with  associated
displacement losses.
        Shut down of resin reactor in many cases is accomplished by blowing the reactor materials
into the  thinning  tank.  This is done  by pressuring the tank with inert gas.  This inert gas becomes
saturated  with solvent  and  must eventually  be vented  to  the  atmosphere  through the reactor
vent or  thinning  tank vents. This normally results in a highly concentrated emission for a short
period.
4.     Operation Above and Below Capacity
           Aside from the  obvious statement that emissions are roughly proportional to production
output, operation at other than rated  capacity should, in itself, offer no unique problems. Productivity
increases  are  accomplished primarily  by  increasing the  number of  batches. Since  equipment is
sized on a per batch basis, the plant should operate smoothly.
        The  potential problem  areas would more  likely involve employee  diligence in adhering to
proper procedures. As productivity is increased beyond normal levels there might  be a tendency
for plant housekeeping and control to become  sloppy.  Operation  significantly below capacity might
present  the  temptation to cut operating costs  by  turning down the operation of scrubbers, etc.
The effectiveness of supervision and  management will determine  the extent  to which  emissions
are adversely affected  by production changes.
5.     Process Operation Upsets
        Several events can occur which could have an adverse effect on emissions. Loss of power
                                           136

-------
would  cause a shut down of pumps,  stirring devices, controllers,  etc. If the dowtherm heater is
at a higher elevation than the reactors, a pump will be required to return condensate to the heater.
Consequently, fail safe devices must activate which shut off heat to the reactors to prevent accumu-
lation of condensate. Condenser water flow will continue while the scrubber-ejector will cease to
function. The inert gas generator will shut down; though the inert gas  storage tank will  provide a
continued supply of  sparge gas for a short length  of time. The plant will revert to a "status quo"
situation in which air pollution effects should be small.
        If power is returned soon  enough  it will be possible to resume operations at the point of
interruption. It may be desirable initially to increase  the sparge  rate  in a fusion  process reactor
until water which has accumulated  is removed. Likewise, a period of sparging of the solvent process
reactor may be required  for the same  purpose. For some interval  of time after power is resumed,
an increase in the emission rate may be observed due to increased sparging.
        Condenser failure (due to loss of cooling water, leaks, or other causes) would have unfavor-
able consequences.  The reactor vent would have to remain  open until the  reactor  had cooled
sufficiently to lower the solvent  vapor pressure to a safe value. Even if the  sparge gas is turned
off immediately,  a considerable  amount of solvent would be lost.  It is  likely  that the batch would
be lost. It is likely that the  batch would have to  be cooled immediately with cold  dowtherm and,
unless there is reason to believe that  condenser operation  will resume soon,  dropped to the thin
tank. If condenser failure is on the reactor condenser  only, this  should  result in minimum  emission.
If, however, there is a general loss of cooling water  to the plant there seems no way to avoid a
significant emission  problem whether the emissions  came from the kettle or  from the  thin  tank.
Partial failure of condenser (due to fouling, improperly operating controls, or other causes) is common.
Often processing is continued in spite of this with a significant increase in emission levels.
        Finally, there are several  other upsets which can occur to the detrement of air  quality.
Any  upset which results in  a higher  than  anticipated temperature (e.g., failure  of temperature
controller, improper charging of reactants, etc.) will tend to increase  emissions. Any increase in
sparging rate  will tend to increase emissions. Use of inert gas pressure to force resin from  the
reactor into the thin tank  (e.g., if the transfer line is tending to plug) will cause increased emissions.
As discussed  earlier, when the last of the resin  comes through,  the  pressure in the reactor  will
be released through  the thin tank condenser vent causing a surge  in the amount of solvent vapors
emitted from the thin  tank.
                                          137

-------
E.     Raw Data Tabulated
1.     Questionnaires — Emission data has been reported by some of the plants responding to
the industry questionnaire that was distributed  to a sampling  of the industry.  The data for those
plants having reasonably complete emission inventories is summarized in Tables 38 to 40.
       There is wide diversity in the manner in which the data has been submitted. The numbers
as reported are difficult to  interpret or compare as they stand. It  is felt that the only meaningful
presentation of the data is to relate total emission rate to production. Emission data by itself contains
limited information unless the production rate is also known. This  correlation will be presented in
Chapter 4.
       The tabulation of emission rates do provide  an  indication of possible non-compliance
(depending on local  regulations) by some plants. Also, it suggests the range of  values that might
be encountered in source testing.
       One  of  the  paint  industries  more persistent  problems has always been odor  nuisance
complaints. Data on this subject has also been reported in the questionnaires. Of  76 Type 1  plants,
15 reported odor complaints from residential areas and six from commercial areas. Of the 39 Type
3 plants, nine reported  complaints from residential sections. None of the Type  2 plants reported
odor nuisance complaints. This information is tabulated in Table 41.
       The detection and measurement of odors is a  very difficult  area to predict. The odor levels
around a plant  depend not only on the types and quantities of odorants emitted but also on local
atmospheric conditions, presence of competing odor sources, and proximity of neighboring residential
or commercial areas. Ultimately, subjective criterion must be relied upon.
       The  information reported  by  the questionnaire  sample  suggests that  resin processing
represents  the primary odor problem. This may  be due to the presence of high temperatures which
tends to produce small quantities of particularly noxious substances.
       Industry source  test results have  been listed  in various parts of this  report  where it was
deemed most appropriate. Test results were obtained by air pollution control equipment manufacturers
as well as paint and resin producers. Information on reactor emissions can be found in Section ll-C-2
of Chapter  1. Information on performance of control equipment can be found in Section IV of Chapter
5. Test results obtained by the Federal EPA can be found in Section II-G of Chapter 1 and in Appendix D.

F.     By-Products
       The only reaction by-product present in any quantity is water formed in the  esterification
reaction by which alkyds are produced at about 4 to 5% by weight of the final  resin product solids.

                                           138

-------
















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                                        TABLE 39
                        EMISSION DATA FROM QUESTIONNAIRES
                                      PAINT PLANTS

  Organic                               Paniculate                   Plant Size*, MM Gal
     5.4lb/hr                                                                3.1
     2.09 Ib/hr                                                               0.5
     8.94 Ib/hr                                                               0.6
    30.0 Ib/hr                                                                3.3
23,650 Ib/yr                                                                  0.2
 1,300gal/yr                                                                0.1
     2 Ib/hr                                                                  1.3
    10 Ib/hr                                                                  0.4
                                        183 ton/yr                           —
 3,425 gal/yr                                                                0.3
     4 Ib/hr                                                                  2.2
     5 Ib/hr                                                                  0.2
    48.9 Ib/hr                                                               15.4
                                 8.7 gr/SCF @ 800 SCFM                     —
                                        2.78 Ib/hr                           —
68,000 Ib/yr                                                                  2.7
   248 Ib/day                                                                1.7
*Plant size represent  solvent based  production  only  and is  based on  16 Hr operating  day
 6 day work week
                                        140

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                                        TABLE 40
                        EMISSION DATA FROM QUESTIONNAIRES
                                      RESIN PLANTS

                  Organic Emissions       Plant Size* (MM Lb)
                      360  Ib/hr                20.5
                        2  Ib/hr                  3.8
                        3  Ib/hr                  8.6
                        8.7 Ib/hr                25.5
                       15  Ib/hr                  3.6
                       1.27 Ib/hr                39.1
                       66.6 Ib/hr                21.7
                        3.3 Ib/hr                14.7
                        4.5ib/hr                  1.8
                       24  Ib/hr                11.7
                        7  Ib/hr                10.3
                       39.1 ton/yr                 4.0
                       15.7 Ib/hr                60.3
                      668  Ib/hr**               47.0
 'Based on 16 hour day — six day week
"Most of this emission is from "Resin Dryers"
                                          141

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        In addition to water, various reaction by-products are formed in very small quantities. Often
these are detectable only by very  sensitive analytical procedures. These  products are important,
nevertheless,  in that they  constitute a primary source of odor  problems even  when present in
minimal quantities. These substances include aldehydes, esters and organic acids.
1.     Liquid  Wastes — Waste materials  constitute  a  major source of  potential  liquid pollutants.
These include spoiled batches, residues and  solvent and  aqueous solutions for washing equip-
ment. The industry questionnaires have provided a source  of information on this subject.
        The questionnaires requested information on the amounts of resin and of paint disposed of
as well as solvent and water usage for clean up. The  results have been tabulated and are given
in Table 41. Note that even plants which produce no water based coatings reported use of aqueous
solutions (probably caustic) for washing purposes. It would not be entirely accurate, then, to assign
all the aqueous waste to water based paint production.  Nor, in the case of Type  1  plants, is  it
possible to  assign the portion of waste which  is  attributable to paint production as  opposed to
resin production. It is apparent from the questionnaires that the term "kettle" means different things
to different  people. To some,  "kettle" is reserved  for resin and  varnish cooking  vessels while in
other cases mixing  and finishing tanks are also  included  in the term.  One cannot necessarily
assign washing solutions for kettles to resin  production in the case of Type 1 plants. Some generali-
zations can  be made:
        a.   Aqueous waste far exceeds solvent wastes for all types of plants.
        b.  The  major portion  of solvent wastes can probably be attributed  to coating production
            as such.
       c.  Waste resin and paint account for less than 0.5% of shipments.
2.     Solid Waste — Most solid waste, with the exception of that  which  can be considered part
of an air pollution emission, is incorporated into the liquid wastes  described in the previous section.
These  include pigment  particulate  and latex emulsion  as well as the non-volatile portion  of  the
film former which would be left if the paint or resin were allowed to dry.

G.     EPA Source Test Data
       The U. S. Environmental Protection Agency retained Scott Research Laboratories, Plumstead-
ville, Pa., to  source test several resin kettles. Flow rates, total  hydrocarbons and gas chromatography
data were obtained  from several processes. The  test methods  used are described in Chapter 3,
Section I-C.  The results are presented in Appendix D.  Portions of this section have been taken from
                                          143

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the report prepared by Scott Laboratories for the E.P.A.
       A summary of the batches tested follows:
       Three basic types of varnish cooks were tested. These consisted of a polyester fusion cook,
an alkyd-fusion  (oil modified polyester) cook, and  an alkyd-solvent cook. In addition, some thinning
operations were tested. A detailed description of each process tested is given below.

                              Linseed Soya Alkyd Fusion Cook
       This alkyd resin is a long oil  alkyd produced from linseed oil, soybean oil, pentaerythritol,
and molten phthalic anhydride.
       The two oils were added to  the kettle and heating began. After  the oils were added, a
blanket  of  inert gas  was maintained over the batch. When the oils  had heated sufficiently, the
pentaerytritol (PE) was  added. The steam ejector  was turned on in order to create a vacuum in the
stack while the PE was being  dumped from bags into the reactor porthole. The temperature was
raised and a liquid catalyst was added. The batch was then heated to 440ฐF and kept at this temperature
until samples of the  batch passed a  clear  test (test used to indicate completion of reaction). The
temperature was then reduced  and molten  phthalic  anhydride was added. The batch was reheated
to 460ฐF; upon reaching 460ฐF, the  inert gas blanket was removed and 20 SCFM of inert gas was
blown into the batch from the  bottom of the kettle. This inert gas blow-through aids in removing
water produced  in the process reaction. The inert gas flow as increased to 30 SCFM and maintained
until the  proper acid value and viscosity were measured. Samples were  obtained by  opening a
porthole and removing some resin by means of a dipper.  The 30 SCFM inert gas blow was removed
and a 5 to 10 SCFM  blanket of  inert gas maintained while the resin was cooled to 425ฐF. The batch
was then dropped into a thinning tank containing solvent.
       A description of Kettle 4 may be found in Appendix D, Figure  D-1.
                                  Soya Alkyd-Fusion  Cook
       This alkyd resin is a medium oil alkyd produced  from soybean oil, pentaerythritol (PE), and
molten phthalic  anhydride. The  oil was heated  and then  part of the PE added. A clear test was run
and then the remainder of the PE  and molten phthalic anhydride was added. The steam ejector
was on only during the time that PE was being loaded into the reactor. A 5 to 8 SCFM inert gas blanket
was maintained during the initial period of heating and loading the reactor. A 10 SCFM inert gas blow
was started when the cook reached 480ฐF and was increased to 20 SCFM during the last part of the
cook. Resin was cooled to 430ฐF  and  dropped into solvent.
                                          144

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       A description of reactor number three is also shown on Figure D-1* since reactors three and
four are identical.

                                  Soya Alkyd-Solvent Cook
       This resin is considered a long to medium oil alkyd made from soybean oil,  pentaerythritol,
crotonic acid, and phthalic anhydride; it is used as a major ingredient in producing an acrylic resin.
Soybean oil, pentaerythritol and crotonic acid were placed into the reactor with the steam ejector
turned on; fumes were vented out the main stack (A) during this time. Upon completion of loading,
the ejector was turned off and a 10 SCFM blanket of inert gas was maintained over  the batch while
it was heating. Upon  reaching temperature molten phthalic anhydride  was added,  the main stack
was closed, and the kettle sealed. Xylene was added and the inert gas flow turned off.  The condenser
was turned on and the batch was heated so that the solvent and water (reaction product)  began
refluxing. During this  period of the process the emissions were vented from the receiving tank stack
(B). The water driven off the kettle was drained from the receiving tank several  times during the
cook; the solvent was returned to the batch. After the cook was completed, the batch was cooled
to 400ฐF and dropped into an empty thinning tank.
       A description of reactor number two and associated equipment is presented  in Figure D-2.*

                                       Polyester Cook
       This resin is a saturated polyester produced from propylene glycol, butylene glycol, glycerine,
and dimethyl terephthalate (DMT). This resin is used in producing  powder  coatings. The use of
DMT to fulfill the acid functionality results in the evolution of methanol rather than water as a reaction
product. The steam ejector was turned on while the raw materials were being added. During this
time emissions were  vented to the main stack "A". The  solvent was then added and the reactor
was sealed. Heating of the batch was begun; fumes were vented from stack "B" during  this time.
As the temperature increased distillation began. The temperature was then held constant. When the
amount of distillate coming off decreased considerably, a 10 CFM inert gas blowthrough was begun
to step up the reaction.
       All of the distillate collected in the receiver tank was drained into drums. When the reaction
stopped, the batch was placed under a vacuum. During this time all emissions to the atmosphere
were  vented to stack  "C". The batch was left under vacuum until the proper viscosity was reached.
Upon completion the resin was dropped into 55 gallon drums.
 'Appendix D

                                           146

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       A description  of reactor eight and its associated  equipment is  presented in Figure D-3.*
                                     Thinning Operations
       With the exception of one case, the thinning operations consisted of dropping the completed
resin directly from the reactor  into a thinning tank containing the appropriate  amount  of solvent.
In one case, the resin was dropped into an empty tank  and then the  solvent was added to the
resin. In  all cases,  the emissions to the atmosphere simply  consisted of fumes forced out of the
tank by positive displacement. All the tank vents were equipped with condensers to reduce emissions.
Figures D-1, D-2, and D-3* indicate the thinning  tank, condensers and vent locations.
                                         Discussion
       The primary difficulty associated with measuring  mass  emissions from the  various fume
stacks was the  extremely low  flow and  "breathing" flow  situations encountered. For most of the
larger stacks (8-9 in. diameters) where  the pitot tube and hook gauge  were used, the pressure
differentials were, in many cases, approaching the minimum sensitivity of the apparatus.  In sampling
the smaller 2 inch stacks where the bag systems were more easily adapted, more confident data
were obtained.  Where the "breathing" flow situations occurred, a high degree of care was required
to insure that the one-way flow valve was operating properly.
       After  having experienced the various flow situations  associated with this type of process
operation,  a more sophisticated flow measuring  system could  probably  be engineered for future
investigations.
       The kettle operator also had a direct effect  on the flow rate at certain times during a particular
cook. He had control over the quantity  and duration of inert gas and  steam  ejection, and as  a
result, two different cookers processing similar batches of resin could create dissimilar mass emission
rates at the kettle outlet.
       The results  of the Orsat and chromatographic  analyses  for oxygen and carbon dioxide in
the bag samples yielded a large variation in stack  gas molecular weight for the various stack gases
sampled. As  a  result an average  molecular weight was determined using the  extremes of 28.96
for ambient air and 29.88 for the inert gas stream  that was used as a gas blanket in all the process
operations. This average molecular weight of 29.42 was used in all stack gas velocity measurements.
       All  the flowrate  averages  used  to  calculate mass emissions  are included in Tables D-1
to D-16.*
 'Appendix D
                                           147

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       The total hydrocarbon measurements were reasonably complete with the exception of the
reflux cycles on polyester resin cook  #1 where the heated prefilter was  not closed properly and
a leak occurred.
       Upon examination of the data included in Tables D-1 to D-7*, it can be noted that relatively
good comparison  exists between the average ppm-C levels for  similar modes  within  process run
pairs. A similar comparison involving mass emissions, however, does not yield the same reasonable
duplication. The problem exists with the variations in flowrates experienced between similar modes
of the process run pairs.  Some explanations for these variations have been discussed previously.
       Tables D-1  to  D-7* describe the process  mode  breakdown  for  each  cook and includes
average flow and mass emission rates for each process mode. The flow and mass emission data
for the eight thinning tank tests are presented in Tables D-8 to D-9*.
       All  gas chromatography traces  were reduced  by first  identifying specific hydrocarbons,
where possible, and then measuring peak areas and comparing them to standards. In an effort
to condense the data in a more useable form, the specific hydrocarbons were reduced to four main
groups:  Aliphatics (Ce-Cio), Aromatics  (Cs-Cs), identified oxygenates, and branched Aliphatics
(C8-Ci2). The data  summaries (Tables D-10 to  D-16)* present  each process cook sampled with
average flow rates,  total hydrocarbon emission rates,  and the percentage  of specific hydrocarbons
found in each of the above groups.
       A summary of thinning tank emission data is presented in Table D-9* using the  same format
described previously.
       The GC  data obtained for the alkyd solvent  cooks were a great deal easier to interpret
than that of the  fusion cooks  due to the  basic  three component makeup of their effluents. One
difficulty arose when an attempt was made to compare the total carbon found with the  hydrocarbon
analyzer, to that found with the gas chromatograph.
       Even though the total hydrocarbon analyzer and the gas chromatograph  were both adjusted
for carbon response, the data did not always coincide. The following sources of error could explain
this discrepancy.
1. The total hydrocarbon  analyzer gives  a continuous plot of the hydrocarbon concentrations, while
   the G.C. gives only  a point sample. With the  fluctuating organic concentration, this point sample
   may or may not be representative of the effluent.
2. Since the  nature of the work  did not  permit duplicate injections into the  chromatograph,  an
* Appendix D

                                         148

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   injection error, perhaps sample pressurization, could have occurred.
3.  The concentration of xylene was so high that even with the .25 cc sample loop, the column was
   nearly overloaded. This could add another non-linearity aspect to the system.
                                         149

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                                        CHAPTER 2
                                   INDUSTRY STATISTICS
I.      TYPE, SIZE AND LOCATION OF PRESENT DAY PLANTS
       The Paint and  Allied  Product Industry (SIC 2851) is  made up  of  approximately  1,727
establishments operated by some 1,365 companies.7
       These plants and companies primarily manufacture  coatings such as paints,  varnishes and
lacquers, along with  such allied  products as putty, caulking compounds, cleaners and other paint
sundries.
       Primary to the Paint Industry are two broad categories of products, generally referred  to
as "Trade Sales"  and "Industrial  Finishes".
       Trade  Sales  products  are usually "shelf  items"  to be  used on  the  exterior  and interior
surfaces  of houses  and buildings.  These are  manufactured  in  a wide range  of colors and are
usually applied with  brushes or  rollers,  although other  application  techniques are also employed.
       Industrial  Finishes are generally produced for and  sold  to other manufacturers for  appli-
cation to durable customer products. The final application  varies from spraying,  dipping, etc.,  to
electrostatic methods.
       Although some of the  smaller manufacturers still tend to specialize in either Trade  Sales
or Industrial Finish products, this tendency is not as strong  as it has been  in the past. Most of the
larger companies  now produce both  types.
       A breakdown of the industry  by product class is provided in Figure 29. The major categories
indicated are listed below in order and with product class codes:
       (2851)  1. Exterior, oil-type  sales paint products.
       (2851)  2. Exterior, water-type paint products and tinting bases.
       (2851)  3. Interior, oil-type trade sales paint products.
       (2851)  4. Interior, water-type paint products and tinting bases.
       (2851)  5. Trade sales lacquers.
       (2851)  6. Industrial product finishes, except lacquers.
                                          151

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10,000
 5,000
 1,000
  500
                                                         U.S. PAINT  S. VARNISH
                                                                   INDUSTRY
                                                                  DISTRIBUTION
                                                                          BTV
  PRODUCT  CLASS

VALUE OF  SHIPMENTS . IOSf/YR
                                                             NO. OF  EMPLOYEES
                                                             NO. OF  ESTABLISHMENTS
                                                          SOURCE :  I96T  CENSUS  OF
                                                                      MANUFACTURERS
                                                                 FIGURE  29
                                                                           PUTTY,
                                                                         CAULKING,
                                                                            ETC.
                        MISC.
                        PAINT
                      PRODUCTS
  INDUS.
LACQ.  INCL
 ACRYLICS
    INTERIOR
   TYPEIWTR. TYPE
TRADE   TINT. BASE
  INDUS.
  EXCEPT
LACQUERS
     EXTERIOR
OIL  TYPE WTR.
  TRADE  TINT. BASE
                                           152

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        (2851)   7. Industrial lacquers, including acrylics.
        (2851)   8. Putty, caulking compounds and allied products.
        (2851)   9. Miscellaneous paint products.
        This histogram uses abbreviations of the above categories and is a plot of value of shipments,
number of establishments and number of employees for each of the (product) classes.  Statistics
are based  on the 1967 Census  and no effort has been  made  to estimate corresponding figures
for other years. The number  of  establishments shown accounts for little  more than  50% of the
total and provides a distribution of those showing some degree of specialization.
        Figure 30 provides a distribution of paint plants by size as measured by production value.
It was based on estimates from data for individual companies reported by Kline's Marketing Guide
to  the Paint Industry.1 This distribution follows the log-probability law rather well and is, consequently,
plotted  on  a probability x 2 log  cycle grid. In practice, the small percentage of very  large plants
show wide  variations, partly because data on  an individual plant basis is often withheld  In addition,
it is common in  statistical  data of this nature  to find that the  extreme values do not follow the log-
normal distribution.
        The example,  shown  by  arrows in Figure 30,  illustrates one of the useful aspects of a
log-probability plot.  At the $6.4  million  plant  size lies the  median production  —  half  the paint  is
produced by plants  smaller than (or larger than) this size. Only 7% of the plants, however, are
larger than this size. The  median plant  produces somewhat less than $1 million worth of product.
        It is of interest to note  that the  Model  Plant discussed in Chapter 1 produces product
valued  at about $6.6  million.  This  production value level  is indicated bv an arrow in Figure 30.
        Figure 31 provides a distribution of plants and industry employees by plant si?M as measured
by the number of people who work  in the plant.  It is based on figures taken from County  Business
Patterns.''3  This Bureau of Census publication lists  the number of  plants  in various size ranges
such as 1 to 3 employees, 4 to  7 employees, etc. From these tabulations, it is possible  to obtain
the percentage of plants with fewer  than n given number of employees Figure 31  plots percentage
of  plants smaller than indicated  plant size The total  number of employees in any plant size can
also be computed and expressed as a percentage of total employment in the Paint  and Varnish
Industry. For example, as  shown by arrows on Figure 31, 30% of the plants in the  industry employ
less  than 8 people,  30%  of  the  industry employees work in plants that have a  plant employee
size of less than 50, and this plant size accounts for 78% of the industry plants.
        Statistical measures of distribution: median,  mean and mode have been  included in this
                                          153

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              155

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figure. These measures were similarly computed for past years and changes in them were used to
make projections for future plant  sizes.  Further discussion on projections will be found  in part  II
of this section under the subtitle "Size of  Plants."
       Geographical locations of  areas  of concentrated production are  indicated in Figure 32. To
arrive at volume production for each state in  1972, state-by-state dollar production figures for 1967
(as reported  by  the Census of Manufacturers) were converted to gallons using  average cost  per
gallon, as computed from Current Industrial Reports. Computed production growth rates were used
to arrive at 1972 production volumes of each state. Since these volume production figures represent
a second  generation estimate,  they are indicated as  ranges on the map. Estimated volumes of
the eight largest producers are shown in rectangular boxes.
       Locations and number of plants by state for 1967 can be found later in Figure 35, a histogram
used for making  projections in the  following section.

II.    PAST, PRESENT AND PROJECTED INDUSTRY TRENDS TO  1985
       Several references, mostly published  by  Bureau of the Census, have been employed in
computing past and present production and in projecting future levels. Three main sources used are:
       1.   Current Industrial Reports, Series M28F8
       2.   Census of Manufacturers, 196714
       3.   County Business Patterns™
Various  Industrial Reports were used to tally annual productions for 1965 to 1972 (Figures for 1972
are based  on estimates  for  December  1972) in dollar value and gallon volume.  Geographical
distribution on a state-by-state  basis is  based on the  1967 Census — the  most recent  available
at time  of  writing. Distribution of  plants  by employee  size class are based on  County Business
Patterns.
A.     Production
       Average annual growth  of production rates were computed for the seven year base period
and applied to years in the 1972  to 1985 period. Projections for these years are plotted  in Figure
33 as million gallons, and in Figure 34 as million dollars of shipments  per year. Computed average
growth rates are indicated in terms of percent of current production per year for Trade Sale Finishes,
Industrial Finishes and total sales in each figure. Results are summarized on the following page.
                                          156

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                   Trade Sales               Industrial                  Total
Year
1965
1972
1985
\vg. Annual
Million
Gallons
411.0
456.0
550
1.50
Million
Dollars
1247.0
1663.7
2845
4.21
Million
Gallons
365.0
474.4
770
3.82
Million
Dollars
922.3
1355.6
2775
5.66
Million
Gallons
776.0
930.4
1320
2.63
Million
Dollars
2169.3
3019.3
5620
4.84
   Rate %
       The average growth  rate was calculated in  a manner similar to  compound interest. For
example, let A be the production volume for the first year and B the volume for the nth  year. The
average annual growth rate, a, is determined by solving the following equation for a:
                                       A (1 + a)n  = B
For total gallon production, this becomes
                                   776.0 (1  + a)7 = 930.4
and  a = 0.0263. The projected growth curve  will plot as a straight line on semi-log coordinates.
The  line, by definition, will pass through the first and last points.
       It is apparent from  these figures that in 1972 Trade  Sale  Finishes accounted for 49%  of
the volume and 55% of the dollar value.  In terms of gallons, this compares with 53% in  1965 pro-
jected to shrink  to 41.5% in  two decades. Over the same time period, however, revenues from
Trade Sales are expected to register a much smaller drop: from 57.5% of the total in 1965 to 51% in
1985. This comparison  is readily apparent in the plots of Figures  33 and 34. The higher growth
rates (in terms of both volume  and value) for Industrial finishes are attributed to the trend for pre-
coated materials such as siding for houses, paneling  and  certain plastics. Industrial finishes display
higher growth  rates than Trade Sales. Their share of the  market increases even more dramatically
when measured in gallons than in  dollar value. This is  attributable in part to the lower cost  of
packaging and transportation required for  industrial products.
       Total  production figures for  1967 as reported in the Census of Manufacturers  differ from
those reported in the Current Industrial Reports by  about 25% (variations  between these sources
are somewhat smaller for the census years 1963 and 1958). The Current Industrial Reports are
published  monthly and  present a source of up-to-date  information. They are estimates from a
sampling of about 310 plants and do  not represent the accuracy that might be expected from the
larger sampling  used in the  Census  of  Manufacturers  reports.  Unfortunately, these  reports are
prepared only about every four years.
                                         157

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-------
 10,000






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 •,000
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                               160

-------
        Statistics presented by the Census are, nevertheless, the most detailed available and Figure
35  is based  on them. This  histogram  provides a state-by-state breakdown, for 1967, of value of
shipments  and  number  of  establishments and  employees.  States with less than $6  million in
shipment value  are not indicated.  Projected values for 1972 and  1985 are also  shown  for each
state; these values are based on growth rates computed from the Current Industrial Reports.
        It can be assumed  that, despite the difference of total  production as stated by the two
sources, growth rates derived from one can be applied to geographical distribution obtained from
the other. The second simplification assumed  in estimating  1972 and  1985 productions  was that
each of the  30 states would increase at the same  industry-wide  rate. This accounts for equal
increments on the logarithmic scale used in Figure 35.
        Whereas projections based on average annual growth rates over preceding years do  not
directly take  into account several variables that could affect production (such as projected growth
rates of all industry, GNP, population,  per capita  consumption, technological  breakthroughs, etc.),
it is expected that a similar number and nature of variables existed and determined output over the
base period.  Consequently, projections based on increasingly complex  and seemingly sophisticated
indices may be no better than those obtained above. Factors used here and elsewhere represent,
at best, an  approximation of future trends.
B.      Number of Plants
        The number and size of the  plants operating is somewhat  vague,  with  the Census  of
Manufacturers reports perhaps being  the best source of information  available. According  to  the
Census reports, the number of plants and companies operating them  are shown below:
Year
1958
1963
1967
No. of
Plants
1,709
1,788
1,701
No. of
Companies
N/A
1,579
1,459
Plants w/20 or
More Employees
600
654
680
       The number of establishments  (plants)  is only an  approximation  because  those  plants
with less than ten employees  were not  required to complete the census report in  1967,  resulting
in estimates being calculated and incorporated into the figures. The count on those plants with 20
or more employees is far more reliable.
       In terms of geographical location, Figure  35 plots the number of plants for each of the top
30 paint-producing states. There is, apparently, very little direct correlation between  paint produced
                                          161

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162

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and number of plants in a given state indicating emphasis, in some areas, on smaller plants.
C.      Size of Plants
        As indicated in Figure  31,  the median plant, when ranked by  number of employees,  in
1971 had 16 employees whereas the median employee, ranked by the  size of the plant in which
he  worked, was employed  in a plant having 100  employees.  This  merely  implies  that 50% of the
plants employed  more  than  16 people,  but 50% of  industry  work force  were working in plants
having 100 or more workers.  The plot provides a quick and easy method for finding the percentage
of establishments in any selected size range.
        The only plant size projections attempted are in terms of number of employees. As previously
discussed in  Part I of this chapter, the  number of plants in each size category (1  to 3 employees,
4 to 7 employees, etc.) was expressed as a percentage of total plants. These figures were obtained
for  the  years 1965  to  1970  from the  County Business Patterns  of corresponding years. Since
successive years shows small changes, the total  change was  measured in terms  of the statistical
distribution parameters:  geometric  standard deviation,  mean,  median and mode.  As  illustrated
earlier in Figure  31,  a  log-probability plot of the distribution greatly  facilitates computation of these
parameters from which a "bell curve" can be derived, if desired.
        Figure 36 plots percentages of plants smaller than  indicated  employment size  — actual
distributions for 1965 and  1970 and projected distributions (broken lines)  in  five-year increments
to 1985. Actual distributions are completely defined by:21
        1.  Geometric mean,  or median, which is plant size class at  50%, and
       2.  Geometric standard deviation which is  equal to
                                  plant size class at 84.1%
                                   plant size class at 50%
There was found to  be a negligible change in the  latter quantity over the five-year base period.
Had there been a noticeable  difference this would have resulted in  different "slopes" for  1965 and
1970, and the projected distributions would  need to  take this into account.  Instead, since the plots
are "parallel," projections can  be based  on a change of median  size  alone.
       The increase in median plant size appears minor (16 employees in 1965 to 23 employees
twenty years  later). At the 98% point, however, Figure 36 indicates that the number of employees
will  have increased from 230 to almost 400. Conversely,  the  largest  2%  of  the  plants  will  have
increased in size to  employing more than  400. This  increase in size is in spite  of technological
improvements and increased productivity. Table 43 lists percentages of plants in indicated employee
                                          163

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164

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                                    TABLE 43
                        U.S. PAINT AND VARNISH INDUSTRY
                DISTRIBUTION OF PLANTS BY EMPLOYEE SIZE CLASS
                Percent of Establishments in Indicated Employee Size Class
        Year           1971     1970     1969     1968     1967     1966     1965
Employee size
Class
1 to 3
4 to 7
8 to 19
20 to 49
50 to 99
100 to 249
250 to 499
500+
Total units reporting
Total employees

15.2
15.4
26.3
22.0
11.3
7.3
2.1
0.4
1,568
63,865

15.2
15.5
25.1
23.5
11.1
7.1
2.3
0.3
1,597
65,601

15.4
15.8
25.1
23.0
11.1
6.6
2.5
0.5
1,607
66,474

16.3
16.5
25.3
22.2
11.0
6.3
2.0
0.5
1,624
63,623

17.8
15.5
25.7
21.6
11.1
5.9
1.9
0.6
1,654
64,959

17.8
17.4
25.9
20.7
10.2
5.6
2.0
0.4
1,690
62,359

17.9
18.0
25.4
21.3
9.5
5.7
1.7
0.5
1,734
63,255
Source:  "County Business Patterns", U.S.  Summaries for 1971, 1970, 1969, 1968, 1967,  1966
      and 1965
                                     165

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size classes. It is noteworthy that the total number of plants has  registered  a decline for every
year from 1965 through 1971.
       This increase in average size is  not surprising since the paint industry is labor intensive.
It is not feasible to operate on a continuous production basis as  in chemical manufacturing. Larger
equipment can be used to increase batch size and productivity, but the wide range of products
and colors still precludes the use of any other technique except batch processing.
       In Figure  35  a comparison between the bar indicating number of  plants and the line giving
number of employees will yield an average plant size for each state.
D.     Capacity — Production Relations
       There  are no statistics available  on theoretical capacity for the  industry. One can  "pick"
a reasonable number, such as 80% or 90%  and assume that all  plants, on an average, operate
their equipment at this fraction of full  capacity.  If necessary, one could calculate  industry capacity
by dividing production data previously presented by 0.80 to 0.90.

E.     Typical Plant  and Equipment Ages
       It is suspected that a vast majority of the some 1,700 establishments will have  quite old
structures and equipment.  There are several reasons for arriving at this conclusion:
       1.  To avoid  high  shipping cost, most of the plants are established in geographical sections
           of the country  where the paint demand is high (see Figure 32).
       2.  Most  have been  established  for quite a number of years, having  evolved from single
           ownership to corporate  structure  in these geographical areas where  land values and
           construction cost  have increased at a very rapid pace.
       3.  Paint  manufacturing does not cause extensive damage to buildings,  nor does  it have
           a deteriorating effect on a  majority of the equipment used.
       4.  Inspection of capital expenditures (see Figure 37 and the accompanying discussion  on
           capital expenditure, Section III) shows us that for the period of 1963 to  1970 an average
           of  35% has been expended for buildings and structures, while 65% has gone for new
           machinery and equipment.
       Within  the Paint Industry the following  types  of equipment will be found:
         1.  Storage tanks
         2.  Reaction kettles
         3.  Pumps  and motors
         4.  Filters and strainers
                                           166

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 1.000
     U.S.  RAINT &.  VARNISH  INDUSTRY

    	CAPITAL   EXPENDITURES


    	     	 MILLION  DOLLARS 	    	
     SOURCE: STATISTICAL   ABSTRACTS

         -1-    OF  THE.  U.S.    1903 - I97O
 500
                       FIGURE  37
                                                           ^	/-
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                                              EQUIPMENT
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  20
  10
                                   167

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        5.  Filling and capping equipment
        6.  Packaging equipment
        7.  Mixing and dispersing machinery
        8.  Grinding machinery
        9.  Electronic instruments of various types
       10.  Material handling equipment.
       Much of this type of equipment is common to other industries and requires  little change
to adapt to paint manufacturing.
       In general, we would expect to find quite old structures, many of which may be 50 years old
or older.  However, the  equipment should be  relatively newer due to changes in manufacturing and
increasing batch size. The average age of equipment may run in the range of  ten to twenty years.
F.	Technological  Revolutions  and  Outside  Influences Causing Changes  in the  Industry
       The paint and varnish industry as a whole is not a large investor in research and development.
Less than 10% of the research and  development dollar goes for basic research. The vast majority
goes  for the support  of existing products,  solution of manufacturing difficulties,  and customer
assistance. Certain selected areas  of research are being intensively studied, however. These are
discussed below.
       Many of the smaller firms cannot afford sizable research and development expenditures
and depend upon  raw material suppliers and group research firms  who pool their efforts for the
member companies. The  most prominent group research firms are the Paint Research Association
in Chicago and  the Coatings Research Group in Cleveland.
1.     Application  Techniques — Perhaps the  most dynamic changes in  the industry are being
brought about by advances in the  state-of-the-art; advances which could well be termed techno-
logical breakthroughs, in retrospect, if current developmental work is successful and results in wide
acceptance. Such advances include:
       1.  Powder coatings
       2.  Electrostatic spray
       3.  Electrodeposition
       4.  Radiation curing
       Powdered coatings  represent one significant advancement, in recent years, for the  industry.
In addition to its several technical advantages this method eliminates the use  of solvents, thereby
reducing  atmospheric pollution as  well  as fire hazards at points  of  production and application.
                                          168

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Although some powders present  a dust explosion hazard, this  problem can be taken into account
during design of the process.
        It is expected that the industry will concentrate much attention on development and use of
powder coatings. Powder coatings can be applied with flocking guns, electrostatic spray equipment,
or electrostatic fluidizing chambers. The  best known method uses  a preheated object  immersed
into  a fluidized  chamber where  the powder  is  kept in motion  by ascending  gas flow.  Powder
coming in contact with the preheated surface melts and fuses to  the surface. The coating is cured
in an oven. A patent was recently issued to Grow Chemical Company covering  the production of
powder coatings in water slurry form. It is said that these can be applied with existing solvent based
equipment.22
        Much recent interest in this field  has been expressed by  automobile manufacturers  who
claim that recycling permits material utilization of 98%.23 Ford has been powder coating truck wheels
for a few months and is expected  to announce in  late 1973 a pilot line for applying topcoats. General
Motors has a one-color automatic  spray and recovery unit for topcoats. This unit employs eight guns.
        Estimates  for powder  coating consumption range as high as  200 million pounds/year for
metal  coating by  1980.  In addition, the powder coating of glass containers is  said by some to
offer an equal potential  consumption by 1979,24 for a total of 400  million pounds per year by 1980.
These estimates are admittedly  somewhat optimistic but more stringent air  pollution regulations
could tip the scales in their direction.
        Electrostatic  forces have  been employed  in spraying methods. Basically,  a charged (paint)
particle will follow  an electric field. If an electrical potential difference exists between a particle and
a surface, the particle will tend to flow to the surface and  be deposited there.  Various available
methods differ only in the method whereby the particles are charged and brought to the proximity
of a surface. Any material loss occurs only for  those particles whose momentum  in a direction
away from  the  piece to be coated overcome the electrostatic force of attraction.  A reduction of
spraying velocity will, therefore, minimize losses.
        Electrodeposition differs from the  above  in that electric forces are  used to deposit liquid
paint particles much like in an electroplating operation. The coating material contains resins, additives
and pigments. Complete and uniform coverage of all exposed surfaces can be obtained.  Film thick-
ness is uniform  since the deposition ceases when the film is thick enough  to act as an insulator
at the applied voltage. Materials used are generally water-based thus reducing solvents.
       Radiation curing utilizes free radicals and  ions to initiate  polymerization  or other reactions
                                           169

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required for a complete cure. A thin beam of electrons is generated by applying 300 kilo-volts to
a high  vacuum  accelerator tube; this  beam  can be used for curing with  very  little heat build-up
making  it particularly desirable for coating wood, rubber and fabric materials. Although  this method
is suitable  for continuous  curing its use has  been curtailed by high  costs  and technical problems.
Ultraviolet and high intensity visible radiation have also been utilized for curing.
2.      Pigment  Industry — Another important area where technology is expected to set the trend
is  in  the pigment  industry,  in the production of titanium  dioxide.  Estimates25  indicate that the
production  by the chloride process will surpass that using the sulfate process by 1975. Currently
the chloride process accounts for about 47% of the production, its  share is  expected to grow to
60% while  total production advances by 18%. Listed below are estimates for totals of seven leading
producers of the pigment:
                                           MM Ibs
             Process                    Current      1975       1973*
             Sulfate                       918         818         737
             Chloride                      820       1,230         837
             Total                        1,738       2,048        1,574
       The sulfate process uses a lower grade, iron containing, ore known  as ilmenite or high
TiO2 slag. The ore is dissolved in concentrated sulfuric acid to form sulfates of both iron and titanium,
and titanium dioxide is precipitated as a hydrate. The chloride process,  on the other hand, starts
with  Rutile, a high grade ore or upgraded ilmenite.  Technology for using ilmenite  directly has
recently been developed by duPont.26 Also, anatase production by the chloride  process is presently
under  investigation.  The  sulfate  process  results in a significant potential for  emissions of sulfur
oxides. The chloride process is inherently cleaner. It not only has a lower potential  contribution to
air pollution but also has fewer liquid wastes.
       Foreign trade is generally  not expected to be a major factor in the coatings industry. However,
imports have been  increasing recently for titanium dioxide with a  significant increase in 1972.
Aided  by the general economic upturn in industry that year, demand so far outstripped supply of
TiC-2 that  suppliers reduced inventories by more than 50% of the previous year. Imports of this
vital  pigment almost doubled, with West  Germany  and  Canada providing  most of  the  difference
(75% of the increase over 1971 and 48% of the total imports in 1972).
       While demand grew, domestic production remained essentially static. Two leading suppliers
*E. I. duPont estimate
                                           170

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of TiO2 have either plants or an interest in plants in West Germany and Canada.
       The same companies have also shut down some  plants in the U.S. Analysts feel that the
surge in imports was caused by their efforts to satisfy market demand with imported material.
       Production capacity is  expected  to head upward again over  the 1972  to 1975 period with
several suppliers planning expansions and new plants.26
       DuPont is planning  chloride process expansions at Edge  Moor, Delaware, and New John-
sonville, Tennessee, which  combined with phasing out of  sulfate capacity  at Edge Moor will  result
in a net increase of 188,000 tons/year.  New Jersey Zinc  and Kerr-McGee are planning additional
chloride process capacity, also. No new sulfate process expansions have been announced.
3.     Environmental &  Health Considerations — A significant influence on the industry in recent
years has  come from the  laws and  regulations  at  every  level of government. In general,  these
regulations  have been  concerned  with the  environmental  effect  of heavy metals, such as
lead and mercury,  the pollution of water and waterways, and  the pollution of the  atmosphere with
organic emissions. Some others have been concerned with the safe use  and shipment of paints.
       In January,  1971, the "Lead-based Paint Poisoning Prevention Act" was enacted. This law
prohibited the  use of paints containing more than 1%  lead by weight in the non-volatile portion of
liquid paints or in the dried film  on all surfaces accessible  to  children  in residential  structures
constructed or rehabilitated by the Federal  Government or with Federal assistance. The surfaces
include all household interiors and such exteriors as  stairs,  porches, windows, and doors.
       In March, 1972,  the Food and Drug Administration ordered a reduction of  the lead content
in paints  used in and around households to a maximum of 0.5% by January 1, 1973, and possibly
to 0.06%. Household surfaces were extended to include such manufactured products as toys.
       The proposed enforcement of  a  0.06% lead content level by  December 31, 1974, will not
only require the use of higher priced substitutes but also time consuming and cbstly reformulation of
many paint products. This lower  limitation  may not be enforced if the Consumer  Products Safety
Commission determines  a higher level to a maximum of 0.5% is safe.*
       Mercury is also toxic to humans at some level of exposure. Organic compounds of mercury
are used in water-based paints as  preservatives to prevent  bacterial action. Mercury fungicides
are used  in many exterior paints to prevent fungi from attacking the dried film.
       The curtailment by the EPA of mercury usage has again  required  a search for substitutes
and reformulation.
'Public Law 93-151
                                          171

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       Air pollution  legislation has also had its effect on  the  Paint  Industry,  particularly  those
regulations patterned after "Rule 66"  which seeks  to control  the emissions of photochemically
reactive hydrocarbons which react with nitric oxide in the  presence of  ultraviolet radiation to form
oxidants.
       The Water Pollution Control Act as amended in 1965 and  1972 has,  and will cause many
paint  manufacturers  to design alternate ways of discharging waters. The  industry contributes to
water pollution primarily through the discharge of slurries.
III.     DISTRIBUTION OF CAPITAL EXPENDITURES
       The Paint and Varnish Industry has  shown a fairly steady  increase in capital expenditures
over the  1963 to 1970 period.  Figure 37 is a plot of expenditures for new buildings and structures
and for new machinery and equipment. Totals are also plotted for the seven-year period. Although
this industry does  not spend as large  a percentage  of its revenues in this category as does the
entire Chemical Industry,  it has maintained a steady input of funds in response  to growing demands.
Since  1963,  approximately 65%  of all capital expenditures have  been for  new  machinery and
equipment with the remainder going for new buildings  and structures.
       Average  annual growth rates for capital spending  were computed for the base  period, for
each  category, and for the total.  These rates were used in projecting  to 1985.  The rate for total
spending  averages 15.3% — a rate that seems unrealistically high, especially when compared to
the rate  of increase in value  of shipments. This is further  emphasized  by selecting  the six-year
base  period 1963 to 1969 which reduces the growth  rate substantially resulting in capital expendi-
tures  less than 50% of those  obtained by using the  1963 to 1970  period (to illustrate, the reader
may draw an  imaginary line through the corresponding points for  1963  and 1969 and extend this
line to 1985).  This apparent discrepancy seems unavoidable where data is subject to  very  large
year to year fluctuations as in the case here.
       While  Figure 37 attempts to provide  a long range picture  of the capital  spending pattern,
Table 44  provides a comprehensive distribution of labor and finance within the industry. Statistics
here include a listing for Inorganic Pigments.
                                         172

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                                         TABLE 44

                U.S. PAINT, VARNISH AND INORGANIC PIGMENTS INDUSTRY

                           1967 LABOR AND FINANCE SUMMARY
 Establishments

 Establishments with 1 to 19 Employees
 Establishments with 20 to 99 Employees
 Establishments with > 100 Employees

 Employees

 Payroll

 Production Workers
 Wages
 Man Hours
 % Man Hours
 % Man Hours
 % Man Hours
 % Man Hours

 Cost of Material
Materials, Containers, etc.. Consumed
Cost of Resales
Fuels Consumed
Purchased Electricity
Contract Work

Value of Shipments

Value of Resales

Value Added by Manufacture

Manufacturers Inventories
Total
Beginning 1967

Finished Products
Work in Process
Material, Suppliers, Fuel, etc.
Total
Millions of Dollars
Millions of Dollars
Millions of Hours
January to March
April to June
July to September
October to December

Millions of Dollars

Total
(Including Resales)
Millions of Dollars
Total
Paint &
Allied
Products
1,701
1,701
1,021
521
159
66,100
492
36,300
223.4
73.1
24.2
25.45
25.5
24.9
1 ,606.4
1,461.0
125.9
7.8
9.8
1.9

Inorganic
Pigments
98
98
38
33
27
12,600
97.2
8,900
63.2
17.7
26.0
25.4
23.7
24.9
235.0
197.3
15.2
15.4
6.3
0.9
2,911.4

  173.2

1,318.5



  406.1

  224.8
   23.9
  157.4
549.3

 20.1

316.3



104.3

 45.0
  9.6
 49.7
                                          173

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                                  TABLE 44 (continued)

               U.S. PAINT, VARNISH AND INORGANIC PIGMENTS INDUSTRY
                          1967 LABOR AND FINANCE SUMMARY

                                                                         Paint &
                                                                          Allied     Inorganic
                                                                         Products    Pigments

End of 1967                                     Total                       426.7      108.6
Finished Products                                                            234.6
Work in Process                                                               27.7        9.6
Material, Supplies, Fuel, etc.                                                   164.4       51.9

Expenditures for Plant and Equipment                                           73.5       21.7

New Plant and Equipment Total                                                 70.7       20.8
New Structures and Additions to Plants                                           28.8        3.1
New Machinery and Equipment                                                 41.9       17.7
Used Plant and Equipment                                                      2.8        0.9
Source:  1967 Census of Manufacturers, Bureau of the Census
                                        174

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                                        CHAPTER 3
                             MEASUREMENTS OF EMISSIONS

I.      SAMPLING AND ANALYTICAL PROCEDURES
A.     General Requirements for Source Testing
       Several comments  can be  made concerning source testing for the Paint and  Varnish
Industry.
       1.  The testing personnel should become as familiar  as  possible with the process under
investigation before testing begins. Products produced, raw materials used, conditions of operation,
location of sampling points, etc., should be ascertained as much as possible.
       2.  The chemical  identity of the  probable  emissions species  should be  anticipated  in
advance  and their chemical and physical properties determined.  A brief description of the  species
that may  be encountered in various types of operations follows.
       Some of the emissions characteristics of resin and varnish cooks are covered in Chapter 1.
The major  part of the emissions from these  operations consists of solvents, steam, and some of
the more volatile  reactants. Also  present will be  various reaction and  degradation products that
can be formed during  processing such  as aldehydes and  organic acid. The latter products are
usually present in relatively  small  amounts. However,  they  often  constitute the  most  noxious
components of the fumes. Table 45 lists the more  common  raw materials and solvents  used in
the manufacture of various resins. This  list is  not intended to be comprehensive, but should be
used only as a guide as to what to expect when source testing a particular resin operation.
       Since thinning is sometimes done in the resin  cooker,  solvents can represent a major
emission  even from fusion processing. The properties of the solvents used should be kept  in mind
when  designing an analysis train for source testing. The chemical composition and vapor pressure
characteristics are of  particular importance.  The  boiling  range  of selected  solvents  is given  in
Table 46. A boiling range is given even  for specific  compounds since the grades usually  used in
the paint  industry are of varying degrees of purity.
                                         175

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Resin
Alkyd
Urethane
Acrylic
 (solution)
Phenolic
Vinyl
  (solution)

Amino
                TABLE 45

COMMON RAW MATERIALS AND SOLVENTS

 USED IN THE MANUFACTURE OF RESINS

     Raw Materials                Solvents
     Polybasic Acids
       Phthalic Anhydride
       Maleic Anhydride
       Fumaric Acid

     Polyols
       Glycerol
       Pentaerythritol

     Oils
       Soya
       Tall Oil Fatty Acids

     Benzoic Acid

     Toluene Diisocyanate
     Polypropylene Glycol
     Linseed Oil
     Acrylic Monomers
     Methacyrlic Monomers
     Formaldehyde
     Phenols
     Cresol

     Vinyl Monomers
      Dimethylol Urea
      Urea
      Formaldehyde
      Butanol
      Melamine
Xylene
Mineral Spirits
Toluene
Naphtha
Xylene
Mineral Spirits
MEK
Ethyl Acetate

Aromatic Hydrocarbons
Ketones
Esters

Alcohols
Ketones
Esters

Ketones
Aromatic Hydrocarbons

Butanol
Xylene
                                    176

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                     TABLE 46
             SOLVENT BOILING RANGES
       Solvent
Hexanes
Naphtha (light)
Xylene
Toluene
VMP Naphtha
Regular Mineral Spirits
Aromatics (medium)
Ethyl Alcohol
n-Butyl Alcohol
Acetone
Ethyl Acetate
Methyl Ethyl Ketone
Ethylene Glycol Monoethyl Ether
Boiling Range, ฐF
   140 to 160
   205 to 250
   275 to 290
   230 to 232
   210 to 300
   31010395
   315to390
   170 to 174
   241 to 246
   133 to 135
   162 to 176
   172 to 178
   270 to 279
Source:  Martens4
                        177

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       In addition to  the  raw materials and solvents, the source tester should be  aware of the
possible  side reactions that may occur in processing. Certain  of these reaction products have a
very low odor threshold and their presence in  even very low concentrations may  be undesirable.
For example, polyols  can  undergo oxidation or dehydrogenation to form aldehydes  and ketones.
These  can undergo further oxidation  to  acids. The breaking of the  carbon chain can occur on
oxidation to give an aldehyde and ketone each of which  has fewer carbon atoms than the original
alcohol. Some of these reactions may occur in the kettle while others may require more  severe
conditions such as would be encountered in a fume incinerator.
       3.  The sampling team should have the capability to perform continuous, on-line measure-
ments  as well as discrete sampling.  The highly  cyclical emission  curves  of such operations as
resin cooking makes continuous measurements  virtually mandatory.
       4.  Cross checking of the measurements should  be made whenever possible. This should
preferably be through  on-site analysis to minimize the necessity of return trips. Wherever feasible,
an over-all material balance on the sample should be used to check the consistency of the analytical
results.
       5.  Equipment used should be as simple and as portable as possible and require a minimum
of utility hook-ups.
       6.  Explosion  proof equipment is required  when in close proximity to volatile hydrocarbons.
       7.  A  complete  log should be made,  if possible,  correlating emissions levels with kettle
temperature, addition of raw materials and solvents, etc.

B.     Description of Source Sampling and Analytical Procedures
1.     Flow Measurement  — The most widely accepted technique presently consists of flow measure-
ment per ASTM/PTC-27 using a reverse pilot  tube  (S type). Care  must be exercised to see that
a representative traverse  is made and that the measurement  points are  sufficiently far from any
flow disturbances.  Duct temperature and pressure should  also be recorded.
       Pilot tubes, however, cannot  be  used  with  much  accuracy below  linear gas velocities of
10 to 15  feet/second. For lower gas velocities, various types of anemometers are available including
vane,  hot-wire, swinging  vane and  heated thermocouple types. These  instruments often  have
limitations as to the types  of environments in which they  can be used so care should be exercised
in selecting them. Hot-wire types may present an explosion hazard in some atmospheres.
       Resin  kettle vents are sometimes quite small in diameter (four inches or  less). For  small
                                          178

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diameter vents, the use of a pitot tube can be undesirable in that its very presence in the vent may
disturb the flow pattern so as  to give a faulty reading.  This problem can be overcome in some
cases by the use of very small L shaped pitot tubes. These, however, are more prone to clog by,
for instance, phthalic anhydride.
       An alternate method of measuring low flows in small ducts is through the use of a calibrated
orifice. These have been used  with some degree of success  in  the  field. A low pressure drop,
pre-calibrated  orifice is  mounted in  an assembly which can then  be fitted to the end of a  reactor
vent. All of the gas flow is made to pass through the orifice.
       A variation  on  this  scheme, which has met with  less success, is the use of a plastic bag
provided with a hole. The bag is slipped over the end of a vent  and the pressure in the bag during
gas flow is measured and correlated with gas flow.
       For very low flow situations, the use of a bag without an orifice can be used. A completely
evacuated  bag can be slipped over the  end of the vent and allowed to fill with the effluent  gas. In
this* case, the bag  collects all of the gas emitted.  The bag can then be sealed and  the contents
pumped out through a meter.  The total quantity of gas is then recorded.
       A further  complication,  particularly in resin cooking, is  flow rate fluctuation.  For instance,
when the kettle is opened for raw materials addition,  a vacuum  is  drawn in the kettle causing large
volumes of air to pass through the open port, into the  kettle, and  through the vent. Likewise sparging
rate may vary during a cook.  If  a measure of the total quantity of emissions is to be obtained, flow
rate as well as emissions concentration must be known at all times during the process cycle.
       For some ducts, such as those associated with baghouses, a pitot tube is suitable. For any
device which measures linear gas velocity,  the flow profile across the duct should  be known at all
times. This is  often impractical,  however, in many process situations. A useful  compromise might
be to take a traverse during a  period of constant flow and monitor the centerline velocity continuously
during the  rest of the run. If the velocity profile is well shaped,  and if the Reynolds'  number does
not pass through the transistion region  between laminar and turbulent flow during velocity fluctu-
ations, then the centerline velocity can be related to the average velocity with  reasonable accuracy.
In extreme cases, it may be necessary to continuously monitor the velocity at more than one point.
2.     Particulate Measurements
a.  General Considerations —  Here again,  considerable variations  will be encountered  in  the
amount and nature of paniculate emissions. Some  of the situations which  may be  encountered
are listed below.
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       1.  Solid, inorganic participate — An example of this type is  pigment participate. These
are essentially non-volatile and have little, or no, solubility in pure water. This type is the easiest
to handle from a collection standpoint.
       2.  Liquid organic aerosol — This represents  a more  difficult situation. The aerosol  will
usually be present in a gas stream which is saturated in the vapor phase with the same hydrocarbons
present in the liquid droplets. The amount and composition of the  aerosol may vary with location.
When the gas stream leaves the process unit it  is at high temperature and only small amounts of
entrained liquid should be present; whereas downstream where the temperature is lower, significantly
more may have formed.
       The physical properties  of some aerosols can  significantly complicate source sampling
techniques. Where very high boiling components  are involved, if the sampling is done by one of the
common  methods of drying and weighing the collected  material, the aerosol will be included in  the
total particulate measurement. Where a  more volatile aerosol has been collected, it may  evaporate
before weighing and be lost. The intermediate situation is more troublesome in that part may be  lost
and part  retained.
       3.  Solid organic particulate — A good example of this type is phthalic particulate. Some of
the same comments apply here that  were stated in the preceding case. The organic particulate
may be volatile under conditions of subsequent sample processing.
       4.  Organic vapor — This can  be a relatively  easy situation to handle providing  that  the
vapor is  kept above its dew point in the sampling equipment. Problems can  arise due to the large
number of chemical species that  may be present  in a given sample.
b.  Collection and Analysis Techniques — The usual procedure for particulate sampling is to sample
a portion of the effluent over  a period of time using some kind of sampling train. Instantaneous, or
"grab" samples, are not well suited to particulate collection. The sampling train consists of a sampling
probe, collection device or devices, gas flow meter and a gas pump for drawing the sample.
       Sampling of streams containing particulate should always be done "isokinetically" whenever
possible. That is, the gas velocity in  the probe tip should be the  same as that in  the bulk  gas
stream in the vicinity of the sample point. In the case of very small particles, say 5 microns or less,
some deviation from isokinetic sampling  conditions is acceptable.
       Sampling under unsteady state  conditions presents special problems. A given stream  may
be in an unsteady state with respect to flow rate, particulate loading, or both. If the flow rate  fluctuates,
gas velocity in the vicinity of the probe tip must be monitored and corrections made to the sample
                                          180

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flow rate as necessary to maintain isokinetic conditions. If participate loading changes, then samples
must be taken at several times in the process  cycle. Unsteady state conditions can be expected
to occur often in the Paint and Varnish Industry.
        A particulate sampling train in use by the EPA is  described  in the Federal Register  (Vol.
36, No. 247, Dec. 23, 1971). A sketch of the sampling train is presented  in Figure 38.  The probe
and filter  holder  are heated to prevent unwanted condensation.  The first  two impingers are filled
with water, while the third  is left empty and the fourth is filled with pre-weighed silica gel.  Details
of the operation of this train may be found in the Federal Register referenced above.
        The Los  Angeles Air Pollution Control District Source Test  Manual describes an apparatus
similar to the EPA train. The major exceptions are that a  small cyclone is placed  before the filter
and three impingers are used instead  of four.
        A third alternative  is to  place the filter holder assembly into the stack itself. In this way,
condensation  on  the filter is avoided  since  the filter temperature will tend to  approach  that of the
gas stream. This  technique also reduces the amount of particulate that could settle  on the surfaces
of tubing  between  the probe tip and the filter.  This can be particularly important  in the  case of
sticky particulate  material.
        All of the above methods  work  well on dry inorganic particulate  such  as pigment  dust.
When sticky or tarry material is  measured, all methods are subject to problems of clogging in the
probe and filter, and deposition of material in the lines. In such cases, it is sometimes helpful to  pass
the gas sample into the impingers first with the filter placed downstream (but before the  silica gel).
with a volatile solvent, evaporating to dryness and  weighing the residue.  The disadvantage  here
weighing the residue. Material deposited in  lines can sometimes be collected  by  washing the lines
with a volatile solvent, evaporating to dryness, and weighing the  residue. The disadvantage here
is that it is not possible to distinguish between  aerosol at stack conditions and other condensible
materials.

3.     Hydrocarbon Analysis
a.  Discontinuous Sampling — Included under this  classification are any  samples drawn over an
interval  of time comprising only a portion of the process  cycle and analyzed on a  batch basis to
give an  average concentration for that time interval. For instance, "grab" samples taken instantane-
ously as  well as semicontinuous  samples drawn at constant  flow rate for a specified period of
time (on the order of 20 to 30 minutes) are considered in this section.
                                           181

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        1.  Los Angeles County APCD Methods — The Los Angeles County APCD manual describes
several methods of total hydrocarbon analysis. Each method utilizes the same sampling technique
which consists of "grab" sampling in evacuated containers. If fitted with an orifice or other control
device,  the evacuated container can be used to  draw semicontinuous samples. Two* liter round
bottomed flasks are the containers normally used. Protective wrapping should be applied to minimize
breakage where glass containers are used.
        Prior  to evacuation,  the container should  be thoroughly cleaned  and dried.  The sampling
line should be equipped with a filter to  exclude paniculate and provided  with a means of flushing
with stack gas prior to sampling.
        The advantage of  this technique is that samples can be taken very quickly.  In  principal,  it
is possible to draw  a sufficient number of samples over a period of time to catch fairly rapid fluctu-
ations in concentration. For a typical resin cook, however,  the number of samples required may be
unwieldy.
        Potential problems with this approach include clogging of the inlet components, deposition
by condensation or adsorption on  the walls  of the container, and  the inability to obtain results in
the field. These difficulties make this method unsuitable  for testing  the  effluent from  alkyd  type
cooks and, in fact, the LAAPCD does not recommend it for this type of process. It may,  nevertheless,
be useful for processes which do not produce high boiling organics,  particulates, or aerosols.
        Various approaches  can be used to minimize, at least partially,  some of the  objections.
Dilution of the sample can  eliminate dew  point problems in some cases. Adsorption can  be minimized
by using teflon bags. Heated syringes are available for "grab" sampling. Used with sample dilution
techniques these can provide good accuracy and reproducability. Analysis of the sample can be by
infrared, combustion analysis, flame ionization techniques,  chromatographic,  or combinations  of
these.
        2.  Semicontinuous Sampling Trains  — The Graphic Arts Technical Foundation has devised
a  method for sampling  hydrocarbon emissions in the  printing industry. The  sample is drawn by
an evacuated cylinder through a cold trap immersed in dry ice. This separates the hydrocarbons
into "condensible"  and  "noncondensible"  fractions which are then  analyzed separately.  The
noncondensibles in the cylinder are analyzed using gas chromatographic  techniques on a Poropak
Q column. The contents of the cold trap are analyzed by heating the trap at a controlled rate and
analyzing the vapors with  a  flame ionization detector. If the sample line  is heated up to the  cold
trap and fitted with  a filter, this technique should work reasonably well. Its chief disadvantages are
'Currently using 8 liters
                                           183

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the time required for analysis and the inability to analyze the samples in the field.
       Another variation  involves  collection  of  a "condensible"  fraction in ice water impingers
accompanied by continuous, on site measure  of noncondensibles using a portable flame ionization
detector. The condensibles are measured in the laboratory by evaporating the water and weighing
the residue. This is subject to error in some situations due to loss of some  of the samples during
drying. An alternative to evaporating the water is solvent extraction of the organics in the impingers
followed  by fractional  distillation to remove the solvent.  The condensible organics can be further
characterized in the laboratory by chromatographic or other means.
       Deposition  of phthalic or heavy organics in the lines upstream from the impingers can be a
problem with this  technique. Also, the use  of a FID in the field can be difficult  and cumbersome.

4.      Analytical Techniques
a.   Infrared Analyzers — Infrared analyzers are well suited to continuous measurements. Normally,
they are set up to  monitor a single component. This is the source of their chief disadvantage. One
must know in  advance what components will be present and the instrument modified to detect a
specific chemical. The  level of the  chosen component must be representative of the level of total
hydrocarbon emissions. The primary  use of IR analysis may be as a detector in some other form
of  analysis  system.
b.   Combustion Analyzers — Two  types of instruments of this type are available. In the first, the
sample stream, mixed  with air if necessary, is passed over a heated platinum  wire which catalytically
oxidizes the hydrocarbons. The heat of combustion causes the wire to heat up  which changes its
resistance.  The wire forms one leg of a bridge circuit. The change of resistance unbalances the
bridge  and  this is used as a measure of total combustibles.
       The disadvantage  of this system is that the platinum is easily  poisoned  and so cannot be
depended upon to have constant activity over a  period of time. Also, for  simple hydrocarbons the
heat of combustion follows a regular pattern with  the number of carbon atoms. For more complex
molecules,  the heat of combustion follows a more variable pattern so that one must know the principle
components present to relate instrument output to total hydrocarbons. Finally, other combustibles,
such as CO, interfere with  the analysis.
       In another  type of  combustion analyzer, the organics are burned completely over a catalyst
such as  copper oxide. The CO2 produced is measured,  typically by  infrared,  and is used  as a
measure of total hydrocarbons. Poisoning is  not  a problem here and response  depends only on
                                          184

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the number of carbon atoms and not on the particular molecules present. The  presence of  CCb
and CO in  the original sample  interferes with  the  analysis and  must be determined separately.
Dual  column  chromatographic techniques, with backflushing,  have been used  with this  type  of
system, but are not applicable to continuous monitoring.
c.  Flame  lonization  Detection  — This  technique is probably the most promising at the  present
time.  When hydrocarbons pass through a hydrogen  flame they are ionized. This enables the flame
to carry an electrical current. By measuring this current, it is possible to get a measure  of the carbon
atoms present. The method is not sensitive to CO2, CO or water vapor. It adapts easily  to continuous
measurements and  is the  most sensitive to  low  concentrations.  Furthermore,  instruments are
commercially available which are entirely enclosed  in a temperature controlled oven  which allows
operation at high temperatures.
        The chief  disadvantage  is  that  the principal components of the stack  must be  known.
Response for  simple hydrocarbons is regular with carbon number.  However, correction factors must
be applied if the stream  contains significant amounts of hydrocarbons  containing oxygen or other
groups. In extreme cases, calibration mixtures will be required. Also, the instrument requires a supply
of hydrogen and pure air or oxygen. A schematic of a typical flame ionization detector system set
up for continuous  measurement  is shown in Figure  39.  Particulate and aerosol must be excluded
from the sample stream prior to the hydrogen flame.
d.  Gas Chromatography — The previous methods attempt to  measure  total  organics  without
regard to identification of individual components. (Infrared can be used for the latter purpose but
it  requires  a far more elaborate  and sophisticated  instrument than is  usually used in air pollution
analysis.) Gas Chromatography, on the other hand,  permits a separation of a sample into its com-
ponents. A detector,  usually thermal conductivity or flame ionization, is then used to identify  and
measure the fractions. A wide variety of techniques and columns are available  to permit identification
of practically  any  material that may be  encountered. The requirements can  be quite elaborate,
however, and  do  not lend themselves to field use.  Nor is GC suitable for continuous monitoring.
Also,  the multiplicity of components usually involved  may make column selection difficult. It is useful
as a support device for the previously described  devices.
C.      E.P.A. Test Methods*
        The location of the instrumentation relative to the sample source, necessitated transporting
the sample more than 100 feet through  a heated sample transport system (Figure 40), consisting
This  section has  been  adapted from a  report prepared for the E.P.A.  by Scott Laboratories,
Plumsteadville, Pa. The technique described herein was devised for sampling a particular plant and
may not be completely general in its applicability.
                                           185

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of a 1/4" O.D. x 18" stainless steel sample probe connected to six feet of externally heated 1/4"
O.D. teflon sample line. This flexible section of sample line was connected to a heated 7 cm clamshell
prefilter joined to a heated stainless steel bellows pump. From this point the sample was transported
approximately 100 feet through resistance heated 3/8" O. D. stainless steel tubing. With the exception
of the sample probe  all components  of this  system were  maintained  at approximately  250ฐF to
prevent hydrocarbon losses due to condensation. The hydrocarbon analyzer and gas chromatograph
were connected in parallel at the end of this section of sample line.
       Total hydrocarbons were continuously  monitored with a Scott Model 215 heated total hydro-
carbon analyzer, utilizing a flame  ionization detector. The detector  bench and sample pump were
maintained at 300ฐF to prevent condensation losses  of high molecular weight  hydrocarbons. The
analyzer was optimized to yield an oxygen  response  of less  than  0.2%. The carbon  response
linearity was checked by comparing hexane, toluene and  propylene standards against  propane.
The average carbon response for  the three  classes of hydrocarbons was 98.9%. The instrument
was spanned with  "Close  Tolerance"  (ฑ2.0% analysis) blends  of propane in  air and zeroed with
hydrocarbon free air (<0.1  ppm Ci). The fuel and oxidant  for  the flame ionization  detector were
40% hydrogen in helium and  blended air respectively. The continuous total hydrocarbon trace was
recorded on a Texas Instrument Servo/Riter II  recorder.
       For all tests the sample backpressure was maintained  at 2.0 psig with a bypass flowrate
of 6 SCFH. The analyzer was zeroed and spanned before and after each  test and at regular intervals
during each test. In order  to  correlate total  HC  emissions with  process conditions, notations were
made  on the charts of process  mode changes,  time  checks,  gas  chromatograph  injections,
reactor temperatures and other pertinent information.
       Each total hydrocarbon strip chart was divided into  specific intervals based on the various
modes of operation for each  process  cook.  An average hydrocarbon  level in ppm-Ci  was then
calculated for each  process interval. Mass emission rates in Ib/hr were then calculated based on the
average flowrates measured for each process interval. The mass emissions per tons of resin  produced
was calculated  by first finding tons of resin produced per hour  and comparing  that with the mass
emissions rate (Ibs/hr).
       While the T.H.C. analyzer  was continuously monitoring  hydrocarbon concentrations, point
samples were injected periodically into  a gas chromatograph.  The gas chromatograph,  a Varian
Model 1200 equipped with a flame ionization detector  and  a  (1 mv.) Texas Instrument  Recorder
was used to provide a qualitative and semi-quantitative analysis of the  effluents from their kettles.
                                          188

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       Ideally, for a quantitative analysis, it would be necessary to prepare a standard to analyze
each component of the effluent. Since this was impractical, an alternate procedure, to give a semi-
quantitative analysis, was chosen. Through proper manipulation of the fuel to oxidant ratio, the flame
ionization detector of the  gas chromatograph was rendered linear for carbon response.  Linearity
was checked by comparing cylinders of known concentrations of  m-xylene, benzene, and n-hexane.
The variation in response factor for these  compounds was approximately 6%. Thus, a cylinder
containing known carbon  concentration (59.7 ppm m-xylene or 477.6 ppm Ci) could be used to
determine carbon concentration  of each component  in the sample.  Operating parameters for the
gas chromatograph with the flame ionization  detector are summarized below:
                         GAS CHROMATOGRAPH PARAMETERS
                      VARIAN MODEL 1200 GAS  CHROMATOGRAPH
Parameters
Detector Temp.
Gaseous
Injection
Sample Loop
Column
Temp.
Program
Fuel (H2)
Press (psi)
Flow Rate
(cc/min.)
Oxidant (02)
Press (psi)
Flow Rate
(cc/min.)
Alkyd Solvent
Cook
200ฐC
.25 cm3
IGEPAL
Capillary
(50' x .02" I. D.)
40ฐC-110ฐC
@ 4ฐ/min.
20
62.5
35
600
Polyester
Cook
250ฐC
1 cm3
Poropak Q
(3V2')
100ฐC-230ฐC
@ 6ฐ/min.
20
62.5
35
600
Alkyd Fusion
Cook (soya)
200ฐC
1 cm3
IGEPAL
40ฐC-130ฐC
@ 4ฐ/min.
20
62.5
35
600
Thinning
200ฐC
1 cm3
IGEPAL
40ฐC-130ฐC
@ 4ฐ/min.
20
62.5
35
600
Carrier gas (He)
Flow Rate
(cc/min.)
50
       Expecting to see solvent emissions from the kettles, an IGEPAL (Nonyl Phenoxypoloxyethylene
Ethanol) capillary column, (50' x .02"  I. D.) was chosen to perform the analysis. With a quick
qualitative analysis in mind, sample chromatograms were prepared from the vapors of various paints.
                                         189

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Then, having a previous knowledge of the paint  solvents and holding  chromatographic conditions
constant, each component was  identified  by comparing  its retention  time to  that of standards.
Duplicating these chromatographic conditions in the field would enable a reasonable analysis to be
performed.
       After the initial testing of  the stacks began, however, it became obvious that light solvents
were involved in only the  alkyd  solvent  cook, where xylene and ethyl benzene vapors were the
major components of the effluent. The IGEPAL column,  as field chromatographic conditions were
designed, was not capable of handling the heavier constituents (high boilers) or the aliphatic hydro-
carbons in  the effluent  of the alkyd fusion  or polyester resin cooks. It was necessary therefore  to
obtain additional chromatographic data by  taking five liter  Tedlarฎ bag samples during the fusion
and polyester cooks. These bags were returned to a laboratory where other columns and operating
conditions could be utilized in an effort to  identify and quantify the major hydrocarbons. Bag samples
were also taken of the thinning tank emissions.
       Several techniques were  employed in an effort to obtain accurate stack gas flow rates  at
the various sampling locations.  Most of  the  measurements were made with an S-type  pilot tube
and hook gauge capable  of measuring  pressure differentials of 0.002 to  2.000 inches of water.
Where pressure differentials greater than 2.0 inches of water were found, a 10-inch water manometer
was used. When the pilot tube was calibrated in the laboratory, a pilol factor of 0.850 was calculated
for pressure readings of 0.01 inches of HaO or greater. For pressure readings of less lhan 0.010,
a pilol faclor of 0.758 was calculated. For  lower  flow conditions  where the  pilot lube could  nol be
used,  Iwo differenl  bag samples were configured.  The first of Ihese  consisted of a 5 cubic fool
Tedlarฎ  bag filled wilh a lapered silicone  rubber bool, large enough lo fil over a Ihree inch diameter
slack. The  flow measuremenl was made by attaching ihe bag lo the  desired  stack opening and
recording ihe lime required lo colled a sufficienl  volume of sample. The bag was Ihen attached  lo
a pump  and evacuated  ihrough a dry gas meter to measure the volume collected.
       This melhod proved to  be adequate until  it was  noticed that some of the stacks were
"breathing" i.e., drawing in ambient air and exhausting stack gases in a cyclic manner. This meanl
that a new system  had to be configured lhal would permil only Ihe measuremenl  of Ihe  posilive
portion of Ihe flow and nol yield a nel flow over Ihe brealhing  cycle.  This was accomplished by
adding a silicone rubber one way flapper valve al Ihe exit of the stack. Since Ihe flow rale  under
Ihese condilions was exlremely low, a smaller 2.5 cubic fool bag  was used. The inlel lo ihe bag
was filled wilh the  same silicone rubber  boot used on the  original  bag, and Ihe oullel connections
                                          190

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used  for evacuating the bag  consisted of a short piece of 1/4" O.D. Teflonฎ tubing fitted with a
syringe cap to prevent leaks  during the sampling period. The bag was placed inside a cardboard
box to protect it from the wind while sampling.
        Flow measurements were made at half hour intervals during each process, when possible,
and at more frequent intervals when process changes required. Stack gas temperatures were also
measured in conjunction with each flow measurement.

II.     CONTINUOUS SOURCE MONITORING TECHNIQUES USED BY INDUSTRY
        Industry has generally not used continuous monitoring techniques on any kind of a routine
basis.  Sampling  has  been done on a "grab" or semicontinuous basis and then  only as  needed
for a specific situation, such as design information or to gather emission data for operating permits.
The grab samples have not proven to be too reliable and have further decreased the desire of
industry to monitor emissions in any fashion.
        A continuous hydrocarbon analyzer has been used by one  manufacturer for  monitoring
emissions from resin  manufacturing. The system uses an explosion proof flame ionization detector.
The sampling line is fitted with an entrainment separator. This was supplemented with a gas chromato-
graph for determining the composition of the sample stream. Sampling was  done at the condenser
vents  of the reactors.  Their procedure did not include methods for determining paniculate or aerosol
loadings.
        Some thermal and catalytic incinerator manufacturers also use continuous flame ionization
monitoring of a kettle cook for determining design parameters. They usually measure only for the
two or three cooks that represent the plant's maximum emissions.
        The continuous monitoring of emissions from an incinerator outlet could be very successfully
applied. All problems of condensation, line plugging and hold up of  heavy materials in the sample
train should  be eliminated after the gases have been incinerated.
        How well the  flame ionization detector would stand  up under continuous use is not known;
however,  it  is  anticipated  it  would require more service  and  operator time than the  incinerator
itself.
        This flame ionization  detector could also be used for control of hydrocarbon concentration
at an  incinerator outlet.  This  would be especially helpful and adaptable for catalytic incineration.
Control would be accomplished by adjustment of the catalyst temperature to compensate for decrease
in catalyst activity as the catalyst ages with time.
                                         191

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192

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                                        CHAPTER 4
                                INVENTORY OF EMISSIONS

I.      EMISSION FACTORS FOR EACH SOURCE
       The emission data  reported  in the questionnaires  has  been examined in an  effort  to
correlate quantity of emission with production volume. A primary reason for this effort was to obtain
an approximate geographical distribution of air  pollution "potential" for the industry. Those sections
of the questionnaires dealing with emissions were on the whole the least comprehensively filled
out.  Fewer than 10% of the questionnaires reported  sufficient information to enable an estimated
emission factor to be computed. The extreme variations  in the calculated values and the lack  of
any discernable pattern casts some doubt on the realiability of the estimates so obtained.
       Three  types  of emission factors were  sought. From plants which make coatings  only (no
resins or varnish), pounds of gaseous emissions per million  gallons solvent based coatings and
pounds of  particulate emission  per million gallons of all types of coatings were correlated. These
distinctions were made on the  assumption that most gaseous emissions are attributable to solvent
based coating production  and  that particulate  emission,  mainly  pigment, are attributable  to most
surface coating production. Table 47 presents the emission factors calculated from these plants.
       Plants which  manufacture only resins were used to obtain pounds of gaseous emissions per
million pounds of resin solids. This data is summarized in Table 48.
       Plants which  produce both finished coatings and resins permitted the calculation of all three
types of emission factors. Data from plants in this category were used only where particular emissions
reported  could be assigned to  either paint or resin  production with some degree of confidence.
Information from these plants is  summarized in  Table 49.
       Only those plants whose emission inventory was reasonably inclusive of most of the major
sources were used. Major sources in this context include raw material handling and storage operations,
reactor  vents, filling  operations,  ventilation hood  exhaust vents, and  general  building  exhaust
systems. Most emission data was reported in pounds per hour. This was multiplied by the  number
                                           193

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                  TABLE 47
EMISSION FACTORS FROM SELECTED PAINT PLANTS
Plant
2A
28
2C
2D
2E
2F
2G
2H
21
2J
2K
2L
2M
2N
20
2P
2Q
iuorano
Gaseous
(Ib/MM gal solvent based)
8,800
21,000
71,500
45,800
102,800
89,300
7,700
141,200
95,900
9,200
104,000
15,900

25,200
46,100
e:fi nnn
Participate
(Ib/MM gal)







295,000


58,100
3,600


               Source:  Questionnaire data
                      194

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                                 TABLE 48
           EMISSION FACTORS FROM SELECTED RESIN PLANTS
Plant
3A
3B
3C
3D
3E
3F
3G
3H
31
3J
3K
3L
3M
3N
Average
      Gaseous
(Ib/MM Ib resin solids)  Principal resin types
       87,600        Polyester, alkyd
        2,600        Alkyd, varnish
        1,750        Rosin types
        1,700        Water based acrylic
       21,100        Water based vinyl
         162        Acrylic (water & solvents)
       15,350        Hydrocarbon
        1,120        Alkyd, water based vinyl
       12,600        Varnish
       10,500        Amino, polyester
        3,400        Epoxy
       19,500        Epoxy
        1,300        Alkyd, polyester
       73,150*        Vinyl (solvent and water)
       13,700
*Most of this emission is from "resin dryer" operation.
Not included in average.

Source:   Questionnaire data
                               195

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                                      TABLE 49
                     EMISSION FACTORS FROM SELECTED PLANTS
                         PRODUCING COATINGS AND RESINS
   Plant
     1A
     1B
     1C
     1D
     1E
     1F
     1G
     1H
  Average
Resin Production
   Gaseous
   (Ib/MM Ib)
       824
       560

     1,100
     1,800
    22,000
     6,500
           Coating Production
       Gaseous
(Ib/MM gal solvent based)
         36,800
         5,300
        22,000*
        113,000
         46,400
         35,100
         37,700
         65,000
Particulate
(Ib/MM gal)
  19,400
     5,460
        45,000
*ln addition to this, the plant also emits 235,000 pounds/year from spray booths and drying ovens.
       Source:  Questionnaire data
                                      196

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of plant operating  hours  per year on  the assumption that the source in question operates at the
stated emission  rate for  the same number of hours.  In some cases, at least, this assumption  is
probably not correct. Emissions were correlated for the uncontrolled process assuming no emission
control devices.
       No particular pattern has emerged  to  help interpret the results summarized in Tables 47
to 49. The magnitudes of the emission factors  calculated for coating production, for instance, show
no dependence on solvents used, production volume, per cent industrial sales, etc. Similarly, emissions
from resin production do not seem to correlate with types of cooks,  types of resins, or solvents
used. In  any event,  simple averages were calculated and are also presented in the Tables. No
attempt was made to average the particulate emissions due to wide scatter and few data points.
II.     EMISSION INVENTORY FOR THE INDUSTRY
       The emission factors  obtained  above  permit one  to  estimate potential emissions for  a
geographical area for which production figures are available. Production by states has been estimated
for 1972 in Chapter 2. Using these outputs and  assuming a uniform ratio of solvent based production
(77% of total gallons produced), gaseous pollution potential  from  uncontrolled paint manufacturing
operations has been estimated for each state.  The results  are presented in Figure 41.  An average
emission factor of 50,000 pounds gaseous emissions per million gallons of  solvent based paint
was  used  in  the calculation. Total  gaseous emissions for the U.S.A. from paint  production are
estimated to be 23,200 tons for the year 1972.
       The emission factors presented in this section can be applied to the model plant discussed
in Chapter 1. The  model plant produces 1.1 million gallons of solvent based paint and 2.1  million
pounds of  resin solids. Based  on the  average  emission factor for  this type of  plant given in Table
49, the model plant should emit (1.1  x 45,000) + (2.1 x 5,460) = 60,966 pounds per year of gaseous
emissions. The source-by-source calculation in Chapter 1 totaled 65,590 pounds. The two calculation
methods agree quite well as far  as totals are concerned. The relative  amounts of emissions  attributable
to resin production as opposed to paint production show wider variations between  the two methods.
The emission factors predict less from  paint production and  more from resin production.
       The degree of consistency between the two methods is remarkable considering the extreme
scatter present in the emission factor data and the assumptions used in the model plant calculation.
It would be unwise, however, to  draw any strong conclusions concerning the applicability of either
approach to coatings manufacturing operations  selected at random.
                                         197

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198

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                                        CHAPTER 5
                            EMISSION CONTROL TECHNOLOGY

        In this chapter a detailed discussion of the existing state of the art of air pollution  control
for this industry will be  presented. The discussion  will include a description of the  best  control
technique for each emission source,  alternate control techniques,  methods of control other than
add on equipment, types of performance of currently used systems and capability of best  control
systems to meet more stringent standards.  Potential water and solid  waste disposal  systems will
also be reviewed.
I.       DESCRIPTION OF  BEST CONTROL SYSTEMS
        As discussed in  Chapter  1, the two  mam types of  non-fugitive  emissions  are gaseous
organic pollutants and pigment and resin particulate. The best control techniques for these pollutants
are discussed below.
A.      Control of Particulate Emissions
        The best control  device for pigment  and resin particulate is a  fabric collector.  The system
for collecting and  controlling  pigment  dust during  the loading  operation of mixers, ball  mills and
the like is shown in Figure  42.  Depending on the plant layout  there may be one or more of these
systems. The principal part  of the system is the baghouse or fabric filter.  It is by far the best  control
device  and  is ideally suited  for this  application.  Collection efficiency of  the submicron pigment
particulate (0.05 to 0.25/x) is very high,  in the  range of 99.9%. The  gas  stream is low  temperature
and the grain loading is  low.  The collected product can be recycled for  use in dark primer  paints.
The installed cost  for this system  can be quite expensive, depending upon the  collection system
used. Basically there are two types. A fixed collection hood for each  loading  station  that collects
both dust and  empty pigment bags or a movable flexible hose that  can  be placed at one or more
loading stations  while the pigment  bags are  being emptied. In  some cases the hose  is connected
directly to the mixing tank and ventilation air is drawn through the loading hatch with  the pigment
particulate. This  is a very efficient  method of capturing the fugitive dust. The  disadvantage  occurs
due to increased solvent losses from the mixing tank.
                                           199

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200

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        There is a large variety of baghouses currently available as "off the shelf" items from over
 a  dozen manufacturers. They all operate in essentially the same manner. The  pigment laden  air
 is filtered by the cloth tube or bags contained  in the house. The house itself is divided into four
sections — the dirty air plenum, the bag area,  the  clean air plenum and the particulate collection
 hoppers. The function of the two plenums is to properly distribute the air flow to and  from the bags.
 Many types of bag materials may  be used, but woven cotton bags are not only adequate but also
 the least expensive and, therefore, the most commonly used for this service. The collected particulate
 needs to be periodically cleaned from the bags. This can be done either intermittently or continuously.
 Intermittent baghouses are designed for periodic cleaning, such as once a day, and are easily adapted
 to the low dust loadings and batch operation encountered in the  paint industry. They are normally
 the lowest cost baghouse. Continuous baghouses are cleaned automatically and are able to operate
 24 hours per day. They can also handle high dust loadings.
        Cleaning of the bags can be accomplished by a variety  of methods which includes shaking
 the bags,  reversing the air flow through the bags,  blowing a jet of air on the bags from  a reciprocating
 manifold,  or rapidly expanding the  bags by a pulse of compressed air. The method most commonly
 used with the intermittent  baghouse is shaking  which can be done manually at the  end of  a days
 operation. The  bags in a  shaker-type baghouse are supported  by a  structural framework which  is
 free to oscillate. If this type of baghouse is used on a continuous  basis the bags  are cleaned auto-
 matically.  Periodically,  by use of a timer, a damper isolates  a compartment of the shaker baghouse
so that  no air flows. The  bags in the isolated compartment are  then  shaken for a minute or so,
during which time, the  collected pigment or resin is  dislodged and falls into the baghouse hoppers.
Another type of continuous baghouse commonly used in this industry, as characterized by its cleaning
method, is the  reverse pulse baghouse. This type  utilizes  a short (100 millisecond or  less) pulse
 of compressed air through a venturi or diffuser. The primary air  pulse is directed from the top to
 the bottom of the  bag  and aspirates secondary  air  as  it passes through the venturi. The resulting
 high flow air pulse travels the length of the bag  rapidly expanding the cloth and  dislodging  the
collected dust cake.
        The primary variable used in applying a baghouse to this or any  application is the air-to-
cloth ratio as defined below:
                                         R   =   Q/A
where:- R = air-to-cloth ratio, feet/min
      Q = volumetric  air flow, ACFM
      A = net cloth area, ft2

                                          201

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Air-to-cloth ratios normally run from 1 to 3 for  shaker and reverse air  baghouses  while reverse
pulse units will run between 5 and 18.  The basis for  selection  will vary with dust loading, dust
type,  desired bag life  and allowable  pressure drop. Typical air-to-cloth  ratio  utilized in the paint
industry are 8.4/1  for a reverse pulse jet baghouse with polyester bags and  2/1 for a shaker baghouse
with cotton satin bags.
       In most cases,  pigment emissions are of a minor nature and do not violate existing air
pollution  control regulations. Because of this and the extra  cost  involved, the use of a baghouse
collection system is not a wide spread practice. Those in existence have been motivated by occupational
health, good housekeeping and product recovery.
       A similar  problem  exists  for resin  manufacturing  plants  in the  grinding  or  flaking  of the
hardened resin. The same approach is normally  used. The air from the baghouse may still contain
a significant odor  and further treatment may be required if a local nuisance exists.
B.     Control of Gaseous Emissions
       The best  control technique for gaseous emission from the  paint and varnish  industry  is
oxidation or combustion of the organic pollutants  to CC>2  and  HkO.  This is  the only control technique
currently being  used that has  proven  effective for all cases.  Three general methods  are employed
to oxidize waste gases, as follows:
       Flame Incineration or Direct Combustion
       Thermal Combustion or Oxidation
       Catalytic Combustion or Oxidation
All of the above methods are oxidation processes. Ordinarily, each requires that the gaseous effluents
be heated to the point where oxidation of the combustible  will take place.  The three  methods
differ  basically  in the  temperature to  which the  gas stream must be heated.  These methods will
be briefly described for better understanding of  their application to the paint and varnish  industry.
1.     Flame Incineration
       Flame incineration is the easiest of the three to  understand,  as it comes  the closest  to
every day experience. When  a gas stream is contaminated with combustibles at a concentration
approaching the  lower flammable limit, it is frequently practical to add a small  amount of natural
gas as an auxiliary fuel and sufficient air for combustion when necessary, and then pass the resulting
mixture through a burner. The  contaminants in the mixture serve as a part of the fuel.  Flame inciner-
ators  of this type are  most often  used for closed chemical reactors. Figure 43  is  a schematic illus-
tration of a flame  incineration unit. This unit resembles a flare operated within a  combustion  chamber

                                           202

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        LADEN
        PROCESS
         STEAKS
COMBUSTION
    AIR
                      NATURAL
                         GAS
                    FIGURE:
SCHEMATIC DIAGRAM OF A FLAME INCINERATION UNIT
                         203

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where the combustion conditions may be controlled carefully.
       Flame incineration cannot be used for open kettle cooking because of the high volume and
low combustible  concentration of the exhaust. It would be  ideally suited for closed  reactor kettles
if these could be run at a high enough pressure to supply the  driving force through the  system.
Unfortunately most kettles  must be opened periodically for additions of various materials such as
pentaerythritol and phthalic anhydride. Also, many resin cooks must be run under a vacuum. Aside
from these limitations, a suitable transfer line would  have  to be developed to be both functional
and comply with  insurance safety requirements.
       Flame incineration systems are generally difficult to handle with regard to either self-recuper-
ative or  makeup types  of  heat  exchangers because of  the  extremely  high  temperature of  the
effluent from  the combustion chamber.  For this reason, it is usually most economical to provide a
steam  generator to recover the waste  heat rather than a gas-to-gas heat  exchanger.  With water
as the cooling fluid, the hot side of the heat exchanger may be exposed to the temperatures generated
in the combustion zone.
2.      Thermal Combustion
       It  is far  more likely that  the  concentration  of combustible contaminants in  an air  stream
will be well below the lower limit of flammability. When this is the case, thermal oxidation  is considerably
more economical than flame incineration. Thermal  oxidation is carried out  by equipment such as
that illustrated schematically in  Figure  44.  In this equipment, a gas burner is used to raise  the
temperature of the flowing stream sufficiently to cause a slow thermal reaction to occur in a residence
chamber.
       Whereas flame temperatures bring about oxidation by free radical mechanisms at temperatures
of 2500ฐF,27 28 29 high conversions are produced by thermal afterburners at temperatures in the order
of 1400ฐF with  1/2 second residence time.27 28 29 Thermal afterburners can operate at conversion
efficiencies in excess of 97% depending upon a number of operating variables. These conditions can
be summarized as follows:
       a.  Operating Temperature
       b.  Quantity of Hydrocarbon
       c.  Residence Chamber Size or Residence Time
       d.  Type of Fume
       e.  Uniformity of Temperature — Good Mixing
       The theoretical  aspects  of the  reaction kinetic for thermal oxidation are discussed on  the
following page.
                                          204

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           205

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       If a gas containing species A and B which react to produce C, such that there is substantially
no reverse reaction of C decomposing into A and B, we can write the equation
                                        A + B-ป C
or for the reaction of a hydrocarbon in air
                                   He + O2 -ป CO2 + H2O
       For flow processes, let us assume steady state conditions of a gas stream passing through
a tube with good uniformity  across  any  given  cross-section. The concentration of He, O2, COz,
and  h^O will vary with time as an element of the flowing  fluid moves through the  reactor, or with
distance, in that time and distance into the  reactor are interchangeable for steady-state conditions.
       We  can expect the concentration of He and O2  to drop  off and can define the rate of
disappearance of He as follows:
                                     R = - k (Hc)m (O2)n
where:
       R = Rate of disappearance of He, mol/hr
       k = Reaction Rate Constant,  function  of temperature
       (He) = Concentration of He, mol/fraction
       (O2) = Concentration of O2, mol/fraction
       For almost all cases, including varnish cooking, the  O2 content of the gas stream is high
and  the He content is low.  Because  of this, the O2 concentration is substantially constant  and  can
be omitted. The exponent of (He) can be taken as 1.
                                         R =-k (He)
Using x as the concentration of combustible:
                                dx              dx
                                     =  —kx or   —  = —kt
 Integrating this gives x = Ae
 Using initial conditions x = XQ at t = o
                                 dt                x
                           -kt
                                        x = x at t = t-i
                                     x0 = Aeฐ or A = x0
                                            =e-kt
 If conversion is defined as: c =
 Then 1  - c = e ~kt
                               XQ-X
                                           206

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RE
                      LU



                    - (0
                    DC -fc
                    -I F


                    !'
                    ho
                    0
                    i 2
                    o u
205

-------
       If a gas containing species A and B which react to produce C, such that there is substantially
no reverse reaction of C decomposing into A and B, we can write the equation
                                        A + B^ C
or for the reaction of a hydrocarbon in air
                                   He + O2 -ป CO2 + H2O
       For flow processes, let us assume steady state conditions of a gas stream passing through
a tube with good uniformity  across  any  given cross-section.  The concentration  of He, 02,  CC>2,
and  hbO will vary with time as an element of the flowing fluid moves through the reactor,  or with
distance, in that time  and distance into the  reactor are interchangeable for steady-state conditions.
       We  can expect the concentration of He and Oa to drop off and can define the  rate of
disappearance of He as follows:
                                     R = - k (Hc)m (O2)n
where:
       R = Rate of disappearance of He, mol/hr
       k =  Reaction  Rate Constant,  function  of temperature
       (He) = Concentration of He, mol/fraction
       (62) = Concentration of O2, mol/fraction
       For  almost all cases, including varnish cooking, the C-2 content of the gas stream is high
and  the He content is low. Because  of this,  the 62 concentration is substantially constant  and can
be omitted. The exponent of (He) can be taken as 1.
                                         R =_k (He)
Using x as the concentration of combustible:
                                 dx              dx
                                —   =  —kx or   —  =  —kt
                                 dt                x
                           —kt
 Integrating this gives x = Ae
 Using initial conditions x = xo at t = o
                                        x = x at t = t-i
                                     x0 =  Aeฐ or A =
                                        — =e"kt
                                        x,.
                               XQ -X
 If conversion is defined as: c =  —5	
                                 xo
 Then 1  - c = e ~kt

                                           206

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        From  this, knowing the  reaction rate constant and residence time, the conversion can be
 easily predicted. This formula  applies directly  only  for an isothermal system. However,  for most
 afterburner applications of contaminated air, k  is a function of temperature which varies along  the
 length of the  afterburner. Calculation of conversion, then,  requires a more lengthy solution of  the
 rate equation over differential elements of the incinerator.
        Past research indicates that most combustibles follow the pseudo first  order reaction pattern
 described above and rate constants can be correlated by plotting In k vs.  —.
        The few points required to plot these curves are experimentally determined in the laboratory
 by measuring conversion rates for a known combustible material at two or more operating temperatures
 in a reactor of fixed residence time.
        This type of experimental work, to our  knowledge, has not been done on open or closed
 varnish or resin kettle fumes. Experimental work on  other hydrocarbon vapors indicates, however,
 that general guidelines can be applied to this type of contaminant. For example, 0.3 to 0.6 seconds
 residence appears to be  the optimum range of  reaction time  and has been adopted  as a  standard
by most afterburner manufacturers and air pollution regulatory bodies.
        Figure 45 shows a relationship between temperature and residence time at a fixed conversion
 level of 95% and fume concentration of 2 Btu/SCF.
        Figure 46 shows  the relationship between conversion and temperature at a fixed residence
 time of 0.6 seconds.
        Most  afterburners are capable of operating  at a temperature high enough to oxidize any
 organic material, except carbon particulate, and the actual  operating temperature can be developed
 for  a given type of afterburner after  installation by trial and error. It is important when this approach
 is taken to insure the afterburner has at least 0.6 seconds residence  time and the ability to operate
 at 1500ฐF.
        Afterburners  are designed to operate at a controlled outlet temperature and  heat  is added
 by  the burner to the contaminated  air stream to be  incinerated  until this temperature is obtained.
 Assuming the burner outlet is  set  high enough for  the oxidation reaction to initiate, the heat of
 reaction of the combustibles will also be added to the air stream  in the afterburner. This, in turn.
 will  reduce the heat requirements of the burner. Less fuel will be added to the burner. Temperature
 rise across the  afterburner will increase and the afterburner inlet temperature will  drop.  The gas
temperature in the residence chamber now varies from inlet to outlet. The higher the fume loading
the  greater the temperature variation across the afterburner. If the afterburner outlet temperature is
                                          207

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                                      FIGURE 4.5



                      RESIDENCE  TIME VS.  TEMPERATURE

                                                AT

                         9.5%  C.ONVERSION  &  2BTU/SC.F
ii
0)
  N,
y


h
y
o
i/)
y
      1.7
      I.S
0.9
      O.T
      0.5

         ISOO
                               I35O
                                                      I4-OO
                             OUTLET   TEMPERATURE, ฐF
                                       208

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        From this, knowing  the reaction  rate constant and residence time, the conversion can be
 easily predicted.  This  formula applies directly  only for an isothermal system. However,  for most
 afterburner applications of contaminated  air, k  is a function of temperature which vanes along  the
 length of the afterburner. Calculation of  conversion, then,  requires a more lengthy solution of  the
 rate equation over differential elements of the incinerator.
        Past research indicates that most combustibles follow the pseudo first  order reaction pattern
 described above and rate constants can be correlated  by plotting  In k vs.  —.
        The few points required to plot these curves are experimentally determined in the laboratory
 by measuring conversion rates for a known combustible  material at two or more operating temperatures
 in a reactor of fixed residence time.
        This type of experimental work, to our  knowledge, has not been done on open  or closed
 varnish or resin kettle  fumes. Experimental work on other hydrocarbon vapors indicates, however,
 that general guidelines can be applied to this type of contaminant. For example, 0.3 to 0.6 seconds
 residence appears to be  the optimum range of  reaction time  and has been adopted as a  standard
by most afterburner manufacturers and air pollution regulatory bodies.
        Figure 45 shows a relationship between temperature and residence time at a fixed conversion
 level of 95% and fume  concentration of 2 Btu/SCF.
        Figure 46 shows  the relationship  between conversion and temperature at a fixed residence
 time of 0.6 seconds.
        Most  afterburners are capable of operating at a temperature high enough to oxidize any
 organic material, except carbon particulate, and the actual operating temperature can be developed
 for  a given type of afterburner after  installation by trial and error.  It is important when this approach
 is taken to insure the afterburner has at least 0.6 seconds residence time and  the ability to operate
 at 1500ฐF.
        Afterburners are designed to operate at a controlled  outlet temperature and heat  is added
 by  the burner to the contaminated  air stream to be incinerated  until this temperature is obtained.
 Assuming the burner outlet  is set  high  enough  for the  oxidation reaction to initiate, the heat of
 reaction of the  combustibles will also be added to the air  stream  in the afterburner. This, in turn.
 will  reduce the heat requirements of the burner. Less fuel will be  added to the  burner. Temperature
 rise across the afterburner  will increase  and the afterburner inlet temperature will  drop.  The gas
 temperature in the residence chamber now varies from inlet to outlet. The higher the fume loading
 the  greater the  temperature  variation across the afterburner. If the afterburner outlet temperature is
                                          207

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                               FIGURE
               RESIDENCE  TIME  VS.  TEMPERATURE

                                        AT

                         CONVERSION &. 2BTU/SCF
0
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                       OUTL.ET   TEMPERATURE, ฐr
                                208

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                               FIGURE  "4-e

                    CONVERSION VS.  TEMPERATURE

                                     AT"

              0.6 SEC. RESIDENCE  TtME  & 2BTU/SCF
         100
         90
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0
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C
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         TO
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                                                   14-00
                        OUTLET TEMPERATURE,*F
                               209

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held constant, the average temperature in the afterburner will decrease as the fume load increases.
Since the reaction rate is a function of temperature, it will also decrease.
       The theoretical relationship between conversion and fume loading at a fixed outlet temperature
and residence time  is described  in Figure 47. This relationship is applicable only to systems having
a fixed outlet temperature. If the  inlet temperature is held constant, the opposite effect will occur and
conversion efficiency  could increase with higher inlet concentrations. This is due to the first order
dependence of oxidation rate on initial concentration, the effect of local heat of reaction, the effect
of increased  concentration of free radicals and the higher  reaction temperatures reached. These
effects are discussed  in more detail in the Afterburner Systems Study, EPA Contract EHS-D-71-3.27
       From the above discussion, it can be seen that for a given  conversion level, the higher the
fume  load  the higher the outlet  temperature must run to assure the required conversion. In fact,
for very high fume  loads, if the  outlet temperature  is not  set high  enough, the temperature out of
the burner can drop below the reaction initiation temperature and the reaction will cycle on and off.
       Field experience indicates the above discussion is not applicable at low fume concentrations.
This is caused by difficulties of  measurement, generation  of combustible  material from the burner,
and  generation  of small quantities of partially reacted  material that are normally  insiginificant at
high fume concentration levels.
       Frequently it  is possible to identify  specific  materials which  must be oxidized in order to
conform  to the  prevailing air correction  ordinances, or  to good practice. For example, for closed
kettles emitting  a mixture of xylene  and phthalic anhydride, one  should consider the  residence
time-temperature curve for P.A.  and  select conditions which will give a  90% or  better conversion
of this material. As the xylene is  less refractory than the P.A., this selection is "safe".
       Often, however, it is not possible to chemically identify the specific compounds  involved.
In such cases, the emission must be treated on the basis of past experience or by using pilot after-
burner equipment  for field  testing.  Because the oxidation  rates  given  are influenced by burner
design, distribution  in the combustion chamber, etc., it is wise  to  follow the  recommendations of
the manufacturer supplying  the  equipment rather than  transfer  data of  this  sort from one design
to another.29
       In general terms,  a thermal afterburner consists of a preheat burner, a mixing device, and
a residence chamber. The gas to be disposed of is first passed by and mixed with burner combustion
products  to preheat it to at least the reaction initiation temperature.  The type of mixing device used
is the single  most important design feature in that it affects  the amount of direct flame incineration
                                          210

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                             FIGURE
         CONVERSION  VS. INL-EIT CONCENTRATION

                                AT

          0.6 SEC.. RESIDENCE  TIME & I3ฃ>O~F OUTLET
      90
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           INLET CONCENTRATION,



                                 211

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that occurs and the temperature uniformity of the gases in the residence chamber.
       As  high as 20%  of the gas can be mixed with and  incinerated  by the  high temperature
flame. This is a desirable effect in that it decreases the burner preheat fuel requirement and decreases
the combustible load on the afterburner.
       Gas flow and temperature uniformity  out of a mixing device and into  the residence chamber
are important to assure that  all the combustible is held at the proper temperature for the design
time period. This  effect is sometimes  called turbulence, which is a misleading word.  Uniform flow
and temperature with or without turbulence is the important criteria. The importance of this variable
is explicitly outlined in the Afterburner Systems Study, EPA Contract EHS-D-71-3,27 and is quoted
below.
            "Mixing of bypassed fume and hot combustion gases is  the  most crucial step
       in attaining good  afterburner performance. Typically, afterburners are designed with
       -.5 second total  residence time. This time is nearly all required for this mixing step
       and many designs fail to complete the mixing in the distance (time) available. Some
       fume escapes  without being  raised  to a sufficiently  high temperature. To  meet a
       performance specification  (if possible at all) more fuel must be burned than would
       be  needed if mixing were complete. Distributed burners are  placed directly in the
       fume stream and  divide the flame into  many individual jets or lines of flame sur-
       rounded by fume. This subdivision greatly speeds the  mixing process, and these
       burners are well  suited to  use oxygen from the fume for combustion. The use  of
       outside air requires an additional 30 to  50% of the fuel to  be burned to heat it  to
       1400ฐF. Distributed burners are subject to fouling, have somewhat limited  turndown,
       aren't available for use with oil fuel, may be difficult  to use with outside air, and have
       a few other  potential drawbacks. Therefore,  many  afterburners employ discrete
       burners which give either long or short point sources of flame. The  mixing problem
       is much more  difficult since there is no  subdivision  at  the burner.  Internal baffles
       are required in the relatively short afterburner chambers utilized in available designs.
            Many designs stress "flame contact" in an attempt to mix fume and flame as
       rapidly as possible. This often leads to  flame quenching  and an increase in pol-
       lutants  in the fume  stream since,  as was mentioned  above, complete fume/fuel
       mixing gives a noncombustible mixture. Fuel should be burned as rapidly as possible
       and the hot gases should  be mixed with bypassed fume. Pressure drop must be
       expended in achieving good mixing through baffles and/or a  long chamber. Mixing
       will be faster when there is initial fume/flame subdivision."
       A schematic illustration of a typical thermal afterburner and control system has been presented
in Figure 48. As  indicated on this Figure,  most afterburners are equipped with heat exchangers
to decrease the fuel requirements of the preheat burner. The burner fuel  consumption is the  major
operating cost of thermal afterburners, and self-recuperative heat exchangers, except for very small
flow rates  or unusual  circumstances, are an economic necessity  with rapid payout. The use of

                                           212

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additional heat exchange, where possible, has become more attractive in recent times with the advent
 of fuel shortages and increased fuel costs.
        Another technique commonly used to reduce operating cost through reduced fuel savings
 is preheating  of the contaminated air with a raw  gas  or  secondary air burner.  This type burner
 utilizes the oxygen in the contaminated air for combustion of the natural gas.
        This type of operation saves the cost of heating the combustion air and  fuel consumption
 can be reduced about 30%. These burners, however, do not operate well at oxygen concentrations
 below 16% which would be the case for the  emissions from a closed varnish  or resin  kettle or
 reactor. The maximum  allowable fume concentration to the afterburner as set by most insurance
 companies is  1/4 of the lower explosive limit, or 13 Btu/SCF. This requires that the  kettle exhaust
 be diluted sufficiently with air to raise the oxygen concentration above 16%.
        As mentioned earlier, heat  exchange is the  most  common type of fuel  saving applied to
 thermal afterburners.
        The type most often used is the self-recuperative  type of  exchanger which  allows part of
 the heat in the effluent gas to be used for preheating  the inlet gas before it  reaches the combustion
 chamber. Gas-to-gas heat  exchangers of this kind are  generally supplied as a part of the thermal
 afterburner unit and are ordinarily available only from the  manufacturers of equipment. Inherently,
 such exchangers are costly, and have a  low heat transfer coefficient,  4 to 6  Btu/ft2 — ฐF. Aside
 from the refractory regenerative type heat exchanger,  most exchangers are of metal construction
 and have a hot gas or  afterburner outlet limitation  of 1 SOOT. The  most common  type in use is the
 shell and tube exchanger, and they are available in either parallel flow or countercurrent flow.
        Parallel flow is  most commonly supplied as a standard, especially where the fume  load and
 outlet temperature  are  high. At high fume loads,  there is a danger of temperature spiraling. At
 fume  loads approaching 1/4  LEL,  a  7.5% change  in concentration will  result  in a temperature
 change in  the residence chamber of SOT. It  is possible  with  sudden increase  in fume  loads to
 raise the afterburner  outlet temperature  above the  control  point which, via the  heat  exchanger,
 raises the  inlet temperature above the burner's low fire control  ability. The increased inlet, in turn,
 raises the  outlet some more which, in turn, raises the inlet, and so on.  Parallel exchangers having
 equal thermal flows on shell and  tube side have  a  maximum  thermal efficiency of 50% and are
 self-limiting with respect to temperature spiraling. They also have the advantage of running the lowest
 mean material temperatures, since the hottest gas is always exchanged  with the coolest gas.
        Countercurrent heat exchangers are much  more thermally efficient  for the same amount of
                                           214

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heat exchanger area.  They do run  at  higher material  temperatures, however,  and require  more
expensive materials of construction. They are also more susceptible to temperature spiraling when
running at high fume  rates.  Because  of  this, a system designed  around this type of  exchanger
should use a  burner duty of at least 50ฐF. An afterburner heat exchanger system using a parallel
flow heat exchanger is designed for a burner  duty  of  at least 25ฐF. Burner  duty in this context,
means the temperature rise added to the fume stream by the burner between the heat  exchanger
outlet and the residence chamber inlet.
        Rotary heat exchangers are available and will run at thermal efficiencies of 80%. They are
of metal construction (321 SS)  and are still limited to a maximum  operating temperature  of 1500ฐF.
Their disadvantages are high  initial and maintenance cost, as well as cross leakage. The cost  of
an 80%  rotary ($84,000) is about double a 60% cross flow shell and tube ($47,000) for a flow  of
12,000  SCFM. The rotary exchanger  is still in the  development stage and,  along  with its many
operating problems, is  limited to smaller sizes.

3.     Catalytic Afterburners
        While thermal afterburners bring about oxidation at concentrations below the limits of flame
 combustion, catalytic afterburners operate both below the limits of flammability and below the normal
 oxidation  temperatures  of the contaminants as well. The  reaction is instantaneous by comparison
 to thermal oxidation and  no residence chamber is required.  Catalytic oxidation  is carried out by
 equipment such  as that  illustrated  in Figure 49. This particular arrangement  provides  an ideal
 location for the fan used  in the system. Generally speaking, catalytic afterburner systems are the
 least costly when comparisons are made at the optimum level of heat recovery. Detailed installation
 and operating and maintenance costs for both catalytic  and thermal afterburners are presented
 in Chapter 7.
        While catalytic oxidation is attractive from an economic standpoint, several factors must be
 considered in selecting this form of waste  gas treatment. Catalysts require regular maintenance
 in the  form of periodic washing to remove  atmospheric dust and dirt and, in the  case of  higher
temperature cooking,  to remove traces of  particulates and  other ash-like residue originating  in
kettle materials.  In addition,  it  is necessary to  reactivate the  catalysts  periodically.  There are a
number of materials,  such as phosphorus,  silicon and lead,  known to  shorten the  active  life of
 these catalysts. However, when the characteristics of the gas to  be treated  are suitable, catalytic
 oxidation is a highly satisfactory method for air pollution control.27
                                          215

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216

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        Because catalytic units are not automatically functional when operated at design temperatures,
they may not be approved for installation until means for  ensuring  adequate performance of the
catalyst on a long term basis can  be demonstrated.
        As is the case  for thermal afterburners, catalytic units can also operate at efficiencies in
excess of 97% depending upon a number of operating variables. These conditions can be summarized
as follows:
        a.  Type of Hydrocarbon  —  Reaction Rate
        b.  Quantity of Hydrocarbon
        c.  Type of Catalyst — Activity
        d.  Quantity of Catalyst — Space Velocity
        e.  Operating Temperature
        f.  Presence of Catalyst  Suppressants or Poisons
        Some hydrocarbons  react faster  or  oxidize at lower temperatures  than  others. Relative
reaction  rate constants  for various hydrocarbons in the presence  of a precious metal catalyst are
given in Figure 50.
        As discussed earlier, the  higher the hydrocarbon content of the exhaust stream, the greater
the heat release, and the  higher the temperature rise for an equal conversion efficiency. This is
less of  a problem  than  with thermal incinerators for two reasons.  First, catalytic afterburners con-
structed  of aluminized  steel can sustain  a temperature  rise of 700ฐF, and units constructed of
stainless steel can sustain temperature rises of 1,000ฐF. High temperature  rises do  not result in
a lower average catalyst temperature or reaction rate  since catalytic units are normally controlled
on the catalyst inlet side.
        The catalysts in common use for oxidation reactions involved in stationary source  control
are metals of the platinum-palladium group. The only catalysts used in significant amounts for oxidation
of trace  hydrocarbons other than the platinum-palladium metals are merchandised in Europe and
consist of cobalt, copper, and chromium oxides incorporated  into a ceramic substrate.
        Oxidation,  which is of primary concern  in  air pollution control,  generally takes place only
over metal  catalysts, and is inhibited by acidity in the support. The  kinds of metals that are capable
of bringing  about oxidation reactions  are listed  in order of the frequency of their utilization.
        a.  Platinum and Palladium
       b.  Nickel, Cobalt, Iron, Vanadium
       c.  Silver and Copper
       d.  Tungsten, Chromium,  Molybdenum
                                           217

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                                    FIGURE
         GATAL.YTIC  OXIDATION  RATES  FOR  SOLVENTS
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                                  TEMPERATURE ฐF
                                      218

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        Because the reactions take  place  only on the surface of  the  active metals, very small
crystallites are generally preferred  as they  provide a much larger surface area per unit weight of
precious metal.
        The available surface area of the substrate may be a  critical factor, but  is more  likely to
be of marginal importance in oxidation reactions.  The  substrate surface area must be sufficiently
adequate that the active  metal crystallites do not pile  up one above the other and thus  limit the
surface area exposure to the bulk gas stream.
        In general, the metal ribbon catalysts have very little substrate surface area. The spherical
catalysts ordinarily have  extremely large surface  areas  associated with a  "micropore structure".
Generally the area is  measured in square  meters per  gram of material with values frequently as
high as 250 square  meters per gram. The ceramic honeycomb  materials manufactured by duPont,
Minnesota Mining and Manufacturing  and Dow Corning have somewhat greater superficial surface
area than do the metal ribbon catalysts, but have  substantially no micropore area as the spherical
supports have.
        Generally,  catalysts  of  higher activity   can  be  produced  from  a  porous  catalyst
support of high surface area than from a metal substrate. However, for ordinary applications at  high
temperatures the precious metal  located  away from the outside surface of the spherical  catalysts
is not used effectively, and the advantages of the porous bases seem  to lie only in  their having
more superficial surface area than  it  is convenient to pack into  the same volume  with the metallic
ribbons or ceramic honeycombs.
        Even though the oxidation reaction over a catalyst is instantaneous in comparison to thermal
oxidation reaction time, the more  catalyst it contacts the greater the conversion  rate.  The disad-
vantages of adding  additional catalyst in an afterburner are increased  pressure  drop across the
catalyst bed and higher capital cost. For this reason, the expected operating temperature and type
of hydrocarbon must be considered when sizing the catalyst volume for a  catalytic afterburner.
        The effect of  operating temperature on catalyst activity is  illustrated  on the previously
presented Figure 50. Basically, catalysts function by altering the rate of a reaction.  If a gas contains
species A  and B which react to produce C, such that there is substantially no  reverse  reaction
of C decomposing into A and B, we write the equation:
                                          A + B^ C
        For flow  processes, if we  assume steady conditions of a gas stream passing through a
container with good  uniformity  across any given cross-section,  the  concentration of A, B, and C
                                           219

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will vary with time as an element of the flowing fluid moves through the reactor, or with distance,
in that time and distance into the reactor are interchangeable for steady-state conditions. We will
expect the concentration of A or B to drop off and can define the rate of disappearance of A as
follows:
                                            dA
           dA                               dt
    where, —~ = rate of disappearance of A, mol/sec.
           dt
        For a normal gas phase reaction, the rate of disappearance of A will vary with the concen-
tration of A, the concentration of B, and the temperature. If we assume that the reaction is controlled
primarily by the concentration  of A, as in the case of  burning  traces  of hydrocarbons in  an air
stream, the equation becomes:
                                       dA
                                       —   = -ka
where,                                 dt

                                  k = reaction  rate constant
                               a = concentration of A in mols/liter
The solution to this equation is:
where:
                                 ao = initial concentration of A
which simply says that the concentration of A will drop off exponentially with time, or with distance
as the flowing stream moves down  the reactor. If it does  so, the reaction is defined  as  a first
order reaction  with respect to A. In order to predict the course  of  a reaction such as this, all
we need to do is know what k will be. Generally speaking,  for any given reaction,  k  is a function
only  of temperature.
       For most purposes, we may use:
                                                    -Eo
                                          k = (A) (e) RT
where
       A = collision coefficient
       Eo = energy of activation, Btu/lb mol
                                           220

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        R = universal gas constant = 1.92 Btu/lb mol ฐR
        T = temperature, ฐRankine
        The constant A is a measure of the  likelihood of a molecule of A bumping into one of the
more plentiful B  molecules. The exponential function measures the probability  that a collision  of
A  and B will have sufficient energy to bring  about a  reaction. The energy of activation determines
the temperature  level  to which  the mixture  must be raised before the  reaction will proceed at a
significant rate.
        The function of the catalyst is to reduce the activation energy,  and  bring about reactions
at a lower temperature than can be accomplished by thermal means alone.
        The reaction rate constant plot is ordinarily straight only over a relatively narrow temperature
range. At low temperatures, the catalyst surface tends to be fully occupied by gases and the reaction
rate may be limited by the availability  of unoccupied surface. For  example, at  low  temperatures,
oxygen adsorbs on platinum surfaces almost to the exclusion of methane or other light  hydrocarbons.
In the middle range, the  rate at which  the  reaction occurs on the  metal surface is limiting, and
adsorption and desorption occur with relative  ease.
        At high temperatures the catalyst surface is likely to remain relatively free of adsorbed gases,
and the difficulty of  adsorbing  the reactants onto the surface limits the  reaction curve. Figure 51
indicates the shape of the reaction rate curve over these three ranges.
        As mentioned earlier, oxidation  reaction rates of hydrocarbons in the  presence of catalysts
are significantly  higher than those encountered  in thermal oxidation. A comparison of thermal and
catalytic reaction  rates for maleic anhydride is presented in Figure 52. From  this comparison it can
be seen that catalytic oxidation is instantaneous by comparison  at a significantly reduced temperature.
        Since catalytic units can operate at relatively low temperatures, they can be  designed with
inner walls of aluminized  carbon steel. This low construction cost offsets  the  high cost of the
catalyst contained in the  afterburner  and overall  capital  costs of catalytic afterburners run about
the same as other types of afterburners.
        Heat exchangers  are  also frequently used as  heat recovery devices with  catalytic units.
They may also be designed of carbon steel or aluminized carbon steel. Being relatively less expensive,
they have payouts equivalent to those exchangers used with other types of afterburners. The design
of heat exchangers  for catalytic units  should follow the  same  rules outlined  earlier for thermal
afterburners.
        While  the scientific basis of catalysis is not as clear as that of many of the other industrial
                                           221

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                                  FIGURE 51

                       REAC.TION  RATE C.ONSTANTS
                                      FOR
            LOW, INTERMEDIATE, AND HIGH  TEMPERATURES
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                                 222

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                          FIGURE
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arts, the thermodynamics are sufficiently well known that catalysts can be characterized with good
success. Catalytic afterburners have been widely used in the past for the oxidation of paint solvents,
and emissions from open and closed varnish kettles. Most  new installations,  however, are using
thermal afterburners. It is anticipated that this trend will  reverse itself in the near future due to the
ever increasing shortage of fuel.

II.     DESCRIPTION OF EMISSION CONTROL OTHER THAN BEST CONTROL
A.     Scrubbers
        Wet scrubbers can be relatively effective for the control of phthalic anhydride particulate
and very heavy organics if properly designed.  Efficiencies will run between 85 to 95% at pressure
drops ranging from 4 to 8 in. w.c. They  have little  effect,  however,  on solvents  and other light
and medium weight organics. For the type of material which  was measured in the emission curves
given in Chapter 1,  scrubbers are not suitable control devices. Source test engineers from air
pollution equipment manufacturers have reported that the typical scrubber installation removes at
most 10% of these contaminants.
        Water treatment and/or disposal of waste can be expensive in many cases.  With increasing
emphasis  on water pollution control, treatment of effluent  streams will be required  in  more and
more localities. The use of chemicals, e.g. permanganate, in the scrubbing solution further increases
cost.
        Relatively low cost, as well as safety considerations,  have traditionally  been the primary
advantages of scrubbers in the resin industry. While it will probably cost more to operate scrubbers
in the  future  than  in the past, their use  as pre-treatment devices to remove phthalic and add  a
measure of safety before incineration may still be desirable, particularly in fusion cooking.
B.      Vapor Condensation
        The use of refrigerated condenser systems has sometimes been proposed as an air pollution
control  device. A system of this type is in use in at least one location, the Sherwin-Williams plant
in Oakland, California. Sherwin-Williams  has supplied design and  operating information for their
system so that it can be included in this report.
        A schematic of the  system is shown in Figure 53. Four kettles are controlled by this system.
Kettles A and B are conventional Dowthermฎ heated kettles used for alkyds and polyesters. Kettle A
contains a reflux condenser  as  well as a final water  cooled  condenser  while Kettle B has only
the final condenser. Kettle C is steam heated and is used only for cutting resin into solvent. Kettle  D
                                           224

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is Dowthermฎ heated and used for alkyds  and polyesters.  While the mechanical details of D are
considered proprietary, it does contain a water cooled final condenser.
       The exhaust streams from Kettles A, B and D are controlled by identical two stage refriger-
ated condenser systems. Kettle C requires only a single stage. A separate condenser system is
used for each reactor but all condensers are supplied by a single refrigeration system. The refriger-
ated condensers are used only during solvent cooking.
       The refrigeration system is shown in Figure 54. All temperatures shown are to be considered
nominal only. They  can vary from run to run over a range of several degrees. Two separate glycol
circulation systems are employed. The "sub-zero" loop is cooled directly by the refrigeration system.
A branch of this loop is used in the cold side of a heat exchanger to cool the "40ฐF" circuit.
       The design  basis for this system  requires a  refrigeration duty of  54,800 Btu/hr. Almost  1/3
of this is due to heat gained in the transfer lines. Two  5 ton refrigeration units  are provided. Only
one operates at a time except when cooling down the entire system at start-up. The design was
based on  the assumption that all kettles are operating simultaneously. It was further assumed that
each kettle exhaust rate can  run as high as 15 cfm noncondensibles and that this gas is saturated
with solvent  at the  operating temperature of the final condenser (~100ฐF). The refrigeration unit
has sufficient capacity to handle a continuous  discharge exhaust at that  level even though  the
kettles are operated in such a way that the inert gas flow is intermittent. Furthermore, measurements
by Sherwin-Williams have shown that the final condenser vent  averages  only 50 to 60% saturation
for these kettles. The 54,800 Btu/hr, then, represents a worst case situation.
       A  schematic of one  of the two stage condenser systems is shown in  Figure 55. The exhaust
gas from the water cooled  condenser flows to the shell side of the first  stage condenser which is
cooled by the "40ฐF" glycol. From  there it flows  to the second stage condenser which is operated
at sub-zero. The majority of the condensate is collected in the first stage.
       On occasion, the second  stage condenser accumulates an excessive amount of frost. To
alleviate this, a system of four-way valves  is provided which enables the streams to be switched.
In this case, the kettle exhaust flows first to the second stage which is  now cooled by the  "40ฐF"
glycol, and so on.
       Kettles A, B  and D  use systems .identical to that shown in Figure  55. Kettle C uses a single
stage condenser  cooled  by the sub-zero circuit. Frost formation is not  a problem here since no
water is formed in this kettle.
       The results of two tests, conducted by an outside consultant, have  been supplied by Sherwin-
                                          226

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 Williams. A tall oil fatty acid alkyd cook was conducted in Kettle A by the solvent process. Testing
 and observation was done over the entire cooking cycle even  though  no inert gas flow was  used
 until the last 80  minutes. The results are  presented  in Table 50. No condensate was collected
 until the stripping operation was started. Inert gas rate during stripping was about 8 SCFM.
        Light organics were determined by  GC analysis of gas samples  collected in sample bulbs
 at the second  stage condenser vents. Heavy organics were determined by GC  analysis of gas
 samples absorbed in silica  gel at the second stage condenser  vent  and by GC analysis of the
 condensate collected in the two condensers.
        A solvent process polyester cook was conducted in Kettle D. The results of this batch are
 presented  in Table 51.  The inert gas flow was turned on for a short period of  time during the
 cook and then turned off.  Figure 56 shows cumulative gas vented and cumulative condensate formed
 during this run. The results from this run  are not typical of  those  for Kettle D. The large volume of
 condensate collected during the fourth hour was due to  improper operation of the water cooled
 condenser during this time. Consequently,  a higher than  normal amount of material passed the
 water cooled condenser. Inert gas flow rates of about 6 SCFM were observed  in the early part
 of the run.
        Examination of Tables  50 and 51  show that for the alkyd cook on Kettle A, the condenser
 system  was 84.6% effective on total organics and 85.7% effective on  reactives, while for the run
 on Kettle D, the efficiencies were 98.4% and 98.9% respectively.
        The extremely high efficiencies in the second case are probably due to  the fact  that the
 majority of the condensate was collected  while the inert gas flow  was negligible. During this period
 the vapor entering the first  stage condenser was  almost  100%  condensible. This represents an
 optimum situation from  the standpoint of  condenser efficiency provided adequate refrigeration duty
 is available.
        In any event, the systems performed well enough  in both cases to bring the kettles into
 compliance with Bay Area APCD Regulation 3 which requires 85% reduction in reactive organics.
        During the test period while both  the previously described cooks  were taking place, power
 consumption  by the compressor and  glycol  circulation  pumps  ranged  from a low of 3,720 watts
to a  maximum of 9,150 watts with  a time average value of 7,790 watts.  The reason for the variation
 is that the compressor cycles  on and off as required  to maintain the coolant temperature.  This
represents  the  primary operating cost of  the system. No additional manpower is required as this
system can be  attended  to by  normal staff. The system has  not  been  in operation for a sufficient
                                          229

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                 TABLE 51
         KETTLE D — POLYESTER


Light organics
(Cs, and less)
Toluene
Ethylbenzene
Hexane
Benzene
Light carbonyls
(as HCHO)
Total organic
Water
Total

First Stage
Inlet, Ib/Batch
0.001
7.838
5.375
1.196
0.339
Tr.
14.749
1.663
16.412

First Stage
Condensate, Ib/Batch

6.95
4.80
0.85
Tr.
—
12.60
1.63
14.23

Second Stage
Condensate, Ib/Batch

0.785
0.565
0.240
0.328
—
1.918
0.033
1.951
Total Emission
to Atmosphere
Ib/Batch
0.001
0.103
0.010
0.106
0.011
—
0.231


Gas vented total
Average emission rate,
  before control
Peak emission rate,
  before control
Average emission rate,
  after control
Test period
% reduction, total organics
% reduction, reactives
= 125 SCF inerts
= 1.55 Ib/hr organics (first stage inlet)

= 52 Ib/hr organics (first stage inlet)

= 0.0243 Ib/hr (second stage outlet)

= 9.5 hr
= 98.4%
= 98.9%
                231

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 length of time to determine equipment repair and replacement requirements.
        The capital cost of the entire emission control system in 1971 was about $90,000. Estimated
capital cost for a thermal afterburner system, without heat exchange, is $32,000. With a 42%  heat
exchange, the capital cost would be about $50,000.
       Thermal oxidation has a substantial advantage as far as initial cost is concerned. The operating
 cost advantage probably lies with the  condenser system,  though insufficient information is available
 to determine the extent of this at present.
        The condenser  possesses some features which  are attractive in spite  of  its higher initial
 cost.  It is an inherently  safe control device since no flame or high temperatures are involved. This
 is demonstrated by its performance on the polyester cook in Kettle D described earlier.  As mentioned
 before, this  cook was not typical  in that the water cooled condenser failed to operate properly for
 a time. During this period,  instantaneous emissions ran as high as 52  Ib/hr as  compared to an
 overall average of 1.55 Ib/hr.  Such a sudden increase over  the expected rate could  be disastrous
 for an afterburner installation unless elaborate safety devices were installed. The condenser system
 handled the increased emission rate without problem.
        On the other hand, the condensers are not suitable for use when fusion cooking. Also,
 the efficiencies are high only when the gas stream is very  concentrated in condensibles. This means
that condensers are  impractical for controlling emissions  from other parts of a paint plant such as
mixing tanks, filter presses, etc. An afterburner installation can be designed to handle both resin
 kettles as well as other sources simultaneously. Perhaps  the ideal solution would be  to control the
 kettles with refrigerated  condensers, where safety is a prime  consideration, and to  control  the other
 sources by collecting their emissions in hoods and ducts and  then incinerating the fumes.

 III.    METHODS OF CONTROL OTHER  THAN ADD ON EQUIPMENT
       As is the case with most industrial operation,  it is possible to reduce and sometimes eliminate
emissions of pollutants by modification of the manufacturing  operation. Various approaches of this
 type,  applicable to this industry, are listed below.
A.     Raw Material Substitution
       Raw  material substitution  in many  cases  can provide an excellent  and inexpensive method
of emission  reduction for the  manufacturer.  Unfortunately, this may not also be true for the  user
since  raw material substitution can lead to both higher prices  and poorer quality.  These potential
problems should be  remembered when considering this method  of emission  control.  An  example,
                                           233

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unrelated to air pollution, of product degradation in this industry caused by raw material substitution
is the removal of mercury fungicides and lead drying agents.  Industry spokesmen have indicated
it may be as long as three years before  an equal raw material  substitution  may be found and the
quality of paint returned to its former position.
1.	Solvents — As discussed earlier, the major emission in the paint  manufacturing industry
comes from the solvents used in  the various production  operations.  The quantity of  emission is
small, however, when compared to that emitted by the final user.
       Current regulation in most states allow for significant emissions of the non-photochemically re-
active solvents described earlier in Section I. Because of this there has been significant pressure to
develop paint products with a non-solvent system, or with a non-photochemically reactive solvent system.
       Significant progress has been made by the paint industry in the use of exempt systems through
the development of the water emulsion paints. These products have been developed without sacrifice
of quality or increased cost.
       The current development of dry powder systems also appears to offer these same advantages
and may result in a significant reduction of solvent emission from both production and application of paint.
       Another technological development which has great potential in reducing solvent emissions,
particularly by the user, is the formulaticn of water reducible industrial coatings. Heretofore, the use of
water based coatings has been restricted  almost exclusively to trade sales products. In the opinion of
some experts, use of such industrial coating systems will come to fruition before powder coatings.
       Use of high solids systems is a further area for potential improvement. The net result  of this
approach is to reduce the amount of solvent present per unit coverage of the applied coating. Conse-
quently, solvent emissions by the user will be reduced.
       There has also been  a  significant switch in the industry  to non-photochemically reactive
solvents; and, as might be suspected, this has lead to a reduction of objectionable emission by both
manufacturer and user.
       It appears that in many cases, either singly or in combination,  these changes  in the solvent
system paints have resulted  in either or both a higher price product  or  a  poorer quality product.
Some  paint manufacturers feel  it  would be  less expensive, overall,  for their customer to apply
pollution  abatement to existing solvent emissions than it  would be to pay the additional product
cost of special paint solvent  systems that are currently exempt. This, coupled with possible poor
product quality and the  likelihood that these solvents may not  be exempt in the future, may make
this raw material substitution a poor choice.
                                          234

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2.	Pigments and Other Solids — The quantity of pigment emission can be reduced by the use
of liquid slurries, which  eliminates the dusting  problem associated  with  handling of the bagged
solid products. The use of water slurries of TiC>2, currently being practiced by many manufacturers,
is a good example of such a raw material substitution This substitution, as well as can be determined,
will not result in additional cost, providing the usage level approaches 500 tons/year
       The use of liquid phthalic anhydride in resin manufacturing can also result in reduced kettle
emissions.  Introduction of PA into the kettle (as a liquid) eliminates the  necessity of evacuating the
kettle when this material is loaded as a solid through the hatch door As described earlier, significant
PA and solvent emission occur during this loading period
       The disadvantage to the  use of liquid PA is the  potential for  emissions from  the  heated
PA storage tank. This can be easily avoided, however, by venting the tank through a water jacketed
vertical condenser with  provision for admitting steam to the jacket. The tanks are blanketed with
inert gas during storage with  the appropriate provision for pressure and  relief control. During filling
the condensers remove PA vapors which can later be melted off  and run back into the tanks.
B.	Changes in Process or Operating Conditions

       As  discussed many times,  there are two major types of resin cooking, solvent and  fusion.
In the solvent cooking process it is  possible to maintain a substantially closed system by:
       1.  Not using sparge  gas
       2.  Use of adequate condensers
       3.  Use of liquid polyols and acids
       4.  Use of proper unloading or transfer methods
       Operations in this manner can almost completely eliminate emissions from  this process.
Continued development of closed kettle cooks is probably the most significant process and operating
change that can be effected.

IV.     PERFORMANCE OF  CURRENTLY USED METHODS OF EMISSION REDUCTION
A.	Performance Data
       Data describing  the control efficiency of  the  various air pollution control devices currently
being used by  the  paint and varnish industry is presented and discussed  below. The data was
gathered from the questionnaires  used in  this study,  industry  measurement  not reported in the
questionnaires and source testing conducted by the EPA.
                                          235

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1.      Scrubbers — Scrubbers are frequently encountered in the paint and varnish industry. Simple
spray towers are usually installed as part of closed resin kettle systems. As discussed in Section I,
these are not considered pollution control equipment for the purpose of this report. Some perform-
ance data for these devices has been reported in the questionnaires and will be discussed below.
       Scrubbers which qualify  as air pollution control devices in the present context have also
been  reported in the questionnaires. The reported data for these devices  has been  described in
Tables 52, 53, and 54.
       These are predominately  spray type scrubbers. Either plain water or water to which some
chemical (e.g., caustic) has been added is used as the scrubbing liquid.
       The efficiencies of these devices are reported in the  questionnaires to range from 50% to
99% with practically all at 90% or better.  Those who report efficiencies for  spray  towers which
serve as process equipment generally claim efficiencies in excess of 90%.
       The accuracy of these reports would seem  to be questionable. The  efficiency of a well
designed scrubber could be good on relatively large particulate or on readily condensible organics.
On small particulates or relatively volatile organics, the types of scrubbers generally reported would
probably be  ineffective. They  are inherently  limited  where volatile, non-soluble  contaminants are
concerned. Aside from  this problem, they  also frequently violate the opacity  regulations  of  most
states.
       Furthermore, it appears that in many cases an arbitrary number was picked for efficiency
rather than  a number based on  actual  measurements. Often, the  inlet and  outlet loadings  were
unknown yet a very high efficiency was claimed which seems contradictory.
       If  large amounts of condensible  materials  are emitted from a reactor, actual tests could
indicate good efficiency. This  could lead to  a false sense of security, however, if  the analytical
technique ignores the noncondensibles.  As  reported in  an earlier section, actual  measurements
have  been performed on the noncondensible fraction of the  emissions. Levels as high as several
hundred  thousand parts per million  (CHU equivalent) have been measured.  It was further found
that the typical scrubber was at best 10% effective on these emissions.
2.      Afterburners — Tables 54 and 55 summarize the questionnaire data reported for thermal and
catalytic afterburners. Efficiencies for thermal afterburner  are  reported from "poor" to "excellent".
Where a numerical value is given, it is always reported in excess of 90%. On the whole, these
values are probably somewhat more reliable than those given for scrubbers. The  inlet loading must
generally be  known for design and safety purposes and it is possible to estimate the effectiveness
                                           236

-------
                                  TABLE 52*



                                TYPE 1 PLANTS



                 AIR POLLUTION CONTROL — LOADING MILLS, ETC
Paint
Production
MM gal/yr
6.4
2.6
1.0
5.6
1.2
4.3
2.6
3.0
2.4
0.1
1.9
14.9
8.6
8.2
5.6
1.0
0.7
1.0
2.4
2.7
8.3
8.7
1.1
1.0
FABRIC
Number
of Devices
4
1
1
4
1
7
3
1
14
1
1
1
4
1
3
1
3
1
2
1
1
1
1
4
FILTERS
Total Gas
Flow. SCFM
1,000
—
—
6,200
3,600
18,000
5.362
3,250
18,620
—
1,071
—
12,700
5,370
—
—
1,155
2,000
2,600
2,058
—
15.000
6,000
	
Air to
Cloth Ratio
6.1
—
—
3.5
4.5
3.0
7.7
42
7.0
—
7 1
4,0
62
26
—
—
7.7
67
30
18.3
—
2.9
2.6
	
'Questionnaire Data
                                    237

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  Resin
Production
 MM Ib/yr
   0.4

   2.8

   3.0

   1.2

  14.9

   2.4

   3.6
 Number
of Devices
                             TABLE 52 (Continued)

                                 SCRUBBERS
 Total Gas
Row, SCFM
   1

   1

   1

   1

   1

   2

   1
                                                      Efficiency
  2,500

  4,500



  9,610

  6,000
99%
95%
                                                        Type
Wetted baffle

Water spray

Roto-clone

Water spray


Spray
                                     238

-------
                                     TABLE 53*
                                  TYPE 1 PLANTS
                 AIR POLLUTION CONTROL — REACTORS AND KETTLES
                                    SCRUBBERS
Resin
Production
MM Ib/yr
1.9
11.1
0.0
20.0
0.5
5.7
33.7
20.7
5.4
16.4
0.3
17.6
2.9
16.0
3.5
Number
of
Devices
1
4
1
1
3
1
2
1
1
3
3
5
2
3
2
Gas Flow
(cfm) Efficiency" Type
— — —
— — —
— — —
— — KMnO4
— 90% Spray
134 50% —
— — —
— — —
15 85% —
— — Caustic
600 99% Caustic
500 98% —
— — —
2,500 90% —
1,180 — Cyclone
Operating
Cost
($/year)
—
2,000
—
—
15,340
—
—
—
2,600
15,400
175,000
13,300
—
—
1,1700
*Questionnaire Data
**See comments in text concerning reported efficiencies.
                                      239

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                                 TABLE 55*
               AIR POLLUTION CONTROL — REACTORS AND KETTLES
                        THERMAL AFTERBURNERS
Resin
Production
MM Ibs/yr
8.2
38.5
1.9
10.6
0.3
0.2
0.0
3.5
20.7
Number
of Devices
1
1
(flare)
1
1
1
1
1
1
2
Gas Flow
(CFM)
2,000
4,200
2,000
7,000
1,200
500
920
10,000
—
Temp
(ฐF)
1,500
1,800
1,200
1,100
1,500
1,400
1,200
1,300
1,200
Res. Time
(Sec)
0.5
2.4**
2.1
2.0
—
0.3
—
0.5
—
Efficiency
98%
—
Excellent
Fair
99%
Excellent
—
Poor
—
Operating
Cost
($/Year)
10,000
—
—
—
1,800
370
267
30,600
—
                        CATALYTIC AFTERBURNERS
Resin
Production
MM Ibs/yr
1.2
0.2
33.0
17.6
16.0
Number
of Devices
1
2
2
1
1
Gas Flow
(CFM)
1,200
—
7,500
2,980
3,000
Temp.
(ฐF)
1,200
1,000
750
500-1,000
900
                                                        Efficiency
                                                       Excellent
Operating Cost
  ($/Year)
  4,800
                                                         Good         —
                                                         90%        6,300
                                                         Good         —
 'Questionnaire Data
"This device is a true flare and, as such, residence time is not a measurable parameter.
                                  241

-------
of well designed afterburners by noting  the  outlet temperature and residence time.  Furthermore,
afterburners do not possess the inherent limitations to which scrubbers are subject. Any combustible
material can be  incinerated if the temperature and residence time are sufficiently high. The temper-
atures and residence times  reported are usually consistent,  in a  general way at least, with the
efficiencies reported.Beyond that, it is not possible to either affirm or deny the reported  performance.
       Similar comments apply  to the questionnaire returns on catalytic afterburners. Again, if the
temperature is high enough (up  to the point  at which the catalyst  is damaged), enough  catalyst is
used  and  the catalyst  is  maintained properly,  most materials can be oxidized  efficiently. The
efficiencies reported ("good" to  "excellent",  or 90% to  95%)  are  at least feasible in the light of
the operating conditions reported. Since no information is given on catalyst maintenance or replace-
ment, it is  not possible  to determine which,  if any, of the respondents  is optimistic in his reports.
3.     Fabric  Filters —  Fabric filters,  usually bag type filters,  were the most commonly employed
pollution  control  device  reported in the  questionnaires. Tables 52, 56 and  57  summarize the
questionnaire  results obtained. They are  used for control of dry particulate from loading, mills, etc.
Bag filters  are known to attain very high efficiencies (99% + )  even on  sub-micron  particulate in  a
properly designed system. Where reported, efficiencies usually were given as 90%  or better.  Since
the normal application of fabric  filters in  the  paint industry is  for clean, dry particulate at ambient
temperatures,  there is no reason to doubt that very high efficiencies  can  be obtained.
       Some  additional source test data other than that contained in the questionnaires has  been
collected from  other plants and source test groups. This data is presented on Table 58.
       The Environmental Protection Agency retained a subcontractor to perform tests to determine
the efficiency  of thermal afterburners. The test methods were  discussed earlier in  Chapter 3. The
results of their testing is presented in Table 59.
B.     Operating Life and Maintenance Experience for Control Systems
       This subject was not  well covered by the respondents to the study's questionnaire and the
results presented in Table 60 are  based on data supplied from other sources. The Normal Life
listed  are based on trouble-free operation and do not consider the past losses caused by explosions
and fires.
       In general maintenance  is  not a significant operating cost. Cost for thermal afterburners
with heat exchangers will run higher than those without.  This  is caused by tube fouling,  tube  burn-
out and metal failure due to  thermal  expansion inherent with the  use of metal exchangers. Good
design will  keep these maintenance costs to a minimum.
                                             242

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                                TABLE 56*
                            TYPE 2 PLANTS
             AIR POLLUTION CONTROL — LOADING, MILLS, ETC.
                            FABRIC FILTERS
Paint
Production
MM gal/yr
1.7
2.4
0.5
0.7
1.1
2.5
0.8
1.2
0.5
0.2
0.2
6.0
0.1
1.8
0.6
0.7
2.5
1.3
0.1
0.7
0.6
Number
of Devices
1
11
1
1
2
3
1
1
1
1
2
3
1
1
1
1
1
1
1
1
1
Total Gas
Flow, SCFM
5,000
7,000
—
5,000
3,850
10,500
—
—
2,000
83
1,231
—
—
5,600
—
—
2,376
2,700
875
1,231
—
Air to
Cloth Ratio
2.5
2.0
—
6.3
4.0
2.9
—
—
25.0
25.5
8.2
—
—
7.0
—
—
2.0
9.0
41.7
8.2
—
*Questionnaire Data
                                 243

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                             TABLE 56 (Continued)
  Paint
Production                Number                 Total Gas                 Air to
MM gal/yr               of Devices               Flow, SCFM              Cloth Ratio
   2.4                      1                    1,200                    8.0

   2.7                      1                      200                    1.8

   0.8                      2                      924                    3.5

   0.1                      1                     —                      —

   2.4                      4                   11,500                    —

   1.3                      1                    2,100                    —

   0.6                      2                    2,788                    —

   0.6                      2                    5,600                  20.9

   1.2                      1                    1,200                  10.7

   1.2                      3                   18,000                    —
                                    244

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                                    TABLE 57*
                                 TYPE 3 PLANTS
                 AIR POLLUTION CONTROL — LOADING, MILLS, ETC.

                                 FABRIC FILTERS
 Resin Production, MM pounds/yr                          38.0              80.0
 Number of Devices                                      1                 3
 Total Gas Flow, SCFM                               1,900             12,000
 Air to Cloth Ratio                                        2.8               3.9

                                   MECHANICAL
 Resin Production, MM pounds/yr                           2.6              80.0
 Number of Devices                                      4                 4
 Total Gas Flow, SCFM                              11,000               —
 % Efficiency                                           90               —
'Questionnaire Data
                                    245

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-------
                          TABLE 60
       OPERATING LIFE AND MAINTENANCE REQUIREMENT
           FOR AIR POLLUTION CONTROL EQUIPMENT
              TYPE
SCRUBBERS
  Carbon Steel
  Stainless Steel
THERMAL AFTERBURNERS
  Without Heat Exchanger
  With Heat Exchanger
NORMAL LIFE
  YEARS
    5
    10


    15
    10
CATALYTIC AFTERBURNERS
  Unit Only With & Without Heat Exchanger     15
  Catalysts Only                           3
FABRIC FILTERS
  Unit Only
  Bags Only
    20
   2 to 4
                                                   — MAINTENANCE EXPERIENCE —
                                                    AMOUNT       ANNUAL COST*
 High
Medium

Medium
Medium

 Low
 High

 Low
Medium
10%
 5%


 2%
3.5%


 2%
10%


 2%
10%
*Percent of initial equipment cost—does not include replacement cost.
                                 248

-------
        For catalytic afterburners the maintenance cost for units with or without  heat exchangers
are about  the  same. This is true since these units operate at  much lower temperatures and  in
either case are built of all metal construction.
        Maintenance  costs  for  scrubbers are primarily  dependent  on the  degree of  corrosion
experienced. This is primarily a function of the acidity of the scrubbing liquid which will vary sig-
nificantly with the amount of fresh water  used. Scrubbers utilizing  once-through water will  have a
longer life than that listed on Table 60.

V.      CAPABILITY TO MEET MORE STRINGENT STANDARDS
A.      Fabric Filters
        Removal of pigment  and other dry  particulate is  accomplished by use  of fabric filters. As
discussed  earlier, this control device is capable of efficiencies approaching 99.9 and should  have
no difficulty meeting more stringent standards.
B.      Afterburners
        Either catalytic or thermal afterburners can be operated  at increased efficiencies to  meet
more stringent air  pollution  control standards.  For thermal  afterburners this can be accomplished
by  increased operating  temperature  assuming additional fuel  is available. For reactions that are
time limited, efficiencies can be increased by increasing the residence time. This can be accomplished
by reducing gas flow or adding length to the existing unit.
        The efficiency of catalytic afterburners can  also be increased by increasing the  operating
temperature  and/or increasing the  amount  of  catalyst used. To maintain higher efficiency it will
probably also be necessary  to shorten the catalyst  maintenance cycle  and the reactivation or
replacement period.
C.      Scrubbers
        There is  little that can be done to  improve the efficiencies of the type of scrubbers that
are currently used in this industry.  They are fairly effective for  removal of  large particulate and
heavy  condensibles.  They are  very ineffective on noncondensible  organic materials and  small
particulate. Changes in operating conditions that would normally improve  scrubber efficiency (i.e.
pressure drop,  gas to liquid  ratio) should have little effect  on these emissions. This is typical of
scrubber operation on emissions which have a wide size range  of particulate.  The large material
is easily collected with any type of scrubber while  small particulate and gaseous emission  require
a special scrubber operated at very high pressure drops.
                                           249

-------
D.    • Refrigerated Condensers
       There has been only limited experience in  the operation of  this device. It  appears that
its average maximum efficiency will run around 90%.  The possibility  of this device  meeting high
efficiency standards that might develop in the future is remote.

VI.     WATER AND SOLID WASTE PROBLEMS ASSOCIATED WITH BEST CONTROL
       One of the many advantages of the use of afterburners for best control is the elimination
of all water and  solid  waste problems associated with  other  control  methods. In  fact,  in many
cases the liquid waste solvent discussed earlier in Section  III B-6 can be used as a fuel for the
afterburner. This not only solves  a waste disposal problem but also reduces afterburner operating
cost.
       The pigment dust collected in fabric filters presents no serious solid waste disposal problem.
The  quantities are small, non-hazardous, and may be disposed of by scavenger services in land
fill operations. In  many  cases, they are also recycled back into  paint production for use in such
items as dark primers.
                                          250

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                                        CHAPTER 6
                                INSPECTION PROCEDURES

       This section is written for a compliance inspector who is familiar with inspection procedures
and testing procedures in general. The best single source of background information for the com-
pliance inspector  is the  Field Operations and  Enforcement  Manuals  for Air Pollution Control,
Volume I, Organization and Basic Procedures — APTD-1100, and Volume II, Control Technology
and General  Source Inspection — APTD-1101. These two volumes are published  by the Federal
Environmental Protection  Agency and  may be obtained  from the National Technical Information
Center, Springfield, Virginia 22151.  The purpose of this chapter will  be to  detail the particular
emission problems and control techniques specific to the paint and varnish industry and to  help
enforcement officers when entering and inspecting these facilities.
I.      NATURE OF SOURCE PROBLEMS
       The paint  and varnish  industry is one of the  more  complex of the  chemical industries.
The three basic manufacturing operations in  this industry are varnish cooking,  resin cooking and
paint  blending. The air pollution regulations most often  applied to this  industry are the nuisance
regulations covering odor  and visible  emissions.  The other significant problem  of  this industry
is the emission of fugitive solvent vapors which as yet is not covered by law in most states.
       The quantity of emissions released from varnish cooking are small but still present a  signifi-
cant local air pollution problem because of the wide variety of highly  odorous substances.  The
amount of varnish  cooking carried out by the  industry has been steadily declining and is expected
to  continue to decline in the future.  This  is especially  true of the small open kettle batch which
represents the more difficult to control emissions.
       Resin  manufacturing emissions tend to be highly cyclical  in nature and consist of solvent
vapors, phthalic  (or other acid) anhydride,  polyols (either solid or liquid)  and  a variety of  partial
reaction products. The last category is usually present in the smallest quantities  but may represent
the most  noxious component from an  odor standpoint.
                                          251

-------
        Exhaust volumes for a given kettle can  peak at up to 100 to 200  SCFM for short periods
of time and may be essentially  zero  during other portions of  the cook.  Concentration can vary
from zero up to several hundred thousand ppm.
        Every  cooking formula will exhibit its own particular emission characteristics. The greatest
quantity of emission  occurs from the paint manufacturers operation and consists primarily of solvent
vapors and pigment  particles. They are usually fugitive in nature and exit to the atmosphere through
the general building ventilation. Their concentrations are usually quite low (<50 ppm) but the overall
quantity is high due to the large quantity of ventilation  air. Future OSHA and air pollution regulations
will probably require  the capture of these emissions at their source. This should result in low volume
                                                ป
higher concentration  emissions which can be more easily controlled.
II.     PROCESS DESCRIPTION
       The process narratives that follow will be specific to oil based paints and varnishes. The
manufacture of water based paints  is of minor importance from  an air pollution point of view. This
is also true of the manufacture of the resins used in the blending of water  based paints since they
are normally provided outside this industry in chemical process plants.
A.     Paint Manufacturing
       Starting with  all purchased raw material,  the manufacturing process for pigmented products
is deceptively  simple from a process viewpoint. Basically it consists of mixing or dispersing pigment
and vehicle to give the final product. This is schematically illustrated in Figure  57.
       The paint vehicle is defined as the liquid portion of the paint and consists of volatile solvent
and non-volatile binder such as oils and resins. The  non-volatile portion is also called the vehicle
solid or film former.  The pigment portion of the  paint consists of hiding pigments such as titanium
dioxide (TiOa), extenders or fillers  such as talc or barium sulfate, and any mineral  matter used
for flatting or other purposes.
       The incorporation of the pigment in the  paint vehicle is  accomplished by a combination of
grinding and dispersion or dispersion alone.  When it is necessary to further grind the raw pigment,
the pebble or  steel ball  mills are  normally used.  With the  advent of fine particle grades of pigment
and extenders, as well as the widespread use of wetting agents, the trend is toward milling methods
that are based on dispersion  without grinding. This dispersion  consists of breakup of the pigment
clusters and agglomerates, followed by wetting of the individual particles with the binder or vehicle.
Some of the more popular methods currently being used are high speed disc impellers, high speed
impingement mills and the sand mill.
                                           252

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       Aside from this dispersion step, pigment paint manufacturing involves handling of raw material
as well as handling and packaging of finished product. Operations of a typical  plant may be sum-
marized as a raw material and finished product handling  problem with a variety of  interdispersed
batch operations. The interrelationship of all these operations  is schematically  illustrated in  Figure
58. The operations depicted are those of a  plant that  makes its own resins  and produces both
trade sale and industrial finishes.
       Some of the  larger and a few of the  medium  size manufacturers produce a significant
amount of their formulation ingredients, including pigments, resins and modified  oils. Certain  manu-
facturers produce these ingredients in an  amount exceeding  their requirements  and sell the excess
to other manufacturers. A significant number also produce only a portion of their resins and purchase
the remainder from their competitors or suppliers who specialize in resin manufacturing.
B.     Varnish Cooking
       The manufacturing of  resins and  varnishes is by far the most  complex process in a paint
plant, primarily as the result of the large variety of different raw materials, products and cooking
formulas utilized. The complexity begins  with the nomenclature used  in classification of the final
product. Originally, varnishes were all made from naturally occurring  material and they were easily
defined as a homogeneous solution of drying  oils and resins in organic solvents. As  new synthetic
resins were developed, the resulting binders or varnishes were classified on the basis of the resins
used. Examples of this are alkyd, epoxy and polyurethane resin varnishes.
       There are two basic types of varnishes, spirit varnishes and  oleoresinous  varnishes. Spirit
varnishes  are formed  by dissolving a resin  in a solvent. They dry by solvent evaporation. Shellac
is a good example of a spirit varnish. Another  material  that might fall in  this category is lacquer.
Technically, lacquers  are defined as a colloidal dispersion or solution  of nitro-cellulose, or of  similar
film-forming compounds, with resins  and plasticizers, in solvent and diluents  which dry primarily
by solvent evaporation.  Oleoresinous varnishes, as  the  name implies, are solutions of both oils
and  resins.  These varnishes dry by solvent evaporation and by reaction  of the non-volatile liquid
portion with oxygen in the air to form a solid film. They are classified as oxygen convertible varnishes
and  the film formed on drying  is insoluble in  the original solvent. A summary of the various types
of material used in the production of classical varnishes is given in Table 61.
       Varnish  is cooked  in both portable  kettles  and large reactors. Kettles  are used  only to a
limited extent and primarily by the smaller manufacturers.  The very old, coke fired, 30 gallon capacity
copper kettles are no  longer used. The varnish kettles which are used, have capacities  of  150 to
                                           254

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375 gallons. These are fabricated of stainless  steel,  have straight sides and are equipped with
three or four-wheel trucks. Heating is done with natural gas or fuel oil for better temperature control.
The kettles are fitted with retractable hoods and  exhaust pipes, some of which may incorporate
solvent condensers. Cooling and  thinning are normally  done in special  rooms.  A typical varnish
production operation is illustrated in Figure 59.
       The manufacturing of oleoresinous varnishes  is  somewhat more complex than  for spirit
varnishes. This manufacture consists of the heating or cooking oil and resins together for the purpose
of obtaining compatability of resin  and oil and solubility of the mixture in solvent, as well as for
development of higher molecular weight molecules  or polymers.
       The time and temperature of the cook are the operating variables used to develop the desired
end product polymerization  or  "body".  The chemical reactions  which  occur  are  not  well defined.
The resin is a  polymer  before cooking  and  may or may not increase in molecular size during the
cook. This  resin  may react with the  oil  to produce copolymers of oil and  resin or it may exist
as a homogeneous mixture or solution of oil homopolymers and  resin homopolymers.
       It  is possible to  blend resins and  heat-bodied oil and obtain the same varnish that can be
produced  by cooking the resin and the unbodied  oils. This indicates that copolymerization is not
the fundamental reaction in varnish cooking.
       Heat bodying  or polymerization  of an oil  is done to increase its viscosity and is carried out
in a kettle in a fashion similar to  varnish cooking. The fundamental reaction that occurs  is poly-
merization of the oil monomers to form dimers with  a small portion of trimers.
C.     Resin Manufacturing
       There is a large variety of synthetic resins produced for use in the manufacture of surface
coatings. A listing of the more popular resins is given below. They are listed by order of consumption
by the coatings industry:3
               Alkyd                         Amino
               Vinyl                         Urethane
               Acrylic                        Rosin Ester
               Epoxy                        Styrene Butadiene
               Cellulosic                     Phenolic
                                            Hydrocarbon
       By far the most widely used of these resins are the alkyds and the vinyls. Alkyd consumption
is approximately twice that of the vinyl. Further discussion will concentrate on alkyd resins.

                                           257

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        Alkyd resins comprise a group of synthetic resins which  can be described as oil-modified
polyester resins. They are produced from the reaction  of polyols or polyhydric alcohol, polybasic
acid and oil or fatty monobasic acid.  A listing  and discussion of commonly used raw materials
will follow.2
1.   Oils or fatty acid
               Linseed                       Castor
               Soybean                      Coconut
               Safflower                     Cottonseed
               Tall Oil Fatty Acid             Laurie Acid
               Tall Oil                        Pelargonic Acid
               Fish                          Isodecanoic Acid
               Tung (minor)
               Oiticica (minor)
               Dehydrated Castor (minor)
        The materials in  the first column are oxidizing or drying types. The materials in the second
column are non-oxidizing and yield soft non-drying alkyds which  are used primarily as plasticizers
for hard resins.  The acids shown in this column  are the only materials that are strictly synthetic in
origin.
2.   Polyols
          Name                               Formula                            Form
Ethylene glycol
Liquid
                                               H
                                              HC - OH
                                              HC - OH
                                               I
                                               H
                                        H   H         H    H
Diethylene glycol                        I     I         |    |               Liquid
                                 HO-C-C-0-C-C-OH
                                        II         II
                                        H   H         H    H
                                            259

-------
                                      H H  H
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                                   H-C-C-C-OH
                                       I   I   I
                                      H 0  H
                                         H
                                          H
Glycerine                                  I
                                         HC  - OH
  CP-95% glycerine                        |                               Liquid
                                         HC  - OH
  Super-98%                              |
                                         HC  - OH
                                          H
                                         v        .2
Pentaerythritol                               .C                            White Solid
                                 HOH2C       \H2OH
       Glycerol or glycerine was the first polyol used for alkyds and is still widely used.
       The first polyol, based on  usage, is pentaerythritol (PE), which came into common use in
the 1940's.  PE is supplied as "technical grade"  material and contains mono, di,  tri and polypen-
taerythritol. The material consists  primarily  of the mono  form which was illustrated  previously in
the list of polyols.
       The important distinguishing feature of the  various polyols is the number of potentially reactive
hydroxyl  groups in the molecule,  known as functionality.  The glycols with  a functionality of two
produce only straight chain polymers and their resins are soft and  flexible. The resultant products
are used primarily as plasticizers for hard resins.  Glycerine has a functionality of three and is used
primarily  in short and medium oil alkyds. Pentaerythritol, with a functionality  of four, cross-links to
a greater extent, forming harder polymers. It  is ideal for use in long oil alkyds.
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3.  Acids and Anhydrides
          Name
Formula
Form
Phthalic
  anhydride
  (ortho)

                            White Solid
Isophthalic acid
  (meta)
                            White Needles
Terephthalic
  acid (para)
                            White Crystals
                                           261

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Maleic                                H  •      j                         White Solid
  anhydride                             ^Cx /C^
The acidic material can be used as an acid or anhydride. The anhydride is formed from two molecules
of acid minus a molecule of water or removal of one molecule of water from a diacid. It is preferred,
since it reacts faster and yields less water for removal from the cook.
       For many years, phthalic anhydride (ortho) (PA) was the only polybasic  acid used in sub-
stantial proportions in alkyds. It  still  remains the  predominant dibasic acid.  PA is produced from
the catalytic oxidation of naphthalene  or ortho-xylene.
       The chemistry of alkyd  resin systems is very complex. So much so that theoretical con-
siderations offer only  a good starting  point.  Final formula and variations are developed  by  trial
and  error changes, based  on performance  requirements and shortcomings of  previous batches.
       Condensation  is the reaction basic to all  polyester resins, including alkyds.  This reaction
follows the elementary equation for esterification as shown below:
                          .0                         o
                    RC             +    R1 OH  ฃ R(T           +    H20
                           OH                      \)Rl
                          Acid     +    Alcohol    =   Ester     +    Water

                                      For Alkyd Resins
                               PA  +  Glycerine ?ฑ  Ester + H2O
       The ester monomer formed  is very complex and further reacts to form large  polymers
called resins.  The polymers formed are low in molecular weight by comparison to other resins. For
example  alkyd resins  have molecular weights ranging from 1,000 to 7,000 while some  vinyl  and
acrylic  resins  have average molecular  weights in excess of 100,000 and in some cases as high
as 500,000.
                                          262

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       The alkyd polymers  also react with  oil  or  fatty acid and  are  generally classified by the
amount of oil or PA used in the formulation, as described below:
                                           % Oil              % PA
       Short Oil                           33 to 45               35
       Medium Oil                         46 to 55            30 to 35
       Long Oil                           56 to 70            20 to 30
       Very Long Oil                        71 up                20
       The resulting reactants of the PA, polyol and oil may be represented in part as shown below:

                                PA                  G(OH)3
                           Phthalic Anhydride   +    Glycerine     	->
                      HO-G-PA-G-PA-G-PA-G-PA-
                             I           I          I          I
                            0        PA         PA         0          +   H90
                            H                              H                 2

                                  Glyceryl phthalate                       +   water
       This will then react  with the long chain oil  monoglyceride or fatty acid  (FA) to yield:
                       HO -  G  - PA  - G  -A - G - PA - G  - PA -
                                        I        I
                                       PA      PA
                              FA                          FA
       Alkyds can be manufactured directly from a fatty acid, polyol and acid  or from oil, polyol
and  acid. The  second combination  (oil, glycerine and  PA) produces glyceryl phthalate  which  is
insoluble in the oil and precipitates. This problem can be  overcome by first  converting the oil  to
a monoglyceride by heating with  a polyol in the presence of a catalyst.  This process  is called
alcoholysis of the oil. The basic reaction is shown below:
    H2COOCR                   H2COH                  H2COH
      HCOOCR        -f   2       HCOH    	>3    HCOH
       I                            I                          I
    H2COOCR                   H2COH                  H2COOCR
       Triglyceride              Glycerine                Monoglyceride
       This is an ester interchange reaction with no loss of water.
       When fatty acid rather than oil is used as the starting material, this is called the "one-stage"
process.  In this process, the  fatty acid  and glycerine are added to the kettle, the agitator is started
                                          263

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and heat is introduced. When the batch reaches 440ฐF, the PA is slowly added  and cooking con-
tinued for another 3 to 4 hours until the desired body and acid number are reached.
       If the fusion process is being used, a continuous purge of inert gas is maintained to remove
the water formed in the reaction. This  water may also be removed by what is known as the solvent
process. It is similar to the fusion process except that about 10%  aromatic solvent (usually xylene)
is  added to the start. The vaporized solvent  is passed into a condenser. The condensate then
flows to a decant  receiver for separation of reaction water. Recovered  solvent is  returned to the
reactor. Inert gas flow in solvent cooking is very low and in some cases is not used.
       As discussed earlier, when oil is used  rather than fatty acid, the alkyds are produced in a
two-stage  process. In the first stage the monoglyceride is first produced from the  linseed oil and
glycerol. Catalyst and oil  are added  and the alcoholysis of the polyol and oil is carried out between
450 and  SOOT  until the desired end point  is reached. When the alcoholysis  is completed, any
additional polyol needed is added.
       Following this, the  required  amount  of PA and  esterification catalyst are slowly added. If
solvent cooking is to be used, the solvent is also added at this time. Cooking then proceeds as before.
       A typical manufacturing formula for a  50% oil-modified glyceryl  phthalate alkyd using the
two-stage process  is given below.
                                                                  Ib
                         First stage
                            Linseed oil                           51.3
                            Glycerol (95%)                       12.8
                            Catalyst, Ca(OH)2                    0.026
                         Second stage
                            Glycerol (95%)                       6.2
                            Phthalic Anhydride                   39.7
                            Catalyst
                            Methyl  p-Toluene Sulfonate            0.2
                                                                110.2
                        Approx. Loss                             10.2
                        Solids Yield                             100.0
       Alkyd and other resins are  cooked in closed  kettles, more  properly called reactors. They
vary in size  in commercial production from  500 to 10,000 gallons.  A typical reactor  system is

                                          264

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shown in Figure 60. They  are  generally fabricated of Type  304 or 316 stainless  steel with  well
polished surfaces to assure easy cleaning. Design  pressure is  usually 50 psig. These reactors
may be  heated electrically, direct fired with gas or oil, or  indirectly heated using a heat transfer
media such  as Dowthermฎ. They are also equipped  with a manway, sight-glass, charging  and
sampling line, condenser system, weigh tanks, temperature measuring devices and agitator.  The
manway is used both for charging solid material and for access to the kettle for cleaning and repair.
       The reactor  may be equipped with a variety of different  condenser systems. The system
shown in Figure 60 includes a packed fractionating column, a reflux condenser and a main condenser.
The condensers are water  cooled shell and tube type  and may be either horizontally or vertically
inclined.  Vapors are processed and condensed on the tube  side and drain to a decant receiver
for separation and possible return of solvent to the reactor. A dual function aspirator venturi scrubber
is often added to the system.  It  is used to  ventilate the kettle  during addition of solid materials and
may also remove entrained  unreacted or vaporized solids and liquids from the venting gases.
       Thinning tanks are always included as  part of the reactor  system. They are  normally water
cooled and equipped with a condenser and agitator. The partially cooled finished alkyd is transferred
from the reactor to the partially filled  thinning tank.  Since  most alkyd resins  are thinned to 50%
solids, the capacities of  these tanks are normally twice the capacity of the reactors. These tanks
are also  frequently mounted on scales so that thinning solvents may be accurately added.
       The final step in  a reactor system is  filtering  of the thinned resin prior to final  storage.
This is normally done while  it is  still hot. Filter presses are the  most commonly used filtering device.
       The manufacturing  procedures and equipment used for the production of other resins listed
at the  beginning of this discussion are quite similar. The major differences are the raw materials
and the  process steps utilized. A detailed discussion of these other resins is beyond the scope of
this narrative.

D.	Air Pollution Control Techniques
       Collection  of particulate  pigment  or resin  emission is  a simple straightforward job.  The
only practical  control device is a fabric filter, and it is ideally  suited for this application. Collection
efficiency for the submicron pigment dust  (0.05 to 0.25 microns)  is in  the range  of 99.9%. There
are no temperature problems since the exhaust system runs at ambient temperatures. The grain
loading is very low and baglife is extensive. Approximately  0.01% of the loaded pigments are lost
and collected. Grain loadings to the  fabric filter run around  0.19 grain/SCF.  A  typical collection
                                           265

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                     -SPRAY  TOWER
                                                      REFLUX   VEMT
                                                    /CONDEIXISETR
                                  F RAC T ION AT i NG
                                   DISTILLATION
                                                          PORTHOLE
                                                          FOR  SOLIDS
                                                        DIRECT FIRED  OR
                                                        JACKETED FOR HIGH
                                                        TEMPERATURE  VAPOR
                                                         R  LIQUID
TO RES INI
STORAGE
         PUMI
                                FIGURE   6O
         MODERN  REISIN  PRODUCTION   SYSTEM
                                       266

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system is shown in Figure 61. The collection system can be a fixed hood which can handle both
dust and pigment bags or a flexible hose positioned above the loading hatch or attached to the top
of the tank. The tank attachment  provides the most positive control of fugitive dust emission but
also increases pigment and solvent losses slightly.
        The application  of control  equipment to this problem is quite  simple and can  be solved
with standard off-the-shelf equipment from a host of suppliers.
        The control of hydrocarbon and  odors from  the various emission sources listed earlier is
not quite as straightforward as the dust emission. There are three types of control equipment that
have been applied to this problem.  They  are catalytic and thermal combustion  devices  and  wet
scrubbers.
        As  a general rule, wet scrubbing does not provide  a satisfactory solution for the following
reasons:
        1.  Removal efficiency of  fine hydrocarbon aerosol is not good at economically practical
           pressure drops.
        2.  Noncondensible hydrocarbon  solvent  vapors will not be removed.
        3.  Odor removal without the addition of an oxidizing agent such as potassium permanganate
           or sodium hypochorite is  unsatisfactory.  If an oxidizing agent is  used, operating cost
           will be quite  high  due to  the high concentration  of other oxidizable material such as
           phthalic anhydride, resins and oil.
        4.  Mobile packing and high make-up water  rates are required  to prevent plugging of the
           scrubber beds and spray nozzles.
        5.  Correction of the air pollution problem with wet scrubbing causes an equivalent water
           pollution problem.
        The only control  technique currently being used that has proven effective for all cases is
combustion. Three general methods are employed to combust waste gases, as shown  below.
        1.  Flame Incineration
        2.  Thermal Combustion
        3.  Catalytic Combustion
        All of the above methods are oxidation processes. Ordinarily,  each requires that the gaseous
effluents be heated to the point where oxidation of the combustible will take place. The three methods
differ basically in the temperature to which the gas stream  must be heated.
                                         267

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RECOVERED RIOMEMT
RECYCLE FOR DARK
PRIMER PAINTS
                                                 (0

                                                 LJ
                                                 C

                                                 3
I


8


0
(f)
                                                     u


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                                                     UJ


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                                                     0.
268

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        Flame incineration  is the easiest of the three to understand, as it comes the closest to
everyday experience. When a  gas stream is  contaminated with combustibles at a concentration
approaching the lower flammable limit, it is frequently practical to  add a small amount of natural
gas as an auxiliary fuel and sufficient air for combustion when necessary, and then pass the resulting
mixture through a burner. The contaminants in the mixture serve as a part of the fuel. Flame inciner-
ators of this type are most often used for  closed chemical  reactors. They are not used  on resin
reactors at present. They may be an ideal solution some day, however, when methods of operating
a closed, pressurized resin  reactor are developed.
        It is far more likely  that  the concentration of combustible contaminants in an air stream will
be  well below the lower limit of flammability. When this is  the case, direct thermal combustion  is
considerably more economical than flame combustion. Direct thermal combustion is carried out by
equipment such as that illustrated in Figure 62. In  this  equipment, a gas burner is used to raise
the temperature of  the flowing  stream sufficiently to cause a slow thermal reaction to occur in a
residence chamber. Whereas flame temperatures bring about oxidation by free radical mechanisms
at temperature of 2500ฐF  and higher, thermal  combustion of ordinary  hydrocarbon compounds
begins to take  place at temperatures as  low as 900 to  1000ฐF.  Good conversion efficiencies are
produced at temperatures in the order of 1400ฐF with a residence time of 0.3 to 0.6 seconds.
        Catalytic combustion is  carried out by bringing the gas stream into intimate contact with a
bed of catalyst.  In this system, the reaction takes place directly upon the surface  of the catalyst
which is usually composed of  precious metals such as platinum  and  palladium.  While thermal
combustion equipment brings about oxidation at concentrations below the limits of flame combustion,
catalytic combustion operated  below  the  limits of  flammability  and  below the normal  oxidation
temperatures of the contaminants. The reaction is instantaneous by comparison to thermal combustion
and no  residence chamber is required. Catalytic combustion is carried out by  equipment such  as
that illustrated in Figure 63.
        In general,  catalytic afterburners are less expensive to operate, however, they  depend
directly  on the  performance of  the catalyst for their effectiveness. It will not  function properly if
the catalyst becomes deactivated. Because of this, catalytic units are not inherently functional when
operated at design temperature. In many areas, means for  ensuring adequate  performance of the
catalyst on a long term basis will be required by environmental control offices.
       The basis for design of either catalytic or thermal combustion is the hydrocarbon concentration
of the exhaust gases handled by  the afterburner.  The maximum hydrocarbon level is set  by  most
                                          269

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I]
                                              270

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271

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insurance companies at one-quarter of the lower explosive limit (LE.L.) which is equivalent to 13
Btu/SCF of exhaust gas. Once the rate of  emission is determined, it is then necessary to calculate
the dilution air required to meet 1/4 L.E.L. and set up the ductwork system to provide for this dilution.
When possible, dilution air should be utilized to help capture as many fugitive fume emissions as
possible. For example,  this can be accomplished by taking the dilution air from a hood positioned
over the resin filter press and venting the thinning tanks and product run-down tanks into the same
system.
        The  major problem  with catalytic  or thermal afterburners  as applied to open or closed
resin and varnish kettles  is the danger  of fires  and/or explosions. This has happened in numerous
occasions in the past due primarily to excessive hydrocarbon emission from kettles. These problems
have been all but eliminated  on  newer units  by  assuring that the design was  based on  actual
emission measurements  of  the highest emitting cook and the  addition of  some of the following
system  safety features:
        1.  High limit temperature alarm to shut off burner and activate a diversion system.
        2.  High velocity duct section to assure  gas flow to afterburner substantially exceeds flame
           propogation velocity of hydrocarbons being burned.
        3.  Double manifolding or hot gas recycle to prevent condensation of heavy hydrocarbons
           or phthalic anhydride.
       4.  Diversion system to block off hydrocarbon emissions to the unit, by-passing them directly
          out a separate exhaust, and introduction of fresh air to purge the unit.
       5.  Pneumatic operation of the  diversion system  to assure fast positive action and provide
          a fail-safe system in the event of either air or electrical failure.
        6.  Purging with inert gas  in the event of power failure.

III.     INSPECTION POINTS
        There are few,  if any,  federal  or state air pollution control  regulations dealing specifically
with  the paint and  varnish industry. General regulations that affect  the industry are  the opacity
regulation and  odor nuisance laws. Solvent emissions  is the other area  of potential problems.
Most plants  are quite likely to be affected by regulations such as Rule 66  of the LOS ANGELES
COUNTY AIR POLLUTION  CONTROL DISTRICT or Regulation 3  of the SAN FRANCISCO BAY
AREA AIR POLLUTION CONTROL DISTRICT.
        In preparing for an inspection of a  paint and varnish plant, the air pollution inspector should
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be familiar with:
        1.  The conduct of an odor survey
        2.  Opacity observation
        3.  Classification of photochemically reactive solvents
His main task during the inspection will be:
        1.  Determination of visible plumes and boundary line odor levels
        2.  Review of process flow sheet
        3.  Inspection of production facilities
        4.  Determination of source testing requirements
        Determination of compliance of the odor nuisance regulation is difficult. Consistant previous
odor complaints are a good  indication that a plant may be out of compliance in this area. If possible,
the inspection should be arranged when the wind is blowing toward the area from which the complaints
have  occurred  in the past.  In  any event, determination of odor  nuisance should be made  down
wind from the plant before  the on-site visit, since exposure to high levels inside the plant will dull
sensitivity to  lower odor levels. A listing  of odor thresholds for material  likely to be used by a paint
and varnish plant was given previously in Table  28 and is presented again on the following page.
        Inspection for visible stack plumes should also be  made at  this time. Any violation can
then be further  detailed during the plant inspection.
        Prior  to the plant  inspection,  an  attempt should be made to meet with the plant  engineer
and obtain and/or develop a process flow sheet listing all potential emission points. This will aid in
conducting a  proper on-site  inspection and a good emission inventory.
        The next step is the on-site inspection of the facilities. This can be divided into the  following
three  areas:
        1.  Raw material handling and storage
           a.  Liquids
           b.  Dry materials
        2.  Manufacturing
           a.  Resin manufacturing
           b.  Varnish cooking
           c.  Paint blending
       3.  Filling, packaging and product storage
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                                      TABLE 28*
                   ODOR THRESHOLDS OF SOME ORGANIC VAPORS
                               Chemical
                       Acetaldehyde
                       Acetone
                       Acrolein
                       Benzene
                       Ethanol
                       Ethyl acrylate
                       Formaldehyde
                       MEK
                       Methanol
                       Methyl methacrylate
                       Methylene chloride
                       Phenol
                       p-Xylene
                       Styrene (inhibited)
                       Styrene (uninhibited)
                       Toluene
Odor threshold, ppm
        0.21
      100.0
        0.21
        4.68
       10.0
        0.00047
        1.0
       10.0
      100.0
        0.21
      214.0
        0.0470
      .  0.47
        0.10
        0.047
        2.14
*Air Pollution Control Assoc. Journal, Volume 19, Number 2, Feb. 1969, pages 91 to 95
                                       274

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A.     Raw Material Handling and Storage
       Liquid raw materials handled in bulk quantities  will  be considered first. Oils  and polyols
are not very volatile and can sometimes be neglected  as emission sources at this  point in  the
process.  Solvents (and materials, such as resin  solutions,  that contain solvents) are the major
potential  vapor emission sources in  the handling  and storage  stage of  the plant operation.  Even
in this category many substances can be neglected. Many parts of the country have no regulations
concerning non-photochemically reactive organics.  In those localities, tanks containing such material
can often be  neglected if there is no apparent odor  nuisance. Likewise,  many localities  exempt
solvents  having vapor  pressures  below some  specified value. These  solvents  can usually  be
neglected on this basis. The size (capacity), contents,  venting arrangement and  frequency of filling
of all  other tanks should be noted. Particular attention should  be given  to the  solvents known to
have  a high odor potential, such as isophorone, styrene, ethyl acrylate, etc.
       The most important solvents that must be considered when determining compliance in most
parts  of the country are the relatively  volatile, photochemically reactive organics. A listing of solvents
commonly used in paint and varnish manufacturing is given in Table 62. Of  these, the ones most often
used  in sufficient quantities to justify bulk storage are toluene, xylene and  the lower boiling aromatic
naphthas. The pumping  rates for these solvents should be determined so that displacement losses
can be calculated. For example, for  toluene  at 20ฐC,  a pumping rate of 144 gal/min or more  will
give emission rates in excess of 8 pounds/hr which would violate allowable emission rates in some
states. Filling losses for selected solvents is given in Table 63. Vapor pressure is strongly temper-
ature  dependent so that a solvent that can be neglected in a cold climate may have to be considered
where ambient temperatures tend to be higher.
       Dry materials are usually received  and stored in bags  or drums so they normally present
no pollution potential until dumped during  the  manufacturing process. The same is true of  liquid
materials received and stored in cans and drums.  Any area where mechanical transfer or handling
(such as sifting, blending, etc.) of solid  powders takes place in contact with  air should be noted
as a potential emission source.
B.     Manufacturing
       Attention can now be directed towards the manufacturing  area. It is  necessary to locate
and identify all vents serving the equipment in this area. As before, in many localities, a distinction is
made between photochemically reactive and non-photochemically  reactive organics with the latter
often  exempt from the regulation. The potential for  odor nuisances for non-reactive materials should
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                                       TABLE 62

                        CLASSIFICATION OF TYPICAL SOLVENTS

                                            Vapor Pressure @ 20ฐC
                 Solvents                           (mm Hg)
Status*
Alcohols
Methyl
Ethyl
Isopropyl
n-Butyl
sec-Butyl
Ketones
Acetone
MEK
MIBK
Isophorone
Esters
Ethyl acetate
Isopropyl acetate
n-Butyl acetate
Amyl acetate (mixed)
Ethers (and derivatives)
Ethylene glycol monoethylether
Ethylene glycol monoethyletheracetate
Aromatics**
Xylene
Toluene
Other
2-Nitropropane
Methylene chloride
Trichloroethylene
97.3
43.9 '
32.8
4.3
12.5
186.0
70.2
15.0
0.18
74.4
43.2
10.0
3.8
0.1
2.0
7.1
22.0
12.9
360.0
65.0
exempt
exempt
exempt
exempt
exempt
exempt
exempt
not exempt
not exempt
exempt
exempt
exempt
exempt
exempt
exempt
not exempt
not exempt
exempt
exempt
not exempt
 These solvents are classified according to a LAAPCD Rule 66 type of definition.

"Large  quantities of various mineral spirits  and napthas are  consumed. Some of these contain
  sufficient quantities of aromatics to be classified as "reactive".  Each case must be considered
  individually, however. This is also true  of vapor pressures.
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                            TABLE 63
                 FILLING LOSSES FOR SELECTED SOLVENTS @ 20ฐC
Solvent
Acetone
Ethyl Acetate
Toluene
Mineral Spirits
V.P. @ 20ฐC, mm
186
74
22
2 (est.)
Mol. Wt.
58
88
92
160 (est.)
Filling Loss,
lb/100gal
0.494
0.299
0.0927
0.0147
SAMPLE CALCULATION
   Material:   Acetone
   Filling loss = 186mm  x
                      760 mm
                            1
Molar volume @ 20ฐC=24 liter/g-mole
       x 100 gal x 3.79 liter/gal
                      24 liter/g-mole
                                    x 58 gram/g-mole
                          1
                      454 g/lb
   = 0.494 Ib
                                 277

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not be overlooked. Where this is true, attention can be concentrated on those vents having photo-
chemically reactive or odorous emissions. Regulations can change, of course, so that in the future,
regulation of all organic emissions may become typical, or more refined measurements  of reactivity
may lead to different classifications.
       The resin plant  represents by far the most difficult area in which to determine compliance.
The processes are so  cyclic in  nature and industry practice  so diversified that there seems no
alternative other than a continuous (or, at  least,  a semi-continuous) emission monitor of  an entire
cook. It should be noted that two vents are involved in a solvent cook and one in a fusion cook.
The thin tank condenser vent and, where  applicable,  hood vents over the resin filter presses are
other points to be considered in the resin plant. A portable anemometer capable of measuring very
low velocities and a portable total  hydrocarbon detector (both explosion proof) are helpful  in determin-
ing compliance for these operations.  Where separate standards exist for toxic materials  (such as
isocyanates from polyurethane  production) it may be  necessary to  use  special techniques  for
measuring the concentration of such  materials. There is no adequate  substitute  for a competently
conducted source test over the period of the cook to  establish  compliance for a resin operation.
       Operations in the paint plant are relatively easier to monitor. If the only ventilation in these
areas is the general building ventilation  system then,  in many localities, no control  regulations
apply. Likewise,  if no reactive organic solvents or solvents with  pronounced odor characteristics are
used, regulations may not  apply. The use  of a weight  balance calculation to determine emissions
is not recommended in that  a small difference between large  numbers is  usually involved. Where
emissions are collected  in ducts and exhausted at one or more point sources, they should be investi-
gated for compliance. In paint plants,  particulate as well as organic emissions must be  considered.
One system often employed in paint plants is to collect emissions (solvent vapor as well as particulate)
in ductwork,  pass the gas  stream through a particulate collector (usually a fabric filter  type) in
which pigment solids are removed, and exhaust through a stack to the atmosphere. The  inlet and
outlet loadings for this particulate collector  ordinarily need  not be measured if the filter appears to
be intact and the organic concentration at the stack determined. Much higher flows are encountered
here than in the  resin plant, and conventional source velocity and concentration measurement tech-
niques are likely to be satisfactory.
       Types of emission control devices encountered in the paint and resin industry include scrubbers,
fabric filters and thermal and catalytic afterburners. The typical scrubber installation  of  the type
usually found on resin kettles set  up for fusion cooking tends to be rather ineffective on all  but large
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 particulate and heavy condensible materials.  Furthermore, such scrubbers can sometimes be the
 source of visible plumes. Where  these devices  represent the only pollution  control equipment in
 a given resin plant, some consideration might be given to source testing the plant, particularly if
 severe odor or visible emission problems exist.
        Fabric filters probably represent the only  practical reliable means of collecting pigment dust
 emissions applicable to most paint manufacturing facilities. Electrostatic precipitators would also be
 effective but so far as is known they find little if any use in the paint industry due to cost considerations.
 They are sometimes  used in pigment manufacturing but in  that case their primary purpose  is to
 collect acid mist.
        Unless there is some evidence to  the contrary, fabric filters operating at air to cloth ratios
 of 2 to 3 can probably be assumed  to comply with most existing  air pollution  regulations (based
 on weight only) provided bag  integrity is  maintained (this is not to imply that higher  air to  cloth
 ratios may not also be effective). Regulations aimed specifically at the submicron respirable particulate
 size range may require further investigation of filter performance, however.
        Thermal and catalytic afterburners are the most effective control devices for organic emissions.
 Thermal afterburners can also  be  effective for combustible particulate, such as phthalic anhydride,
 though the proper operating conditions may be considerably different than those for vapors.
        Where afterburners are used  as emission control devices, it is often possible to determine
 compliance by inspecting the system. It must first be  determined whether all possible sources of
 organic vapors are vented into the afterburner inlet.  For  thermal afterburners,  a determination that
 both temperature and residence time are acceptable is sometimes sufficient to establish compliance.
 Temperatures of 1250 to  1450ฐF  and residence times  from  0.3  sec  to  0.6 sec are commonly
 acceptable. For catalytic  afterburners, compliance is somewhat more difficult to ascertain. Proof that
 a regular catalyst maintenance schedule has been adhered to as well as a measurement of operating
 temperature,  or temperature rise across the catalyst  bed, can suggest that a unit is in compliance,
 but only a measurement of discharge hydrocarbon concentration can confirm adequate performance.

 C.      Filling and Packaging
        Some of the same comments apply to the filling and packaging areas as apply to the paint
 manufacturing area. Solvent vapors represent the principle emissions from this area.  Any exposure
of solvent-containing materials  to air should be viewed as a potential source.  Low reactivity,  lack
of odor nuisance potential or measurement of low emission rate are the grounds for demonstrating
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compliance.
       A complete compliance survey should identify as potential sources all of those points at which
process equipment  is vented to the atmosphere, or at  which the solid or liquid  materials being
processed  are exposed to the air. These points are most conveniently noted on  a flow diagram
of the process in question. Each such point should be noted as:
       1.   Likely to be in compliance by virtue of the materials being handled having  little tendency
           to become airborn, or
       2.   Being exempt from regulation as non-reactive, non-odor-causing vapors, or
       3.   Having  measured  emissions  low  enough to be  in  compliance or having  adequate
           collection and/or disposal equipment for the particular materials involved.
       Many potential sources may be found to be in  compliance by virtue of face-value evidence
of the types indicated. Other potential sources should be considered suspect and accepted source
testing methods used to establish compliance.
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                                       CHAPTER 7
                           ECONOMICS OF EMISSION CONTROL
       Specific among the goals of this study was the  determination  of  financial impact of air
pollution control on the paint industry. In order to accomplish this  goal,  the effort was subdivided
into three parts as follows:
        I.  Cost of Best Control Equipment
        II.  Model Plant Study
       III.  Industry Wide Studies
These elements of the study are covered in the following pages.
I.      COST OF BEST CONTROL EQUIPMENT
       In order to develop current and accurate  costs for best  control as applied to the paint and
varnish industry, a number of  equipment manufacturers and the Industrial  Gas  Cleaning  Institute
were retained as subcontractors to furnish cost information.
       The Industrial Gas Cleaning Institute (IGCI)  is an association of air pollution  equipment
manufacturers and  represents a  majority of the larger suppliers to  the  marketplace.  The IGCI
has had considerable experience in supplying information of the type  required in this study to the
Federal Environmental Protection Agency in a number of "Air  Pollution Control Technology and
Costs" contracts. The IGCI was retained as  a consultant in order to select the member companies
most  qualified to provide  the  required cost information.  In addition to selecting companies,  the
Standards Committee of the IGCI was used to review and approve all technical information supplied
in the study.
       The IGCI  member companies and equipment manufacturers selected were each supplied
the following information:
       1.   Process narrative for the paint and varnish industry
       2.   Specifications for abatement equipment
       3.   Instructions for submitting cost data
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       4.   Process descriptions for thermal and catalytic  afterburners for a resin reactor and for
           an open kettle
       5.   Operating conditions  for  thermal or  catalytic afterburners  (with  and  without  heat
           exchange) for large and small closed  kettles; and (without heat exchange)  for large
           and small open kettles
       6.   Data forms for estimated capital and annual operating cost
The  process  narrative and cost data  forms (items 1 and  6  above) are included in this report  as
Appendix B and  Appendix C, respectively. Other information supplied above (items 2 thru 5) follow
as Tables 64 to 81 which can be found at the end of this chapter.
       Based on information supplied, participating IGCI member companies furnished equipment
bid information and estimates of erection or installation of the system required. According to instruction,
the erection or installation estimates were based on a Milwaukee, Wisconsin location or an alternate
city with a  construction cost index  near  the national average. Therefore, the installation cost infor-
mation presented was adjusted based on the cost  indices presented in Table 82. This information
was  taken  from  Building Construction Cost Data 1970* which presents a construction cost  index
for 90 cities using 100 to represent the national average. The  indices presented are for the building
trades only and are used as representative for general rates on field construction. Since the indices
do not account  for  differences in  labor productivity,  the cost  variations  among cities  may  be
understated.
       Direct operating cost information was also  provided for the best control equipment by the
participating IGCI member companies. These costs were developed using estimated requirements
and the following basis:
                                 Units                  Unit Price
                                                                                Operator
                                                                                Supervisor

Labor

Maintenance materials
Replacement parts
Electric power
Fuel
Water (process)
Water (cooling)
Chemicals

Dollars/hour

Dollars/year
Dollars/year
Dollars/kwh
Dollars/MM Btu
Dollars/M gal
Dollars/M gal
Dollars/year
$6.00

$8.00
Cost**
Cost**
$0.011
$0.80
$0.25
$0.05

 'Published by Robert Snow Means Company.
"See Appendix C.                         282

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With this information, annual operating costs were  developed using direct costs  estimated on  the
preceding plus an annual capital charge.
        Cost information  for  fabric collectors was developed using  equipment  quotations  and
operating conditions obtained directly from equipment suppliers. In this  manner, information was
developed using a single  air rate  for the pulse test and shaker type fabric collectors.  With  this
information, Air Resources, Inc., developed installation and operation cost estimates using  the same
bases as  for  the  IGCI  work.  The  estimate information  is  presented  on  the following  page.
        Capital and  operating costs presented herein are based on  1972 dollar values. Caution
should be  exercised in using the cost information  presented as a basis  for preliminary estimates
of air pollution control cost. Dollar  values may require adjustment  due to inflation  and labor rates
and productivity may require adjustment to prevailing conditions.
A.     Thermal Afterburners
        Process descriptions were developed as follows:
        1.  Thermal  afterburner process description for resin reactor specification
       2.  Thermal  afterburner process description for open kettle specification
Operating conditions were developed for  the  resin  reactor case with and without the use of heat
exchange.  Operating conditions for the  open  kettle  specification were  developed  without  heat
exchange.
       The process description for Resin Reactor  Specification is  presented in Table 66. Related
operating conditions of afterburners without heat exchange  are presented in  Tables 67 and  68.
Similar conditions with  heat exchange are  presented in Tables 69 and 70.
       The Process  Description for Open  Kettle Specification  is presented in Table 71. Related
operating conditions of thermal afterburners without heat exchange are presented  in Tables 72
and 73.
       Capital cost  information shown in  Figures at the end of this chapter was based  upon  the
specification bid information as previously described. Capital cost information for thermal afterburners
without heat exchange is presented in Figure 66. Similar  cost information with heat exchange (42%
efficient) is presented in Figure 67. Total  installed  costs  for thermal afterburners are presented in
Figure 68 and a comparison is presented  with  catalytic afterburners.  This figure  also compares
systems with and without heat exchange.
       Annual operating  costs were developed using methods described previously. Figure 69
presents direct annual operating costs for thermal  afterburners,  without heat exchange,  and also
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includes  a comparison with catalytic afterburners. Similar information with heat exchange included
is presented  in Figure 71. Figure 70 presents total  annual  operating cost for thermal afterburners
without heat  exchangers and  also includes a comparison with catalytic afterburners. Similar infor-
mation with heat exchangers is presented in Figure 72.
B.     Catalytic Afterburners
       Process descriptions were developed for catalytic afterburners as shown:
       1.  Catalytic afterburner process description for resin reactor specification
       2.  Catalytic afterburner process description for open kettle specification
Operating conditions  were developed for the resin reactor  case with  and without heat exchange.
Operating conditions were developed for the open kettle without heat exchange.
       The process  description for resin  reactor specification is presented in  Table 74. Related
operating conditions without heat exchange are presented in Tables 75 and 76. Similar conditions
with heat exchange are presented in Tables 77 and 78.
       The process  description for open kettle specification  is presented in  Table 79. Related
operating conditions without heat exchange are presented in Tables 80 and 81.
       Capital cost  information was  developed based  upon  specification  bid information  as
previously described. Capital cost  information for catalytic afterburners without  heat exchange are
presented in  Figure 64.  Similar cost information with heat  exchange  (23% efficient) is presented
in Figure 65. Total installed costs for catalytic afterburners are presented in Figure 68 and a compari-
son is presented with thermal afterburners.  This figure also compares systems  with and without
heat exchange.
       Annual operating costs were developed using methods described previously.  Figure  69
presents direct annual operating costs for catalytic afterburners, without heat  exchange,  as well
as comparative data for thermal afterburners. Similar information, with  heat exchange, is presented
in Figure 71.
 C.      Fabric Collectors
        Cost  of  fabric collectors was  estimated using  a single  case for pigment  recovery. This
 was based on the following operation conditions:
        Air handling rate, CFM                 3,800
         Pigment recovered, Ib/yr               2,850
 Using these  conditions,  air to cloth ratios were  selected and cost information developed. This infor-
 mation is presented in Table 84.

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II.      MODEL PLANT STUDY
        In order to develop current and accurate cost information for the paint and varnish industry,
Air Resources, Inc. enlisted  the  assistance of the Sherwin-Williams Company as a subcontractor.
The Sherwin-Williams Company is a large multiplant company in the paint and varnish industry
and possesses a  thorough  knowledge of investment and  operating costs for plants of the  type
considered herein.
        As a basis for estimating costs for the Model Plant the following were established:
        1.  The plant site consists of a hillside location approximately 37 miles northwest of Chicago
           and in or around the  city of Elgin, Illinois.
        2.  Land costs are not included in the estimate.
        3.  All required utilities are available at the property line.
        4.  Uniform  Building Code,  OSHA and  National  Fire  Protection  Association  regulations
           are applied to the plant.
        5.  Construction costs are  based on December,  1972 for the Chicago, Illinois, metropolitan
           area.
Using the above bases, capital costs were developed for the model plant along with balance sheets,
operating statements and financial impact of control. These are discussed below.
A.     Capital Cost of Plant
        Using bases described previously, an estimate of capital investment was developed for the
Model  Plant.  The  estimate was  based on an  item-by-item  cost breakdown which  is presented  in
Appendix A of this report. The specific equipment selected for inclusion in  the estimate  is believed
to be representative of that  which might be installed in  a plant of the model type.  Certain of the
equipment was selected based on accessability of information  and does not necessarily represent
the optimum  or the lowest cost  equipment that could be utilized.  Inclusion of specific equipment
items should not be considered to be an endorsement of any brand or model.
        The total  estimated cost for the Model Plant is $3,755,000. A summary  of the cost items
is presented in Table 95. In  addition, Table 96 presents  a summary of equipment and utility costs.
B.      Balance Sheet and Operating Statement
        In developing financial  information  for the  uncontrolled plant, an attempt  was made  to
utilize a realistic approach while at the same time trying to avoid unnecessarily complex handling
and accounting situations. In order to simplify accounting, the model plant was assumed to be
fully operational with start-up costs and  investment credits having expired  in a prior period. Labor
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availability, specific geographical raw material supply and geographical competitive market forces
were  not  considered. All data  is based  upon the  model with  operations on  a two-shift basis.
With these bases, the following information was developed:
       Table 85 — Annual Raw Material Requirements and Estimated Annual Costs
       Table 86 — Annual Package and Package Material Requirements and Estimated Annual Costs
       Table 87 — Annual Wage and Salary Estimated Costs
       Table 88 — Annual Depreciation Costs
       Table 89 — Income Statement Year Ending December 31, 19	2
       Table 90 — Annual Production Schedule Detailed by Month Showing Sales and Inventory Levels
       Table 91 — Balance Sheet at Year-end, December 31, 19_2
       Table 92 — Cash Flow Statement for Year 19_2
       Table 93 — Return on Investment Year 19	2
       Table 94 — Annual Product Mix
       Figure 73 —  Factory Manning and  Organization Chart
Discussion of the schedules are presented on the following pages.
                                  Raw Materials (Table 85)
       This schedule details the raw material requirements necessary to  produce the product mix
included  in  Table 94.  The raw material  prices used in this schedule  are based upon vendor
quotation and include delivery  charges.
                        Packages and Associated Materials (Table 86)
       Table 86  details the packages  and associated materials to satisfy the product mix and the
packaging schedule for the model plant.
                               Wages and Salaries (Table 87)
       Table 87  establishes the wage  and salaries  estimates for the Model. These requirements
were  based  upon the organization shown  in Figure 72. While the salaries assumed may represent
a very subjective viewpoint, these are thought to be representative.  The hourly wage  rate was
calculated by using  the average rate for  SIC 2851  for 1971 from the Statistical Abstract of the
United States, with a factor of 10 per cent added. For second shift requirements a shift differential
of 100/hr was added.  FICA taxes are calculated using current employer percentages. Fringes exclusive
of FICA were estimated at 5 per cent of wage and salary cost.
                                  Depreciation (Table  88)
       Table 88  presents the depreciation costs associated with  the model plant. The straight line
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method was used for calculating depreciation without deducting any salvage costs. The buildings
were depreciated over an 80 year life and the equipment over a 10 year life.
                                Income Statement (Table 89)
       This table was prepared based  on several  assumptions  and estimates which include the
following:
       1.   Selling price was developed using an average from the Current Industrial Reports M28F
           for 1971. The average from this report was increased 4 per cent for industrial shipments
           to adjust for growth rise.
       2.   Estimates were made for "other manufacturing costs" of 500/gal on trade shipments and
           300/gal on industrial shipments. Industrial  shipment  costs are  estimated lower since
           less operating cost is associated with the equipment and filling of large industrial packages.
       3.   The estimate used for selling, general and administrative  expense are directed primarily
           at  selling expense.  For trade sales  an  estimate of 15  per  cent of sales was used,
           and for the  industrial products only 5%. The differences in these percentages reflect
           alternate levels of effort required by a small  industrial manufacturer to service a specific
           industry (or at  best several small manufacturers) compared to servicing a large number
           of retailers.
In addition,  taxes, both federal and local, were estimated and these percentages are  shown  in
the schedule.
                               Production Schedule (Table 90)
       The table presents a detailed estimate breakdown by months of production, shipments and
inventory.  Also included is a  safety  reserve amounting to approximately  5 per cent of annual
shipments.
                                  Balance Sheet (Table 91)
       In  preparing the balance sheet, liabilities were recognized for taxes and accounts payable,
but such items as prepaid  expenses were specifically avoided.
       Inventory  accounts were developed using an average cost basis  and the gallonage shown
in ending inventory in Table 90 for December 31, 19_2.
       Plant financing was assumed to consist of a  capitalization of  one million dollars and  a
bank loan  of four million dollars over a ten-year term  at 7 per cent interest.
       The balance sheet shows negative cash which would indicate the need for at least seasonal
borrowing  currently.  This solution would  become less  acute as interest expense decreases with
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long term debt.
                               Cash Flow Statement (Table 92)
       A  simplified cash flow statement is presented which  assumes that no  change occurs in
accounts receivable, accounts payable and in inventory levels between years.
                               Return  on Investment (Table 93)
       Table 93 presents  returns on  investment calculations  using four  separate calculation
techniques. These include the total gross assets  available  method, the total net assets available
method, stockholders equity plus long term debt method and the stockholders equity method.
                                   Product Mix (Table 94)
       Table 94 shows the product mix assumed for model plant. Fifty per  cent of the industrial
output was selected by the subcontractors in preparing the table. Considering the size of the plant
and the associated difficulties of manufacturing industrial finishes, the following mix was established:
         Gallons        	Name	
       1.   95,000      Monomer modified alkyd for fast dry coatings
       2.   95,000      Acrylic baking  enamel
       3.   190,000      Alkyd urea baking enamels
           380,000      50% of industrial output

C.     Balance Sheet and Operating Statement for Controlled Plant
       The balance  sheet  and operating  statement for the controlled plant were prepared using
the same  assumptions  and basis which  were documented previously for the controlled plant. That
financial information which is changed for the controlled plant solution is as  follows:
       Table 97 — Annual  Depreciation  Costs Including Air Emission Control Devices
       Table 98 —  Income Statement  Year  Ending December  31, 19—2 adjusted  to show the
                     effect of air emission control devices
       Table 99  — Balance sheet at year-end, December  31, 19	2  adjusted to show the effect
                  of air emission control devices
       Table 100 — Cash flow statement year 19	2 adjusted to show the effect of air emission
                    control devices
       Table 101 — Return on investment year 19	2 adjusted to  show the effect of air emission
                    control devices
       Table 102 — Financial information on recommended  air emission control devices
       Each table above is presented in  respective order at the end of this chapter.

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 D.      Cost of Control Other Than Add-on Equipment
        The high costs associated with air pollution control in the paint industry invites consideration
 of alternative means for reduction of emission levels. Significant among these alternatives  is the
 potential for raw material substitution and/or process modification.
 1^	Raw Material Substitution — Appreciable reduction in emissions of air pollutants can  be
 achieved when it is possible to substitute raw materials with compounds which from an air pollution
 standpoint offer more desirable physical and chemical properties. The most beneficial choice  for
 substitution is the solvent  base of the paint since such  materials represent the  major source of
 emissions from paint plants. Paramount among the possibilities for solvent substitution is the use of
 water or the  conversion to water base coatings. Where water based formulations can be developed
 to satisfy any of  a variety of end uses, an order  of magnitude of emission reduction is possible in
 the paint industry. This is not always easily accomplished since product quality must be maintained.
        Significant progress has been made in the paint industry through the development of water
 emulsion trade sales paints. Many of these developments have been achieved without increase in
 cost or sacrifice in quality.
        Current development work is underway on the use of dry powder paint formulations.  Where
 such formulations will fulfill the end-use requirements, significant emission reduction is possible in
 not only  production, but  in paint application  as well.
        Another technology  development which has great potential in reducing solvent emissions,
 particularly by the user,  is the formulation of water reducible industrial coatings. Heretofore, the use
 of water based coatings has been restricted almost exclusively to trade sales products. In the opinion
 of some experts,  use of such industrial coating systems will come to fruition before powder coatings.
        Use  of high  solids systems is a further area for potential  improvement. The net result of
 this  approach is to reduce the amount of solvent present per unit coverage  of the applied coating.
 Consequently, solvent emissions by the user will be reduced.
        Good potential exists  for  reduction in the quantity  of  undesirable emissions  using  either
 alternative solvents or preparations which entirely eliminate the use of solvents. While considerable
development work remains  to be accomplished  in  the "no-solvent" area, a significant effort has
been expended toward the substitution of alternative solvent materials. Much of this effort has been
devoted to substitution with "non-photochemically" reactive solvents. This latter work has been very
successful and a significant switch is now  underway or being contemplated by the industry. Such
conversions are resulting in sizeable reductions in photochemically reactive  emissions by both the
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manufacturer and the user.
        Aside  from consideration of solvents, potential exists for emission  level reduction through
substitution  of other  constituents  in the paint formulation.  Use of the liquid instead of the solid
form of certain raw materials, e.g., phthalic anhydride (PA) in resin manufacture, can result in reduced
emissions. This is economically feasible when large quantities are  being used. Introduction of liquid
materials eliminates the necessity  for evacuation of the equipment during  loading operations. In the
case of phthalic anhydride the potential for emission  is transferred to another point in the process
when the liquid form  is used. Emission potential exists at the heated PA storage tank vent. Such
emission can  be  easily controlled, however, by venting the storage tank  through a water jacketed
vertical  condenser  with provisions for admitting  steam to the jacket. The  tank is  blanketed with
inert gas and appropriate pressure relief control provided. During loading the water cooled condenser
collects PA vapors as a solid which is later melted and returned to the storage tank.
        Raw material substitution  as outlined above  can provide  an excellent  and sometimes  in-
expensive  method  for emission  reduction  by the  manufacturer. Unfortunately, these benefits may
not necessarily accrue  to the users since  raw material substitution can lead to both higher costs
and lower quality.  An example of this which is unrelated to air pollution is the product deterioration
which has  occurred as  the result  of the elimination of mercury fungicides and lead drying agents.
Industry spokesmen point out in this  latter case  that a period as long as several years may  be
required to develop substitute  raw  materials which will restore paint to its former quality.
        In many  cases to date where raw material substitution  has  been made, the net  result
has been either a higher product  cost and/or a lower quality  product. It is the conclusion of some
paint manufacturers that it would be less expensive  overall for  their customers  to add control
equipment for existing solvent emissions than to absorb the cost for special solvent systems. This
factor coupled with the  potential  for degradation in  product  quality  as well as the possibility  for
future regulatory changes, e.g., the exempt solvent definition, suggest that raw material substitution
should be carefully evaluated as an alternative means for control.
2.      Process Modification  — Some potential  exists for reduction in emission through process
modification. Possible modification includes:
        a.   Reduction in use of sparge gases
        b.   Use of adequate or refrigerated condensers
        c.  Use of proper unloading and transfer methods
        d.   Use of liquid slurries in pigment handling
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Taking  maximum  advantage  of these  modifications  can  substantially  reduce  emissions  in
some operations such as resin cooking by the solvent method. The actual  benefits  to be derived
depend on the  specific operation involved and  should be subjected  to a cost/benefit analysis in
relation to corresponding requirements and costs for air pollution control.
E.      Varying Types and Levels of Control
        Varying types and levels of control can be achieved with the thermal  or catalytic afterburner
segments of the air pollution control system for the  paint  plant. However, significant cost variations
will be encountered which are dependent on the variation  in control desired.
        For example,  suppose a  hypothetical thermal  afterburner  is operating at an outlet temper-
ature of 1370ฐF obtained from a burner AT from fuel gas of 550ฐF  and a fume combustion  efficiency
of 90%. If the burner AT is increased by SOT,  the efficiency might, for some  fumes,  increase to
95% and give an outlet temperature of 1450ฐF. For  a situation with these parameters, this variation
in control level  would result in an increase  in  fuel costs of  around  9%  without  heat exchange.
For the same afterburner to which 42% heat exchange  has been added,  the  same  increase in
control  level would result in an increase in fuel  cost that would be less in actual dollars than the
increase for the first case but could amount to about 30% of  the fuel cost of the heat exchanged
afterburner before increasing the temperature.
        In the increased efficiency case above, additional  maintenance  costs would be encountered.
This arises from increased maintenance resulting  from higher temperature  This maintenance  in-
crease  is not an easily assignable cost on  afterburners  since the number of start-ups and shut-
downs  influence  this  cost  markedly.  For the  same operation  cycle,  howpver, maintenance cost
will be significantly higher for the heat exchanger case and will partially offset the lower  fuel cost
indicated above.
        Other operating costs for higher efficiency  operation in the thermal afterburner will not  be
significant. Slight increase in fan  horsepower  requirements, however, might be involved. Operating
labor requirements should be identical for either the high or low efficiency case.
        Higher efficiency levels in baghouse operations are not readily obtainable since these systems
already  operate  at 99+  per cent efficiency (weight basis)  when the system  is in good working
order. Regular  maintenance and  observation will maintain  these systems at  very high  levels of
efficiency.
F.     Impact on Income, Cash Flow and Investment
        The impact of air pollution control costs for  the paint industry will be  significant. Basing  an
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assessment of this impact on the model plant described previously, the following comparison may
be made between the controlled and uncontrolled plants:
                              ANNUAL INCOME STATEMENT
Uncontrolled
plant
$6
5
$1

$

$

,604,400
,020,374
,584,026
761,141
822,885
252,000
570,885
342,531
Controlled
plant
$6,604,400
5,029,602
$1,574,798
761,141
$ 813,657
254,101
$ 559,556
335,733
Change for
controlled
plant
—
+ 9,228
$ - 9,228
—
$- 9,228
+ 2,101
$-11,329
- 6,798
Revenue (net)
Cost of goods sold
Gross profit
Selling, general and admin, expense
Operating income
Interest expense
Income before taxes*
Income taxes
Net income                                  $  228,354        $  223,823          $- 4,531
* Includes local, state and federal taxes.

       This information  indicates a reduction in annual income after tax of $4,531  for the addition
of  air pollution  control equipment to the  model plant. This loss in income amounts to 1.98  per
cent of the total net income of the model plant or an average of $0.006  per gallon of paint produced.
       The  information above regarding loss of income is based on the assumption that the model
plant would  not encounter a  price  increase as a  result  of the effect  of control on its supplier of
purchased resins. Of the 8,115,300 pounds of resin used by the model plant, 1,992,600 pounds of
solvent based  resins are purchased from outside suppliers.  A significant  portion of  the control
cost is directly attributable to resin manufacture. The design basis for  manufactured resin incorpor-
ates a production capacity of 2,166,000 pounds annually.  The average capital cost  of control for
the resin plant  has  been shown  previously  as $26,000.  The operating cost attributable to control
on the model resin plant  at design capacity is as follows:
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   INCREASED ANNUAL MANUFACTURING COST OF RESIN RESULTING FROM CONTROL
       Depreciation (installed cost)                    $2,600
       Annual operating cost                          5,595
       Decrease in operating income                  $8,195
       Interest expense (assumed 7%)                  1,638
       Decrease in pretax income                     $9,833
       Tax reductions (Federal & Local)                 5,900
       Decrease in net income                        $3,933
Applying this reduction in net income to the 2,166,000 pounds of resin used as the design basis, the
model plant will show increased production and interest costs of $0.00182 per pound of resin. With the
assumption that  the outside resin supplier would incur the  same  increase in per pound cost and
pass this  along  as a  cost  increase,  the loss in income to the model plant would be increased
significantly. Applying the $0.00182 per pound cost increase to 1,992,600 pounds of resin purchased
would increase income loss by $3,626.53 annually or to $0.00191  per gallon  of paint produced.
This assumes that  production  of water based latex resins do not require equivalent control devices.
       While the assumption  made above for purchased resin  cost increase is rather general, the
order of magnitude of  increase deserves consideration in all of the financial  calculations relating to
best control. Therefore, in the following financial data the influence of this factor will be pointed as an
effect of purchased resin cost  increase.
       Effect of  control on cash flow  also is significant. Based on  information previously presented
for the model plant, the following comparison can be made:
                               NET CASH FLOW (ANNUALLY)
                                                 Net cash flow
       Uncontrolled plant                           ($14,512)
       Controlled plant                             (   19,043)
       Change in cash flow                         ($  4,531)
       While a cash out flow is indicated for each case,  the  cash  out flow will be increased by
$4,531  for the addition of control equipment.  The negative cash flow calculated suggests that some
seasonal  short-term financing would  be necessary to furnish  cash requirements  and  that such
debt would be increased for  the controlled plant case.
       Each of several methods for assessment of return on investment  illustrates the impact of
addition of air  pollution control. These methods  of calculation and the resultant conclusions have
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been shown previously for the model plant. A summary of the calculations is as follows:
                          RETURN ON INVESTMENT (PER CENT)
                                                                            Change for
                                       Uncontrolled        Controlled          controlled
                                           plant              plant              plant
Total gross assets                          6.53%             6.42%            -1.68%
Total net assets                            6.96%             6.85%            -1.58%
Stockholders' equity plus
  long-term debt                           7.55%             7.43%            -1.59%
Stockholders'equity                       19.70%            19.36%            -1.73%
       The  largest impact indicated from this  summary is  on the owners of the  business or
the stockholders. Based on stockholders' equity, approximately a 1.73% reduction in annual return
results from the control additions.
       Assuming a purchased resin cost increase as outlined previously, a reduction in income of
$3,627 would be encountered with a resultant $220,196  annual income. With this reduced income,
the loss  of return  on  stockholders' equity for the controlled  situation would be 19.04%. On  this
basis, the net reduction in return based on stockholders' equity would be 3.25%.

III.      INDUSTRY WIDE STUDIES
       An assessement of the impact  of best control  on an industry  wide basis can be made
using the following  assumptions:
       1.  "Best Control" will be a requirement for all plants.
       2.  Cost of control  is directly proportioned to overall production rates, i.e., the model plant
           represents the average plant.
While these assumptions present certain inaccuracies,  they should permit a reasonable estimate
of the order of magnitude of control cost. With these above assumptions, the industry wide influences
are reviewed below:
A.     Present Total Cost to Industry to Meet Best Control Requirements
       Paint production during 1972 was at a level  of 930 million gallons per year. A reasonable
basis for estimating the order of magnitude of total cost to industry to meet best control might use
the capital and  operating  costs developed  for the model  plant above  on the basis  of cost per
gallon. With this basis, the approximate costs can  be calculated as shown on the following page.
                                         294

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                     TOTAL COST TO INDUSTRY FOR BEST CONTROL
                                                   Total Cost
       Capital Investment Cost                     $16,200,000
       Annual Operating Cost*                      $ 4,500,000
       OPERATING COSTS PLUS DEPRECIATION
       In the case of capital investment cost,
       the above  does not reflect a credit for
       any existing air pollution control equip-
       ment. The cost information presented is
       based on 1972 monetary values, costs
       and  productivity and  does  not  provide
       escalation factors.
B.     Fifteen Year Projection of the Cost of Control
       Indicated above was  a 1972 paint  production rate of 930  million gallons  per year. Most
of this production was accounted for by a relatively small number of plants. Paint  production is
projected to increase  to 1,320 million gallons per year in 1985. Extrapolating beyond 1985, total
annual paint production could  exceed  1,700 million gallons per year.
       Approximately 20% of the total operating plants produce about 85% of  all coatings. The
industry trend is toward larger plants combined with a tendency to operate these plants on a three-
shift or 24-hour basis. This trend is  expected to continue with  the result that most  increases  in
production will be  due to the installation of new plants of large capacity or by full utilization  of
presently idle capacity rather than by increasing the operating hours.
       Whether new  plants or idle  capacity are utilized,  air  pollution control requirements would
need to increase beyond  the minimum necessary for today's production. A  reasonable basis for
estimating the order of magnitude of future control costs might  include an extrapolation  of cumulative
capital cost and annual operating cost as  a function of the  projected industry  shipment. This
extrapolation could be based on a proportionate  cost per gallon of paint equal to that for the model
plant based on 1972  cost factors. This extrapolation provided the following  estimate of projected
costs:
                    PROJECTED COST OF CONTROL (15 YEAR  PERIOD)
                                                   Total Cost
       Capital Investment Cost                     $30,600,000
       Annual Operating Cost*                      $ 8,500,000
*BASED ON 1,700 MILLION GALLONS
PAINT PRODUCTION EACH YEAR
These estimates are based upon 1972
dollars. Changes in cost due to inflation,
labor productivity, increased taxes, and
other factors could easily swell  the above
total by a factor of two or more.
                                         295

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C.      Sources of Capital For Pollution Control
        Projections  of  capital  investment based  on the model  plant suggest  that,  at present, on
the order of 16 million dollars in expenditures is required to provide best air pollution control. Further
projections suggest that  at least 30.6 million will need  to be expended in the  15 year period after
1972. This represents  a  substantial capital requirement on the particular  industry and the  optimum
method of financing will be dependent on some of the following variables:
        1.  Business condition of the specific paint manufacturer
        2.  Money market or interest rates
        3.  Strength of the equity market
        4.  National monetary valuation and controls
        In the reasonable future, those manufacturers  representing the majority of production will
all probably utilize the following sources of capital:
        1.  Retained earnings
        2.  Long-term borrowing or bonds
        3.  Portions of new equity capital
The financing technique used  will in all  likelihood result  in an increase in the debt/equity ratios
for the industry.
        Accelerated tax credits and accelerated depreciation allowances are expected to be important
factors in offsetting  a portion of the capital requirements. It is anticipated, however, that eventually
the cost of control  will be absorbed  in price increases to the  extent that competition from other
coatings or construction materials will allow.
D.      Industry Structure
        The paint industry has an oligopolistic  structure. That is to say, the majority of production
is controlled  by relatively few companies. Approximately  1,727 paint plants were being  operated
in the United States during 1972. These plants  were either directly owned  or controlled  by 1,365
U.S. companies. This  does not include those plants which make paint components only, such as
resins, but  not finished coatings.
        As  indicated previously, about 20%  of the total number of plants, or  345, produce about
75%  of the total paint production. This 75% of total production  is controlled  by fewer than 200
companies which, in turn, control some of the smaller plants. The distribution of paint  production
among controlling companies is approximately as follows:
                                            296

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                          DISTRIBUTION OF PAINT PRODUCTION
1.7
                                                                    Approximate
                                                 Number of         Percentage of
                                                 Companies       Total Production
        Major Companies                               36               64
        Intermediate Companies                       164               24
        Small Companies                             1,165               12
                                                    1,365              100.0
The above confirms that the paint industry has an oligopolistic structure.
        In spite of this structure, the coatings business is probably unique among major manufactur-
ing industries in that the  very small  producer is able to survive in the face of competition from
some of the largest corporations in the world. While the trend is towards larger plants, it is a slow
process  and  the continued existence of  the small producer is assured  for the foreseeable future.
There are several reasons for this:
        1.  The diversity of products is so large that there will always be a place for the producer
           of low volume specialty items.
        2.  Finished coatings are expensive to ship due to their weight and volume. Consequently,
           the economy benefits  of large operations are  diminished as the shipping distance  is
           increased.
        3.  A  large amount  of technical  assistance is available from raw material  suppliers which
           enables the small company to remain technologically up-to-date.
        4.  The nature of the  manufacturing operations (batch processing  of  relatively small
           quantities)  limits the economy that can be attained in large scale operations. Indeed,
           with the possible exception of filling and warehousing operations, there is little difference
           in  the manner in which the small  plant does things as opposed to the way large plants
           operate.
E.      Product Elasticity — Production Substitution
        The paint  industry  continues  to demonstrate  an  upward  growth pattern.  This  growth
continues even during periods of rapidly increasing prices. The industry  exhibits a strong indication
of price  inelasticity, i.e., demand and total receipts do not significantly  change  with  rising prices.
In the  case of increasing prices, the separation  of "real"  and inflationary  related  contributions  is
difficult.  In the case of price increases associated with  air emission control devices, little  if  any
effect on demand inelasticity can be projected.
                                           297

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       Future increases in price will be influenced by a number of cost factors  only one of which
is  projected air pollution control costs. Perhaps more significant to the paint industry  will be cost
increases from the following areas:
       1.  Inflation
       2.  Labor productivity reduction and cost increase
       3.  Energy cost increases
       4.  Water treatment and solid waste disposal costs
       5.  OSHA regulations
Also to be considered in price increase is product reformulation in terms  of quality or of pollution
control requirements of the user.
       Product  substitution  is also a  significant factor  in the  present era  of rapid technological
growth. Product substitution has been significant in recent years in the following areas:
       1.  Wall coverings
       2.  Paneling
       3.  Plastics
It is anticipated that a high level of product substitution will continue in the  above areas and extend
into other areas.  However, for the foreseeable future, it  is not anticipated that air pollution control
costs alone will cause a substantial increase in product substitution.
                                           298

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                                         TABLE 64
                      SPECIFICATIONS FOR ABATEMENT EQUIPMENT

1.     SCOPE
      A. This specification  covers  vendor requirements  for air pollution control equipment for the
subject process. The intent of the specification is to describe the service as thoroughly as possible
so as to secure vendor's proposal  for equipment which is suitable in every respect for the service
intended. Basic information is tabulated in sections 2 and 3. The vendor should specify any of the
performance characteristics which cannot  be guaranteed without samples of process effluent.
      B. The vendor shall submit a bid showing three separate prices as described below.
       1.  All labor, materials,  equipment and services to furnish one pollution abatement device
           together with the following:
           a.   All ladders, platforms  and other  accessways to  provide convenient access  to all
               points requiring observation or maintenance
           b.   Foundation  bolts as required
           c.   Six (6) sets of drawings,  instructions, spare parts list, etc., pertinent to the above
       2.  Auxiliaries including:
           a.   Fan(s)
           b.   Pump(s)
           c.   Damper(s)
           d.   Conditioning Equipment
           e.   Dust Disposal Equipment
       3.  A turnkey installation of  the  entire system  including the following installation costs:
           a.   Engineering
           b.   Foundations & Support
           c.   Ductwork
           d.   Stack
           e.   Electrical
           f.    Piping
           g.   Insulation
           h.   Painting
           i.   Startup
                                        299

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                                    TABLE 64 (continued)

           k.   Performance Test
           I.   Other (including general tradework such as erection, rigging, etc.)
      C. For the "pollution abatement device only" quotation, the vendor shall furnish the equipment
FOB point of manufacture, and shall furnish as a part of this project competent supervision of the
erection, which shall be by others.
      D. Vendor shall furnish* the following drawings, etc., as a minimum:
        1.  With his proposal:
           a.   Plan and elevation showing general arrangement
           b.   Typical details of collector internals proposed
           c.   Data  relating projected performance with respect to pressure drop, gas absorption
               efficiency and particulate removal efficiency to operating parameters such as gas flow
        2.  Upon receipt of order:
           a.   Proposed schedule of design and delivery
        3.  Within 60 days of order:
           a.   Complete drawings of equipment for approval by customer
        4.  30 days prior to shipment:
           a.   Certified drawings of equipment, six sets
           b.   Installation instructions, six sets
           c.   Starting  and operating instructions, six sets
           d.   Maintenance instructions and recommended  spare parts lists, six sets
      E. The design and construction of the collector and auxiliaries shall conform to the  general
conditions given in  Section 5, and to good engineering practice.
2.    PROCESS PERFORMANCE GUARANTEE
      A. The equipment will be guaranteed to reduce the particulate and/or gas contaminant loadings
as indicated in the  service description.
      B. Performance test will be conducted in accordance with  IGCI test methods where applicable.
      C. Testing shall be conducted at a time  mutually agreeable to the customer and the vendor.
      D. The cost  of the performance test is to be included in vendor's turnkey proposal.

*This is a  typical  request. The member companies are  NOT  to furnish this material under the
present project.

                                         300

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                                    TABLE 64 (continued)
      E. In the event the equipment  fails to comply with the guarantee at the  specified  design
conditions, the vendor shall make every effort to correct any defect expeditiously at his own expense.
Subsequent retesting to obtain a satisfactory result shall be at the vendor's expense.
3.    GENERAL CONDITIONS
      A. Materials and Workmanship
       Only new materials of the best quality shall be used in the manufacture of items covered
by this specification.  Workmanship shall be of high quality and performed by competent workmen.
      B. Equipment
       Equipment not of vendor's manufacture furnished as a part of this collector shall be regarded
in every respect as though it were of vendor's original manufacture.
      C. Compliance with Applicable Work Standards and  Codes
       It shall be the responsibility of the vendor to design  and manufacture the equipment specified
in compliance with the practice specified by applicable  codes.
      D. Delivery Schedules
       The vendor shall arrange delivery of equipment  under this contract  so  as to provide for
unloading at the job  site within a time period specified by the customer. Vendor  shall provide for
expediting and following shipment of materials to the extent  required to comply with delivery specified.
                                        301

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                                         TABLE 65
                       INSTRUCTIONS FOR SUBMITTING COST DATA

Two forms (two copies  each)  are enclosed  with each  specification.  These  are for submitting:
       (A)  Estimated Capital Cost Data
       (B)  Annual Operating Cost Data
These forms will also be  used to exhibit averages of the three cost estimates for each process and
equipment type. Because your costs will be  averaged with  those  of  other IGCI  members,  it is
necessary to prepare them in accordance with instructions given in the following paragraphs.
       (A)  Estimated Capital Cost Data
The upper part of this form  should already be  filled out for the particular application when you
receive it. This information  on operating  conditions should be identical to that in the specification
and is repeated here only for the convenience of those reading the form.

You should fill in the dollar amounts estimated  in the appropriate spaces  on the bottom half of
the form.  It should not be  necessary to add any information  other than the dollar  amounts. If
you wish to provide a description of the equipment proposed, please do so on one or more separate
sheets of paper, and  attach  it to the form.  If  any item is not involved in the  equipment you  are
proposing,  please indicate this by writing "none" in the space rather than leaving it blank or using
a zero.
       (1) The "gas cleaning device" cost should be reported just as you  would report a flange-
to-flange equipment sale to the IGCI.  That is, a complete device including necessary auxiliaries
such as power supplies,  mist eliminators, etc. Do NOT include such items as fans, solids handling
equipment, etc., unless these are an integral part of your gas cleaning device.
       (2) "Auxiliaries"  are those  items of equipment which are frequently supplied with the gas
cleaning device. There is  a purely arbitrary definition of those items included here and those included
in  the "Installation" Costs.  Do NOT include any of the cost of erecting or  installing auxiliaries in
this category.
       (3) "Installation  Cost"  should include all of the material not  in (1)  or (2) and  the  field
labor required to complete a turnkey installation. In cases where the equipment supplier ordinarily
erects the equipment but does not supply labor for foundations, etc., it is necessary to include an
estimated cost for these items. General tradework, including rigging, erection, etc. should be included
in  the "Other" category.
                                           302

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                                    TABLE 65 (continued)

The installation should  be estimated for a  new plant,  or  one in  which there are no limitations
imposed by the arrangement of existing equipment. Installation labor should be  estimated on the
basis that the erection  will take place in an area  where labor rates are  near the  U.S. average,
and the distance from your plant is no more than 500 miles. Milwaukee, Wisconsin is an example
of a city with near-average labor rates.
       (B)  Annual Operating Cost Data
Some of the information will be supplied by Air Resources, such as  unit  costs for labor and  utilities,
and annualized capital charges. You should  fill in  the usage figures for the complete abatement
system in the units indicated below. Please include the unit price.
                        Labor                   hr/year
                        Maintenance Materials    $/year
                        Replacement Parts       $/year
                        Electric Power            kw-hr/year
                        Fuel                     MMBtu/year
                        Water (Process)          MM gal/year
                        Water (Cooling)           MM gal/year
                        Chemicals               $/year
Air Resources will average the consumption figures reported, and convert them to dollar values for
inclusion in the final report.

Be sure  that the operating factor,  in hours per year,  supplied by ARI,  is  used for estimating the
utility and labor requirements.
                                           303

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                                        TABLE 66


                    THERMAL AFTERBURNER PROCESS DESCRIPTION

                          FOR RESIN REACTOR SPECIFICATION
    This specification describes the requirements for a thermal combustion system for abatement of
the hydrocarbon emissions from the resin production facility of a paint and varnish plant. The system will
be similar to that shown in Figure 9. All reactor thinning tanks and product rundown tanks will be vented
to the collection system. Dilution air will be supplied through a hood over the resin filter press(es). A
minimum flow damper is to be supplied in this part of the ventilation system. It is to be sized to allow fora
maximum fume concentration of40%LEL in the fully closed position. A high velocity Venturi section is to
be located at the afterburner inlet to assure gas flow is in excess of flame propagation velocity at 112
design  flow rate.

    The afterburner is to be natural gas fired. Sufficient gas, having a specific  gravity of 0.60 and an
upper heating value of 1040 Btu/SCF, is available at a pressure of 1.0 psig.

    The exhaust gas contains sufficient oxygen, greater than 16% Oa fo allow firing of the afterburner
with a raw gas or process air burner. A  combustion air system is not required. Fume load to the
incinerator is composed of 75% kettle emission and 25% from other sources. Average emissions are
60% of peak. The system is to be designed on peak emission but operating costs are to be based on
average emissions. Operating conditions listed are based on peak emissions. Fume destruction in
burner is to be calculated as follows:

        10% for catalytic units with or without heat exchange

        10% for thermal units with heat exchange

       20% for thermal units without heat exchange

       Please fill in estimated efficiency of afterburner and burner duty.

    The afterburner is to be supplied with a suitable control panel and all equipment is to be designed
for outdoor operation. Incinerator operating and safety  controls are to be designed to meet  F.I.A.
(Factory Insurance Association) requirement. All dampers are to be pneumatically operated and
contain an integral fail safe air reservoir. The system is to automatically divert in the event of low flow,
high afterburner temperature,  high reactor pressure,  and afterburner preheat burner failure. The
exhaust system should also be purged with inert gas on fan failure or loss of flow. Damper operating is
to be  sequential  with the position switches mounted on the damper arm and  not the operator. The
system fan shall be located after the preheat burner or the incinerator outlet and  shall be constructed to
withstand 200ฐF higher than design operating temperature. The fan shall have a vee belt drive and fan
and motor shall have the capacity to overcome the pressure drop of the ductwork, afterburner and any
heat exchanger that may be used. System ductwork should be sized for a maximum &Pof2in. w.c.hot.
The fan  motor  may be sized for restricted flow cold start. The ductwork to the incinerator should be
heated either by the use of a double manifold or hot gas recycle or a  combination of both.

    The heat exchanger when included is to be the parallel flow shell and tube type and designed to
operate at an afterburner outlet temperature of 1500ฐF. Maximum exchanger pressure drop, both sides,
should not exceed  a  total of 6 in. w.c. hot. Dirty gas is to flow through the tube side.
                                         304

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                                     TABLE 66 (Continued)
                                       INSTALLATION

    A complete turnkey proposal including ductwork, structural steel, fuel and inert gas piping, etc., is
requested. For the purpose of this proposal fan and damper including operators are to be considered
as auxiliary.  The controls and control cabinet are to be included with the afterburner price. The
afterburner will be assumed to be located on a structural steel  base on  the resin plant roof. No
modification to the building structural steel is required. A tie through  the roof from  the base to the
building  steel is required. The base and tie in are part of the installed  structural cost. All utilities are
available within 30 ft of the control cabinet, motor, and burner. Plant air is available at 100 psig and
located within 30 ft. Inert gas is available and will require 30 ft of piping from supply to ductwork. The
existing stack can be used  for the  diversion stack.  A 10 ft exhaust stack will be mounted on the
afterburner,  double manifold or exhaust fan. A total of thirty-five (35) feet of new  exhaust ductwork and
twenty-five (25) feet of double manifold will be required.
                                          305

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                            TABLE 67
         THERMAL AFTERBURNER OPERATING CONDITIONS

               FOR RESIN REACTOR SPECIFICATION
                      (Without Heat Exchange)
                                               Small         Large

Process Conditions

    Reactors, Number                               1             2
       Size each, gal                            1,700         5,000
    Hcbn Emission Max, Ib/hr                       42.4           254
    Hcbn Emission Ave, Ib/hr                       24.7           148
    Total Exhaust Rate, SCFM                     1,000         6,000
    Exhaust Temperature, ฐF                        110           110
    Heat of Combustion of
       Reactor Fume, Btu/lb                    17,000        17,000
    Hydrocarbon Concentration
       Maximum, Btu/SCF                         12            12
    Average, Btu/SCF                               7             7
    Unit Residence Time, sec @ 1500ฐF               0.6           0.6


Afterburner Without Heat Exchange

    Unit Inlet, ฐF                                  325           325
    Burner AT from Fuel Gas, ฐF                    550           550
   * Burner AT from Flame Combustion, ฐF            125           125
    Burner Outlet Temperature, ฐF                  1,000         1,000
  ** Unit A7 from Thermal Combustion, ฐF             435           435
    Unit Outlet Temperature, ฐF                    1,435         1,435
    Burner Duty, MM Btu/hr                        	          	


Estimated Unit Removal Efficiency                   	          	
   * Assumes 20% fume combustion in burner flame
  ** Assumes 95% overall fume combustion
                                306

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                            TABLE 68
         THERMAL AFTERBURNER OPERATING CONDITIONS

               FOR RESIN REACTOR SPECIFICATION
                      (Without Heat Exchange)
                                               Small         Large

Process Conditions

    Reactors, Number                               1             3
        Size each, gal                            5,000         5,000
    Hcbn Emission Max, Ib/hr                       125           423
    Hcbn Emission Ave, Iblhr                        74           246
    Total Exhaust Rate, SCFM                     3,000        10,000
    Exhaust Temperature, ฐF                        110           110
    Heat of Combustion of
        Reactor Fume, Btulib                     17,000        17,000
    Hydrocarbon Concentration
        Maximum, Btu/SCF                         12            12
    Average, Btu/SCF                               7             7
    Unit Residence Time, sec @ 1500ฐF              0.6           0.6


Afterburner Without Heat Exchange

    Unit Inlet, ฐF                                  325           325
    Burner AT from Fuel Gas, ฐF                    550           550
   "Burner AT" from Flame Combustion, ฐF            125           125
    Burner Outlet Temperature,  ฐF                  1,000         1,000
  **Unit AT from Thermal Combustion, ฐF             435           435
    Unit Outlet Temperature, ฐF                    1,435         1,435
    Burner Duty, MM Btu/hr                        	          	


Estimated Unit Removal Efficiency                   	          	
   * Assumes 20% fume combustion in burner flame
  ** Assumes 95% overall fume combustion
                              307

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                            TABLE 69
         THERMAL AFTERBURNER OPERATING CONDITIONS

               FOR RESIN REACTOR SPECIFICATION
                       (With Heat Exchange)
                                               Small         Large

Process Conditions

    Reactors, Number                                             2
        Size each, gal                                         5,000
    Hcbn Emission Max, Ib/hr                                    254
    Hcbn Emission Ave, Ib/hr                                     148
    Total Exhaust Rate, SCFM                                   6,000
    Exhaust Temperature, ฐF                                     110
    Heat of Combustion of
        Reactor Fume, Btu/lb                                  17,000
    Hydrocarbon Concentration
        Maximum, Btu/SCF                                        12
    Average, Btu/SCF                                             7
    Unit Residence Time, sec @ 1500ฐF                            0.6


Afterburner with Heat Exchange

    Inlet Tube Side, ฐF                                          325
    Unit Inlet, ฐF                                                825
    Burner AT from Fuel Gas, ฐF                                  115
   * Burner AT from Flame Combustion, ฐF                            60
    Burner Outlet Temperature, ฐF                                1,000
  ** Unit AT from Thermal Combustion, ฐF                          500
    Unit Outlet Temperature, ฐF                                  1,500
    Outlet Shell Side, ฐF                                        1,030
    Burner Duty, MM Btu/hr                                      	
    Exchanger Duty, MM Btu/hr                                   	
    Thermal Efficiency                                          -42%
    Overall Heat Trans. Coef., U                                  	
    Tube Surface Area, ft2                                       	
Estimated Afterburner Removal Efficiency
   "Assumes 10% fume combustion in burner flame
  "Assumes 95% overall fume combustion
                               308

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                             TABLE 70
         THERMAL AFTERBURNER OPERATING CONDITIONS

               FOR RESIN REACTOR SPECIFICATION
                       (With Heat Exchange)
                                               Small         Large

Process Conditions

    Reactors, Number                                1            3
        Size each, gal                           5,000         5,000
    Hcbn Emission Max, Ib/hr                       127          423
    Hcbn Emission Ave, Ib/hr                         74          246
    Total Exhaust Rate, SCFM                     3,000        10,000
    Exhaust Temperature, ฐF                        110          110
    Heat of Combustion of
        Reactor Fume, Btulib                    17,000        17,000
    Hydrocarbon Concentration
        Maximum, BtulSCF                          12            12
    Average, BtulSCF                                7            7
    Unit Residence Time, sec @ 1500ฐF              0.6           0.6


Afterburner with Heat Exchange

    Inlet Tube Side, ฐF                             325          325
    Unit Inlet, ฐF                                   825          825
    Burner AT from Fuel Gas, ฐF                     115          115
   * Burner A7 from Flame Combustion, ฐF              60            60
    Burner Outlet Temperature,  ฐF                  1,000         1,000
  ** Unit AT from Thermal Combustion, ฐF              500          500
    Unit Outlet Temperature, ฐF                    1,500         1,500
    Outlet Shell Side, ฐF                          1,030         1,030
    Burner Duty, MM Btu/hr                        	          	
    Exchanger Duty, MM Btu/hr                     	          	
    Thermal Efficiency                            -42%        -42%
    Overall Heat Trans. Coef., U                    	          	
    Tube Surface Area, ft2                         	          	
Estimated Afterburner Removal Efficiency
   "Assumes 10% fume combustion in burner flame
  **Assumes 95% overall fume combustion
                               309

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                                        TABLE 71


                    THERMAL AFTERBURNER PROCESS DESCRIPTION

                           FOR OPEN KETTLE SPECIFICATION
    This specification describes the requirements for a thermal combustion system for abatement of
the hydrocarbon emissions from the resin production facility of a paint and varnish plant. The system will
be similar to that shown in Figure 9. All reactor thinning tanks and product rundown tanks will be vented
to the collection system. Dilution air will be supplied through a hood over the resin filter press(es). A
minimum flow damper is to be supplied in this part of the ventilation system. It is to be sized to allow fora
maximum fume concentration of 40 % LEL in the fully closed position. A high velocity Venturi section is to
be located at the afterburner inlet to assure gas flow is in excess of flame propagation velocity at 1/2
design flow rate.

    The afterburner is to be natural gas fired. Sufficient gas, having a specific  gravity of 0.60 and an
upper heating value of 1040 Btu/SCF, is available at a pressure of 1.0 psig.

    The exhaust gas contains sufficient oxygen, greater than 16% 02, to allow firing of the afterburner
with a raw gas or process air burner. A combustion air system is not required. Fume load to the
afterburner is composed  of 75% kettle emission and 25% from other sources. Average emissions are
60% of peak. The system is to be designed on peak emission but operating costs are to be based on
average emissions. Operating conditions listed are based on peak emissions. Fume destruction in
burner is to be calculated as follows:

       10% for catalytic units with or without heat exchange

       10% for thermal units with heat exchange

       20% for thermal units without heat exchange

       Please fill in estimated efficiency of afterburner and burner duty.

    The afterburner is to be supplied with a suitable control panel and all equipment is to be designed
for outdoor  operation. Afterburner operating and safety  controls are to be designed to meet F.I.A.
(Factory Insurance Association)  requirement. All dampers are to be pneumatically operated and
contain an integral fail safe air reservoir. The system  is to automatically divert in the event of low flow,
high afterburner temperature,  high reactor pressure,  and afterburner preheat burner failure. The
exhaust system should also be purged with inert gas  on fan failure or loss of flow. Damper operating is
to be sequential with the position switches mounted on the damper arm and  not the operator. The
system fan shall be located after the preheat burner or the afterburner outlet and shall be constructed to
withstand 200ฐF higher than design operating temperature. The fan shall have a vee belt drive and fan
and motor shall have the capacity to overcome the pressure drop of  the ductwork, afterburner and any
heat exchanger that may be used. System ductwork should be sized for a maximum AP of 2 in. w.c. hot.
The fan motor  may be sized for restricted flow cold start. The ductwork to the afterburner should be
heated either by the use  of a double manifold or hot gas recycle or a combination of both.

    The heat exchanger when included is to be the parallel flow shell and tube type and designed to
operate at an afterburner outlet temperature of 1500ฐF. Maximum exchanger pressure drop, both sides,
should not exceed a  total of 6 in. w.c. hot. Dirty gas is to flow through the  tube side.
                                        310

-------
                                  TABLE 71  (Continued)
                                       INSTALLATION

    A complete turnkey proposal including ductwork, structural steel, fuel and inert gas piping, etc., is
requested. For the purpose of this proposal fan and damper including operators are to be considered
as auxiliary.  The controls and control cabinet are to be included with the afterburner  price. The
afterburner will be assumed to be located on a structural steel  base on the resin plant roof.  No
modification to the building structural steel is required. A tie through the roof from the base to the
building  steel is required. The base and tie in are part of the  installed structural cost. All utilities are
available within 30 ft of the control cabinet, motor, and burner. Plant air is available at 100 psig and
located within 30 ft. Inert gas is available and will require 30 ft of piping from supply to ductwork. The
existing stack can be used for the  diversion stack.  A 10 ft exhaust stack will be mounted on the
afterburner,  double manifold or exhaust fan. A total of thirty-five (35) feet of new exhaust ductwork and
twenty-five (25) feet of double  manifold will be required.
                                           311

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                            TABLE 72
         THERMAL AFTERBURNER OPERATING CONDITIONS

                FOR OPEN KETTLE SPECIFICATION
                      (Without Heat Exchange)
                                               Small         Large

Process Conditions

    Kettles, Number                                 2             4
        Size each, gal                             300           300
    Hcbn Emission Max, Ib/hr                        45            90
    Hcbn Emission Ave, Ib/hr                       26.2            52
    Total Exhaust Rate, SCFM                     1,000         2,000
    Exhaust Temperature, ฐF                         80            80
    Heat of Combustion of
        Kettle Fume, Btu/lb                       16,000        16,000
    Hydrocarbon Concentration
        Maximum, Btu/SCF                         12            12
    Average, Btu/SCF                               7             7
    Unit Residence Time, sec @ 1500ฐF               0.6           0.6


Afterburner Without Heat Exchange

    Unit Inlet, ฐF                                  300           300
    Burner A7 from Fuel Gas, ฐF                    575           575
   * Burner AT from Flame Combustion, ฐF            125           125
    Burner Outlet Temperature,  ฐF                  1,000         1,000
  ** Unit AT from Thermal Combustion, ฐF             435           435
    Unit Outlet Temperature, ฐF                   .1,435         1,435
    Burner Duty, MM Btu/hr                        	          	


Estimated Unit Removal Efficiency                   	          	
   * Assumes 20% fume combustion in burner flame
  ** Assumes 95% overall fume combustion
                              312

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                            TABLE 73
         THERMAL AFTERBURNER OPERATING CONDITIONS

                 FOR OPEN KETTLE SPECIFICATION
                      (Without Heat Exchange)
                                               Small         Large

Process Conditions

    Kettles, Number                                  1             6
        Size each, gal                            300           300
    Hcbn Emission Max, Ib/hr                       22.5           135
    Hcbn Emission Ave, Ib/hr                       13.1          78.8
    Total Exhaust Rate, SCFM                      500         3,000
    Exhaust Temperature, ฐF                         80            80
    Heat of Combustion of
        Kettle Fume, Btu/lb                      16,000        16,000
    Hydrocarbon Concentration
        Maximum, Btu/SCF                         12            12
    Average, Btu/SCF                                7             7
    Unit Residence Time, sec @ 1500ฐF              0.6           0.6


Afterburner Without Heat Exchange

    Unit Inlet, ฐF                                  300           300
    Burner AT from Fuel Gas, ฐF                    575           575
   * Burner AT from Flame Combustion, ฐF            125           125
    Burner Outlet Temperature,  ฐF                  1,000         1,000
  ** Unit AT from Thermal Combustion, ฐF             435           435
    Unit Outlet Temperature, ฐF                    1,435         1,435
    Burner Duty, MM Btu/hr                        	          	
Estimated Unit Removal Efficiency
   "Assumes 20% fume combustion in burner flame
  ** Assumes 95% overall fume combustion
                               313

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                                        TABLE 74


                   CATALYTIC AFTERBURNER PROCESS DESCRIPTION

                          FOR RESIN REACTOR SPECIFICATION
    This specification describes the requirements for a catalytic combustion system for abatement of
the hydrocarbon emissions from the resin production facility of a paint and varnish plant. The system will
be similar to that shown in Figure 9.'All reactor thinning tanks and product rundown tanks will be vented
to the collection system. Dilution air will be supplied through a hood over the resin filter press(es). A
minimum flow damper is to be supplied in this part of the ventilation system. It is to be sized to allow for a
maximum fume concentration of40%LELin the fully closed position. A high velocity Venturi section is to
be located at the afterburner inlet to  assure gas flow is in excess of flame propagation velocity at 112
design  flow rate.

    The afterburner is to be natural gas fired. Sufficient gas, having a specific  gravity of 0.60 and an
upper heating value of 1040 Btu/SCF,  is available at a pressure of 1.0 psig.

    The exhaust gas contains sufficient oxygen, greater than 16% Oz to allow firing of the afterburner
with a raw gas or process air burner.  A combustion air system is not required. Fume load to the
afterburner is composed of 75% kettle emission and 25% from other sources. Average emissions are
60% of peak. The system is to be designed on peak emission but operating costs are to be based on
average emissions. Operating conditions listed  are based on peak emissions. Fume destruction in
burner is to be calculated as follows:

        10% for catalytic units with or without heat exchange

        10% for thermal units with heat exchange

        20% for thermal units without heat exchange

        Please fill in estimated efficiency of afterburner and burner duty, catalyst face  velocity, and
        catalyst volume.

    The afterburner is to be supplied with a suitable control panel and all equipment is to be designed
for outdoor operation. Afterburner operating and safety controls are to be designed to meet F.I.A.
(Factory Insurance Association)  requirement. All  dampers are to be pneumatically operated and
contain an integral fail safe air reservoir. The system is to automatically divert in the event of low flow,
high afterburner temperature,  high reactor pressure,  and afterburner preheat burner failure. The
exhaust system should also be purged with inert gas on fan failure or loss of flow. Damper operating is
to be sequential with the position switches mounted on the damper arm and not the operator. The
system fan shall be located after the preheat burner or the afterburner outlet and shall be constructed to
withstand 200ฐFhigher than design operating temperature. The fan shall have a vee belt drive and fan
and motor shall have the capacity to overcome the pressure drop of  the ductwork, afterburner and any
heat exchanger that may be used. System ductwork should be sized for a maximum APof2/n. w.c.hot.
The fan  motor  may be sized for restricted flow cold start. The ductwork to the afterburner should  be
heated either by the use of a double manifold or hot gas recycle or a combination of both.

    The heat exchanger when included is to be the parallel flow shell and tube type  and designed to
operate  at an afterburner outlet temperature of 1200ฐF. Maximum exchanger pressure  drop, both sides,
should not exceed a total of 6 in. w.c. hot. Dirty gas is to flow through the tube side.

'Appendix B
                                         314

-------
                                    TABLE 74 (Continued)
                                       INSTALLATION

    A complete turnkey proposal including ductwork, structural steel, fuel and inert gas piping, etc., is
requested. For the purpose of this proposal fan and damper including operators are to be considered
as auxiliary.  The controls and control cabinet are to be included with the afterburner price. The
afterburner will be assumed to be located on a structural steel  base on the resin plant roof. No
modification to the building structural steel is required. A tie through  the roof from  the base to the
building  steel is required. The base and tie in are part of the installed  structural cost. All utilities are
available within 30 ft of the control cabinet, motor, and burner. Plant air is available at 100 psig and
located within 30 ft. Inert gas is available and will require 30 ft of piping from supply to ductwork. The
existing stack can be used  for the  diversion stack.  A 10 ft exhaust stack will be mounted on the
afterburner, double manifold or exhaust fan. A total of thirty-five (35) feet of new exhaust ductwork and
twenty-five (25) feet of double manifold will be required.
                                           315

-------
                            TABLE 75
         CATALYTIC AFTERBURNER OPERATING CONDITIONS

               FOR RESIN REACTOR SPECIFICATION
                      (Without Heat Exchange)
                                               Small        Large

Process Conditions

    Reactors, Number                                1            2
        Size each, gal                           1,700        5,000
    Hcbn Emission Max, Ib/hr                      42.4          254
    Hcbn Emission Ave, Ib/hr                       24.7          148
    Total Exhaust Rate, SCFM                     1,000        6,000
    Exhaust Temperature, ฐF                        110          110
    Heat of Combustion of
        Reactor Fume, Btulib                    17,000        17,000
    Hydrocarbon Concentration
        Maximum, Btu/SCF                          12           12
    Average, Btu/SCF                                7            7


Afterburner Without Heat Exchange

    Unit Inlet, ฐF                                   300          300
    Burner A7 from Fuel Gas, ฐF                     240          240
   * Burner AT from Flame Combustion, ฐF              60           60
    Burner Outlet Temperature, ฐF                    600          600
  ** Unit AT" from Thermal Combustion, ฐF              500          500
    Unit Outlet Temperature, ฐF                    1,100         1,100
    Burner Duty, MM Btu/hr                       	          	


Estimated Unit Removal Efficiency                   	          	
  ***Catalyst Face Velocity, SF/min
    Catalyst Volume, ft3
   ''Assumes 10% fume combustion in burner flame
  ** Assumes 95% overall fume combustion
 *** Basis 70ฐF exhaust temperature
                               316

-------
                            TABLE 76
        CATALYTIC AFTERBURNER OPERATING CONDITIONS

               FOR RESIN REACTOR SPECIFICATION
                      (Without Heat Exchange)
                                               Small         Large

Process Conditions

    Reactors, Number                                1             3
        Size each, gal                            5,000         5,000
    Hcbn Emission Max, Ib/hr                       127           423
    Hcbn Emission Ave, Ib/hr                        74           246
    Total Exhaust Rate, SCFM                     3,000        10,000
    Exhaust Temperature, ฐF                        110           110
    Heat of Combustion of
        Reactor Fume, Btulib                     17,000        17,000
    Hydrocarbon Concentration
        Maximum, Btu/SCF                         12            12
    Average, Btu/SCF                                7             7


Afterburner Without Heat Exchange

    Unit Inlet, ฐF                                  300           300
    Burner AT from Fuel Gas, ฐF                    240           240
   * Burner AT from Flame Combustion, ฐF             60            60
    Burner Outlet Temperature,  ฐF                   600           600
  ** Unit AT from Thermal Combustion, ฐF             500           500
    Unit Outlet Temperature, ฐF                    1,100         1,100
    Burner Duty, MM Btu/hr                        	          	


Estimated Unit Removal Efficiency                   	          	
  ""Catalyst Face Velocity, SF/min
    Catalyst Volume, ft3
   "Assumes 10% fume combustion in burner flame
  ** Assumes 95% overall fume combustion
 *** Basis 70ฐF exhaust temperature
                              317

-------
                            TABLE 77
         CATALYTIC AFTERBURNER OPERATING CONDITIONS

               FOR RESIN REACTOR SPECIFICATION
                       (With Heat Exchange)
                                               Small         Large

Process Conditions

    Reactors, Number                                             2
        Size each, gal                                         5,000
    Hcbn Emission Max, Ib/hr                                    254
    Hcbn Emission Ave, Ib/hr                                     148
    Total Exhaust Rate, SCFM                                   6,000
    Exhaust Temperature, ฐF                                     110
    Heat of Combustion of
        Reactor Fume, Btulib                                  17,000
    Hydrocarbon Concentration
        Maximum, BtulSCF                                        12
    Average, Btu/SCF                                             7


Afterburner with Heat Exchange

    Inlet Tube Side, ฐF                                          300
    Unit Inlet, ฐF                                                500
    Burner AT from Fuel Gas, ฐF                                    40
   * Burner A7 from Flame Combustion, ฐF                            60
    Burner Outlet Temperature, ฐF                                 600
  ** Unit AT from Thermal Combustion, ฐF                          500
    Unit Outlet Temperature,  ฐF                                  1,100
    Outlet Shell Side, ฐF                                         915
    Burner Duty, MM Btu/hr                                      	
    Exchanger Duty, MM  Btu/hr                                   	
    Thermal Efficiency                                          -23%
    Overall Heat Trans. Coef., U                                  	
    Tube Surface Area, ft2                                       	
Estimated Unit Removal Efficiency
  """Catalyst Face Velocity, SF/min
    Catalyst Volume, ft3
   "Assumes 10% fume combustion in burner flame
  "" Assumes 95% overall fume combustion
 ""Basis 70ฐF exhaust temperature
                               318

-------
                             TABLE 78
         CATALYTIC AFTERBURNER OPERATING CONDITIONS

                FOR RESIN REACTOR SPECIFICATION
                        (With Heat Exchange)
                                                Small         Large

Process Conditions

    Reactors, Number                                1             3
        Size each, gal                            5,000         5,000
    Hcbn Emission Max, Ib/hr                       127           423
    Hcbn Emission Ave, Iblhr                        74           246
    Total Exhaust Rate, SCFM                      3,000        10,000
    Exhaust Temperature, ฐF                        110           110
    Heat of Combustion of
        Reactor Fume, Btu/lb                     17,000        17,000
    Hydrocarbon Concentration
        Maximum, Btu/SCF                          12            12
    Average, Btu/SCF                                7             7


Afterburner with Heat Exchange

    Inlet Tube Side, ฐF                             300           300
    Unit Inlet, ฐF                                   500           500
    Burner AT from Fuel Gas, ฐF                      40            40
   * Burner AT from Flame Combustion, ฐF             60            60
    Burner Outlet Temperature, ฐF                   600           600
  ** Unit AT from Thermal Combustion, ฐF             500           500
    Unit Outlet Temperature,  ฐF                     1,100         1,100
    Outlet Shell Side, ฐF                            915           915
    Burner Duty, MM Btu/hr                         	          	
    Exchanger Duty, MM Btu/hr                      	          	
    Thermal Efficiency                            -23%         -23%
    Overall Heat Trans. Coef., U                     	          	
    Tube Surface Area, ft2                          	          	
Estimated Unit Removal Efficiency
   "Catalyst Face Velocity, SF/min
    Catalyst Volume, ft3
   * Assumes 10% fume combustion in burner flame
  ** Assumes 95% overall fume combustion
 *** Basis 70ฐF exhaust temperature


                                 319

-------
                                        TABLE 79


                   CATALYTIC AFTERBURNER PROCESS DESCRIPTION

                           FOR OPEN KETTLE SPECIFICATION
    This specification describes the requirements for a catalytic combustion system for abatement of
the hydrocarbon emissions from the resin production facility of a paint and varnish plant. The system will
be similar to that shown in Figure 9. * All reactor thinning tanks and product rundown tanks will be vented
to the collection system. Dilution air will be supplied through a hood over the resin filter press(es). A
minimum flow damper is to be supplied in this part of the ventilation system. It is to be sized to allow for a
maximum fume concentration of 40 %LEL in the fully closed position. A high velocity Venturi section is to
be located at the afterburner inlet to  assure gas flow is in excess of flame propagation velocity at 112
design  flow rate.

    The afterburner is to be natural gas fired. Sufficient gas, having a specific  gravity of 0.60 and an
upper heating value of 1040 Btu/SCF, is available at a pressure of 1.0 psig.

    The exhaust gas contains sufficient oxygen, greater than 16% 0% to allow firing of the afterburner
with a raw gas or process air burner. A  combustion air system is not required.  Fume load to the
afterburner is composed of 75% kettle emission and 25% from other sources. Average emissions are
60% of peak. The system is to be designed on peak emission but operating costs are to be based on
average emissions. Operating conditions  listed are based on peak emissions. Fume destruction in
burner is to be calculated as follows:

        10% for catalytic units with or without heat exchange

        10% for thermal units with heat exchange

       20% for thermal units without heat exchange

       Please fill in estimated efficiency  of afterburner and burner duty, catalyst face velocity, and
       catalyst volume.

    The afterburner is to be supplied with a suitable control panel and all equipment is to be designed
for outdoor operation. Afterburner operating and safety  controls are to be designed to meet F.I.A.
(Factory Insurance Association)  requirement. All dampers are to be pneumatically operated and
contain an integral fail safe air reservoir. The system is to automatically divert in the event of low flow,
high  afterburner temperature,  high reactor pressure,  and afterburner preheat burner failure. The
exhaust system should also be purged with inert gas on fan failure or loss of flow. Damper operating is
to be  sequential with the position switches mounted on  the damper arm and not the operator. The
system fan shall be located after the preheat burner or the  afterburner outlet and shall be constructed to
withstand 200ฐF higher than design operating temperature. The fan shall have a vee belt drive and fan
and motor shall have the capacity to overcome the pressure drop of the ductwork, afterburner and any
heat exchanger that may be used. System ductwork should be sized for a maximum AP of 2 in. w.c.hot.
The fan motor may be sized for restricted flow cold start. The ductwork to the  afterburner should be
heated either by the use of a double manifold or hot gas recycle or a  combination of both.

    The heat exchanger when included is to be the parallel flow shell and tube type and designed to
operate at an afterburner outlet temperature of 1200ฐF. Maximum exchanger pressure drop, both sides,
should not exceed a  total of 6 in. w.c. hot. Dirty gas is to flow through the tube side.
"Appendix B

                                        320

-------
                                   TABLE 79 (Continued)
                                       INSTALLATION

    A complete turnkey proposal Including ductwork, structural steel, fuel and inert gas piping, etc., is
requested. For the purpose of this proposal fan and damper including operators are to be considered
as auxiliary.  The controls and control cabinet are to be included with the afterburner price. The
afterburner will be assumed to be located on a structural steel  base on the resin plant roof.  No
modification to the building structural steel is required. A tie through the roof from the base to the
building  steel is required. The base and tie in are part of the  installed structural cost. All utilities are
available within 30 ft of the control cabinet, motor, and burner. Plant air is available at 100 psig and
located within 30 ft. Inert gas is available and will require 30 ft of piping from supply to ductwork. The
existing stack can be used for the  diversion stack. A 10 ft  exhaust stack will be mounted on the
afterburner, double manifold or exhaust fan. A total of thirty-five (35) feet of new exhaust ductwork and
twenty-five (25) feet of double  manifold will be required.
                                           321

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                            TABLE 80
         CATALYTIC AFTERBURNER OPERATING CONDITIONS

                 FOR OPEN KETTLE SPECIFICATION
                      (Without Heat Exchange)
                                               Small        Large

Process Conditions

    Kettles, Number                                  1            6
        Size each, gal                             300          300
    Hcbn Emission Max, Ib/hr                      22.5          135
    Hcbn Emission Ave, Ib/hr                       13.1          78.8
    Total Exhaust Rate, SCFM                       500        3,000
    Exhaust Temperature, ฐF                         80           80
    Heat of Combustion of
        Kettle Fume, Btu/lb                      16,000        16,000
    Hydrocarbon Concentration
        Maximum, Btu/SCF                          12           12
    Average, Btu/SCF                                7            7


Afterburner Without Heat Exchange

    Unit Inlet, ฐF                                   280          280
    Burner AT" from Fuel Gas, ฐF                     260          260
   * Burner AT from Flame Combustion, ฐF              60           60
    Burner Outlet Temperature, ฐF                    600          600
  ** Unit A7 from Thermal Combustion, ฐF              500          500
    Unit Outlet Temperature, ฐF                    1,100         1,100
    Burner Duty, MM Btu/hr                       	          	
Estimated Unit Removal Efficiency

  "''Catalyst Face Velocity, SF/min
    Catalyst Volume, ft3
   * Assumes 10% fume combustion in burner flame
  "Assumes 95% overall fume combustion
 *** Basis 70ฐF exhaust temperature
                                322

-------
                            TABLE 81
         CATALYTIC AFTERBURNER OPERATING CONDITIONS

                 FOR OPEN KETTLE SPECIFICATION
                      (Without Heat Exchange)
                                               Small        Large

Process Conditions

    Kettles, Number                                  2            4
        Size each, gal                            300          300
    Hcbn Emission Max, Ib/hr                       45           90
    Hcbn Emission Ave, Ib/hr                       262           52
    Total Exhaust Rate, SCFM                     1,000        2,000
    Exhaust Temperature, ฐF                        80           80
    Heat of Combustion of
        Kettle Fume, Btu/lb                      16,000        16,000
    Hydrocarbon Concentration
        Maximum, Btu/SCF                         12           12
    Average, Btu/SCF                                7            7


Afterburner  Without Heat Exchange

    Unit Inlet, ฐF                                  280          280
    Burner  AT from Fuel Gas, ฐF                    260          260
   * Burner  AT from Flame Combustion, ฐF             60           60
    Burner  Outlet Temperature,  ฐF                   600          600
  ** Unit AT from Thermal Combustion, ฐF             500          500
    Unit Outlet Temperature, ฐF                    1,100        1,100
    Burner Duty, MM Btu/hr                        	         	


Estimated Unit Removal Efficiency                   	         	
  ***Cate/ysf Face Velocity, SF/min
    Catalyst Volume, ft3
   * Assumes 10% fume combustion in burner flame
  ** Assumes 95% overall fume combustion
 *** Basis 70ฐF exhaust temperature
                              323

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    TABLE 82



CITY COST INDICES
Average 1969 Construction Cost & Labor Indices

City
Albany, N.Y.
Albuquerque, N.M.
Amarillo, Tx.
Anchorage, Ak.
Atlanta, Ga.
Baltimore, Md.
Baton Rouge, La.
Birmingham, Al.
Boston, Ma.
Bridgeport, Ct.
Buffalo, N.Y.
Burlington, Vt.
Charlotte, N.C.
Chattanooga, Tn.
Chicago, III.
Cincinnati, Oh.
Cleveland, Oh.
Columbus, Oh.
Dallas, Tx.
Dayton, Oh.
Denver, Co.
Des Moines, la.
Detroit, Mi.
Edmonton, Cn.
El Paso, Tx.
Erie, Pa.
Evansville, In.
Grand Rapids, Mi.
Harrisburg, Pa.
Hartford, Ct.
Honolulu, Hi.
Houston, Tx.
Indianapolis, In.
Jackson, Ms.
Jacksonville, Fl.
Kansas City, Mo.
Knoxville, Tn.
Las Vegas, Nv.
Little Rock, Ar.
Los Angeles, Ca.
Louisville, Ky.
Madison, Wi.
Manchester, N.H.
Memphis, Tn.
Miami, Fl.
Index
Labor
98
86
87
131
88
90
83
79
106
104
104
86
70
81
107
108
121
106
86
100
94
93
117
80
77
98
93
103
90
104
99
92
97
73
78
94
82
115
78
113
92
95
89
83
98
Total
100
95
84
148
94
93
88
86
103
102
107
90
75
84
103
104
112
99
89
103
91
96
111
83
83
99
97
99
92
100
109
89
98
75
79
93
82
107
81
102
93
98
92
82
94

City
Milwaukee, Wi.
Minneapolis, Mn.
Mobile, Al.
Montreal, Can.
Nashville, Tn.
Newark, N.J.
New Haven, Ct.
New Orleans, La.
New York, N.Y.
Norfolk, Va.
Oklahoma City, Ok.
Omaha, Nb.
Philadelphia, Pa.
Phoenix, Az.
Pittsburgh, Pa.
Portland, Me.
Portland, Or.
Providence, R.I.
Richmond, Va.
Rochester, N.Y.
Rockford, III.
Sacramento, Ca.
St. Louis, Mo.
Salt Lake City, Ut.
San Antonio, Tx.
San Diego, Ca.
San Francisco, Ca.
Savannah, Ga.
Scranton, Pa.
Seattle, Wa.
Shreveport, La.
South Bend, In.
Spokane, Wa.
Springfield, Ma.
Syracuse, N.Y.
Tampa, Fl.
Toledo, Oh.
Toronto, Cn.
Trenton, N.J.
Tulsa, Ok.
Vancouver, Cn.
Washington, D.C.
Wichita, Ks.
Winnipeg, Cn.
Youngstown, Oh.
Index
Labor
103
99
94
77
79
122
102
89
132
73
82
90
106
101
110
82
102
98
76
110
109
117
110
93
82
111
124
72
94
104
82
99
101
99
105
81
105
84
114
85
81
98
85
62
107
Total
108
98
90
89
82
109
100
95
118
77
88
93
101
97
106
87
103
97
79
107
109
110
103
95
82
107
109
77
96
99
89
97
100
97
103
84
105
93
103
89
91
94
90
82
106
Historical Average
Year
1969
1968
1967
1966
1965
1964
1963
1962
1961
1960
1959
1958
1957
1956
1955
1954
1953
1952
1951
1950
1949
1948
1947
1946
1945
1944
1943
1942
1941
1940
1939
1938
1937
1936
1935
1934
1933
1932
1931
1930
1929
1928
1927
1926
1925
1924
Index
100
91
86
83
79
78
76
74
72
71
69
67
65
63
59
58
57
55
53
49
48
48
43
35
30
29
29
28
25
24
23
23
23
20
20
20
18
17
20
22
23
23
23
23
23
23
     324

-------
             TABLE 83



AVERAGE HOURLY LABOR RATES BY TRADE
Trade
Common Building Labor
Skilled Average
Helpers Average
Foremen (usually 35<^ over trade)
Bricklayers
Bricklayers Helpers
Carpenters
Cement Finishers
Electricians
Glaziers
Hoist Engineers
Lathers
Marble & Terrazzo Workers
Painters, Ordinary
Painters, Structural Steel
Paperhangers
Plasterers
Plasterers Helpers
Plumbers
Power Shovel or Crane Operator
Rodmen (Reinforcing)
Roofers, Composition
Roofers, Tile & Slate
Roofers Helpers (Composition)
Steamfitters
Sprinkler Installers
Structural Steel Workers
Tile Layers (Floor)
Tile Layers Helpers
Truck Drivers
Welders, Structural Steel
1970
$5.00
6.85
5.15
7.20
7.15
5.20
6.95
6.75
7.50
6.25
7.05
6.60
6.45
6.20
6.50
6.30
6.60
5.30
7.75
7.20
7.30
6.30
6.35
4.75
7.70
7.70
7.45
6.50
5.25
5.15
7.15
1969
$4.55
6.05
4.65
6.40
6.40
4.70
6.15
5.90
6.45
5.50
5.90
5.95
5.60
5.45
5.80
5.60
5.95
4.85
6.90
6.20
6.35
5.55
5.60
4.45
6.90
6.90
6.45
5.60
4.80
4.60
6.35
1968
$4.10
5.50
4.20
5.85
5.85
4.30
5.40
5.30
5.95
5.10
5.40
5.45
5.25
5.05
5.30
5.15
5.50
4.45
6.15
5.65
5.80
5.05
5.10
4.00
6.10
6.10
5.90
5.20
4.35
4.30
5.80
1967
$3.85
5.15
4.00
5.50
5.55
4.05
5.10
5.05
5.60
4.75
5.10
5.20
5.05
4.75
4.95
4.75
5.15
4.15
5.75
5.35
5.45
4.75
4.85
3.75
5.70
5.70
5.55
4.90
4.15
3.95
5.45
1966
$3.65
4.90
3.85
5.25
5.35
3.95
4.90
4.85
5.45
4.60
4.85
5.05
4.90
4.50
4.80
4.55
5.00
4.00
5.55
5.05
5.15
4.65
4.80
3.55
5.50
5.50
5.25
4.80
4.05
3.65
5.10
               325

-------
                                       TABLE 84
                 INSTALLATION AND OPERATING COST FOR BAGHOUSE
               Type Collector
   Type Pulse
                            Shaker
Bag type
Cloth, ft2
Air, CFM
Air/cloth ratio CFM/ft2
Capital cost, $
Installation cost, $
Total cost, $
Operating & Maintenance
    Cost - 8 hr day,  $
Pigment recovered, Ib/yr
Compressed air required
    @ 100 psig
 Polyester felt
     452
    3,800
    8.4/1
    3,900
    2,900
    6,800

    350/yr
    2,850
4.5 SCFM Ave.
9.0 SCFM Max.
Cotton sateen
    1,900
    3,800
     2/1
    4,500
    3,400
    7,900

    245/yr
    2,850

    None
                                        326

-------
                                    FIGURE
                                   CAPITAL  COSTS
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                                     327

-------
                            FIGURE 65


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-------
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-------
                                FIGURE  70


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-------
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-------
                                        TABLE 88

                                     MODEL PLANT
                               DEPRECIATION SCHEDULE
                            (Finished Output 1.9 Million Gallons)
                                                           Asset        Straight       Annual
                                                         Capitalized       Line        Depr.
                                                           Value        Depr. %       Amount
LAND                                                  $  100,000        	       	

BUILDING & SITE PREPARATION:

        Raw Material Warehouse                            219,700        1.25  $    2,746
        Manufacturing Building                              912,450        1.25      11,406
        Finished Goods Warehouse                          526,700        1.25       6,584
        Site Preparation                                    167,100        1.25       2,089
        Engineering                                        217,200        1.25       2,715
        Other Building Costs                                310,300        1.25       2,879

    Total Buildings, Etc.                                  $2,353,450              $   29,419

EQUIPMENT & UTILITIES:

        Paint Plant                                      $  521,900       10.00  $   52,190
        Resin Plant                                        222,500       10.00      22,250
        Storage                                            211,600       10.00      21,160
        Miscellaneous                                      142,750       10.00      14,275
        Utilities                                            178,400       10.00      17,840

    Total Equipment & Utilities                            $1,277,150              $ 127,715


GRAND TOTAL                                         $3,730,600  =====  $ 157,134


Note:
    1. All freight & sales tax was assumed to be expensed in prior year.
    2. Assumption is that plant is operating and on stream: All start-up costs have expired in prior years.
    3. Depreciation will be allocated between trade and industrial products on 60% to 40% basis.
                               Trade       60%    $ 94,280
                               Industrial     40%      62,854

                                                   $157,134
                                        341

-------
                                      TABLE 89

                                    MODEL PLANT
                                 INCOME STATEMENT
                            (Year Ending December 31, 19-2)
                                                         Trade       Industrial
                                                         Sales        Sales        Total
                                                        Products     Products        All
REVENUE (NET)

A)  1,140,000 gal @$3.78/gal                           $4,309,200        	  $4,309,200
A)   760,000 gal @ $3.02/gal                                	  $2,295,200   2,295,200

        Total Revenue                                 $4,309,200  $2,295,200  $6,604,400

COST OF GOODS SOLD

    Raw Materials (See Table 85)                        $1,550,228  $1,203,045  $2,753,273
    Packaging (See Table 86)                              447,078     184,828    631,906
    Salaries & Wages (See Table 87)                        447,051     233,010    680,061
    Depreciation (See Table 88)                             94,280      62,854    157,134
B)  Other Manufacturing Costs
        Trade-Estimated @ 500/gal                         570,000        	    570,000
        Industrial-Estimated @  300/gal                         	     228,000    228,000

        Total Cost of Goods Sold                        $3,108,637  $1,911,737  $5,020,374

Gross Profit	      $1,200,563  $  383,463  $1,584,026


SELLING, GENERAL & ADMINISTRATIVE EXPENSES

    Trade-Estimated @ 15% of Sales                     $  646,380        	  $ 646,380
    Industrial-Estimated @ 5% of Sales                        	  $  114,761    114,761

        Total S, G & A Expense                         $  646,380  $  114,761  $ 761,141

Operating Income                                      $  554,183  $  268,702  $ 822,885

INTEREST EXPENSE

    Long-Term Debt                                   $  151,200  $  100,800  $ 252,000

Income Before Taxes                                   $  402,983  $  167,902  $ 570,885

INCOME TAXES

    Federal Income Tax (50%)                           $  201,492  $   83,951  $ 285,443
    State & Local Taxes (10%)                           $   40,298  $   16,790  $   57,088

Total Taxes                                           $  241,790  $  100,741  $ 342,531

NET INCOME                                         $  161,193  $   67,161    228,354
                                      342

-------
                                        TABLE 89
                                       (Continued)

                                     MODEL PLANT
                                  INCpME STATEMENT
                             (Year Ending December 31, 19-2)


Notes:

 A)   Selling price calculated as follows using data from current industrial reports, M28F - - year 1971.

       TRADE        -$1,563 million divided by 431 million gal = $3.63/gal
                     $3.63/gal times growth rate of 4% = $3.78/gal

       INDUSTRIAL  -$1,268 million divided by 443 million gal = $2.86/gal
                     $2.68/gal times growth rate of 5.5%  = $3.02/gal

 B)   The estimated other manufacturing costs is to cover such items as:
                     1.   Repair parts which are expensed
                     2.   Operating, heating and utility costs
                     3.   Property insurance and taxes
                     4.   Miscellaneous operating expenses
                                       343

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-------
                                       TABLE 91

                                    MODEL PLANT
                                   BALANCE SHEET
                            (Year Ending December 31, 19-2)
                                       ASSETS
Current Assets

    Cash
    Accounts Receivable (Dec. Sales)
    Inventories:
        Finished Goods
            Trade-203,360 gal @ $2.73/gal
            lndustrial-38,000 gal @ 2.52/gal
            Raw Materials (Vt2 Of Annual Cost)
            Packages, Etc. (1/12 Of Annual Cost)

    Total Inventories

               Total Current Assets

Property, Plant & Equipment

    Land
    Buildings
    Equipment

    Total (On The Basis Of Cost)
    Less Allowance For Depreciation

               Total Property, Plant & Equipment
           ($    14,512)
               391,929
$

555,173
95,760
229,439
52,659
$
933,031
$   100,000
  2,353,450
  1,277,150
                       $ 1,310,448
            $  3,730,600
               314,268
                       $ 3,416,332
TOTAL ASSETS
                       $ 4,726,780
                        LIABILITIES & SHAREHOLDERS' EQUITY
Current Liabilities

    Accounts Payable (Via Of R.M. & Pkg. Cost)
    Income Taxes (1/4 Of 342,531)

               Total Current Liabilities
Lortg Term Debt

    Bank Loan ($4,000,000 - - 10 yr Term - 7%)

Shareholders' Equity

    Common Stock
        100,000 Sharesฎ $10
    Retained Earnings
               Total Shareholders' Equity


TOTAL LIABILITIES & SHAREHOLDERS' EQUITY
            $   282,098
                85,633
                       $   367,731
                         3,200,000
            $ 1,000,000
               159,049
                       $ 1,159,049
                       $ 4,726,780
                                        346

-------
                       TABLE 92

                     MODEL PLANT
                CASH FLOW STATEMENT
          (1.9 Million Gallons Sold & Manufactured)
                       (Year 19-2)
REVENUE: NET                                $6,604,400



EXPENDITURES (CASH)

    Raw Materials, Packages, Etc.      $3,385,179
    Salaries & Wages                    680,061
    Other Mfg. Expenses                 798,000
    S, G&A                           761,141
    Interest Expense                     252,000
    Federal Income Tax                  285,443
    State & Local Taxes                   57,088
    Principal Payment Long-Term Debt      400,000

                                               6,618,912


NET CASH FLOW                              $  (14,512)
                         347

-------
                                        TABLE 93

                                     MODEL PLANT
                                RETURN ON INVESTMENT
                                       (Year 19-2)


Return on investment is calculated using four of the more common methods. The first three methods are
essentially asset efficiency measurements while the last method centers attention on the rate of return
that will  be earned  by the business owners.
1.  Total Gross Assets Available Method


                              Income Before Interest                $329,154
                                                                            =  6.53%
                                Total Gross Assets                $5,041,048
2.  Total Net Assets Available Method
                              Income Before Interest                $329,154
                                 Total Net Assets                  $4,726,780



3.   Stockholders' Equity Plus Long-Term Debt Method


                              Income Before Interest                $329,154
                                                                           •=  7.55%
                      Stockholders' Equity Plus Long Term Debt      $4,359,049



4.  Stockholders' Equity Method


                                   Net Income                     $228,354 .= 1970o/o
                               Stockholders'Equity                $1,159,049
                                         348

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-------
                                       TABLE 95

                          MODEL PAINT PLANT COST, DOLLARS
                                                                      Total
                               Item                                   Material       Total
                            Summary

Equipment
    Paint Plant                                                        521,900
    Resin Plant                                                       222,500
    Storage                                                          211,600
    Miscellaneous                                                     142,750

        Sub-Total                                                   1,098,750   1,098,750

    Utilities                                                           178,400     178,400

        Sub-Total                                                   1,277,150   1,277,150

Building
    Sitework                                                          167,100
    Part I - Raw Material Warehouse                                    219,700
    Part II - Manufacturing Building                                      919,450
    Part III - Finished Goods Warehouse                                 526,700

        Sub-Total                                                   1,825,950   1,825,950

        Total                                                                   3,103,100

    Freight and Sales Tax                                                          124,400
    Engineering - 7%                                                              217,200
    Contingency - 10%                                                             310,300

        Project Total*                                                            3,755,000
* Based on Chicago ENR Construction Cost Index of 1964 for December, 1972.
                                        351

-------
                                        TABLE 96

                          MODEL PAINT PLANT COST, DOLLARS
                               Item
                                                                      Total
                                                                     Material
            Total
        Equipment and Utilities Summary

Equipment

    Paint Plant
        Pebble Mills
        Ball Mills
        Sand Mills
        High Speed Dispersers
        Mixing and Finishing Tanks
        Filling and Packaging
        Laboratory

            Sub-Total

        Resin Plant
        Storage
        Miscellaneous

            Sub-Total

        Utilities

            Total
128,150
 37,500
 26,500
 44,800
166,450
105,000
 13,500

521,900     521,900

222,500
211,600
142,750
576,850

178,400
 576,850

 178,400


1,277,150
                                        352

-------
                                        TABLE 97

                              MODEL CONTROLLED PLANT
                               DEPRECIATION SCHEDULE
                            (Finished Output 1.9 Million Gallons)
                                                          Asset        Straight       Annual
                                                         Capitalized       Line        Depr.
                                                          Value        Depr. %       Amount
LAND                                                  $  100,000        	        	

BUILDING & SITE PREPARATION:

        Raw Material Warehouse                            219,700        1.25  $   2,746
        Manufacturing Building                              912,450        1.25      11,406
        Finished Goods Warehouse                          526,700        1.25       6,584
        Site Preparation                                    167,100        1.25       2,089
        Engineering                                        217,200        1.25       2,715
        Other Building Costs                                310,300        1.25       2,879

    Total Buildings, Etc.                                  $2,353,450             $  29,419

EQUIPMENT & UTILITIES:

        Paint Plant                                      $  521,900       10.00  $  52,190
        Resin Plant                                        222,500       10.00      22,250
        Storage                                            211,600       10.00      21,160
        Miscellaneous                                      142,750       10.00      14,275
        Utilities                                            178,400       10.00      17,840
        Resin Plant Afterburner                               26,000       10.00       2,600
        Paint Plant Baghouse                                 7,350       10.00  	735

    Total Equipment & Utilities                            $1,310,500             $ 160,469


GRAND TOTAL                                         $3,763,950  	  $ 160,469


Note:
    1. All freight & sales tax was assumed to be expensed in prior year.
    2. Assumption is that plant is operating and on stream: All start-up costs have expired in prior years.
    3. Depreciation will be allocated between trade and industrial products on 60% to 40% basis.
                               Trade       60%    $ 96,281
                               Industrial     40%      64,188

                                                   $160,469
                                         353

-------
                                      TABLE 98
                             MODEL CONTROLLED PLANT
                                 INCOME STATEMENT
                            (Year Ending December 31, 19-2)
REVENUE (NET)

A)  1,140,000 gal @ $3.78/gal
A)   760,000 gal @ $3.02/gal

        Total Revenue

COST OF GOODS SOLD

    Raw Materials (See Table 85)
    Packaging (See Table 86)
    Salaries & Wages (See Table 87)
    Depreciation (See Table 88)
B)  Other Manufacturing Costs
        Trade-Estimated @ 500/gal
        Industrial-Estimated @  300/gal
C)  Operating Cost-Resin Reactor Afterburner
C)  Baghouse Operating Cost
Gross Profit
                                                         Trade
                                                         Sales
                                                        Products
$4,309,200
              Industrial
               Sales
              Products
                           Total
                            All
                 	  $4,309,200
	  $2,295,200   2,295,200

$4,309,200  $2,295,200  $6,604,400
$1,550,228  $1,203,045  $2,753,273
   447,078     184,828    631,906
   447,051     233,010    680,061
    96,281      64,188    160,469
VI U,UUU
4,476
192
228,000
1,119
106
228,000
5,595
298
$3,115,306  $1,914,296  $5,029,602

$1,193,894  $  380,904  $1,574,798
SELLING, GENERAL & ADMINISTRATIVE EXPENSES

    Trade-Estimated @ 15% of Sales
    Industrial-Estimated @ 5% of Sales

        Total S, G & A Expense

Operating Income

INTEREST EXPENSE

    Long-Term Debt

Income Before Taxes

INCOME TAXES
    Federal Income Tax (50%)
    State & Local Taxes (10%)

Total Taxes

NET INCOME
$  646,380
           $  114,761
                       $  646,380
                          114,761
$  646,380  $  114,761  $ 761,141

$  547,514  $  266,143  $ 813,657
$  152,461  $  101,641  $ 254,101

$  395,053  $  164,503  $ 559,556



$  197,527  $   82,251  $ 279,778
    39,505      16,450      55,955

$  237,032  $   98,701  $ 335,733

$  158,021  $   65,802  $ 223,823
                                       354

-------
                                       TABLE 98
                                       (Continued)

                              MODEL CONTROLLED PLANT
                                  INCOME STATEMENT
                             (Year Ending December 31, 19-2)


Notes:

 A)   Selling price calculated as follows using data from current industrial reports, M28F - - year 1971.

       TRADE       -$1,563 million divided by 431  million gal = $3.63/gal
                     $3.63/gal times growth rate of 4% = $3.78/gal

       INDUSTRIAL  -$1,268 million divided by 443  million gal = $2.86/gal
                     $2.68/gal times growth rate of 5.5% = $3.02/gal

 B)   The estimated other manufacturing costs is to cover such items as:
                     1.   Repair parts which are expensed
                     2.  Operating, heating and utility costs
                     3.  Property insurance and taxes
 Cx   o    T bl  10?    4'  Miscellaneous operating expenses
                                         355

-------
                                      TABLE 99

                             MODEL CONTROLLED PLANT
                                   BALANCE SHEET
                            (Year Ending December 31, 19-2)
                                       ASSETS
Current Assets
    Cash
    Accounts Receivable (Dec. Sales)
    Inventories:
        Finished Goods
           Trade-203,360 gal @ $2.73/gal
           lndustrial-38,000 gal @ 2.52/gal
           Raw Materials (Viz Of Annual Cost)
           Packages, Etc. (Vi2 Of Annual Cost)

    Total Inventories

               Total Current Assets

Property, Plant  & Equipment

    Land
    Buildings
    Equipment
    Air Emission Control Devices

    Total (On The Basis Of Cost)
    Less Allowance For Depreciation

               Total Property, Plant & Equipment
           ($
$   100,000
  2,353,450
  1,277,150
     33,350
 19,043)
391,929
$

555,173
95,760
229,439
52,659
$
933,031
                       $ 1,305,917
           $  3,763,950
               320,938
                       $ 3,443,012
TOTAL ASSETS
                       $ 4,748,929
                         LIABILITIES & SHAREHOLDERS' EQUITY
Current Liabilities

    Accounts Payable (Vi2 Of R.M. & Pkg. Cost)
    Income Taxes (1/4 Of 335,733)

               Total Current Liabilities
Long-Term Debt

    Bank Loan ($4,033,350 - - 10 yr Term - 7%)

Shareholders' Equity

    Common Stock
        100,000 Shares @ $10
    Retained Earnings
               Total Shareholders' Equity
           $   282,098
                83,933
                       $   366,031
                         3,226,680
           $  1,000,000
               156,218
                         1,156,218
TOTAL LIABILITIES & SHAREHOLDERS' EQUITY
                       $ 4,748,929
                                        356

-------
                       TABLE 100

              MODEL CONTROLLED PLANT
                CASH FLOW STATEMENT
          (1.9 Million Gallons Sold & Manufactured)
                       (Year 19-2)
REVENUE: NET                                $6,604,400



EXPENDITURES (CASH)

    Raw Materials, Packages, Etc.      $3,385,179
    Salaries & Wages        .           680,061
    Other Mfg. Expenses                798,000
    S, G&A                          761,141
    Interest Expense                    254,101
    Federal Income Tax                 279,778
    State & Local Taxes                  55,955
    Principal Payment Long-Term Debt     403,335
    Operating Cost of Emission Controls      5,893

                                               6,623,443


NET CASH FLOW                              $  (19,043)
                         357

-------
                                       TABLE 101

                              MODEL CONTROLLED PLANT
                                RETURN ON INVESTMENT
                                       (Year 19-2)


Return on investment is calculated using four of the more common methods. The first three methods are
essentially asset efficiency measurements while the last method centers attention on the rate of return
that will be earned by the business owners.
1)  Total Gross Assets Available Method
                              Income Before Interest               $325,463   _
                                                                            — 6.42 /o
                               Total Gross Assets                $5,069,867
2)  Total Net Assets Available Method
                              Income Before Interest               $325,463     _ 0_0.
                                                                            = 6.85%
                                 Total Net Assets                 $4,748,929
3)  Stockholders' Equity Plus Long-Term Debt Method
                              Income Before Interest               $325,463   _
                                                                           • —  / .T-O /o
                      Stockholders' Equity Plus Long-Term Debt     $4,382,898



4)  Stockholders' Equity Method


                                   Net Income                    $223,823
                               Stockholders'Equity               $1,156,218
                                                                            = 19.36%
                                         358

-------
                                       TABLE 102

                              MODEL CONTROLLED PLANT
                            AIR EMISSION CONTROL DEVICES
RESIN REACTOR AFTERBURNER:
                                                       1200 SCFM
                                                        Thermal
                                                         Type
           1200 SCFM
             Catalytic
              Type
             Average
             of Two
A)  Capital Cost - (Includes Installation)                     $25,000    $27,000     $26,000

B)  Operating Cost Per Year - 16 hrs/day                     6,850       4,340       5,595

    Effect On Yield                                        None        None       None

Note (A)

Capital cost is assumed to be financed with long-term debt and as part of initial financing arrangements.

Note (B)

Operating cost is apportioned between trade sales and industrial finishes. Products on same ratio as
manufactured resins are used within the finished products. This will be 80% trade and 20% industrial.
PAINT PLANT BAGHOUSE:
C)  Capital Cost - (Includes Installation)

D)  Operating Cost Per Year - 8 hr/day
    (Includes Maintenance, Utilities, Etc.)

D)  Pigment Recovered Per Year

Note (C)
                                                         Pulse
                                                         Test
                                                         Type
$ 6,800

    350
 Shaker
  Type

$ 7,900

    245
2,850 Ib     2,850 Ib
 Average
 of Two

$ 7,350

    298



2,850 Ib
Same assumption on capital cost as indicated in Note A above.

Note (D)

Operating cost and credit for pigment recovered will be apportioned between trade sales and industrial
finishes on the same ratio as pigment used between the two. This will be 64.5% for trade and 35.5% for
industrials.
                                        359

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360

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                                        CHAPTER 8
                                    PIGMENT INDUSTRY

I.       INTRODUCTION
        Pigments represent one of the  major building blocks  in the formulation of an acceptable
coating. Historically,  the use of coloring agents was largely for decorative effect.  While this is still
of major importance today, pigments are  now recognized to  produce a variety of other  important
properties in paint films. The  selection  of the correct pigment for a given application must take
into  account factors other  than  coloring ability alone. Pigments can be used which improve the
physical properties of both the liquid paint and the final paint film. They can act as corrosion inhibitors
and  as mildew inhibitors. Some  pigments have the  ability to absorb  ultraviolet  radiation  and  so
protect  the paint film as well as the coated  material from degradation from this source.  Pigments
may react chemically with  the binder to  produce  desirable (and sometimes undesirable)  effects.
Finally,  and  this has become  more important in recent years, the biological effect of the pigment
material must be taken into account.
        The  feature which  distinguishes a pigment from other coloring agents is its insolubility in
the medium  in which it is  employed. A pigment may be defined as a solid material, present in
the form of small particles,  which is essentially insoluble in the medium in which it is present. The
ability to color or opacity the medium is not  considered essential to the definition. As will be seen
later, a class of pigments called extenders is used which impart  little or no color or opacity even
when used in large amounts.
        A coloring agent which  is soluble in its medium is called  a dye. Some of the organic  pigments
such as wood stains could  more  properly  be classed as dyes. Two other types of coloring agents
are "lakes"  and "toners". A lake is a water  insoluble pigment formed  from coloring matter in the
presence of  a  substrate. If the  formation takes place without a  substrate, the  coloring  agent is
called a toner. Lakes and toners are usually organic.
A.     Classification and Statistics3
       Pigments  represent  one  of the most important raw materials consumed by the paint and
                                          361

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coating industry. On a weight basis, consumption of  pigments exceeded  that of any other  single
class of raw materials.  In  1970,  the coatings industry used  1,727 thousand tons of pigments of
all types. Consumption of solvents was a close second at 1,695 thousand tons.
        In addition to their  use in paints, pigments find extensive  use in other industries such as
rubber, paper,  plastics  and  printing.  In  fact,  consumption by  the paint industry represents only
about  half  the  total  pigment production  in this  country.  Total  pigment production  in 1968  stood
at 3,640.6  thousand tons.  Production  by major categories for  1968 is  presented  in Table 103.
In addition to those listed, an estimated  52,500 tons of  metallic pigments, mostly zinc  and  aluminum,
were consumed by the paint industry in  1970.
        The black organic pigments consist almost entirely of carbon blacks produced from petroleum
feed stocks. Inorganic blacks are primarily black iron oxide.
        The white pigments  fall  into two classes:2 hiding (opaque)  and extender  (non-opaque)
pigments. The  extenders are  not pigments in the usual  sense of the word. That is, they do not
add  color or opacity to  the paint film. Their lack of these  properties  is due to their relatively low
index of refraction. Historically, the  extenders  were introduced as a cheap substitute for the more
expensive true pigment.  Extenders, today, are recognized to contribute  to stability, texture, durability
and  a variety of other  paint  properties. Production of the important white hiding and extender
pigments is given in Table 104.
        The organic  color pigments, almost entirely synthetic, include a  wide variety of types.2-3
The  one feature most of the organic dyes and pigments have in common is the presence of  ring
structures in their molecules. The most common starting materials are benzene, toluene, xylenes,
naphthalene and anthracene.  Reactions such  as nitration, halogenation, and sulfonation are used
to transform these materials into the intermediates  from which the final dye or pigment is produced.
Generally speaking,  a dye is a coloring material  which is soluble in the medium in which  it is
employed while a pigment consists of discrete particles  which are insoluble in the medium.  It is
not uncommon  for an organic  coloring agent to be  soluble in one medium and insoluble  in another.
Thus, it may act as either a dye or a pigment.
        No single organic pigment,  or class of pigments,  accounts for more  than a relatively small
fraction of the total. Production of the major types is shown in Table 105.
        Within any given type, there exists a  large variety of pigments.  For instance, among the
azo  group  there  are at least 22 different  pigment materials  having  little in common except the
presence of  a  (— N = N —) bridge  between aromatic groups. Most colors,  except  white,  are
                                          362

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               TABLE 103
 PIGMENT PRODUCTION BY MAJOR TYPE3
                            1968 Production
        Pigment              (1,000 ton/yr)
      Black Organic                 66.5
      Black Inorganic                 3.6
      White Hiding                 682.3
      White Extender             2,670.1
      Colored Organic               27.1
      Colored Inorganic             191.0
          Total                  3,640.6
               TABLE 104
        MAJOR WHITE PIGMENTS3
                            1968 Production
        Pigment              (1,000 ton/yr)
Hiding
    Titanium Dioxide               623.7
    Zinc Oxide (lead free)            36.4
    White Lead                     11.1
    Leaded Zinc Oxide               11.1
Extender
    Kaolin (China clay)            2,153.0
    CaCOs, precipitated             226.0
    Talc                          205.2
    Bartyes                         60.9
    Mica                            25.0

                   363

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                     TABLE 105
        PRODUCTION OF ORGANIC PIGMENTS3

                                  1968 Production
           Organic Pigment           (1,000 ton)
            Insoluble Azo               7.0
            Soluble Azo                 6.8
            Phthalocyanine              6.0
            Condensation Acid           2.5
            Basic                      1.7
            Miscellaneous               2.6
                     TABLE 106
PRODUCTION OF MAJOR INORGANIC COLOR PIGMENTS3

                                  1968 Production
               Pigment              (1,000 ton/yr)
       Synthetic Iron Oxide               72.4
       Natural Iron Oxide                 57.6
       Chromate                        44.2
       Ferrocyanide                       6.0
       Sulfide                            3.0
       Mixed Chromate and
            Ferrocyanide                 2.8
                      364

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available  with the organics. Their principal  disadvantages are high cost and  inferior light, heat
and chemical stability.
        The inorganic color  pigments include several important types. Production of the major types
is given in Table 106. As a group, the inorganics are less expensive and possess higher stability
than the  organics.  They are considered  more suitable for exteriors and for environments where
high temperatures  or  corrosive conditions  are  encountered.  They  do not possess the range of
colors and tones of the organic  pigments, but have representatives in  most of the major color groups.
B.      Purpose and Scope
        The purpose of  this study is  to  identify,  and study further, those  pigment groups  which
represent major contributors to air pollution. This decision  is  based on several factors. First,  it is
impossible from a time standpoint  to study in detail all of the pigments used by the coating industry.
It becomes necessary, then, to concentrate  effort on those areas where the  problem is most acute.
This is reasonable on technical grounds, also; since many of the production processes used are
by  their nature relatively free of air emissions.  Also, some pigments are produced in such small
amounts that diversion of effort to these would be unjustified.
        An initial screening was done to eliminate certain groups from consideration. The  production
of the  carbon black pigments is included in  a separate EPA study and so will not be studied here.
The production of white lead and leaded zinc oxide will not be considered, in  spite of lead's potential
toxicity, since present and  future regulations on lead  content in paint should  virtually eliminate
these  pigments for the coatings industry. Recent trends, as well as industry projections, support
this conclusion. Paint industry  projections predict the use of white lead  to decrease to 20% of its
1970 value by 1975.31
        The white extenders have  been eliminated on several grounds. They are produced primarily
by  mining operations followed  by grinding, classification,  drying,  etc. Any  problems  which  might
exist would be of a paniculate nature. Technology for particulate  control  is well developed  and
the extender industry  does not  present  any unique problems. Furthermore, the  extenders  are
considered non-toxic with one possible  exception.
        Certain types of talc  contain asbestos fibers known as "tremolyte". Asbestos fibers including
tremolyte  are subject to very strict airborne concentration limitations.  Not all varieties of talc contain
tremolyte  and  those that do contain varying amounts.  New York State talc may contain 10% to
30% tremolyte, Montana  talc less  than 1%,  and Georgia steatite talc (soapstone)  10%. The extent
of the  toxicity problem associated with tremolyte has  not  yet  been agreed upon. In  any event,
                                           365

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it is not known to what extent tremolyte is present in the talc used by the paint industry.
       The  organic pigments  have been eliminated  from consideration  also. No  single organic
pigment is produced in sufficient quantity to be a significant factor in the total emissions picture.
Furthermore,  the processes  used are largely  liquid phase reactions under fairly mild conditions.
Air  pollution  problems on either a total emission  basis or on a per unit  product basis should be
quite low.  Many of the compounds involved  in manufacture are considered hazardous to humans,
however, so that there may  exist occupational safety problems but  such  problems are  not within
the scope of this study.
       The  pigments being  studied  in some  detail  include,  among the  whites, titanium dioxide
and zinc oxide. Among the inorganic color pigments the iron oxides, the chrome pigments  and the
cadmiums are included.  The cadmiums are  present by virtue of their potential toxicity rather than
production volume. The  following sections will detail  the  work that has been  completed  on  these
pigments to date.

II.      REVIEW OF MAJOR PIGMENTS
A.     Cadmium Pigments32>33
       A visit was  made to the offices of Harshaw Chemical Company on June 29, 1972 to discuss
the manufacturing of cadmium  pigments. Harshaw is one of the t'wo major producers of  cadmium
pigments and has two plants  which are located in  Elyria,  Ohio and  Louisville, Kentucky.  They
produce 20  cadmium lithopone yellows, 20 cadmium lithopone  reds, 32 full strength  cadmium
yellows  and  64 full strength cadmium  reds. They also  market but do not  produce 12 mercury
cadmium lithopone reds and 12 full strength mercury cadmium reds.  The colors produced range
from primrose yellow  to dark  maroon.  The pure cadmium  sulfide  is a  deep orange color. The
color variations are achieved by the addition of controlled amounts of zinc sulfate for the yellows
and selenium compounds for  the reds as shown below:
               Zinc Sulfide Addition  <	   CdS   	*   Selenium Addition

      Primrose <- Lemon <-  Golden ซ	Orange	ป Lt Reds —ป Dark Reds -ป Maroon
       The cadmium lithopone pigments contain barium sulfate as a diluent and offer better tinting
strength and  hiding power on a equal cost basis  with the high  strength pigments. They  are used
primarily where higher pigment loadings can be tolerated.
       The full strength pigments have approximately twice the tinctorial  strength of the  lithopone
                                         366

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types and are used primarily in the manufacturing of plastic color concentrate where low pigment
concentration and maximum hiding in thin films are desired.
       The  mercury cadmium  pigments are similar in color to the cadmium  sulfoselenide oranges
and reds but are mixtures of mercury sulfide with  cadmium sulfide. They are slightly lower in cost
but resistance to  heat, moisture  and exterior  weathering is not quite as good as the cadmium
sulfoselenides.
       Use  of cadmium  pigments  in trade  sale  products is limited almost exclusively to  artist
paints. Because of  its  high cost,  it  is used primarily for  high quality industrial finishes where its
heat resistance and good  weather ability are  required.  Typical applications would be for  high
temperature  bake enamel finishes and commercial airline and automotive finishes.
       A  simplified block flow diagram  for the production  of  cadmium  sulfide as it pertains to
potential emissions is given as  Figure 74.
       The  cadmium pigments are prepared by reacting an aqueous solution of cadmium sulfate,
CdSO4, (or cadmium chloride) with a solution of sodium sulfide, Na2S, (or HaS) in a stirred reactor.
Zinc sulfate  or selenium  may  be  added in the reactor or calciner to obtain the various shades.
The precipitate is  filtered, washed, calcined, wet ground in a ball mill, dried  in a shelf type steam
heated oven and dry ground  in a hammer mill. Cadmium lithopones are produced in  the same
manner except the  starting materials are  cadmium sulfate and barium sulfide and the precipitate
is a cadmium sulfide — barium  sulfate mixture.
       The  cadmium sulfate solution is produced by dissolving cadmium bar stock or sponge in
sulfuric acid  containing some nitric acid in a percolating tower at about  30ฐC.  Flower of sulfur is
sometimes added to the calciner and results in an SOa emission at the gas exit end.
       This  manufacturing process produces the following  emissions:32'33
       Percolating Tower                   CdO  — About 0.2% of charge
                                          NOz  — Amount unknown
                                          SOs  — Amount unknown
       Calciner                            CdS  — About  1.2% of cadmium charge
                                          Selenium  — Amount unknown
                                          ZnS   — Amount unknown
                                          SOa   — Amount unknown
       Calciner Scrubber                   Liquid  water-to-sewage  pretreatment. Uncollected
                                          emission — amount unknown but considered insignifi-
                                          cant
                                         367

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        Oven Drier                          Some  entrained  pigment  but  not  a significant
                                           emission
        Dry Hammer Mill                    Paniculate pigment emission but collected in a fabric
        and Product Blender                 filter for  recycle raw  material.  Cannot  be  used for
                                           product due  to  color  contamination.  Raw  material
                                           costs high  enough to make recovery economically
                                           desirable.
        In as much as the contribution of environmental pollution from manufacturing of  cadmium
pigment is miniscule  compared to a great number of other pigments, the only justification for
studying it in place of these other pigments would  be its potential as a health hazardous chemical.
This problem was discussed with Harshaw. They  are quite concerned, as one might expect, that
cadmium could be, in their opinion, erroneously labeled a health  hazardous material. They went
to considerable length to  point out  that practically no cadmium  pigments  are used in  trade sales
coatings, that cadmium pigments are manufactured as insoluble cadmium  sulfide (0.000001 gram/
100 ml) and are non-toxic due to their insolubility and that emissions in the manufacturing process
are cadmium oxide and sulfide.  Cadmium oxide  is also  considered an insoluble compound  but
no data was given.
        Harshaw  is very interested  in cooperating  with the EPA in  any way. They would be glad
to let the EPA source  test their plants and are quite interested to learn about any information the
EPA  may  have  on toxicity of cadmium,  especially  chronic poisoning.  They can furnish a bibli-
ography on all work published to date on cadmium  toxicity. They also mentioned that the NPCA
is sponsoring a study for the Fall  of 1972 on the toxicity of 23 heavy metals at the Kettering Institute.

B.      Zinc Oxide2.3-34-35
        Zinc oxide, either  leaded  or unleaded,  is  one of the most important white color pigments
used  by the coating industry. While its optical  properties are inferior to those of titanium  dioxide,
it is  able to  maintain  its  position in the  paint industry through its  ability to impart a variety of
desirable properties to paint films. Also, it is an  effective fungistat and  mildewcide.
        Use of zinc oxide by the  paint industry had been declining somewhat in recent years since
it was not  compatible  with the latex type paints then being formulated. Its  situation is beginning
to improve again and paint industry projections predict an increase in zinc oxide  use  of about
4% per year over the  next several years.31 Zinc oxide production in  1969 was about 220,000
                                          369

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tons.  The U.S.  paint industry accounts  for an  estimated  35,000 tons of this production.  Other
major uses include the rubber, pottery and glass industries.
       Zinc oxide itself  is considered non-toxic. Leaded oxides have a  toxicity in  proportion to
the amount  of lead present. The use of leaded zinc oxide is decreasing  rapidly  and is expected
to continue to do so.
       There  are three  principle  methods  used in  the manufacture of  zinc oxide:  the  French,
modified American and the Electrothermal.
       In the  French process, metallic zinc is vaporized in a retort under  a reducing  atmosphere.
The  zinc vapor  is then burned  in a combustion chamber  to  give zinc oxide particles which are
blown through cooling pipes and then collected  in baghouses and packaged.  In this  process, the
furnace gases do not come  into contact with the zinc  oxide  production system. A flow sheet is
presented in Figure 75.
       The  American process starts with zinc ore. The two types used are franklinite (ZnO) and
sphalerite (ZnS).  Franklinite has the  advantages of being almost free from lead impurities as well
as not requiring  a roasting operation to  remove  sulfur.  Sphalerite is more  available, however, and
most  of the oxide produced by the American process  uses this as its  starting material.  Some
franklinite is still used, however. In addition to lead, other common impurities include iron, cadmium
and  manganese. Cadmium and lead are  usually  produced  as by-products in  zinc processing
operations.
       A typical flow sheet for the American process is shown in Figure 76. A ZnS ore concentrate
is roasted in air to remove the  sulfur and  a portion  of  the lead and  cadmium. The  solid product
from the roaster  is mixed with some fluxes and coke and fed to a sintering machine where it is
sintered at temperatures as high as 1600ฐC but usually 1100 to  1200ฐC. Most of the remaining
lead and cadmium are  released in  the form  of oxide particles which are collected  with electro-
static precipitation or in a fabric filter.
       The product  from the sintering machine is crushed, mixed with coke  and fed  to a furnace
where the  zinc  oxide is reduced  and the  vaporized zinc  subsequently  re-oxidized.  The ZnO is
collected, calcined again to remove residual impurities  and/or control  particle size and packaged.
       The electrothermal process is similar to the  American  process except for the furnace. In
this case, the  product from the sintering  machine is  mixed with coke  and  charged to  an  electrical
resistance furnace. Electrodes are inserted into the  charge which serves as the resistance. The
zinc vapor and CO leaving the furnace are oxidized by air entering at the furnace exit. The product
                                          370

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is then collected and packaged.
       All of the above  processes are  presently in  use.  Most  producers use both the  French
and American  processes with a larger share of the production  from the American. St. Joseph
uses the  electrothermal process exclusively. All  of the producers except  Eagle-Picher roast their
own ore  at the plant  site. In the latter case, the ore is roasted at Blackwell,  Oklahoma by AMAX
and shipped  to the zinc oxide plant. Where roasting is done, the  SOa produced is used to manu-
facture sulfuric acid.
       The characteristics of the three processes described are similar with respect to particulate
emissions. The average particle size  of  ZnO  produced is  0.2 to 0.25  microns. Some  control of
the particle size  can  be accomplished  by a variation  in the rate  of oxidation, rate of cooling,  air
flow rate, etc. In this way, average particle sizes of 0.1 microns or  less can  be produced. Larger
sizes of 0.4 microns and up can be produced by slow chilling or separate calcination of fine particles.
       Product collection  is  achieved through the use  of baghouse type filters. Collection  ef-
ficiencies in excess of 99.9% (weight losses) are usually given for this type of collector. Very little
hard data is  available on  efficiency, however, since designers  tend to be  more interested in such
parameters as bag life,  flow rate  per  square foot, etc. It  must  be  kept in  mind that  extremely
fine particles are involved here  and this may affect efficiency.  Eagle-Picher did some tests a few
years ago and concluded that their filters operated  at  99.9%  efficiency. High efficiency in  a bag-
house is, of course, dependent  upon proper mechanical operation and on the integrity of the bag
filters.
       Since almost all of the 220,000 ton/yr of zinc oxide is from only five producers, an average
plant production of 44,000 ton/yr can  be assumed. Assuming 99.9% collection efficiency this represents
an emission of 44.0 ton/yr per plant, or about 0.12 ton per day per plant.
       In addition  to effluent through  the baghouse filters, losses can occur in the handling and
packaging operations. The amounts lost in this  manner are  largely  a function of plant housekeeping
and control. Product losses  from this source should be confined to the plant site and probably  do
not significantly affect ambient air quality.
       For the American  and electrothermal processes additional particulate  losses  may occur in
raw  materials handling. These are estimated to be about  0.25 tons  per  100 tons of  zinc oxide
produced.
       The  gas  phase effluent from the zinc sulfide roaster  contains SOa,  and some lead and
cadmium, probably  in the  form of oxide particles,  as well as smaller amounts of zinc. The  metals
                                           373

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are recovered in a cadmium  recovery plant. The sulfur dioxide is fed to a sulfuric acid plant. The
emissions characteristics of these materials,  then, are those characteristic of sulfuric acid manu-
facture and  cadmium recovery.  Roasting  of  zinc ores is  being  examined in detail in a  separate
EPA study of smelters.
       Most of the remaining 862, cadmium  and lead are volatilized in the sintering and calcining
steps. The vapors are fed to the acid plant and cadmium recovery units. In addition, small amounts
of chloride compounds from any fluxes used in sintering are released in these steps.
       Each of the three processes  includes a furnace, or burner, in which  the zinc oxide is pro-
duced. In the case  of the American  and  Electrothermal processes a reduction of the crude ZnO
also takes place and  is  included in the description of this  operation. All of the effluent gases from
these operations eventually pass through the baghouse filters discussed previously.
       In addition to particulate materials there exist other  potential sources of gas phase pollutants
from the  furnace. These come from the fuels and reducing agents used. For the American process,
coal is charged to the furnace in the  ratio  of two tons of roasted ore per ton  of coal. In the French
process,  vaporization of zinc metal  takes place under a reducing atmosphere  produced by the
incomplete combustion of about 0.7  ton  of coal per ton of  ZnO product. The quality of the coal
used in these operations can  affect emissions with respect to the oxides of sulfur and nitrogen. The
coke used in the Electrothermal  process should be relatively free of these contaminants.
       There exists, also, some possibility of CO emissions. Carbon monoxide is  part of the zinc
vapor stream leaving the furnace. This is burned in an excess of air  which should minimize the
amount of CO leaving the burner. This is confirmed by field experience.
       Process heat for the retort in the French process and,  perhaps, for air preheating in  all
the processes is supplied by burning either  coal, gas  or  oil. The combustion gases are released
directly to the atmosphere  and present a potential  source of  emissions.  The extent of emissions
depends  on  the quality of the  fuels used.
       There are five major producers of zinc oxide as shown in Table 107.  Two of these facilities
(Eagle-Picher and  American  Smelting &  Refining)  are devoted  solely to zinc oxide production.
The other twa companies  also  produce zinc metal at the  same locations.  All  of the producers
except Eagle-Picher roast their own sulfide ores. Approximately 50% of New Jersey Zinc's production
by the American process starts with franklinite and so does not  require a roasting step.
                                           374

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C.     Chrome Pigments2'30
       The  term  "chrome  pigment"  includes a variety of compounds  containing  the  chromate
group, CrO42ror chromium oxide. The chromates of lead and zinc are used as pigments alone or
in combinations with materials such as lead molybdate, PbMoO4. The colors available with chrome
pigments range from green to yellow to red. Consumption of chrome pigments in 1970 is  estimated
at 65,000 tons.3 The most recent year  for which production by types is available is 1968:3
                                                                      Production
              Type                         Formula                      ton/yr
       Chrome green                   PbCrO4  + Prussian Blue             2,830
       Chromium oxide green            Cr2O3                             6,230
       Lead chromate yellow            PbCrO4                           32,790
       Molybdate orange                PbCrO4  + PbMoO4                11,380
       Zinc chromate                   ZnCrO4                            7,400
       Chromate  compounds are considered toxic. Lead chromes have additional toxicity potential
due to the presence of lead. In both cases they are not  considered as hazardous as  the white
lead pigments.
       Paint industry projections predict a 12% decrease in the use of the lead chrome yellow
by 1975 and slight increases for the  other chrome pigments.31 The  possible introduction of more
stringent  regulations  with respect  to  lead content  in paint could affect this picture considerably,
however.
1.     Lead Chromes — A variety of reaction schemes, all involving precipitation, are used in the
production of lead chromates.  Precipitation  time, concentration of solution, pH and temperature
and other reaction parameters influence the properties of the final product.  The color depends
primarily on the crystalline form of the  PbCrO4. The lemon yellow rhombic form, usually the desired
product, readily converts to the stable,  reddish monoclinic form. Various techniques, such as co-
precipitation  with lead sulfate, have been found which  largely stabilize the  rhombic form. Another
stability problem is the  photochemical conversion of adsorbed soluble lead salts to metallic lead
and/or the lower oxides of  lead, which causes a darkening  of the paint film. Methods are available
to partially, though not completely, overcome this problem.
       Four commonly used reaction schemes are illustrated below:
                         Pb(NO3)2 + Na2CrO4 -ป PbCrO4 + 2NaNO3                       (1)
               2Pb(NO3)2 + Na2Cr2O7 + 2NaOH -ป 2PbCrO4 + 4NaNO3 + H2O             (2)
                                        376

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                      Pb(acetate)2 +  Na2CrO4 ->• PbCrO4 + 2Na(acetate)                    (3)
                   PbO + 2HNO3 + Na2CrO7 -ป 2PbCrO4 + 2NaNO3 + H2O                 (4)
Lighter shades  are  produced  containing  about  40% lead sulfate. Darker shades close to orange
are produced by alkali treatment and contain up to 40% PbO.
2.	Zinc Chromes — Pigmentary zinc chrome is most commonly a basic zinc potassium chromate,
K2CrO4  • 4Zn(OH)2. Zinc  tetroxychromate, ZnCrO4  •  4Zn(OH)2 is  also coming into prominence.
These pigments are lemon yellow in  color and  have some useful  properties, though they are
inferior to lead  chromes in opacity and in  staining power. Their main use is  the manufacture of
anti-corrosive coatings.  Both pigments  are  produced by  precipitation from aquous suspensions of
zinc oxide. Two methods are used in the production of basic zinc potassium chromate:
                         4ZnO + 2CrO3 + K2Cr2O7 + H2O -ป product                      (1)
                       4ZnO + 2K2Cr2O7 + H2SO4 -> product + K2SO4                     (2)
Zinc tetroxychromate is  produced from zinc oxide and chromic acid as follows:
                         5ZnO + CrO3  +  4H2O ->• ZnCrO4 • 4Zn(OH)2
3.	Chrome Green — Lead chrome greens are produced by mechanical mixture of lead chromes
and prussian  blue, KFe • Fe(CN)e • xH2O,  or by precipitation of lead chromes in the presence of
Prussian  blue. Manufacture of  these pigments represents an extreme fire hazard, since prussian
blue is combustible  and lead chrome will act as a source  of oxygen. This enables  chrome green
to burn independently of an external source of  oxygen. Large volumes of ammonia are produced
during combustion.
4.     Chromium Oxide Greens — This pigment consists of pure chromic oxide, Cr2Oa. It is prepared
by burning  a mixture of sodium dichromate and  sulfur.  About  30 to 40% excess sulfur  is used.
The reaction is indicated by the following equation:
                             Na2 Cr2O? + S -ป  Na2SO4 + Cr2O3
The excess sulfur is largely evolved  as SO2. Small  amounts of SO3  might also be present since
Cr2Os is known to catalyze  the oxidation of SO2 somewhat.
       Chromium oxide greens have  exceptional chemical, light  and thermal stability.  Its color,
unfortunately, is considered rather unattractive and this limits  its  use.  It  is  confined largely to
applications where durability is more  important than appearance. It  finds considerable military use
since  its infrared reflectance spectrum approximates that of natural foliage.
5.     Molybdate Orange — Molybdate oranges are produced by coprecipitation of lead chromate,
lead sulfate  and  lead  molybdate to produce a mixed crystal  PbCrO4 • PbSO4  • PbMoO4. This
                                          377

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forms a fairly stable system ranging in color from orange to scarlet. It is often used in combination
with organic reds and maroons to produce a variety of shades.
       As  a general group, chrome pigment  ranks second among the inorganic color pigments
in total tons produced for the paint industry. Of the five major types of chrome pigments produced,
four are made via wet chemistry and offer no significant air pollution  emission. The fifth, C^Oa, is
the only pigment that emits a  significant air pollutant.  The production of this pigment is only 10%
of  the  total  chrome pigment production and its use has  been declining. As outlined earlier,  it is
produced by reaction with elemental sulfur. Assuming a maximum of 40% excess sulfur is required
in  the  production, an emission of 1,050 tons/year  of 862 can be calculated from the yearly  pro-
duction of 6,230 tons/year of chromic oxide. Current technology for control of SOa is well developed
and requires no further  discussion in this report, and  it is sufficient to say that this emission can
be easily controlled.
       It is also anticipated that the use of the leaded chrome  pigment will also be declining in
the future by restriction of the lead content of paint. This decline has been reflected by the National
Paint & Coating Association's  "Raw Materials Usage Survey" for the year 1970. They project, for
example, a  drop of consumption of chrome yellow pigment  of 9% for the year  1972. This is  not
as severe as the 50% drop projected for lead  oxide pigments over the same period; but people
in the  industry are not  as yet  certain how the new ban on lead contents will be applied. It is  fair
to  assume, however, that the lead  ban on paints will reduce the usage of leaded chrome pigment
significantly. This fact coupled with the earlier discussion eliminates these pigments from  more
detailed study.

D.      Iron Oxides2-30
       Iron oxide pigments as  a group represent the most widely used  color pigments  in the
coatings  industry. The estimated consumption of these pigments in 1970 stands at 142,500 tons.3
This represents an  amount  exceeding the consumption of all  other  inorganic color pigments
combined. The popularity of iron oxide pigments can be attributed to their low cost,  good physical
and chemical properties  and the range of colors available. Iron oxide is non-toxic.
       Iron oxide pigments may be broadly classified as either natural or synthetic. About 53%
of 1968 consumption consisted of synthetic oxide.35 Paint industry projections predict only a small
increase  in  the use of  the natural material. An increase  in the use of synthetic  iron  oxide  of
from 25% to 42%, depending on the type, is projected between 1970 and 1975.31
                                         378

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       The color depends on the type of iron compound. Red pigments are essentially ferric oxide,
Fe22 production).
       Yellow  iron oxides,  ranging  in  color from light lemon to  deep orange,  are produced by
the following steps:
       1.  Precipitate ferrous hydroxide, Fe(OH)2, by the addition of alkali. The  precipitate forms
           a suspension.
       2.  Blow air at a controlled temperature through the suspension to form  geothite, -FeO • OH,
           "seed" crystals.
       3.  Provide an  additional  source  of ferrous ion  and  continue  to blow air through the
           suspension. One way this is accomplished is to introduce scrap iron into the tank. As the
           ferrous ion is oxidized, hydrogen ions are formed which simultaneously react with the iron
           to form additional ferrous. The reaction scheme may be  represented by:
                                          379

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                           4Fe2+ + O2 + 6H2O -ป 4FeO •  OH + 8H+
                                  8H++ 4Fe^4Fe2++ 4H2
                            4Fe + O2 + 6H2O -ป 4FeO • OH + 4H2
        The newly formed  oxide  is deposited on the "seed" crystals causing them  to grow until
        the desired size is reached.
        4.  Wash, filter, and dry.
        Paint industry projections predict a  42%  increase in the consumption of synthetic red iron
oxide pigments between 1970 and 1975. Production of  synthetic reds in 1968 was 34,342  tons.35
This figure does  not necessarily reflect production for uses other than as pigments.  Particle sizes
often encountered with red iron oxides range from 0.2  to  0.8 microns. There are three principal
methods used in manufacturing these pigments.
   -,    Copperas reds are produced by calcining ferrous sulfate at a temperature sufficiently high
to cause decomposition to  ferric oxide, Fe2O3- The ferrous sulfate is first subjected to a mild calci-
nation to remove hydrated water. This is followed by a severe calcination in air to cause decomposition.
The  reaction may be represented by the following equation:
                               2FeSO4 -* Fe2O3 + SO2 + SO3
This  reaction has a dissociation pressure of 546  mm at  654ฐC. Copperas reds are considered the
most important group. They accounted for 18,910 tons production in 1968.35
        Ferrite reds are produced by  the dehydration of yellow ferric oxide. If calcined at 400 to
600ฐC, "Turkey Reds" are produced. If calcined at upwards of 900ฐC, "Indian Reds" result.
        Precipitated reds are produced by precipitation from copperas or  ferrous chloride solutions.
The  ferrous hydroxide is precipitated with caustic, aerated at 60 to 90ฐC,  and then washed, filtered
and  dried. No calcining is  involved. This produces a pigment free of aggregates and quite uniform
in size.
        A fourth type of red is made in very small amounts. This is Venetian Red made by precipitating
copperas with lime,  aeration  and calcination to produce a pigment containing  40% Fe2C-3 and
60% CaSO4.
        Brown iron oxide pigments can be  made by blending  the pure  reds, yellows and  blacks
or by precipitation and calcination. Blacks  are produced by complete precipitation  from  copperas
or ferrous chloride followed by aeration at the boiling point of the solution. 6,177 tons of brown and
3,560 tons of black iron oxides were manufactured in 1 968. 35
        With one  exception, all of the processes used for manufacturing iron oxide pigments should
                                          380

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be relatively free of atmospheric emission problems.  Most of the operations are aqueous in nature
and do not produce gas phase pollutants. Since the fine particles of dry pigment eventually produced
represent product, it would be expected that paniculate emissions would be well controlled. Adequate
methods are available for highly efficient collection of fine particulate.
       The one process  which can  produce serious problems  is the manufacture  of  copperas
reds. Here the production of large volumes of SO2 and SCb must be contended with. The production
of 18,910 tons of copperas red  causes the release of 7,600 tons of  862 and 9,500 tons of  SOs.
This must be recovered as  sulfuric acid or otherwise accounted for.
       There are  two major producers of synthetic iron oxide pigments along with a number of
smaller  manufacturers. The largest  producer is Cities Service, Inc. with a plant producing precipi-
tated yellows and  reds at  St. Louis, Missouri  and another producing  synthetic reds  at Monmouth
Junction, New Jersey.  The second major producer is  Pfizer Minerals with plants at East St. Louis,
Illinois, Easton, Pennsylvania and Emeryville,  California. The plants at East St. Louis and Easton
produce calcined copperas.
       The smaller producers include Reichard-Coulston, Bethlehem, Pennsylvania. Their production
includes  calcined copperas. They  report that  they have a scrubber  of unspecified  type on  their
copperas calciner.
       Mineral Pigments Corporation  at the present time does not manufacture red iron oxide and
deals primarily  in natural materials.  Chemtron  and Hilton-Davis both produce a line of transparent
iron oxides for the specialty market, primarily automotive finishes. These are made by precipitation
processes followed by mild  calcining to remove water.

E.     Titanium Dioxide Pigments3'36
       Titanium dioxide  is an opaque, white material. When used  as a pigment in the paint  and
lacquers, it provides excellent hiding power due to the very high refractive index of the two crystalline
forms,  rutile and anatase. This excellent hiding power and lack of toxicity combine to make titanium
dioxide the leading hiding pigment  in the paint industry, measured by either tonnage of material
consumed or dollar value.
       Two processes are  used for the production of titanium dioxide pigments. These are the
sulfate process and the chloride process. These processes use several titanium-bearing raw materials.
The principal  sources of these are:
       1.  llmenite, or iron titanate, which is mined in the U.S., as well as several foreign countries.
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       2.  Slag from the electric-furnace smelting of ilmenite which yields a salable iron product
           and a high — TiOa content slag.
       3.  Rutile, which occurs  naturally in Africa, Australia,  and several other countries outside
           the U.S.
       4.  Leucoxene, a highly-weathered  ilmenite possibly supplemented with minor amounts of
           ilmenite containing 70 to 80% TiC>2.
       The sulfate process is the  oldest and  most  versatile of the two processes. It may use
ilmenite or slag, and is capable of producing either rutile or anatase. The chloride process produces
equivalent  products. The details  of  chloride process  technology  are  often considered  proprietary
by the industry and it is difficult to define  the  state  of the art.  Historically,  the chloride process
has produced rutile pigment only and has required  rutile ore as raw material. Currently, however,
techniques have been developed which permit  use of ilmenite ore  (possibly upgraded). Also, it is
now possible to produce  anatase  TiOa by the chloride process.
       This discussion is concerned principally  with the manufacturing process  for titanium dioxide
as they relate to atmospheric emissions. Much of the information available relating to the economics
of the application of the two principal pigment types and the many variables with  regard to particle
size, surface chemistry,  etc., will be omitted from  the discussion if they do not  have a particular
bearing on the emission-related  characteristics  of  the process. On the other hand,  those  details
of the manufacturing process and properties of the  materials which do relate to variations in atmos-
pheric emissions from one plant to another or within  a given plant,  will be included.
       Of particular interest in the consideration of the process in the following paragraphs is the
fact that there is  a limited  number  of  producers  of  titanium dioxide  in the U.S.  Each of these
practices the processes  described in ways that incorporate some  characteristics peculiar to that
manufacturer. This discussion will not  identify all of the  processing variations  and relate them to
specific manufacturers. However, those which are  important to the atmospheric emission aspects
of the  process have been characterized insofar as possible, with respect to the particular  manu-
facturer.  Those companies  known to be engaged  in the production of titanium dioxide within the
U.S. at this time are tabulated on  the following page.
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                                                     Sulfate                  Chloride
        Manufacturing Company                     Processing               Processing
        American Cyanamid                            Yes                      Yes
        Kerr-McGee                                    No                      Yes
        Cabot Corporation                               No                     Yes*
        DuPont                                        Yes**                    Yes
        New Jersey Zinc                               Yes                     Yes*
        NL Industries                                  Yes                      No
        SCM Glidden                                  Yes                      Yes
        Sherwin-Williams                                No                      Yes
 1 .      Sulfate Process — The most common raw material for the sulfate process is ilmenite. The
 principal constituent of ilmenite is iron titanate,  FeO  • TiO2. This is found associated  with various
 minerals,  such as vanadia, alumina, etc. Table 108  gives the chemical composition of  several of
 the ores with each of the elements reported  as  its oxide form. In addition to the common ilmenite,
 found  in the U.S.,  in the Adirondacks and in Florida, and in  Australia and  Canada, a co-product
 slag produced  by the smelting of Canadian  deposits is a frequent raw material for titania manu-
 facture in the U.S.
        In the sulfate process, the iron titanate is dissolved in concentrated (66ฐ Baume) sulfuric
 acid to yield titanyl sulfate, ferric sulfate, ferrous sulfate  and other soluble mineral sulfates and
 gangue residue. The principal  reaction, greatly simplified, for this digestion  is:
                      FeO •  TiO2 + 2H2SO4 -ป TiOSO4 + FeSO4  + 2H2O
        This reaction is carried out batch-wise in multiple digesters which feed a semi-continuous
 process. The solid sulfate cake is dissolved in water and recirculated acid to yield "sulfate solution".
 The immediate objective is to put as much of the titanium  into solution as possible. At  this point,
 it is objectionable to have metals of high valence present in the solution and the solution is treated
 with a reducing agent such as metallic iron to bring about reduction  of ferric ions and other metal
 impurities to a low valence state. The typical  reduction reaction taking  place in the digester  is:
                                     Feฐ + 2Fe+++^ 3Fe++
 After digestion, all of the insoluble metallic components are filtered and removed from the solution.
 All of the iron remains in solution at this point.
 *N.J. Zinc has recently been reported to have leased the chloride production facilities of the Cabot
  Corporation.
**Will be discontinued by the end of 1974.
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        TABLE 108
ANALYSIS OF ILMENITE ORES
United States
Canada

Virginia
Chemical
Constituent
TiO2
FeO
Fe2O3
Si02
AI2O3
P205
ZrO2
MgO
MnO
CaO
V205
Cr2O3
Piney
River
44.3
35.9
13.8
2.0
1.21
1.01
0.55
0.07
0.52
0.15
0.16
0.27
Roseland
51.4
37.9
1.6
4.6
0.55
0.17

• 2.35
0.70-
0.59
0.07

New York
44.4
36.7
4.4
3.2
0.19
0.07
0.006
0.80
0.35
1.0
0.24
0.001
Florida
64.1
4.7
25.6
0.3
1.5
0.21

0.35
1.35
0.13
0.13
0.1
California
48.2
39.1
10.4
1.4
0.2

0.05
0.6
0.1
0.1
0.05
0.03
Ivry
42.5
39.1
20.7
0.88
1.05


2.0
0.04
0.1
0.36
0.15
Bourget
22.4
36.9
31.2
1.0
6.01
0.93

1.50

0.55


Allard
37.3
26.3
30.0


0.004


0.10

0.39

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        When ilmenite is used, the next processing step consists of cooling the solution to crystal-
lize  out  some  of  the  iron as  FeSO4—7H2O.  The next  processing  step involves the  dilution and
heating  of the sulfate  liquor,  which hydrolyzes the titanyl sulfate  and brings about  precipitation
of titania. The basic chemical equation for this  hydrolysis  step is:
                                TiOSO4 + H2O -> TiO2  + H2SO4
        During subsequent processing, the titania is  present as a precipitate, and most of  the
impurities remain in solution. Several filtering and washing steps follow, in each of which the titania
is retained on  the filter,  and the filtrate  and wash water are recycled or discarded. Although  the
basic TiO2 material is formed during the hydrolysis step, the product of this part  of the  reaction
is a  fine, non-pigmentary material.
        Subsequent processing  steps  are  aimed  at  modifying the particle size and  crystallinity,
conditioning the surface  of the  particles and performing other proprietary treatment steps to produce
a final pigment material  with the desired properties. The  next step in the preparation of the  finished
pigment is calcination.
        In a  rotary  calciner, the  TiO2  "hydrate" cake is dried and calcined  to achieve the  final
crystalline product.  Here, no basic chemical  change takes  place, but the recrystallization of  the
titania to form either anatase or rutile crystals of the desired size, is accomplished.
        Following  calcination, the crystallites are milled  and packaged for  shipment. Alternatively,
the particles  may  be treated with various surface-coating agents to achieve particular properties of
dispersibility, resistance to weathering, etc.
        Figure  77 contains a detailed process flow diagram  for the  manufacture of either  rutile or
anatase from ilmenite by the  sulfate process. Some of  the processing steps in this process  are
carried out batch-wise, while others are continuous. Similarly, some of the emission sources produce
variable  rates and compositions of air pollutants while  others  are relatively  steady and continuous.
        The  ilmenite ore* is  a black,  powdery material of  relatively coarse  particle  size, which
produces some dusting  as  it  is  transferred  from rail  car, ship  or truck to  an ore holding yard
to await processing. Again, some dusting may occur as the ore  is loaded  onto  belt or bucket
conveyors for transfer to the ilmenite dryer, which forms the first step in the  manufacturing process.
        The  ilmenite is  dried  in  a counter-current gas  or oil-fired  dryer.  The dryer is  generally
equipped with  a mechanical dust collector, fabric  collector or electrostatic precipitator at the gas
discharge end. Dust captured  by the collector is returned directly to the process. Because of  the
*lt will be understood that in the following discussion, the term  "ilmenite" is meant to include, also,
 high TiO2 slag.
                                           385

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00
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0
                                                                           J

                                                                           0.
                                                                         9-
                                                                           5
                                            387

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relatively coarse size  of  the  raw ilmenite, there is  little  net  loss  of  dust  from the drier.  Sulfur
dioxide  may be present as a gaseous  emission if fuel oil  is used rather than natural  gas.  The
drier ordinarily  runs continuously and feeds dry  ilmenite ore to a ball or pebble mill for grinding.
        The rotary mill operates without any gas source, and is relatively free of a dusting problem.
Following the mill, the ground ore passes through a  classifier  which separates oversized  particles
for  return to the mill  and passes  particles of sufficient fineness to  one of the batch digesters.
Here again, there is no gas emission from  the classifier and therefore, little likelihood of emission
of dust or fumes, although electrostatic precipitators may be used on  some milling systems.
        The digesters are charged sequentially with dry, milled ilmenite ore.  During charging, there
may be some  dust  emission  through the ventilating  stack on each of the  digesters.  Charging is
complete in a matter of a few minutes,  and the  dust emission ceases when the ore has become
wetted with the sulfuric acid added to the digester.
        The initial digestion reaction  starts relatively slowly, with the reaction mass at  a temperature
slightly  above ambient temperature. Steam is added  to  increase the temperature and the reaction
rate, and air sparging for agitation may  be used.  As the exothermic  reaction  proceeds, the temper-
ature of the  reaction mass increases and the rate of reaction  increases.  After approximately  5 to
30  minutes, the reaction rate reaches a  peak for about 10  to 15 minutes and the maximum  rate
of emission of  steam, sulfuric acid  mist, particulate  matter  and sulfur dioxide  through the stack
occurs.  Subsequently, the reaction  slows down,  but steam emission continues until the reaction
mass has "set" to form a solid.
        After the digestion reaction is  complete, water and possibly some recirculated acid, is
added  to the digester to  dissolve the solid. At this point  in the cycle, scrap iron in a basket-like
container is immersed in  the  solution and allowed to remain in contact with the solution  until the
reduction of ferric ions to ferrous and some slight reduction of titanyl sulfate has taken place. Other
reduction techniques may be used in some plants. When the desired degree of reduction is achieved,
the sulfate solution is transferred to a clarifier.
        The clarifier is  basically a large settling tank in which a rotating rake processes  settled
material toward the  center for removal as  a solid "mud". Although the digesters discharge inter-
mittently, the clarification  tanks operate  on a  continuous  basis. In the clarification  process,  pro-
prietary floculating  and coagulating agents may  be  used to  improve sedimentation of the  solid
impurities.  In some  cases, hydrogen sulfide or other chemical reagents  may be added to aid in
the floculation  and removal of  solids. It is customary  to  use completely closed clarifier vessels,
                                            388

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even if hydrogen sulfide or other gaseous reagents are not  used.  Typically, the clarifiers operate
at 60 to 80ฐC  and some evolution of water vapor is normal. The mud collected at the bottom of
the  clarifier is  washed with recycled sulfuric  acid to remove any  dissolved  titania and the acid
from this washing  is returned  to the digester. The mud is disposed  of by landfill, by  sluicing  or
may be used as a source of minerals in a recovery process.
        The clarified  sulfate solution may be passed through a filter process to remove  the last
traces of solid material and then passed  into an iron sulfate cyrstallizer. This is simply a closed
vessel which is evacuated  through  a steam jet  ejector  to  a  barometric condenser. The pressure
reduction brings about evaporation of water from the sulfate solution which cools the solution and
concentrates it with respect to both titanium sulfate and iron  sulfate. The objective of this step
is to crystallize some of the iron sulfate for removal from the process.*  The crystallization takes
place in multiple-batch vessels which are  mechanically agitated  as the cooling, evaporation and
crystallization take place. After  sufficient  water has been  removed, the slurry of iron  sulfate-titanium
sulfate solution is passed  through a drum filter  where  the ferrous  sulfate solid is removed. This
solid product  consists almost  completely  of  FeSO4 • 7H2O,  and  is  normally called "copperas".
Copperas is not produced when slag is the principal raw material.
       Copperas is the principal raw material used in the manufacture of iron  oxide pigments, and
certain other iron containing pigments. It is fairly common for a plant preparing iron pigments to be
located  nearby and to use  the wet  copperas filter cake, as  it comes off the filter press,  for raw
material. In  some cases, the use of the copperas is restricted to plants located at  some distance
from the titanium oxide plant. When  this is the case, the filter cake is conveyed to a rotary drier
and  copperas is dried for bulk  shipment to distant points.  Where a drier is used,  it is  necessary
to provide a mechanical dust collector and possibly  a fabric  collector on  the  flue gas discharged
from the drier.
       The filtrate  from the copperas filter is conducted to evaporation  and concentration  vessels
in which further concentration of the titanium sulfate solution takes place batch-wise. This vessel
is provided with steam heat coils and operates under vacuum provided by  a barometric condenser.
This concentration step increases the titanium  concentration to the  equivalent  of about 200 grams
(measured as TiCk) per liter of solution.
       Further heating is accomplished  in  a separate stirring-heating  vessel using  steam coils as
the heating  source. After this  heating step, the strong  solution is  diluted and  additional  heating
 •Normally, crystallization is not done when processing slag solutions.
                                          389

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brings about hydrolysis of the titanyl sulfate to hydrated titanium dioxide. It  is in this step that the
predominant color of the titanium  compounds changes. In all prior  steps,  the predominant color
of the solution and  slurry materials  is the black of the ilmenite and the  sulfate solutions. In the
hydrolysis step, the  white color associated with titanium dioxide pigment develops. From this point
forward in the processing, the processing equipment is referred to as the "white end" of the plant.
        After boiling from 3 to 6 hours in the hydrolysis reactor, the  slurry  is transferred to filters
in which the precipitated titania  is separated  as  a solid product and the filtrate is circulated to a
closed  spent-acid clarifier.  The  overflow from this clarifier is  partially recycled to  the digestion
process and to the mud washing step, and the remainder to disposal. The underflow contains some
titania which passed through  the  filters.  This  sludge  is recycled to  the filters  for  recovery. The
solid  titania removed from  the leaf filters  is reslurried with water  and transferred  to a bleaching
reactor. In this step, conditioning agents, dilute acid  and materials  such as aluminum  or zinc are
added to  bring  about  a slight reduction  in the titania  and produce  the optimum  brightness. The
material leaving the conditioner  is  filtered  and dilute acid filtrate recycled through a slurry  settler.
Overflow from  the dilute  acid settler is recycled or discarded while the solids are recycled to the
bleaching step. The titania hydrate  retained by the filter is washed  on  the filter and  transferred
to a  second conditioning step.  Here, proprietary  conditioning agents  are added  to  modify the
crystalline structure  and improve the properties of the final pigment.  For example,  antimony may
be added  at this step to modify the chalking properties of the titanium pigment.
        The slurry is again filtered,  with washing of the filter cake  on the drum,  and recycle of
the dilute acid  filtrate into the dilute  acid settler. The washed solid material is discharged  into the
calciner.
        Catalysts for promotion  of rutile  formation  may be added at the calciner  inlet if  rutile  is
the desired  end product.
        Calcination comprises a  critical step in the pigment processing in that it is in the calciner
that the final crystalline form is established as either anatase or rutile. Also,  the gaseous discharge
from the calcination step comprises  one of the largest and most difficult single emission sources
in the manufacture of titanium pigments.
        The calcination step  involves the  removal  of  water of  hydration from the  titanium slurry,
and, subsequently, crystallation of the titanium dioxide. During the first half of the calcination process,
water alone is removed from the  solids being transported through the rotary calciner. As the temper-
ature reaches 200ฐC or so, water evaporation is complete  and sulfuric acid  vapor is released from
                                            390

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the solid. The temperature  continues to increase as the solid passes through the calciner toward
the firing end and temperatures of 900ฐC or so are reached at the discharge end.
        The equilibrium product from the calciner is the rutile form of TiC>2.  However, the anatase
form tends  to be produced as an  intermediate,  and severe  calcination  conditions, that is, high
temperature and long residence time, are required to  produce recrystallization to the rutile form.
It has  been found  that the formation of rutile is promoted  by the  addition of catalytic materials.
These are used  as  "rutile promoters" if rutile is the preferred product.
        The calciner is generally fired with natural gas or oil. In addition to the products of combustion,
sulfuric acid vapor driven from the titania is released into the gas stream, and this partially decomposes
to produce SOa  and small amounts of 862 by decomposition of the sulfuric acid. In addition, there
may be some entrainment of the titanium dioxide at the feed end, although this is nominal because
of the  large size of  agglomerate particles and  the  relatively high moisture content at the feed
end of the calciner.
        The treatment of the flue  gas discharge  from the  calciner varies from plant to plant. One
of the common combinations of processing steps is shown in Figure 77. This involves water quenching
of the  flue gas to reduce the temperature to well  below the condensation temperature of sulfuric
acid mist (below 240ฐF or so)  and  provides an  initial water wash step.  Effluent  from the cooler-
condenser then  passes upflow  through  a tubular  electrostatic precipitator.  Lead is the  preferred
material of  construction for ductwork,  precipitator tubes  and  housing. The discharge  from  the
electrostatic precipitator then passes through a final scrubber, constructed of redwood. Condensate
from the  precipitator  as well as the water from  the initial quenching step  is recycled to various
parts of the process.
        In the final  washer,  large volumes  of water are  used on a once-through basis and achieve
substantial reductions in sulfur  dioxide concentration  in the gas. This water  is ordinarily discarded
after use in the scrubber.
        An alternative processing scheme utilizes a venturi scrubber with approximately 40  in.
water column pressure drop across the throat to accomplish the  sulfuric  acid mist recovery in
place of the electrostatic  precipitator. This use  of venturi scrubbers at this stage of the process
must be considered experimental, as of this date, since fully satisfactory operation of such scrubbers
has not yet been achieved.
        The  hot titanium dioxide leaving the discharge end of the calciner passes through a cooler
and then into the final finishing  line. Finishing may be accomplished by a sequence of wet finishing
                                          391

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operations, or, alternatively, by dry finishing.
        In the wet finishing scheme, the calcine passes in sequence through a Hammermill and
rotary pebble or ball mill. Water is added in the Hammermill and all of the subsequent operations
are carried  out  with the  titania wet. Wet classification with recycle  of oversized material to the
pebble  mill  is followed  by thickening of the slurry. The underflow from the thickener is treated in
a conditioning reactor in  which surface coating agents and other conditioners may be added to
modify  the  properties  of  the  titania. For example, aluminum hydroxide or  silica may  be added
to alter  the  dispersion  properties of the pigment, according to whether it is intended for dispersion
in oil-based vehicles or  in water.
        After the final conditioning, the pigment is again filtered and washed on a rotary drum filter
from which  the  filtrate  is recycled to the final  thickener.  The filter cake  is  dried and  discharged
into a final  milling step. This  mill  or "micronizer" deagglomerates the titania  to produce the basic
particle  size set originally in  the  crystallization and calcining steps.  The micronizer operates  by
subjecting the dried solid to extremely high velocity jets of steam. The stream  leaving  the micronizer
is condensed and the  finished  dry product is packaged in bags or  conveyed to bulk containers
for bulk shipment.
        The dry  finishing  alternate  consists  of roller milling and Hammermilling prior to  packaging.
The  roller milling step  involves the production of  a substantial quantity of  entrained titania dust
which is collected in a large  cyclone and a final fabric filter. The material collected from both of
these recovery  stages  is  passed  on  to the Hammermill,  which produces  the final particle size
desired. Again, the final product may be bagged or prepared for bulk container shipment. Materials
intended for water base paint applications  or for use in paper manufacture  may be reslurried for
wet transport.
        In a complex industrial process involving many stages, there are numerous potential  sources
of atmospheric emissions. Many of the  potential sources  relate to housekeeping and retention of
product within the process rather  than  to  necessary gas  emissions  into the atmosphere. In the
production  of titanium  dioxide, many opportunities present themselves for loss of product as dry
transfer operations  and handling of the ilmenite ore, calcine or final product are  carried  out. In
this discussion, only those sources which relate to  necessary emissions of gas from the  processing
stages will be considered  as legitimate potential air  pollution emission sources.
        The most significant of these legitimate sources involves the drying of the initial ore, digestion
of the ore  or slag  and calcination of the titania after hydrolysis. In  some of these, the gaseous
                                           392

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emission  consists principally  of the  products  of  combustion of the  drier or calciner into  which
 paniculate matter is entrained.  In addition, sulfuric  acid and SO2  are emitted  by the  calciner as
 the result of vaporization and decomposition of sulfuric acid from the  titania hydrate calciner feed.
In the case of the digester,  the gaseous emission  consists principally of steam  produced by the
vaporization of water as the digestion reaction is carried on. Each of these sources  will be discussed
in some detail in the following paragraphs. In addition, a number of secondary sources exist which
involve limited discharge of gases into the atmosphere or from which the discharge  is routinely
and uniformly controlled in order to preserve the basic product. Examples of these secondary sources
are:
               Ore milling
               Copperas drying
               Final milling of pigment product.

2.      Chloride  Process — The  chloride process  for titanium dioxide pigment  production is an
alternative route  to the  manufacture of rutile  pigments.  The  process is continuous  to  a  higher
degree than is the sulfate process,  yields a pigment of lower impurity content which may be important
in some applications,  and, generally,  has fewer  sources  of emissions requiring control. On the
other side of  the ledger, the chloride process has historically been  limited in the range  of  raw
materials which can be used to rutile or high - TiO2 feed stocks. It involves corrosion, heat transfer
and materials handling problems of unusual severity.
        The fundamental chemical reactions  involved consist of chlorination of  titanium dioxide
according to:
                               C +  TiO2 + 2CI2  ->• TiCU  + CO2
                            and  2C + TiO2 + 2CI2 -ป TiCI4 + 2CO
        After chlorination, the liquid titanium tetrachloride is purified by  various solids removal, chemical
treatment  and distillation procedures and is then oxidized according  to:
                                  TiCU + O2 -ป  2CI2 + TiO2
        These simple equations do not, of course,  express the complexity of, nor sophistication
required for, the manufacture of TiO2 by the chloride process.
       The basic flow scheme  is illustrated in Figure 78. Ore, or  combinations of ore and slag,
are charged into a continuous chlorinator along with  coke. The TiO2 bearing  ore and the coke
are frequently shipped  by rail or  ocean-going vessels and  unloaded for storage in open areas.
                                           393

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394

-------
The moisture content  of both coke and ore stored outside is  likely to become too high for use
in the chlorinator, unless it is dried  in gas-fired rotary driers as shown in the box in the lower
left hand corner of Figure 78.  If these driers are used, the dust generated in handling is a potential
source of pollution,  and the flue  gases must be treated by mechanical  collectors, fabric filters
or other particulate abatement device  prior to discharge into the atmosphere.
       In some cases, it is possible to arrange for unloading and storage of the ore in enclosed
buildings  or sheds.  This prevents  the accumulation of excessive moisture contents in  either raw
material, and obviates the need for drying.
       In either case, some dusting  of the dry ore and coke in the handling process  involved in
removing them from  storage and elevating  them to the reactor level is unavoidable. It is  customary
to ventilate the conveyors, elevators, etc., through a fabric collector, or other high-efficiency particu-
late control device. Figure 78 shows a pressurized fabric collector on  the ventilating air drawn from
two bucket elevators.
       The coke serves as a reducing agent and  receptor for  the oxygen liberated  during chlori-
nation of the titanium  ore. Gaseous  chlorine is fed  into the reactor and  carbon dioxide,  carbon
monoxide and titanium tetrachloride vapor are the principal products. Substantially all of the chlorine
and all of the coke  are used up  in  the chlorination process. Following condensation  to remove
titanium tetrachloride, gases vented from the chlorination reactor consist principally of carbon monoxide
and carbon  dioxide and other impurities such  as HCI,  traces of sulfurous gases  and possibly free
chlorine.
       Where free chlorine is present at  this  point,  it may produce a serious corrosion  problem
in subsequent piping or equipment, and may contribute  to pollution.  For this reason,  the  reactor
is carefully  designed to  minimize  the free C\2 content at the reactor exit, and  methane may be
introduced at this point to eliminate or minimize the Cla content. The reaction of methane with Cb
produces HCI. Also,  there  is a possibility of discharging  substantial  amounts of Cla, oxygen, and
water during an upset  in reactor operating  conditions, and the use of methane to minimize oxygen
and C\2 discharge under these conditions is helpful.
       This gas is potentially valuable due  to the heating content of the unburned carbon monoxide.
However, practice varies as to the purification and use of the carbon monoxide values. Some chloride
process operations involve scrubbing  the off-gases  for chlorine,  HCI,  and TiCU removal and flaring
or direct  discharge to the atmosphere to dispose of the unwanted gas.  Others follow these steps
and then remove the carbon monoxide gas for use as an auxiliary fuel in the titanium tetrachloride
                                            395

-------
burner.
        Where  flaring of the carbon monoxide-rich gas is practiced,  the  removal of  traces of sul-
furous gases, chlorine or chlorides may be required to avoid an emission problem. Scrubbing with
water and  an alkaline liquor in a countercurrent  packed scrubber should  provide satisfactory air
pollution control.
        The titanium tetrachloride produced in the  chlorinator is  purified by distillation and chemical
treatment.  Distillation may consist of a number of flash vaporizations, as shown in  Figure 78, or
it may  be  carried  out  in  rectification and stripping  towers. The removal of unreacted solids  is
accomplished  by sedimentation and  distillation. Generally, these operations are carried out  in a
pressurized system  without any gaseous  discharge  to the atmosphere. In sections of the  plant
containing  liquid titanium  tetrachloride,  particular attention must be given to the handling of  relief
valve vents, potential leaks,  spills,  sampling,  etc.  Titanium tetrachloride hydrolyzes spontaneously
upon discharge into the  atmosphere to form extremely  dense white fumes of  fine particle  size,
and even a minor leak may create emissions of high opacity.
        The heart  of the  chloride process is  the  titanium tetrachloride burner.  In this burner, the
titanium tetrachloride is  burned with air  or pure  oxygen, together with,  in  some  processes, an
auxiliary fuel. The  auxiliary fuel  may consist of carbon monoxide, from the  chlorinator, or a hydro-
carbon,  or  it may  be omitted altogether. The  use of  auxiliary fuel permits an additional degree of
freedom in  controlling the  temperature and  chemical composition of the burner feeds.
        In the specially designed burner, the oxidation of  titanium tetrachloride must be completed,
and  crystallites of  proper  structure  and size must  be formed.  In order to accomplish the chemical
reaction and proper control of the crystallite structure  and size, and to avoid plugging of the burner
by TiOz deposits, the titanium tetrachloride  burner design is critical. Mechanical design of the burner
to produce the desired  product is one of  the key factors in the success of the chloride process.
The  reaction taking place in the burner produces free chlorine plus titanium dioxide as reaction
products. The combination of the high chlorine concentration  in the effluent gas, coupled with the
high temperature generated in the burner (1800ฐC)  produces a corrosive situation much more severe
than that generally encountered in  chemical processes. Exotic  materials  of construction, inorganic
refractories, etc. are the rule rather than the exception in this part of the process.
        The quenching of the hot combustion products in order to prevent undesirable TiO2 sintering,
the separation  of the titania from the gaseous chlorine and the ultimate  removal of  heat from the
process are  among the  most  formidable and  challenging problems encountered  in  a chemical
                                            396

-------
process. In  one process variation (NL  Industries  patent No.  3,560,152) the combustion products
are quenched with cold recycled chlorine. The gas stream then passes to bag filters in which the
TiO2 is removed by means of Inconel fabric filter elements. Process heat removal is then accomplished
by direct contact  scrubbing  of the hot chlorine by concentrated sulfuric acid,  and the heated acid
is  indirectly  cooled by cascade coolers. The chlorine is then  recycled to  the  quenching step, and
to  the chlorination reactors. The titanium dioxide is conveyed from the bag filters, slurried in water,
and further processed by wet-finishing as previously described.
        Practice varies widely with regard to the method of quenching  the hot burner effluent and
separating  the  TiO2  pigment from the hot  gas.  However, regardless of the approach used, there
should be no interconnection of process streams with ambient air, and  no potential for air pollution
during  normal operation.
        The final  pigment product is milled  and packaged as in the sulfate process. These steps
involve  the  routine recovery  of pigment for product conservation, and  are not significant  sources
of  air pollution. Here again, practice in the  finishing steps vary widely  from  one plant  to another.
A  manufacturer may be  required to process TiC>2 for a wide variety of special applications, and,
therefore, need many trains  of finishing equipment, including driers, reslurrying, filtering, washing
and  treating tanks.  On the other hand, it may be  possible  to produce  only a  few products,  all
of  which are treated  in a single train.
        The total  amount of ventilation air  required to avoid  unsatisfactory working conditions in
the treating area  may vary from as little as 1500 SCFM to  many  thousands,  depending  on the
nature and complexity of the treating equipment. However, the potential for air contaminant emissions
from this part of the process is quite limited in either case.
        In summary, the principal source of atmospheric emission in the chloride process  is the
chlorinator  vent gases, consisting mainly of carbon monoxide and  carbon dioxide with traces of
sulfurous gases,  and  possibly hydrochloric acid,  chlorine  and titanium  tetrachloride.  Secondary
sources are equipment and tank vent systems, but these are usually easily controlled by caustic
scrubbers.  Finally, special attention is required to avoid accidental spills of titanium tetrachloride,
and leakage of  gaseous chlorine.
3.	Industry Statistics — Questionnaires —
a.   Products and  Raw Materials — Table 109 presents data obtained from the TiOa industry question-
naires on products and production. Most of the data covers the year ending  12-31-72. Total TiO2
produced by the six  plants which did  not consider such data confidential was 140,040 tons by the
                                            397

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sulfate process and 249,000 tons by the chloride process. Two of the plants produced pigment by
both techniques.
       A summary of production and raw materials  for those five plants which reported both  is
given in Table 110. Examination of this table reveals  some interesting features.  First, even though
the chloride process  has by far the majority of the production, ilmenite is the  dominant titanium
raw  material  with rutile maintaining a rather  minor position. Second,  sulfuric acid consumption  in
the sulfate process amounts to about  3 tons of H2SO4 per ton of finished TiO2 shipped.  A large
part  of this is potentially part of an air or water pollution problem, though a  significant  amount
can be accounted for  in the copperas by-product.
       Finally,  chlorine consumption in the chloride process  is considerably higher than might be
expected in light of the fact that chlorine recycle is employed. Making  an adjustment for the TiCU
product shipped, chlorine consumption  amounts to somewhat more than 1/2 ton  per ton of finished
TiO2. It cannot be concluded that all of this  chlorine represents potential  atmospheric emissions.
Instead,  it  may be related to the use of ilmenite ore.  The manner in which ilmenite is used  in
the chloride process  is a well  kept secret. However, unless some other  means are  available  to
separate out the  iron and other  impurities, it is logical to assume that they are disposed of as
chlorides. This could account for a large part of the chlorine consumption.
b.  Process Equipment — Table 111 summarizes the  major pieces of sulfate process equipment as
reported  in the questionnaires. The information  for chloride process equipment is  listed  in Table
112. The degree of confidentiality required suggests that these manufacturers are somewhat hyper-
sensitive. The data which was reported in the questionnaires reveals no startling or unusual aspects.
A more detailed description of the  mills in use is  presented in Table 113. Only one plant reports
sulfuric acid manufacturing facilities  while one other has a dilute acid concentrator.

III.     EMISSIONS
       The emissions characteristics of the various pigment processes have been briefly discussed
in the process narratives reviewed  earlier. The discussion in this section will be limited to  a more
detailed examination of TiO2 manufacture. This is the pigment manufacturing process whose emission
potential justifies a detailed examination.
A.     Description of  Emission
       Each of the manufacturing processes for TiO2, sulfate and chloride, has associated with it
a particular set of atmospheric pollutants. This  is in addition to particulate emissions which are
                                           399

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                  TABLE 110
        TiO2 INDUSTRY QUESTIONNAIRE
PRODUCTION - RAW MATERIALS INVENTORY FROM
               FIVE TiO2 PLANTS
                                  lon/yr
       Production
          Sulfate TiO2              90,040
          Chloride TiO2            224,000
          TiCI4                    22,500

       Raw Materials
          llmenite                258,600
          Slag                    77,200
          Rutile                   69,800
          Leocoxene                    0
          Coke                    72,000
          H2SO4                 275,600
          CI2                    141,500
          Other Ore                59,000
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                                                  402

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         TABLE 113
TiO2 INDUSTRY QUESTIONNAIRE
         MILLS, ETC.
Plant Tvoe
1 Ball
Roller
Fluid Energy
Pebble
2 Micronizers
Sand
Belt Driers
Rotary Filters
3 Ball
Hammer
Micronizer
Roller
4 Jet
5
6
7
Number
3
9
6
1
3
3
2
7
2
6
5
1
3
CONFIDENTIAL 	
CONFIDENTIAL 	
	 	
Size
7ft x 16ft
50 in. dia.
42 in. dia.
6ft x 22ft
200 ton/day
200 ton/day
200 ton/day
200 ton/day
8ft x 6ft, 8ft x 5ft
4 ton/hr
4-42in., 1-36in.
—
36in. dia



         403

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similar for both processes.
       The major sulfate process emissions can be attributed to the use of sulfuric acid. Emissions
from various parts of the plant include SO2,  SO3, H2SO4, sulfuric acid mist  and possibly various
metal sulfate particulate. The properties of these various pollutants as they pertain to emission control
are sufficiently well understood, due to their widespread occurence, that discussion of their individual
properties will be omitted here.  Their generation in the sulfate process  is such  that they  can all
be  expected to  be present together  in any  given source. Their relative concentrations will vary
from source to source and,  for a  given source, can vary with time and operating conditions. Further-
more, the physical properties (temperature, dew point,  etc.) of the gas streams range from relatively
mild to quite severe. These matters will be discussed in more detail in the  next section.
       Chloride process emissions include (besides ore and TiO2 particulate) CO,  HCI, C\2, TiCU
and coke particles. Large amounts of energy are  often  generated on site and this can be the source
of significant amounts of emissions where oil or coal fired boilers are used.
       Titanium tetrachloride hydrolyzes readily in  air to produce a dense fume of finely  divided
particulate  so that any  leaks in the system  or  stack  emission of this material  tends to  be very
prominent.  Carbon monoxide is often present in large enough quantities that its use as an auxiliary
fuel is sometimes feasible.
B.     Source of Emissions
1_.	Sulfate Process —  The principal digestion reaction, in  simplified form, is:
                      FeO • TiC-2 + 2H2SO4 -> TiOSO4 + FeSO4 + 2H2O
A typical charge to the digester may consist of  1.1  to 1.5 tons  of 94%  H2SO4  per ton of ore.36
The proportions  depend partly on the  composition of the ore.  Water and steam are added to dilute
the acid slightly and to raise the temperature. The reaction is exothermic and once initiated proceeds
vigorously  with considerable evolution of heat and steam.  The  temperature may  exceed  200ฐC
during the peak reaction period which may last from a few minutes to a half hour.
       The severity of the  reaction may in some cases be controlled somewhat by gradual addition
of the reactants. In this way, a period of moderately high reaction will be maintained which eliminates
the high peaks. Temperature  in this case can be  made to remain below 200ฐC.
       The emissions from the digesters will be highly cyclical  in nature. During the peak reaction
periods,  large amounts of steam containing SOs, SO2 and sulfuric acid  mist will be evolved. En-
trainment would be expected to be the principal  mechanism by  which emissions  are released. The
vapor pressure  of H2SO4  for a 95% acid solution is 4.8 mm at  200ฐC. This  is  small but  may
                                            404

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still be  significant. The quantity of contaminants may be  reduced by using gradual addition of
reactants.
        Few measurements are available, at the present time, of the emissions from digester stacks.
An estimate of the amount of steam evolved can be made by  assuming one  mole of steam per
mole  of sulfuric acid charged. This calculation gives about 450 pounds of steam per ton of 95%
acid charged.
        The calcining operation  is the  most critical step in the manufacturing  operation as  well
as the most significant from  a gaseous emission standpoint. Gas  or oil fired rotary calciners are
usually  used.  Temperatures  as high as 900 to 1000ฐC are encountered at the discharge end.
Residence time for the TiOa may be as high as 24 hours.
        The hydrous titanium dioxide undergoes several washing steps prior to calcination. Even
after thorough washing, however, the TiO2 retains around 5 to 10 percent h^SCX36 This represents
the most  important emission from calcining. Processes have been proposed for  neutralizing  this
residual acid with alkaline material prior to calcining, but this is not normally done.
        Most of the water is removed by the time the material reaches 200ฐC. At this temperature,
the sulfuric acid begins to evolve.  Removal of sulfuric  acid and SOa is complete  at about 650ฐC.
        The atmosphere in the calciner is reported in  the literature to contain  2  to  10% oxygen
on a dry basis and 30 to 50% water vapor.36 The oxygen content of the calciner can be important
in that it may  influence the  ratio of SOa  to 862 in the exhaust gas. The reaction equilibrium be-
tween SOa and SOa may be written:
                                                       ''so
                           SO2 +1/2O2 ^ SOa , Kp =	^— 1/2
                                                    Pso2   Po2
At 650ฐC, the  equilibrium constant,  Kp, is about  equal  to 5 (for pressures  measured in atm.)  and
Kp = 23  at 550ฐC. If the  calciner is relatively rich in oxygen, virtually  all the sulfur oxide should
be in the  form of SO3. Where very low oxygen  concentrations  are present, a significant amount
of SO2  will be formed. If a slightly reducing atmosphere is  maintained, even more SOa will  dis-
sociate. This  assumes that the gas will approach equalibrium at some point in the  calciner. This
in turn will depend on the residence time of the gas phase and on the degree of catalytic effect
in the calciner. Furthermore, the kinetics may allow an approach  to equilibrium above a certain
temperature but not below.
       The importance of  this is  that  it may be possible to exercise a degree of control over
the SOa to SC>2 ratio. Economic, or other,  considerations  may  in some cases favor the removal
                                          405

-------
of one form of sulfur oxide over another.
       The digesters  and the calciners represent the major sources of emission in a sulfate process
plant. Ore and pigment handling and grinding operations can be significant sources of dry particulate
emissions. Finally, the various treatment and finishing  steps are potential  sources, primarily of the
odor nuisance type. While  the  nature of such items is usually proprietary, various reduced sulfur
compounds (HsS,  mercaptans,  etc.)  are sometimes cited as  treatment agents. These have  very
low odor  thresholds and, for those plants which use  such substances, present a potential local
odor problem.
2:	Chloride Process — The chloride process, a more recently developed technology than the
sulfate process, is subject to a greater degree  of  process  variation from plant  to plant.  These
variations are difficult to  define since  they are often considered proprietary by the practitioners  of
the chloride process.  The  chlorination and the oxidation  steps are basic to  the process and are
always practiced in some form.
       The principal  source of emission from the chloride process is the chlorinator off gas.  This
may contain  CC>2,  CO,  HCI, Cb  and  small quantities of sulfur compounds (from sulfur  in the
coke).  If air, rather than pure oxygen,  is used in the TiCU burner, then significant volumes of nitrogen
will also be present in the exit gas.
       The various parts of  the plant which contain TiCU are potential emission sources.  Vents,
relief valves  and rupture disks  are found in various parts  of the system such as purification trains,
storage tanks,  etc. These can  be the  source, perhaps  only intermittently,  of the dense, white
hydrolysis product  formed  when TiCU  comes  in  contact with water vapor.  While the  quantities
from these sources tend to  be small, they can present opacity problems.
       As in  the  sulfate process, the various  treatment  steps  offer  potential problems, primarily
odor.  It is believed, however, that chloride process pigment requires less subsequent treatment
so that the pollution  potential from this source may be  less than that from  the  sulfate process.
C.     Measurement of Emissions
       Each of the TiO2  manufacturing  processes deals with  a different set  of pollutants.  The
sulfate process  emissions  are  similar to those encountered  in the manufacture  of sulfuric acid.
The methods for measuring such emissions have been extensively developed and procedures can
be found in  The Federal Register (Vol. 36,  No. 247, p.  24893). This method  makes use of an
impinger train, with a filter between the first and second impinger, and  a barium perchlorate  —
thorin indicator titration. Some investigators have suggested that the filter should be placed before
                                         406

-------
 any of the impingers and the assembly heated up to and including that point to prevent the oxi-
 dation of SO2. TiO2 and metallic sulfate can interfere with the procedure and it is important that
 these be excluded from the sample. Where it is suspected that these interferents have  not been
 totally eliminated,  a sodium hydroxide — phenolphthalein  indicator titration can be used  to check
 the results, though this method will respond to any other acid substance.
       The chloride process emissions include CO, Cl2 and  HCI. Carbon monoxide in chlorinator
 off gas  is usually  present in such quantities that an orsat  type analysis can be performed. A pro-
 cedure for measuring HCI and free chlorine is available and is described in a NAPCA document.37
 The gas sample is drawn through an impinger train using alkaline sodium arsenite in the absorbing
 solution. Total chlorides are  determined using the Volhard  titration  method (back titration  with
 ammonium thiocyanate — ferric alum indicator) on a suitably prepared sample.  Free chlorine is
 determined by titrating an aliquot with iodine solution and  a starch indicator. The Volhard chloride
 titration method will respond to any chloride (e.g. TiCU, FeCb) so care must be exercised in  sampling
 the gas stream and in interpreting results.

 D.      Raw  Data  Tabulated
 1.      Questionnaires — A considerable amount of emission data has been reported in the question-
 naires.  This has been gathered together by type of operation and  summarized below. Wherever
 possible, emissions are summarized at the process outlet before any control devices. In some cases,
 this has involved taking emissions at a control device outlet and back calculating using the reported
 efficiency for the device. It should be  realized, of course,  that there exists some danger in this
 type of approach in  that a slight difference  in the efficiency reported can result in a  large change
 in the number obtained by back  calculation.  This is particularly true  when  very high  efficiencies
 are claimed as in the present case. For this reason, the actual data reported at the control device
 outlet (where this is the only information  given) will  always be reported  in the  summary below as
 well  as the calculated inlet loadings.  The reader should refer to Tables 109 through 113  for pro-
 duction, raw material  and process equipment data on these plants.
 a.  Digestors  — Only one questionnaire  (Plant 5) presented  any numbers which are usable. For
particulate  (including  sulfuric acid), emissions after  control  are 0.66 Ib/ton TiO2  produced. For
SO2, emissions  are 0.31 Ib/ton TiO2.  Since  the details of the  control device  have been requested
confidential, it is  not possible to back calculate the emissions from the digestor stack itself. Total
flow rate from the digestor stacks is reported to be 19,200 to 40,000 SCFM.
                                          407

-------
b.  Sulfate Calciners — Plants 1, 5 and 7 reported emission data from sulfate process calciners.
Plant 1  reports two calciners with gas flows of 65,000 ACFM and 28,000 ACFM, respectively (both
at 170ฐF) and atmospheric emissions after  a 95% efficient control system  of 12 Ib/hr  and 5 Ib/hr
H2SO4,  respectively. Back calculating, this translates to 30 Ib H2SC>4 per ton of TiO2 at the calciner
exit.
        The same plant  reports SO2 emissions  from the  two calciner scrubbers as 110 Ib/hr  and
48  Ib/hr, respectively.  The scrubber system used has minimal effect on  SO2, so these can be
considered to represent emissions at the calciner exits themselves. By calculation, an S02 emission
factor of 17.1 Ib/ton of TiO2 product processed is obtained.
        Plant 5  has reported SO2 emissions from  the  scrubber  stacks  for  its calciners. These
calculated to be 11,830 Ib/day. This results in an emission factor of 80 Ib SO2 per ton of TiO2 pro-
duced.  Insufficient information was presented to permit a calculation of an  H2SC>4 emission  factor
at the calciner exit.
        Plant 7 reports a calciner effluent  of 44,000 cfm at 950ฐF having  a loading of 0.95 gr/cf
for  particulate  including sulfuric acid. This  resulted in a calculated emission factor of 63 Ib/ton of
TiO2 for total particulate including  sulfuric acid.
c.  Drying and Milling — Drying and milling operations find extensive use in the TiOa industry whether
the sulfate process  or the chloride process is  practiced. They can be applied to ore, coke  or
finished pigment. A summary of the emission information  given for this area is presented in  Table
114 for the sulfate process and  in Table 115 for the  chloride process. The last column in  these
tables, the  emission factor, is a calculated estimate based on the information given.
       The emission factors in pounds per ton of TiO2 product show a good degree of consistency,
with one exception, as far as orders of magnitude are concerned. This is  remarkable when com-
pared to similar data obtained for  other aspects of the paint and varnish industry.
d.  Chlorinators — Five  plants reported some information on their  chlorinator emissions, though, in
general, the data was  not as well defined as in the previous section. Plants reported either off gas
analyses or actual emission  rates for various substances. In some cases,  emissions are reported
after an emission control system. In other cases, either no emission control devices are  present or
emissions are  reported upstream  from  such devices. In the summary that follows, an indication will
be  made as to whether the reported emissions are for controlled or uncontrolled processes. Finally,
consistent with  other sections of this report, emission factors for uncontrolled chlorinator emissions
will be estimated.
                                            408

-------
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-------
          Plants 2 and  5 present  emission  information from controlled chlorinator stacks. This infor-
   mation is summarized in  Table  116. Plant  2 has given the off gas analysis for various years.  Of
   interest are the trends of  improvement for all reported constituents except carbon monoxide. Plant
   5 has reported actual  emission rates.
          Plants 4, 6 and 7 have  reported  data for either uncontrolled chlorinator stacks or for con-
   ditions upstream from control equipment. Plant 4 reports a typical off gas analysis which is tabulated
   in Table 117.  Emissions of TiCU for this plant were reported to be 22 to 88 Ib/hr.
          Plant 6 has listed  emissions  directly  out of the chlorinator tail gas  stack.  These are also
   summarized in  Table  117. Emission factors for chlorine and HCI are 4.3 Ib/ton TiC>2 and 39 Ib/ton
   TiOa respectively.  This plant has presented  a complete emission inventory of 48  sources which
   includes  boilers, chlorinator, dryers, kilns,  tank vents, etc. Table 118 lists emissions for the power
   house, chlorinator, and the total  for all sources including power house and chlorinator. Examination
   of the table indicates  that  the power house  and  chlorinator account  for the major fraction of total
   emissions from  this chloride process plant.
          Finally,  plant  7  has listed uncontrolled emissions from  its  chlorinator off gas as including
   1  Ib-mole TiCU/hr  and 6 Ib-moles HCI/hr. Correlating these with production, emissions factors  for
   TiCU and HCI are obtained which calculate  to be  67  Ib/ton TiO2 and 77 Ib/ton TiOa respectively.

        Plants 2 and  5 present emission information from controlled chlorinator stacks. This infor-
mation  is summarized in Table 116. Plant 2 has given the off-gas analysis for various years. Of
interest are the  trends of improvement for all reported constituents except  carbon monoxide. Plant
5 has reported actual emission rates.
        Plants 4, 6, and  7 have reported data  for either uncontrolled  chlorinator stacks or for con-
ditions upstream from control  equipment. Plant  4 reports a typical off-gas analysis which is tabulated
in Table 117. Emissions  of TiCU for this plant were reported to  be 22 to 88 Ib/hr.
        Plant 6  has listed emissions directly out of the chlorinator tail gas stack. These are also
summarized in Table 117. Emission factors  for chlorine and HCI are  4.3 Ib/ton TiO2 and  39 Ib/ton
TiO2, respectively. This  plant has presented a complete emission inventory of 48 sources which
includes boilers, chlorinator,  driers,  kilns, tank  vents,  etc.  Table 118 lists emissions for the power
house,  chlorinator and the total for  all sources  including power house and  chlorinator.  Examination
of the table  indicates that the power house  and chlorinator account for  the major fraction of total
emissions from this chloride process plant.
                                            411

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                   TABLE 116

     CHLORINATOR EMISSIONS AFTER CONTROL

          Plant 2 - CHLORINATOR OFF GAS
          TYPICAL ANALYSIS — PERCENT


Constituent     1972       1971       1970      1968 to 69
CI2
S02
Cl
02
CO2
CO
N2
TiO2
0.00006 0.0001
0.00007 0.0012
0.056 1.5
2.7 4.0
25.5 30.0
27.5 24.0
44.0 40.0
3 Ib/hr 6 Ib/hr
0.0001
—
2.0
4.0
30.0
24.0
40.0
8 Ib/hr
0.0001
—
3.0
4.0
22
26.0
45
12 Ib/hr
Plant 5 - CHLORINATOR OFF GAS
EMISSIONS — LB/HR




Constituent
NOx
CO
Participate
CI2
Rate, Ib/hr
0.34
1570
0.82
10




                        412

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                TABLE 117
CHLORINATOR EMISSIONS BEFORE CONTROL
      Plant 4 - CHLORINATOR OFF GAS
       TYPICAL ANALYSIS, PERCENT

         Constituent           %
N2
CO2
02
CO
TiCU
HCI
SiCI4
5 to 10
50
0.5
10
0.2
0.1
0.1
to 70
to 2.5
to 20
to 0.5
to 0.5
to 0.4
     Plant 6 - CHLORINATOR EMISSIONS, LB/HR
         Constituent       Emission Rate
           SO2            0.00
        Particulate         0.00
           NOx            1.05
           CO          3,195.00
       Hydrocarbons        0.00
           CI2           53.00
           HCI           420.00
                413

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                          TABLE 118
                Plant 6 - EMISSION INVENTORY
                  Power House        Chlorinator       Total All Sources
  Constituent            Ib/hr              Ib/hr              Ib/hr
    SO2             855.0            0.00            855.13
  Particulate          104.0            0.00            126.38
    NOx             130.2            1.05            140.57
    CO             17.4           3,195.00         3,213.94
Hydrocarbons          8.4              0.00             10.84
     C\2              —              53.0             86.40
    HCI              —              420.0            422.2
                              414

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        Finally, plant  7  has listed uncontrolled emissions from its chlorinator off gas as including
1 Ib-mole TiCU/hr and 6 Ib-moles HCI/hr. Correlating these with production, emissions factors for
TiCU and HCI are obtained which calculate to be 67 Ib/ton TiO2 and 77 Ib/ton TiO2, respectively.
e.  Summary of  Emission  Factors — The above information was used to calculate the emission
factors  presented in  Table  119 for the various steps in  TiC>2 pigment manufacture. It should be
emphasized that  these represent estimates for uncontrolled processes.  Most of the plants reported
emission control equipment on most of these processes. Where required, stated control  efficiencies
and outlet loadings were used to back calculate the uncontrolled emission factor. With the exception
of SC>2  and CO, existing controlled plants report a significant reduction in emissions from the  levels
suggested by the emission factors.  Sulfur dioxide  and  carbon monoxide are relatively unaffected
by the types of control devices presently in use.
        It should  be  emphasized  here that considerable variation exists in the  manner in  which
these various process are run, particularly the chlorinators. The emissions from chlorinators can be
a function not only of control devices but also of process variations, type  of ore used, etc.  Since
much of the technology in this area is proprietary in nature, not all processing options are available
to all producers. Consequently, a producer operating a process that is inherently higher in emissions
than a  process used by some of his competitors  may not be able to achieve as  low  emissions
by  process  modification and  may require the addition of an  economically unfeasible  amount of
control  equipment. This could put him in a non-competitive position  if uniform  emission standards
were set for the industry.
        One other source of emission is mentioned in  one of the questionnaires which seems to
be  unique to that particular plant (Plant 4). This plant reports a significant emission of sulfur mono-
chloride, SaCb, from an off gas stream from the TiCU oxidizer. Emission rates of 5.1 to 22 Ib/ton of
TiO2 produced are reported.  In the  normal operation of the chloride  process, the oxidizer does
not vent to the atmosphere directly  so that the precise source of this  emission  is  not clear. It is
believed that, as this plant operates the chloride process,  S2CI2  is used to  temporarily absorb
the chlorine from  the oxidizer.  Chlorine recycle can then  be accomplished by stripping the absorbed
material from the  SaCb. The S2CI2 emissions may result  from the tail  gas from a chlorine absorption
step.

Z	Other Sources — Two other sources of information have been obtained on digester emissions.
The St. Louis County Health  Department supplied test results for the  ML  Industries sulfate plant
in St. Louis.  They report emissions  downstream  from  a set  of  scrubbers to be "nil"  for sulfuric

                                            415

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                                        TABLE 119
          ESTIMATE OF EMISSION FACTORS FOR UNCONTROLLED PROCESSES
                       Process
               Sulfate Digester*
               Sulfate Calciner
  Pollutant
                                                             Emission Factor*
                                                           (Ib/ton TiO2 Produced)
H2SO4
SO3
SO2
H2S
H2SO4
SO4
14.1
8.8
4.2
0.9
46
48
               Ore Drying
                   Sulfate
                   Chloride
Participate
Participate
47
44
               Coke Drying
Paniculate
 75
               Ore Milling
                   Sulfate
                   Chloride
Particulate
Particulate
 42
               Pigment Milling
                   Sulfate
                   Chloride
Particulate
Particulate
 49
               Chlorinator
   TiCI4
   CI2
   HCI
   CO
 32
4.3
 55
260
 "These are average emission factors. Ranges are given on the preceding tables and discussed in the
 text.
"Emission factors for this process based on paper by L.L. Falk discussed in the following section. The
 remainder of the factors based on the TiO2 Industry Questionnaires.
                                          416

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acid and 7 Ib/hr for  SC>2. These scrubbers are claimed to be "100%" efficient for H2SO4 so it is
not possible to determine the inlet loading.
       The best defined information obtained thus far is contained in a paper presented by L. L.
Falk.38 He reports digester emissions from  the  duPont  plant in  Baltimore  (not included in  the
questionnaires). Figure 79 gives total gas evolution from  the  digester as  a function of time after
oleum addition. It can be seen that the  reaction  proceeds at a negligible rate for about the first
45  minutes and then proceeds at  a vigorous rate for a very short period  of  time. A considerable
amount of gas (mostly steam) is evolved during this period.
       Typical emissions per batch are given below:
                                 Material                  Ib/batch
                                  Steam                    8,000
                                  H2SO4                     120
                                   SO2                      36
                                   H2S                        8
                                   SO3                      76
       The quantity of materials  charged  to the digester in a typical run was not given  but  it
is possible to make an estimate. Assume a batch  charge of 20 tons of ilmenite (Barksdale, p. 220).
Further assuming the  ilmenite to  contain 50% TiO2,  and overall  plant recovery to  be 85%,  the
emission factors can  be estimated as follows:
                         Emission Factors for Sulfate Process Digestors
                                                         Quantity
                                Emission          (Ib  per  ton TiO2  Product)
                                Steam                      940
                                H2SO4                       14.1
                                SO2                          4.2
                                H2S                          0.9
                                SO3                          8.8
       Atmospheric  emissions tests  on the  National Lead  Company,  Sayreville,  New  Jersey,
sulfate process plant was conducted by  the Division of Air Pollution of the Public Health  Service
in September, 1966.39 This plant has seven calciners. The sampling team tested the emission control
system for one of the calciners.  The system consisted of an initial water scrubber, followed by
electrostatic precipitators, followed  by another scrubber. A  sketch of the system is shown in Figure
                                          417

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                              FIGURE 79

EXHAUST RATE FROM SULFATE PROCESS DIGESTION TANKS
                                  418

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80. They were unable to obtain reliable measurements  at the calciner outlet (due to  interference
with the  analytical technique from TiOa) and made  no  attempt  to monitor the exhaust from the
first scrubber.  They reported the results of measurements at the outlet from the precipitators and
on the water from the last scrubber. The average results obtained after the precipitators are shown
in the following table:
                                    Pollutant           Rate (Ib/day)
                                      SO2                7,900
                                      SO3                  310
                                   Paniculate               380
                                    Acid Mist                180
       Total gas flow rate at this point was measured (on a dry basis) to be about 3 x 107 SCF/day.
Several comments should be made before making any conclusions from this data.  First, the results
of individual runs  showed deviations of as much as a factor of two.  It is not known whether
these are due to inherent difficulties in obtaining good samples or whether there are, in fact, large
fluctuations in the calciner exhaust.
       The quantity of emissions reported raises some questions. It was assumed by the sampling
team  that each calciner  handles about  the  same amount of material.  If this is  correct, then the
calciner in  question processes about 62 ton/day of TiO2. If the charge had  retained 10%  HfeSCU,
then this would result in  an emission of about 4 tons of sulfur  (as 862) per day.  It can be seen
that the  862 reported after the precipitators is about sufficient  to account  for almost the entire
total.  It is not  known how much SO2 had  been removed by  the first scrubber nor how much  acid
mist was removed in the precipitators.
       If these devices account for considerable amounts of sulfur oxides, then the reported emissions
seem to  be too high. On the other hand, most of the calciner exhaust emissions  can be in the
form of SO2 only if a somewhat reducing atmosphere is  maintained in the calciner. Since no infor-
mation is available on these aspects of the problem, some caution should be exercised  in accepting
the data as typical.
       NL Industries  has reported that, due to an  error in  the method of calculation, the Public
Health Service results are high  by  a factor of two.  Variable oxidation of sulfite to sulfate in the
last tower  was felt to have further increased the  error, making the results  high  by  perhaps as
much as  a factor of three.
       In view of  the above comments, several suggestions can be  made for source testing. If
                                          420

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at all possible, the calciner exit itself should be sampled. The problem here is that TiO2 participate
may interfere with the analysis for sulfate. Techniques should be sought to overcome this.
        It should  be  determined  whether the calciner operates in a relatively steady state condition
or whether  large fluctuations occur in  operating  conditions. A sample  of  the TiC>2 cake prior  to
calcination should be obtained and  analyzed for sulfuric acid. This, plus a knowledge of the calciner
throughput,  should  provide a good estimate of  the total  emissions. Finally,  an  analysis of the
calciner exhaust for oxygen would provide a means to check whether the SOa to SC>2 ratio measured
is reasonable.

IV.     EMISSION CONTROL TECHNOLOGY
A.      Description of Currently Used Control Systems
        Table 120 summarizes the particulate emission control devices reported in the  question-
naires.  Included in this table are those  devices which collect dry,  solid particulate from drying and
milling type  operations only.  Table 121  discusses those devices whose purpose is to control pro-
cesses  applicable only to TiO2 manufacture such  as digestion, chlorination, etc.  Plant 4 reported no
emission control at  all, while plants 5 and 6 considered at least part of the information proprietary.
        A wide variety of devices  is reported including cyclones,  fabric  filters,  several varieties  of
scrubbers and electrostatic precipitators. There are several instances of devices connected in series
in order to  obtain good control. Over  all control efficiencies,  where  reported, are said to range
from 90 to 99+% depending to some extent on the process being controlled.
B.      Other Methods of Control
        Most conventional pollution control devices that would  be applicable to the types of emis-
sions found  in TiO2 plants  are  presently  in use. The  application  of  more advanced  concepts  is
discussed in Chapter 9.
C.      Performance of Currently Used Control Systems
        Performance data on presently  used systems,  as reported  in the industry questionnaires,
is included in Tables 120 and 121  listed earlier.  For particulate control  devices, efficiencies up  to
99%, and higher, are reported. Such efficiencies, on  a weight basis at  least, can  be  achieved
under favorable conditions with the types of devices  in use. Beyond  that,  it is  not possible  to
comment on the accuracy of the reported performance  figures.  It  is not known whether  the ef-
ficiencies are based on actual tests.
        For  other processes  (calciners,  chlorinators, etc.), data on  efficiencies is not  consistently
                                            421

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reported. For calciners,  three plants report efficiencies in excess of 90%. The basis of calculation
is not stated. In each case, the emission control system consists of two or more devices in series.
       One plant reported control efficiency for a chlorinator emission control system. Efficiency of
90% or better was reported  for  TiCU and  HCI. An overall pressure drop of 45  inches  of water
through three devices in  series (one a venturi  scrubber) suggests that the level reported is  not
unreasonable. As before, however, no further evaluation of the data can be made.
                                          424

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                                      CHAPTER 9
              RECOMMENDED RESEARCH AND DEVELOPMENT PROGRAMS
       Significant among the purposes of this industry study is the recommendation of Research
and Development programs which can lead to improvement in air pollution measurement and control.
In the following pages, the deficiencies in both air pollution technology and emission measurement
are treated in detail. Consideration is also given to that control technology which is more efficient
than "best control" but is considered to  be  economically unfeasible.  Based on the findings of the
Research  and Development study presented herein, priorities  to improve control technology are
recommended along with suitable programs to achieve these improvements.
I.      EMISSION CONTROL TECHNOLOGY
       The areas of  control technology within the  coating industry which would benefit most by
the application of research and development efforts are described. In those  segments of industry
where a problem has been selected, an attempt has been made to assess the probable requirements
in time and cost for successful program accomplishment.
A.     Technical Developments for Reduced Levels of Emission
       The areas where improvements could be made to reduce levels of emission are categorized
as follows:
                        PROCESS CHEMISTRY AND KINETICS
                        PROCESS EQUIPMENT AND/OR OPERATIONS
                        CONTROL EQUIPMENT AND/OR OPERATIONS
Requirements in these categories are outlined below.
1_.	Process Chemistry and Kinetics  —  Odor  and  solvent emissions from opened and closed
kettles represents one of the  major air  pollution  problems for the  industry, due primarily to the
local nuisance problem  generated by this type of emission. Cooking in open kettle has dropped
off to the point where it no longer deserves further attention. Most resin and varnishes are  now
cooked  in closed  kettles  which  have  resulted in significant  reduction  in emission levels. These
emissions could be further reduced  if process  chemistry or cooking formulas could be developed
for processing in a truly closed or pressurized kettle.

                                         425

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2^	Process Equipment and/or Operations — Raw material handling as well as process chemistry
also must be developed for the use of pressurized  kettle  cooking.  These are required to allow
for  addition  and  removal of materials  during  the  cook while still maintaining a closed system.
Development of an in-line, closed thinning, blending and filtering system for handling of the materials
after cooking would also substantially eliminate the emission  currently encountered with existing
thin tanks and leaf filters.
3.     Control Equipment and/or Operations — Although a wide variety of air pollution control devices
are used in the paint industry, only a few types may be considered applicable. These are:
       Thermal and catalytic afterburners for cooking operations
       Scrubbers or condenser-scrubbers for cooking  operations
       Fabric collectors for milling, grinding and other dry solid processing operations
       The principal deficiencies associated with the operation of afterburners fall  into two categories:
       1.  Those problems dealing with the inherently large fuel consumption and cost.
       2.  Potential for safety hazards and damage to the equipment by fire or  explosion.
       The first of these two problems is becoming increasingly urgent as natural gas becomes more
difficult to obtain. The second problem has caused numerous casualty losses,  as well as injury to
employees over many years in the cooking industry.
       For those process  reactions which are not amenable to closed or pressurized cooks, or in
circumstances where physical or capital  limitations do not permit replacement of  the present cooking
equipment, a more economical form of oxidation, with regard  to operating cost and fuel conservation,
is needed. Three directions suggest themselves for the correction of deficiencies in afterburner systems
for kettle operations. These are:
       1.  Improved heat exchanger efficiency for thermal afterburner units
       2.  Improved activity and stability of  catalysts for  use in catalytic afterburner units
       3.  Direct flame incinerator
Of these three, a  direct flame incineration system of low first  cost offers the most potential to provide
optimum cost-benefit relationships for the public.
       Thermal afterburners are inherently expensive. Their capital cost  increases as the gas flow
rate increases, almost without relationship to the concentration of organics in the fume stream. The
addition of heat exchangers increases thermal efficiency, decreases operating cost and significantly
increases initial capital cost. The best heat exchangers of conventional design (i.e. fixed tube exchangers
and rotary matrix heat exchangers) have thermal efficiencies on the order of 60  to 70%. Some
nonconventional regenerative designs using fixed beds of checkerwork, stone, etc. are being  offered
                                          426

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with design efficiencies in the range of 80%.  Continued competition  among the  manufacturers of
afterburner equipment is likely to lead to marginal  improvements in the relationship between first
cost and heat exchanger efficiency. Therefore, it is not felt that thermal oxidation should be considered
as an area for funded R&D work.
        Catalytic afterburners have  been used for many  years  in the abatement  of organic fumes
from kettle cooking operations. Operations on a single kettle tend to be widely varied as alternative
formulations are prepared, and,  therefore,  the potential  for inclusion in the cook of one  or more
catalyst deactivating  or poisoning agents is always  present. The problem  of maintaining activity in
the presence of contaminating or deactivating agents becomes increasingly severe as the improved
catalyst performance is desired. For  example, a catalyst requiring 1,000ฐF inlet temperature to oxidize
toluene is only marginally better than  a thermal system with no catalyst at all.  This low level of
activity  is likely to be quite  tolerant of  poisons, misoperation and the like..On the other hand,  a
very active catalyst,  capable of oxidizing toluene at 450ฐF is likely to exhibit a marked sensitivity
to overheating, contamination, etc.  The "fine  edge" of activity is easily damaged by a variety of
chemicals and  by non-uniform or extreme operating conditions.  These factors suggest that a major
R&D effort should not be made in the area of catalyst development.
        Since  most emission from  kettle cooking is high enough in combustible concentration to
be flammable,  the direct flame incinerator discussed earlier in Chapter  5  offers great potential for
incineration  with little or no fuel cost.  These  units are  also commercially available.  The area of
research and development required  is in the transfer system from the kettle to the unit.
B.	Economic Deficiencies Preventing Reduced Levels of Emissions
        The minimum size of the independent paint manufacturer is  quite small.  Even seemingly
modest demands for pollution abatement equipment may present a substantial economic burden
to a small independent. Probably  the  most difficult  problem  for the small manufacturer  is the
prevention  of solvent loss during transfer,  storage  and  mixing  processes. Of these, those  losses
associated with storage  of  solvents are most likely to  be of  concern to air pollution agencies,
and  most difficult  for the small manufacturer to cope  with. The small scale  of these emission
problems  and  the high cost-benefit relationship for emission control systems present a  difficult
economic problem.
C.      R&D Priorities to Improve Control Technology
        Four R&D programs  have been  selected as a part of this industry  study to improve control
                                         427

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technology. These programs are as follows:
        1.  Closed Reactor Design Program
        2.  Investigation of Methods for Handling Resin Raw Materials in the Liquid Form
        3.  Development of Inexpensive Scavenging Systems
        4.  Development of Transfer System for Direct Flame Incineration
The details of these programs along with the work and cost requirements are detailed in the next
report section.

D.      Recommended Programs for Achieving R&D Requirements
1^	Closed  Reactor Design  Program — This program involves the analysis of requirements for
general purpose reactors to  produce resin  and varnish products in a  completely closed reactor
system.
        The following paragraphs list the program steps envisioned in the overall R&D program:
        1.  Detailed  library investigation of equipment  literature and  patent literature pertaining to
           closed reactor systems already developed.
        2.  Detailed  investigation of  the nature and scope of  individual reactions  carried out in
           existing kettles.
        3.  Reduction of  the  physical and chemical  requirements of the  cooking process to simple
           concepts regarding those factors which determine the nature  of the equipment required.
        4.  The specification of a design basis for a non-ventilated reactor system.
        5.  The collection of potentially feasible  designs for review and screening.
        6.  The selection of  alternative equipment  types which  appear generally suitable for the
           requirements in the prototype specification.
        7.  The fabrication and testing of a prototype reactor.
The proposed program would be conducted in three phases  consisting of:
        1.  Research and selection of approach
        2.  Design and construction of prototype
        3.  Field testing of prototype
        Phase I should involve approximately 1,000 man-hours of professional R&D work, and about
600 man-hours  of  non-professional  effort. The total  estimated cost for this phase  is  $35,000.
Phase  II should consist of a design portion requiring approximately 750  man-hours of  professional
and non-professional time. The total estimated cost of the labor is approximately $28,000. In addition,
                                         428

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a one-time fabrication cost of the prototype  reactor is estimated at $40,000. The total for Phase II
is estimated at $68,000.
       Phase III, the installation and field operation of the prototype, will vary  in cost depending
upon the  ability to  arrange with a  commercial paint manufacturing  company to contribute  to the
installation and operating costs for the kettle required. The estimated cost  of  this  phase of this
program  is in the range of $100,000 to $150,000 depending  on final commercial arrangements.
Of this total, $25,000 is included to  cover an estimated 900 man-hours of field test  and observation
work.
2.	Investigation of Methods for  Handling Liquid Resin Compounds — This investigation involves
an analysis of methods for handling resin components in liquid or molten form. The inherent problems
with solid  resin powders are two-fold:
       1.  The  ventilating air requirement is large in  order to prevent fuming  through  the kettle
           hatch.
       2.  The added powders tend to become airborne and are swept out of the hood.
       Solid raw materials can potentially be handled in liquid or molten form so that batch additions
could be made without handling dry  powders. The handling of molten  salts  at elevated temperatures
is feasible and has been  demonstrated in  other  industries and should not  involve any radically
new techniques. The potential problems  lie in the development of equipment which can be operated
economically and safely, particularly in connection with small, unsophisticated cooking operations.
The R&D  program consists of three  phases which are outlined below:
       Phase I consists of a literature search to accomplish the  following:
       1.  Review  existing technology and define the types and extent of usage of  solid raw materials
           in resin  cooking.
       2.  Establish the properties of the identified components, including: fusion point, viscosity,
           vapor pressure, corrosiveness, stability and other properties.
In addition, literature research and a field investigation should be made on conventional  equipment
for handling molten  materials in  other manufacturing activities.
       Phase II should include a definition of alternative process schemes and equipment components.
Based on this definition, an  economic evaluation  of alternative process schemes and  equipment
should be made.
       Phase III should  consist of  the selection and definition  of a prototype process scheme for
handling molten salts in the paint and varnish industry.
                                         429

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       In this program, field testing of the proposed prototype system is not considered an essential
step. The development  of  a system design which is  reasonable  from  an engineering  standpoint
combined with publication of the bases, calculating methods, etc., used should be sufficient to make
proposed system available to designers of new plants in the coating industry.
       The cost and timing for the three phases of the proposed program are as follows:
       Phase I should require approximately 320 man-hours of engineering and scientist work and
cost about $10,000.
       Phase II will require about 320 man-hours of engineering  work  as well as 160  man-hours
of drafting and should cost approximately $13,000.
       Phase III  consists  of about  320 man-hours of engineering work  and 160  man-hours of
drafting and should cost approximately $13,000.
3;	Development of  Inexpensive Solvent Scavenging Systems  — This development  program is
proposed with particular emphasis on the needs of the smaller paint manufacturers. The proposed
program  considers the development of a  simple and  inexpensive system for  scavenging solvent
vapors from storage tanks and possibly from transfer points as well.
       Three basic mechanisms deserve consideration in limiting  solvent emissions: prevention of
evaporation, incineration of  the tank effluent and adsorption of organics from the vented gases.
       The steps in this proposed program are as follows:
       1.  Literature and  plant  surveys to establish  the size and type of solvent  storage tanks
           most widely  used in the industry.
       2.  Library and  plant surveys  to establish the most  frequently used  solvents  as well as
           the physical properties of these solvents.
       3.  Preparation of calculated emissions, and comparison of these with test results prepared
           by the EPA.
       4.  Formulation  of performance criteria for abatement systems.
       5.  Screening of available mechanisms for abatement,  and selection of the most feasible
           approach to handle each of the following:
           a.  Prevention  of Vaporization
           b.  Condensation
           c.  Thermal Incineration
           d.  Activated Carbon Adsorption
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       6.  Preliminary design of a system utilizing each mechanism.
       7.  Analysis of the alternative designs for selection of the most economical design approach.
       8.  Preparation of a prototype design.
       9.  Construction and testing of the prototype design.
       This program  can be  conducted on a relatively modest scale. The research and design
phases should  not entail more than  700 hours of  professional  work and  400 hours of drafting.
The cost for this part of the work is estimated at $20,000. Fabrication of the prototype and subsequent
testing is estimated at an additional $30,000.
4.      Development of Transfer System for Direct Flame  Incineration — Direct flame incineration
would  offer a very inexpensive system  to build and operate. It would  also reduce the danger  of
fires and explosions  currently being  experienced by this industry. The main problems preventing
use of this system are:
       1.  Excessive ventilation of reactor kettles when loading materials. This system will work
           better with the closed pressurized  reactor discussed earlier.
       2.  The need for a gas tight low flow process blower capable  of pumping the reactor effluent
           which will  contain resinous material and phthalic  anhydride  particulate. Corrosion
           and heat resistance must also be considered.
       3.  The  need for automatic  safety valves to meet the  requirements outlined in  Item  2.
       4.  The need for a nozzle mix burner to meet the requirements outlined in Item 2.
       The program proposed would be carried out in  three phases and would follow the same
approach outlined for the closed reactor design program. The three phases would consist of:
       1.  Research and selection of approach
       2.  Design and construction of prototype
       3.  Field testing of prototype
       Costs and man-hour requirements are estimated to be about 65% of those presented
for the closed reactor design program.

II.      MEASUREMENT OF EMISSIONS
       Significant attention has been devoted to the  development of techniques and instruments
for  testing  particulate and organic  emission  in  general.  In  the paint  and varnish  industry,
certain deficiencies in measurement exist due to the nature of the cooking process which suggest
the need for additional development work. These deficiencies and required  development work are
                                         431

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outlined below.
A.     Deficiencies in Manual Methods of Source Sample Collection and Analysis
       The cooking process is a cyclical batch operation with respect to gas flow and hydrocarbon
concentration.  In  order to  produce an accurate assessment  of the total emissions  per  batch
(or  average emission), it  is essential to  undertake simultaneous  measurements of both gas
flow and of organic  concentration over a period of  several hours.  Using manual  source testing
methods, this is both an imperfect and cumbersome procedure at best.
       The resinous  materials  vaporized  from the cook have high dew-points,  and, therefore,
readily condense  on any surface which is at a temperature lower than that of the  air contacting
the  resinous  mass.  This  leads to  deposition  of  organic  material in  any sort  of  sampling
system  which  operates below the temperatures involved in the cooking operations (as high  as
700ฐF).  These  deposits  are troublesome for mechanical  reasons  and  also since they cause
emissions  into the  gas stream at periods  substantially  later than  the time they  enter  the
sampling system.
B.	Deficiencies  in  Techniques  and/or  Equipment  for  Continuous  Monitoring  of Source
       Emissions
       Continuous monitoring of cooking operations is subject to the same deficiencies as described
previously  for  manual  testing  methods. In the case of  condensation of resinous materials,  the
continuous methods are significantly more sensitive  than the  manual methods. This is primarily
due to the necessity for somewhat remote location on continuous monitoring equipment and the
attendent long length of sample lines.
       Such continuous equipment, as is presently  available, is very  sensitive and is designed
more for laboratory use than for the production  plant. Long sample lines are usually required as well
as  a host of auxiliary materials  such  as calibration gases,  etc. A further deficiency exists in that
present continuous  monitoring equipment  is incapable  of continuous operation over long periods
without regular attention by  highly skilled instrument specialists.
C.     R&D Priorities to Improve Measurement Techniques
       Based on  the deficiencies  which  exist  in measurement  of emissions  in  the paint and
varnish  industry,  only one  R&D program  is  suggested.  This program  is to develop a simple
and inexpensive instrument to detect hydrocarbon emission and measure flow from  kettle cooking
operations. The proposed program is outlined in the next report  section.
                                        432

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D.      Recommended Programs for Achieving R&D Requirements
        An  ideal  monitoring  instrument  for  kettle  cooking  operations  would  simultaneously
measure  the  gas flow  and the  concentration  of total  organic  materials  in the  gas stream.
In this  manner, a weight  rate of  emission of organics could be deduced,  or  even generated
within  the instrument  and  recorded.  This  instrument  would  be  required  to run  continuously
over  long periods of time  without  the  necessity  for  highly skilled  instrument  specialists.  It
would  either operate with the detection element deployed directly  in the gas  stream  and without
inter-connecting sampling tube, etc., or with the entire sampling train operated at a  temperature
high enough to prevent condensation of organics.  It is, of course,  imperative that the instrument
pose no safety hazard.
        The characteristics of this instrument are as follows:
        1.  Organic concentration and gas flow rate must be measured simultaneously.
        2.  Organic concentration  must  be measured  in  terms  of either  total  hydrocarbon or
           equivalent methane.
        3.  Continuous operation must be possible on heavy organic fumes from kettle operations.
        4.  Maintenance  or operation requirements must be simple.
        5.  First cost must be inexpensive (less than $5,000).
        In  addition to handling  organic  emissions,  the  proposed  instrument  would  need to
incorporate  total flow measurement capability with  low  energy loss or pressure drop. Primary
flow elements  and associated connection lines  will need  to  be  designed to  operate at  high
temperature and without interference from deposits of heavy resinous materials.
        With a  low  pressure drop  limitation, the  selection of the  primary  flow  measurement
device should be limited to the following:
        1.  Pilot tube (S type)
        2.  Venturi flowmeter
        3.  Fluidic sensor
        The final  selection  of device and  means  for  eliminating  interference  from organic
deposition  would be  a  part of the proposed development program.  In  addition, the  program
would  include  selection  of a  read-out approach  which  would be   most compatible,  least
expensive and  require the lowest maintenance.
                                        433

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The proposed development would be carried in three phases as follows:
1.  Library and field research.
2.  "Bread board" and flow measurement experimentation.
3.  Design and fabrication of a working prototype.
The suggested content of each phase is as follows:
Phase I
1.  Literature survey  to define the present state of the art  for flame ionization detection
    as well as pitot or venturi flow measurement.
2.  Discussions with  vendors to establish the range  of commercially  available pitot and
    venturi measuring devices.
3.  Definition of alternatives with respect to:
    a.  Detector configuration
    b.  Electronic circuitry
    c.   Hydrogen generation
    d.  Over-all packaging
    e.  Primary flow measurement
    f.   Sample-loop consideration
Phase II
1.  Assembly of test set-up.
2.  Preparation  of alternative "bread board" detectors.
3.  Selection of primary flow devices.
4.  Testing modification of bread board units and alternative flow devices.
5.  Selection of mechanisms applicable to prototype design.
Phase III
1.  Prototype design
2.  Component acquisition
3.  Fabrication of components
4.  Assembly of components
5.  Field trials
6.  Revision of prototype as required
7.  Final testing
                                    434

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       The timing and costs for each of the three phases are indicated below:
       Phase I should  require approximately 400 man-hours of engineering or scientist effort
and cost approximately $10,000.
       Phase II is expected to require  1500 man-hours  of  engineer or scientist effort  and 1000
man-hours of technician effort. This phase of the  program should  cost  approximately $45,000.
In addition, equipment costs of $5,000 would be anticipated.
       Phase III  should require  approximately  1500  man-hours  of engineer or scientist effort
and 2000 man-hours of drafting and technician effort which will cost about $65,000. In addition,
about  $8,000 will be  required to purchase  components.  It is anticipated that installation and
operation of the prototype  unit can  be arranged with  a paint manufacturer  and that it  will be an
advantage for him  to bear the installation and operation expense.
III.      PIGMENT INDUSTRY
        The manufacture of pigments  is nearly as complex as the manufacture  of the coatings.
However, it is easy to divide this industry into three components, which are:
        1.  The manufacture of titanium dioxide by the sulfate process.
        2.  Manufacture of titanium dioxide by the chloride process.
        3.  Manufacture of other pigments by various processes.
        While TiO2 production  by the chloride process probably exceeds that by the sulfate process
today,  the sulfate  process will probably  remain a  significant factor  for some  time.  Also,  the
problems inherent in  the preparation of titanium dioxide pigments by the sulfate process appear
to be more significant and difficult to control than those in the chloride process and development
efforts should be concentrated in this area.
        Unlike the sulfate  process,  there are  a number of different chloride processes used in
the manufacture of TiO2. The large differences in emissions from the various type plant chlorinators
should also be a subject of further study.
        The R&D program in this industry should consist of the following steps:
        1.  Assemble all of the available information on the  design basis used for the selection
           and  sizing of  existing  electrostatic precipitators and  scrubbers  by  contact with  the
           manufacturers  of  titanium  dioxide  by the  sulfate  process,  and  by  contact with  the
                                          435

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           manufacturers of air pollution control equipment.
       2.  Independent  definition  of  the  problem in terms of the physics  and chemistry of the
           fume product and source test information  established by the EPA.
       3.  Preparation of prototype specifications for a satisfactory control system  by each means
           judged as a feasible approach, without regard to commercial duration  of the process.
       4.  Economic evaluation of the alternatives judged feasible.
       5.  Selection  of  one (or  possibly two) technically  feasible alternatives for prototype
           development.
       6.  Small scale pilot testing of a prototype design.
       7.  Recommendations for full-scale testing.
       The cost of the development program  is  likely to  be  large relative  to the economic
advantage  achieved by  any single  pigment  manufacturer  by product recovery  or air pollution
control equipment cost reduction.
       Estimates of the timing  and costs can  be divided  into three phases. The first  involves
the investigatory  and evaluation phase. This should  require  approximately 2000 man-hours of
professional time and  1000  man-hours of non-professional time, and should  cost on the order
of $60,000. At the end  of this phase, a  feasible  approach  should have  been  selected and  a
pilot design prepared. The  second phase  involves the construction, field testing  and evaluation of
a prototype pilot  unit. This is expected to involve an  additional  1500 man-hours of professional
time,  1500 man-hours of non-professional time  and a lump sum cost for fabrication  of the pilot
unit  of $25,000.  The manpower costs are estimated to be  approximately $50,000,  for  a total
cost of $68,000.
       The final  phase,  which is  a preparation for  the testing of a full-scale prototype,  involves
the design of a full-scale  prototype and  a good estimate of the installation and operating cost
of the prototype.  This phase is  estimated to require approximately 1200 professional  man-hours,
100 non-professional man-hours and to cost approximately $30,000.
       The installation  and  operation of  a full-scale prototype  unit  may  be  emitted from the
research and development  program proposed,  and some cost-sharing arrangement  worked out with
a titanium dioxide manufacturer  so that the principal costs  of  installation and operation are borne
by the commercial  process.  The  development costs could reasonably be  funded by the  public
through the EPA.
                                          436

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       The second  area identified for research and  development  work is  that of treatment of
the flue gas  discharged  from the pigment digester. An  alternative course of action involves the
modification of the digestion  process such  that little or no  gas is vented to the atmosphere.
This has been judged to be  less likely  of  success because  of  the large investment in existing
sulfate process digesters  in the industry. However, should a good approach to process modifications
be proposed  within the industry, direct funding of all or a part of the development work would be
appropriate.
                                          437

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                                      REFERENCES


 1.  Marketing  Guide to  the Paint Industry.  Fairfield, N.J., Charles H. Kline & Co.,  Inc.,  Patricia
     Noble (ed), 1969.

 2.  Federation Series on Coating Technology.
      Unit 1 — "Introduction to Coatings Technology", Oct., 1964.
      Unit 2 — "Formation and Structure of Paint Films", June, 1965.
      Unit 3 — "Oils for Organic Coatings", Sept., 1965.
      Unit 4 — "Modern Varnish Technology", May, 1966.
      Unit 5 — "Alkyd Resins", Mar., 1967.
      Unit 6 — "Solvents", May, 1967.
      Unit 7 — "White Hiding and Extender Pigments", Oct., 1967.
      Unit 8 — "Inorganic Color Pigments", Mar., 1968.
      Unit 9 — "Organic  Color Pigments", July, 1968.
      Unit 10 — "Black and Metallic Pigments", Jan., 1969.
      Unit 11 — "Paint Driers and Additives", June, 1969.
      Unit 12 — "Principles of Formulation and Paint Calculations", June,  1969.
      Unit 13 — "Amino  Resins in Coatings", Dec.,  1969.
      Unit 14 — "Silicone Resins for Organic Coatings", Jan., 1970.
      Unit 15 — "Urethane Coatings", July, 1970.
      Unit 16 — "Dispersion and Grinding", Sept., 1970.
      Unit 17 — "Acrylic  Resins",  Mar., 1971.
      Unit 18 — "Phenolic Resins", Mar., 1971.
      Unit 19 — "Vinyl Resins", Apr., 1972.
     Federation Societies for Paint Technology. Philadelphia, Pa.

 3.  Chemical Economics Handbook. Stanford Research Institute, Menlo Park, Ca.

 4.  The Technology of Paints, Varnishes,  and Lacquers. New York, Reinhold Book Corp.,  Charles
     R.  Martens (ed), 1968.

 5.  Parker, Dean H. Principles of Surface Coating Technology. New York, John Wiley & Sons,
     Interscience Publishers Division,  1965.

 6.  Raw Materials  Index  — Resin  Section.  Washington,  D.C.,  National  Paint,  Varnish  and
     Lacquer Association, 1971-72 edition.

 7.  Paint Red  Book. New York, Palmerton Publishing Company,  1972, fifth edition.

 8.  Current Industrial Reports —  Series M28F.  Washington, D.C., U.S. Department of Commerce,
     Bureau of the Census.

 9.  Brewster,  R. F.  Process  Layout and Equipment Selection for One Million Gallons  a Year
     Paint  Plant. Presented at Manufacturing  Management  Forum  of  1972 convention of the
     National Paint and Coating Association, October 31, 1972.

10.  The Ideal Paint Plant. Manufacturing Committee, Toronto Paint Society.

11.  The Story of Alkyd Resins-Processing and Equipment. Cincinnati, the Brighton Corporation, 1959.

12.  Unpublished, First Interim Report.
                                         439

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13.  County Business  Patterns. Washington,  D.C.,  Department of Commerce, Bureau  of the
     Census, 1965-71.

14.  1967 Census of Manufacturers. Washington,  D.C., U.S. Bureau of the Census,  Industry and
     Area Statistics.

15.  Chemical Engineering. February 19, 1973.

16.  Chemical and Engineering News. February 23, 1973.

17.  Air Pollution Engineering Manual. Los Angeles County, Air Pollution Control District.

18.  Unpublished  source tests of 10 different kettles. PPG Industries.

19.  Skelly,  W. K.  Unpublished  report on source test of  Stresen-Reuter International's plant in
     Bensenville,  Illinois, conducted by the  R&D group  of International Minerals  &  Chemicals
     Corporation.

20.  Unpublished  source tests of 11 different kettles.  Montebello, Ca., Hirt Combustion  Engineers,
     August, 1971.

21.  White, H. J.  Industrial Electrostatic Precipitation. Reading, Mass.,  Addison-Wesley Publishing
     Company, 1963.

22.  Chemical Week. June 20, 1973.

23.  Chemical Engineering. February 19, 1973.

24.  Modern Plastics. April, 1973.

25.  Chemical and Engineering News. February 23, 1973.

26.  Chemical Week. April 4, 1973.

27.  Rolke,  et  al.  Afterburner Systems Study, Final Report under Contract  EHS-D-71-3  for the
     U.S. Environmental Protection Agency, Office  of Air Programs.

28.  Hardison,  L.  C. A Summary of the Use of Catalyst for Stationary Emission Source Control.
     Presented at Franklin Institute, Philadelphia, Pa., Nov., 1968.

29.  Hardison, L.  C. Controlling  Combustible  Emissions. Paint and  Varnish Production, July, 1967.

30.  Paint Technology Manual, Part Six, Pigments, Dyestuffs, and Lakes. Oil and Colour Chemists
     Association, New York, Reinhold Publishing Corp., 1966.

31.  Raw Materials Usage  Survey. National Paint, Varnish  and Lacquer Association, June, 1971.

32.  Unpublished  Data. Harshaw Chemical Company.

33.  Nelson,  K. W. Cadmium in the  Environment.  San Francisco,  presented at AIME Meeting,
     February 21, 1972.
                                          440

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34.  Shreve,  R.  N. The  Chemical Process  Industries.  New York,  McGraw-Hill  Book Company,
     1956.

35.  Minerals Yearbook 1968. Washington, D.C., Bureau of Mines.

36.  Barksdale, J. Titanium — Its Occurrence, Chemistry and Technology. New York, The Ronald
     Press  Company, 1966.

37.  Atmospheric Emissions  from Hydrochloric Acid  Manufacturing  Processes.  Durham,  N.C.,
     U.S.  Department of  Health, Education  and Welfare, Public  Health Service,  National Air
     Pollution Control Administration, 1969. Publication No. AP-54.

38.  Falk, L. L. Industrial Hygiene Quarterly. December, 1951. Vol. 12, No. 4.

39.  Report of  Atmospheric  Emission Tests  Conducted  at  Titanium Division,  National  Lead
     Company, Sayreville,  New Jersey. Division of Air Pollution, Public Health Service, Sept.,  1966.
     IND-1-66.
                                         441

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                    LIST OF STANDARD ABBREVIATIONS


actual cubic feet per minute                                        ACFM
atmospheres gage (pressure)                                       atmg
British thermal units                                                Btu
centimeters                                                       cm
change of pressure (delta pressure)                                 AP
change of temperature (delta temperature)                           AT
cubic feet                                                        ft3
degrees Centigrade                                                ฐC
degrees Fahrenheit                                                ฐF
degrees Rankine                                                  ฐR
diameter                                                         dia
dollars                                                           $
feet or foot                                                       ft
gallon or gallons                                                   gal
gallons per minute                                                 gpm
grain or grains                                                    gr
hour or hours                                                     hr
hydrocarbon                                                      Hcbn
inch  or inches                                                    in.
lower explosive limit                                               L.E.L.
meter or meters                                                   m
milliliters                                                         ml
millimeters                                                       mm
millimeters of Mercury (pressure)                                    mmHg
millions  (106)                                                      MM
minute or minutes                                                 min
mole                                                            mol
non-volatile material                                               NVM
parts per million                                                   ppm
per cent                                                          %
pint or pints                                                       pt
pound or pounds                                                  Ib
pounds per square inch gauge                                      psig
quart or quarts                                                    q{
seconds                                                          sec
square feet                                                       ft2
standard cubic feet                                                SCF
standard cubic feet per minute                                      SCFM
temperature                                                       Temp
ton or tons                                                       ton
water column (pressure)                                            w-c-
weight percent                                                    wt-0/ฐ
year or years                                                     Yr
                                  442

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      APPENDIX A






MODEL PLANT COST DETAIL

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                           APPENDIX A
                    MODEL PLANT COST DETAIL
              Item
Equipment - Paint Plant

101 - Pebble Mill

      Abbe - Model 8% - 21" O.D.  x 28" LG,
      Jacketed Mill with Burrstone lining
      complete with 3/4 HP motor  ง
      magnetic brake
         Ni-Hard Balls
         Electrical Wiring
         Foundation ง Supports
         Installation
                                 Total
102 - Pebble Mill
      Abbe - Model 8B - 24" O.D.  x 36" LG.
      Jacketed Mill with Burrstone lining
      complete with 1% HP motor ง magnetic
      brake
         Ni-Hard Balls
         Electrical Wiring
         Foundation ง Supports
         Installation
                                 Total
103 - Pebble Mill
      Abbe -  Model 6 -  32" O.D.  x 36" LG.
      Jacketed Mill with Burrstone lining
      complete with 3 HP motor ง
      magnetic brake
         Ni-Hard Balls
         Electrical Wiring
         Foundation ง Supports
         Installation

                                 Total
Quan.
Unit
Cost
          3,600
            100
          1,700
            500
            400

          6,300
          4,250
            150
          1,700
            800
            500

          7,400
          5,600
            450
          1,700
          1,100
            600

          9,450
Total
           6,300
           7,400
           9,450
                              A-l

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                Item
Equipment - Paint Plant

104 - Pebble Mill

      Abbe - Model 5B - 42" O.D.  x 48" LG.
      Jacketed Mill with Burrstone lining
      complete with 5 HP motor ง  magnetic
      brake
         Ni-Hard Balls
         Electrical Wiring
         Foundation ง Supports
         Installation
Quan
                                 Total
105 - Pebble Mill
      Abbe - Model 2 -  60" O.D.  x 48" LG.
      Jacketed Mill with Burrstone lining
      complete with 15  HP motor  ง magnetic
      brake
         Ni-Hard Balls
         Electrical Wiring
         Foundation ง Supports
         Installation
                                 Total
106 - Pebble Mill
      Abbe - Model 2B -  60" O.D.  x 72" LG.
      Jacketed Mill with Burrstone lining
      complete with 20 HP motor ง magnetic
      brake
         Ni-Hard Balls
         Electrical Wiring
         Foundation ง Supports
         Installation

                                 Total
                                                      Unit
                                                      Cost
                                                      7,350
            550
          1,700
          2,200
            800

         12,600
         11,200
          1,100
          1,800
          4,700
          1,500

         20,100
         12,900
          1,650
          1,800
          5,700
          1,500

         23,550
Total
                                                                12,600
                                                                20,100
                                                                23,550
                             A-2

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                                                      Unit
	Item	   Quan.     Cost      Total

Equipment - Paint Plant


107 - Pebble Mill

      Abbe - Model 0 - 72" O.D. x 96" LG.     1      19,700
      Jacketed Mill with Burrstone lining
      complete with 30 HP motor ง magnetic
      brake
         Ni-Hard Balls                                3,200
         Electrical Wiring                            2,150
         Foundation ง Supports                       10,800
         Installation                                 2,300

                                 Total               38,150     38,150
      Total unadjusted cost for Pebble Mills                   117,550


      Chicago area adjustment             41

      Adjustment from Jan. to Dec. '72    5%

                         Total            9%                    10,600


      Total installed cost for Pebble Mills                    128,150
                             A-3

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              Item
Quan.
Unit
Cost
Total
Equipment - Paint Plant

108 - Ball Mill

      Abbe - Model 6 - 32" O.D.  x 36" LG.
      Jacketed Mill with Burrstone lining
      complete with 5 HP motor and magnetic
      brake
         Ni-Hard Balls
         Electrical Wiring
         Foundation ง Supports
         Installation
                                 Total
109 - Ball Mill
      Epworth - 4'x5'  Ball Mill manufac-
      tured in accordance with Sherwin-
      Williams specifications complete
      with 15 HP motor reducer drive
         Ni-Hard Balls
         Electrical Wiring
         Foundation ง  Supports
         Installation

                                 Total
          6,000
            650
          1,700
          1,500
            700

         10,550
         13,150
          2,500
          1,800
          4,700
          1,700

         23,850
          10,550
          23,850
      Total unadjusted cost for Ball Mills

      Adjustment - 9%


      Total installed cost for Ball Mills
                    34,400

                     3,100


                    37,500
                             A-4

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                                                      Unit
	Item	   Quan.      Cost      Total

Equipment - Paint Plant

110 - Sand Mill

      Standard "Red Head" Mill Model 3P       1       3,350
      complete with 10 HP motor, feed
      pump  and two charges of sand
         Electrical Wiring                            1,800
         Foundations ง Supports                         300
         Installation                                   500
                                 Total                5,950      5,950

111 - Sand Mill

      Standard "Red Head" Mill Model 8P       1       5,100
      complete with 20 HP motor, feed
      pump, discharge pump and two charges
      of sand
         Electrical Wiring                            1,800
         Foundations ง Supports                         600
         Installation                                   700
                                 Total                8,200      8,200

112 - Sand Mill

      Standard "Red Head" Mill Model 16P      1       6,300
      complete with 30 HP motor,  feed pump,
      discharge pump  and two charges of
      sand
         Electrical Wiring                            2,150
         Foundations ง Supports                         900
         Installation                                   800

                                 Total               10,150     10,150
      Total unadjusted cost for Sand Mills                      24,300

      Total adjusted cost for Sand Mills                        26,500
                             A-5

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                                                      Unit
              Item   	            Quan.      Cost	   Total
Equipment - Paint Plant

113 - High Speed Disperser

      Morehouse Cowles - Model 515 VHV -       2        3,300
      Disperser complete with 10 HP
      explosion-proof motor
         Electrical Wiring                            1,800
         Installation                                   400
                                 Total                5,500     11,000

114 - High Speed Disperser

      Morehouse Cowles - Model 520 VHV -       1       4,550
      Disperser complete with 25 HP
      explosion-proof motor
         Electrical Wiring                            2,000
         Installation                                   500
                                 Total                7,050      7,050

115 - High Speed Disperser

      Morehouse Cowles - Model 720 VHV -      1       7,050
      Disperser complete with 50 HP
      explosion-proof motor
         Electrical Wiring                            2,500
         Installation                                   800
                                 Total               10,350     10,350

116 - High Speed Disperser

      Morehouse Cowles - Model 1030 VHV -     1       8,400
      Two Speed Disperser complete with
      100 HP explosion-proof motor
         Electrical Wiring                            3,300
         Installation                                 1,000

                                 Total               12,700     12,700

      Total unadjusted costs for High Speed Dispersers          41,100

         Adjustment                                              3,700
      Total installed costs for High Speed Dispersers           44,800
                             A-6

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                                                      Unit
	Item	  Quan.     Cost      Total

Equipment - Paint Plant

117 - Mixing Tanks

      Portable tank, 220 gallon capacity,    20         350      7,000
      42" I.D. x 34" straight side with
      flat bottom mounted on 6" heavy duty
      casters; lift hooks with 2" half
      coupling outlet
      Carbon steel construction

118 - Finishing Tanks

      Floor mounted 550 gallon tank,         14       2,900
      4' I.D.  x 6' straight side with
      dished bottom and flat top complete
      with 3 HP top mounted agitator
      carbon steel
         Electrical Wiring                            1,700
         Installation                                   300
                                 Total                4,900     68,600

119 - Finishing Tanks

      Floor mounted 1100 gallon tank,          8       4,500
      5'  I.D.  x 8'  straight side with
      dished bottom and flat top complete
      with 7% HP top mounted agitator
      Carbon steel  construction
         Electrical Wiring                            1,700
         Installation                                   400
                                 Total                 6,600     52,800

120 - Finishing Tanks

      Floor mounted 2200 gallon tank,          3       5,700
      7'  I.D.  x 8'  straight side with
      dished bottom and flat top complete
      with 15 HP top mounted agitator
      Carbon steel  construction
         Electrical Wiring                            1,800
         Installation                                   600
                                 Total                8,100     24,300

      Total  unadjusted cost for  Mixing and Finishing Tanks      152,700

         Adjustment                                              13,750


      Total  installed costs for  Mixing and Finishing Tanks      166,450

                             A-7

-------
                                                      Unit
	Item	    Quan.      Cost      Total

Equipment - Paint Plant

121 - Filter

      Cuno - Model - FH-530-CW with           1         200
      support assembly.  Carbon
      steel construction
         Installation                                    50
                                 Total                  250        250

122 - Filter

      Cuno Micro Klean Filter with 6          3         655
      cartridges.  Carbon steel con-
      struction
         Installation                                    75

                                 Total                  730      2,190

123 - Screens

      Lehman Vorti Sieve                      2       3,000
      Support Cart                                      500
         Electrical Wiring                            1,700
         Installation                                   500

                                 Total                5,500     11,000

124 - Can Filler

      Ambrose Model PF-9 Filling and          2      10,000
      sealing machine
      Lid Dropper ง Can Closer                        1,500
         Installation                                 1,000

                                 Total               12,500     25,000

125 - Bail-0-Matic

      Bail-0-Matic - Model "A"                1      16,000
         Electrical Wiring                            1,700
         Installation                                 1,000

                                 Total               18,700     18,700

126 - Barrel Filler

      Mantes - Model 16 MTFF                  1       4,500
      Barrel Filler
         Installation                                   400

                                 Total                4,900      4,900

                             A-8

-------
              Item
             Quan.
Unit
Cost
Total
Equipment - Paint Plant

127 - Labeler

      New .Way Labeler - Model
         Electrical Wiring
         Installation
128 - Packing Station

      New Way Model EC Caser
         Electrical Wiring
         Installation
129 - Case Sealer

      New Way Model F-20 Kiwi
      Kiwi Carton Coder
         Electrical Wiring
         Installation
iEpn
                                 Total
                                 Total
                                 Total
130 - Carton Stencil

131 - Portable Pumps and Carts


      Total. Filling and Packaging Equipment
      Adjusted Cost

         Adjustment

      Total Installed Cost for Filling and
      Packaging Equipment
6,000
1,700
  500

8,200
                        9,550
                          100
                        1,000

                       10,600
                                   8,200
          10,600
1
1
2

7,000
300
1,700
1,000
10,000
500
2,500

10,000
500
5,000
96,340
8,660
                                 105,000
                             A-9

-------
                                                      Unit
	Item	    Quan.     Cost      Total

Equipment - Paint Plant

   Laboratory Equipment

         Viscometers                          4        250       1,000

      Spray Booth - Binks Model PBFL-4
         Electrical Wiring                    2        475
         Installation                         4      1,700
         Installation                                  125
                                 Total               2,300       4,600

      Drying Oven - "Blue M" Model            2        550
         OV-472A-2 with floor stand
         Electrical Wiring                           1,700
         Installation                                  150
                                 Total               2,400       4,800

      Tables, Benches  ง Disks                                   2,000
      Total Unadjusted Cost for
      Laboratory Equipment                                      12,400

         Adjustment                                              1,100
      Total Installed Cost for Laboratory Equipment             13,500
                            A-10

-------
              Item
Equipment - Resin Plant

201 - 500 Gallon Resin Reactor Unit
      Complete with:
         Agitator $ Baffles
         Cooling Coil
         Baffles
         Fume Scrubber
         Spray Tower
         Ej ector
         Circulating  Pump
         1000 Gallon  Thinning Tank
         Thinning Tank Agitator
         Thinning Tank Scale
         Thinning Tank Condenser
         Control Panel

      Material of Construction
       Stainless Steel

         Quotation from
         Brighton Corporation
         Cincinnati,  Ohio

         Electrical Wiring
         Piping - included in the above
                  quotation
         Installation

         Structural Steel
         Insulation
          Unit
Quan.      Cost
Total
         55,300
          5,000
         11,000

          3,000
          1,800
                                 Total
         76,100
76,100
                            A-ll

-------
              Item
Equipment - Resin Plant

202 - 1500 Gallon Resin Reactor Unit
      Complete with:
         Agitator
         Inconel Dimpled Jacket
         Sampler
         Baffles
         Cooling Coil
         Partial Condenser
         Total Condenser
         Decanter-Receiver
         Vacuum System
         Fume Scrubber
         Spray Tower
         Ej ector
         Circulating Pump
         3000 Gallon Thinning Tank
         Thinning Tank Agitator
         Thinning Tank Scale
         Thinning Tank Condenser
         Control Panel
          Unit
Quan.     Cost      Total
         85,400
      Material of Construction
       Stainless steel unless specified
       otherwise

      Quotation from Brighton Corp.
      Cincinnati, Ohio

         Electrical Wiring
         Piping - included in the above
                  quotation
         Installation

                                 Total
          8,500
         17,000


        110,900    110,900
                             A-12

-------
              Item
Equipment - Resin Plant

203 - Filter Feed Pumps

      Viking Model K-124 Cast Iron
      Electrical Wiring
      Foundations ง Supports
      Installation
                                 Total
204 - Resin Transfer Pump
      Viking Model K-124 Cast Iron
      Electrical Wiring
      Foundations ง Supports
      Installation
                                 Total
205 - Filter Presses
      Shriver - 18" x 18" Filter Press
      with 70 ฃt2 of filtering area
      Cast iron with "Hydrd Kloser"
      Installation
                                 Total
206 - Relief Tank

      1500 Gallon
      Foundations
      Installation
                    Carbon Steel
                    Supports
                                 Total
                                            Quan,
      Total Unadjusted Cost for Resin Plant

      Total Adjusted Cost for Resin Plant
Unit
Cost
                                                        600
                                                      1,700
                                                        200
                                                        100

                                                      2,600
                                                        600
                                                      1,700
                                                        200
                                                        100

                                                      2,600
                                                      2,000


                                                        200

                                                      2,200
1,400
  600
  500

2,300
Total
           5,200
           5,200
           4,400
                                                                 2,300


                                                               204,100

                                                               222,500
                            A-13

-------
                                                      Unit
	Item	    Qua a.      Cost      Total

Equipment - Storage Area

301 - Odorless Mineral Spirits Stg.  Tank

      25,000 Gallons - Carbon Steel            1      11,200
         Installation                                 1,500

                                 Total               12,500     12,500

302 - Odorless Mineral Spirits Transfer
      Pump

      Goulds - 1 x 2 x 10 - Carbon Steel      1         700
      Pump complete with 3 HP motor
         Electrical Wiring                            1,700
         Installation                                   100
         Piping                                       3,250
         Tokheim - IV Line Meter                       750

                                 Total                6,500      6,500

303 - Industrial Alkyd Solvent Stg.  Tank

      25,000 Gallons - Carbon Steel            1                 12,500

304 - Industrial Alkyd Solvent Transfer Pump

      Goulds - 1 x 2 x 10 - Carbon Steel      1         700
      Pump complete with 3 HP motor
         Electrical Wiring                            1,700
         Installation                                   100
         Piping                                       3,250
         Tokheim - IV Line Meter                       750

                                 Total                6,500      6,500

305 - Waste Solvent Tank

      1,000 Gallons - Carbon Steel            2       1,200
         Installation                                   500

                                 Total                1,500      3,000
      Pump - Goulds - 1 x 2 x 10 - Carbon     1         700
      Steel with 3 HP motor
         Installation                                   100
         Electrical Wiring                            1,700
         Piping                                       2,000

                                 Total                4,500      4,500


                             A-14

-------
                                                      Unit
	Item	    Quan.     Cost      Total

Equipment - Storage Area

306 - Aqueous Waste Tank

      1,000 Gallons - Carbon Steel            1       1,200
         Installation                                   300
      Pump - Goulds -1x2x10              1         800
         Electrical Wiring                            1,700
         Piping                                         600

                                 Total                4,500      4,500

307 - Industrial Alkyd Tank

      1,000 Gallons - Carbon Steel            4       5,250     21,000
      Tank with Pump ฃ Meter

308 - Interior Latex Tank

      22,500 Gallons - Stainless Steel        1      15,000
         Installation                                 1,000
      Pump - Viking Model K-124               1       1,700
      Stainless Steel with Motor
         Installation                                   100
         Tokheim Meter - IV Stainless Steel          2,500
         Electrical Wiring                            1,700
         Piping - 304 Stainless Steel                 1,100

                                 Total               23,100     23,100

309 - Exterior Latex Tank

      17,500 Gallons - Stainless Steel        1      13,500
         Installation                                   800
      Pump - Viking Model K-124               1       1,700
      Stainless Steel complete with
      3 HP Motor
         Installation                                   100
         Tokheim Meter - IV Stainless Steel          2,500
         Electrical Wiring                            1,700
         Piping - 304 Stainless Steel                 1,100

                                 Total               21,400     21,400
                            A-15

-------
                                                      Unit
	Item	     Quan.     Cost      Total

Equipment - Storage Area

310 - Oil Storage Tank

      12,500 Gallons - Carbon Steel           2       6,300
         Installation                                   700
         Pump - Viking Model K-124                      550
                Carbon Steel complete
                with 3 HP motor
         Installation                                   100
         Tokheim Meter - IV Carbon Steel               750
         Electrical Wiring                            1,700
         Piping - Carbon Steel                          600

                                 Total               10,700     21,400

311 - Industrial Alkyd Storage Tank

      10,000 Gallons - Carbon Steel           1       5,500
         Installation                                   600
         Pump - Viking Model K-124                      550
         Installation                                   100
         Tokheim Meter - IV Carbon Steel               750
         Electrical Wiring                            1,700
         Piping - Carbon Steel                          600

                                 Total                9,800      9,800

312 - Industrial Alkyd Storage Tank

      7,500 Gallons - Carbon Steel            1       4,600
         Installation                                   500
         Pump - Viking Model K-124                      650
         Tokheim Meter -  iy Carbon Steel               750
         Electrical Wiring                            1,700
         Piping - Carbon Steel                          600

                                 Total                8,800      8,800
                            A-16

-------
                                                      Unit
	Item	     Quan.      Cost       Total

Equipment - Storage Area

313 - Trade Alkyd Tank

      10,000 Gallons - Carbon Steel           1       9,800      9,800

314 - Trade Alkyd Tank

      5,000 Gallons -  Carbon Steel            1       3,400
         Installation                                   400
         Pump - Viking Model K-124                      650
         Tokheim Meter - IV Carbon Steel               750
         Electrical Wiring                            1,700
         Piping                                         600

                                 Total                7,500      7,500

315 - Glycerine Storage Tank

      7,500 Gallons -  Carbon Steel            1       8,800      8,800
         Installation, Pump, Piping,
         Wiring and Meter

316 - Portable Pumps with Carts               3       2,500      7,500


      Tank Gauges                            20         250      5,000


      Total Storage Area Unadjusted Cost                       194,100

         Adjustment                                             17,500

                       Total Storage Area Cost                 211,600
                            A-17

-------
Item
Equipment - Miscellaneous
Scales - 0-100 Ibs.
0-500 Ibs.
Ford Trucks
Electric - 4,000 Ib. Capacity
Charger
Total
I.C. Engine - 4,000 Ib. Capacity
Unit
Quan. Cost

3 200
2 250
1 9,350
250
9,600
2 7,300
Total

600
500
9,600
14,600
Racks

   4' wide - 2'  deep               6,250 ft2                9,400

Fire Extinguishers                                         2,200

Emergency Lighting                                        22,500


Furniture

   Office                                       5,000
   Lunch Room                                   2,500
   Locker Room                                  1,500

                           Total                9,000       9,000


Drum and Hand Pallet Trucks                     1,500       1,500
                      A-18

-------
                                                      Unit
	Item   	     Quan.      Cost       Total

Equipment - Storage Area

313 - Trade Alkyd Tank

      10,000 Gallons - Carbon Steel           1       9,800      9,800

314 - Trade Alkyd Tank

      5,000 Gallons - Carbon Steel            l       3,400
         Installation                                   400
         Pump - Viking Model K-124                      650
         Tokheim Meter - i%" Carbon Steel               750
         Electrical Wiring                            1,700
         Piping                                         600

                                 Total                7,500      7,500

315 - Glycerine Storage Tank

      7,500 Gallons - Carbon Steel            1       8,800      8,800
         Installation, Pump, Piping,
         Wiring and Meter

316 - Portable Pumps with Carts               3       2,500      7,500


      Tank Gauges                            20         250      5,000


      Total Storage Area Unadjusted Cost                       194,100

         Adjustment                                             17,500

                       Total Storage Area Cost                 211,600
                            A-17

-------
Item
Equipment - Miscellaneous
Scales - 0-100 Ibs.
0-500 Ibs.
Ford Trucks
Electric - 4,000 Ib. Capacity
Charger
Total
I.C. Engine - 4,000 Ib. Capacity
Unit
Quan. Cost

3 200
2 250
1 9,350
250
9,600
2 7,300
Total

600
500
9,600
14,600
Racks

   4' wide - 2'  deep               6,250 ft2                9,400

Fire Extinguishers                                         2,200

Emergency Lighting                                        22,500


Furniture

   Office                                       5,000
   Lunch Room                                   2,500
   Locker Room                                  1,500

                           Total                9,000      9,000


Drum and Hand Pallet Trucks                     1,500      1,500
                      A-li

-------
                                                      Unit
	Item	     Quan.     Cost      Total

Equipment - Miscellaneous

      Shop Equipment

         Cabinets ง Shelves                           3,000
         Grinders                                     1,900
         Press                                        3,000
         Radial Drill                                12,000
         Wells Saw                                    1,800
         Milling Machine                              3,600
         Lathe                                       25,000
         Benches                                        850
         Vises                                          700
         Welding Machines                               900
         Band Saw                                     2,100
         Hand Brake                                   1,800
         Roller                                       2,200
         Shearer                                      1,200
         Hand Tools                                   1,000

                                 Total               61,050     61,050


      Total Unadjusted Cost for
       Miscellaneous Equipment                                 130,950

         Adjustment                                             11,800

      Total Cost for Miscellaneous Equipment                    142,750
                            A-19

-------
                                                      Unit
              Item	    Quan.      Cost      Total
Utilities
      Dowtherm System

      Two Million Btu/hr Direct Fired         1      36,000
      Heater - Carbon Steel
         Piping                                       5,500
         Insulation                                   2,800
         Electrical Wiring                            2,500

                                 Total               46,800     46,800

      Inert Gas Generator

      Kemp - Model 6 - PH - 5000 CFH          1      23,100
      Inert Gas System
         Storage Tank                                 1,200
         Installation                                 2,500
         Electrical Wiring                            2,150
         Piping                                       4,600

                                 Total               33,550     33,550

      Compressed Air

      150 CFM Packaged Air Compressor         1       3,500
      complete with 50 HP Motor
         Electrical                                   2,500
         Installation                                 1,000
         Piping                                       5,200

                                 Total               12,200     12,200

      Cooling Water

                                                     11,000
                                                      7,000
                                                      2,520
                                                      1,950
                                                      1,000
                                                        975
                                                        600
                                                        275

                                 Sub-Total           25,320

         Insulation                                     500
6"
4"
3"
2"
iy
1"
3/4"
k"
Sch.
Sch.
Sch.
Sch.
Sch.
Sch.
Sch.
Sch.
40
40
40
40
40
40
40
40
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
Steel
Steel
Steel
Steel
Steel
Steel
Steel
Steel
                                 Total               25,820     25,820
                            A-20

-------
                                                      Unit
              Item	    Quan.      Cost      Total
Utilities
      Portable Water

         Piping                                         950
         Hot Water Heaters                              800
         Electrical Wiring                            3,400

                                 Total                5,150      5,150

      Sewers ง Drains

         Process - Piping                             7,150
                   Catch Basins                       2,000
                   Intercepter                        1,500
         Sanitary - Piping                            6,650
                    Catch Basins                      4,000

                                 Total               21,300     21,300

      Natural Gas

         Piping                                                  7,350

      Grounding

         Allowance                                              10,000

      Telephones                                                 1,500


      Total Unadjusted Cost for Utilities                      163,670

         Adjustment                                             14,730

      Total Cost for Utilities                                 178,400



      Building Summary

         Sitework                                    167,100

         Part I   - Raw Material Warehouse            219,700

         Part II  - Manufacturing Arch               912,450

         Part III - Finished Goods Warehouse          526,700

                                 Total             1,825,950   1,825,950


                            A-21

-------
                             SITE WORK
                                                      Unit       Total
	Item	      Quan.	     Cost      Material

Strip Top Soil (8")                      2,080 C.Y.      .65       1,350
Excavation                               3,560 C.Y.     1.36       4,850
Compacted Fill                           5,640 C.Y.     8.90      50,100
Asphalt Paving, Base Course, Grading     6,200 S.Y.     4.20      26,000
Fence (8' Chain Link, w/barb wire)         620 L.F.     5.00       3,100
Utility Building                         2,000 S.F.     8.00      16,000
Drum Storage Pad (6" cone.)              9,000 S.F.      .80       7,200
Tank Farm Pad (6" cone.)                 2,400 S.F.      .80       1,900
Tank Farm Dike                             200 L.F.    37.00       7,400
Seeding                                 48,000 S.F.      .05       2,400
Landscaping                                 L.S.       2,000       2,000
Exterior Lighting                            6          400       2,400

                                                                124,700

   Contractors - Overhead ง Profit  - 25%

   Chicago Area Adjustment          -  4%

   Adjustment from Jan. to Dec. '72     5%

                                      34%                        42,400

                               Total                            167,100
                            A-22

-------
              PART I - RAW MATERIAL WAREHOUSE


                                                              Total
                                                             Material

                                                                850
                                                              8,100
                                                              2,050
                                                             13,600
                                                             13,800
                                                             32,000
                                                             21,200
                                                              1,950
                                                                750
                                                              1,400
                                                              5,300
                                                              1,300
                                                              5,850
                                                              6,600
                                                              3,600
                                                              3,000
                                                              1,000
                                                                900
                                                                450
                                                              2,800
                                                                400
                                                                450
                                                             12,800
                                                             15,300
                                                              8,500

                                                            163,950


Contractors - Overhead $ Profit   - 25%

Chicago Area Adjustment           -  4%

Adjustment from Jan.  to Dec.'72      51

                                    341                      55,750

                      Total                                 219,700
Item
Excavation
Foundations
Compacted Fill
First Floor (6" cone.)
Roof Deck, Insulation ง Roofing
Structural Steel
Insulated Sandwich Panel
Partition Walls (8" Block)
Gravel Stop
Roof Drains ง Piping
Smoke Vents
Doors (31 x 7')
Doors (81 x 8') w/operator 510 + 465
Dock Levelers
Dock Seals
Dock Canopy
Dock Stairway
Ceilings
V.A. Tile
Toilet Fixtures
Toilet Partitions ง Screens
Paint
Heat ง Vent
Lighting
Sprinklers ford, hazard)
Quan.
630 C.Y.
90 C.Y.
230 C.Y.
17,000 S.F.
17,000 S.F.
145,000 #
9,000 S.F.
1,100 S.F.
570 L.F.
2 ea.
6 ea.
5 ea.
6 ea.
6 ea.
6 ea.
1,000 S.F.
1 ea.
900 S.F.
900 S.F.
7 ea.
4 ea.
2,200 S.F.
17,000 S.F.
17,000 S.F.
17,000 S.F.
Unit
Cost
1.36
90
8.90
.80
.81
.22
2.35
1.75
1.30
700
880
265
975
1,100
600
3.00
1,000
1.00
.50
400
100
.20
.75
.90
.50
                         A-23

-------
               PART II -  MANUFACTURING  AREA


                                                             Total
                                                            Material

                                                               1,500
                                                             25,200
                                                               7,300
                                                             17,600
                                                             44,000
                                                             36,300
                                                             10,100
                                                            131,000
                                                             11,700
                                                             10,700
                                                               2,000
                                                                 500
                                                               6,200
                                                               1,400
                                                             12,300
                                                               2,650
                                                               4,900
                                                            109,500
                                                             10,600
                                                             92,500
                                                             70,500
                                                             33,000
                                                             39,500

                                                            680,950


Contractors - Overhead ง  Profit   -25%

Chicago Area Adjustment           -   4%

Adjustment from Jan.  to Dec.  '72     5%

                                    341                     231,500

                           Total                            912,450
Item
Excavation
Foundations
Compacted Fill
First Floor (6" cone.)
Second Floor (6" cone.)
Roof (8" Flexicore)
Roof Insulation ง Roofing
Structural Steel
Walls (8" Block ง 4" Brick)
Walls (8" Cone. Block)
Coping
Flashing
Windows
Roof Drains ง Piping
Smoke Vents (4 ' x 8')
Doors (31 x 7')
Doors (8f x 8') w/operator
Fire Proof Structural Steel
Paint Walls
Heat and Vent
Lighting
Sprinklers (call system)
Walls (12" Cone. Block)
Quan.
1,100 C.Y.
280 C.Y.
820 C.Y.
22,000 S.F.
22,000 S.F.
22,000 S.F.
22,000 S.F.
570,000 #
3,600 S.F.
6,100 S.F.
620 L.F.
620 L.F.
880 S.F.
2 ea.
14 ea.
10 ea.
5 ea.
52,000 S.F.
53,000 S.F.
44,000 S.F.
44,000 S.F.
44,000 S.F.
16,800 S.F.
Unit
Cost
1.36
90
8.90
.80
2.00
1.65
.46
.23
3.25
1.75
3.25
.80
7.00
700
880
265
975
2.10
.20
2.10
1.60
.75
2.35
                         A-24

-------
            PART III - FINISHED GOODS WAREHOUSE
Item
Excavation
Foundations
Compacted Fill
First Floor (6" cone.)
Roof Deck, Insulation ง Roofing
Structural Steel
Insulated Sandwich Panel
Partition Walls
Gravel Stop ง Fascia
Roof Drains
Smoke Vents
Doors (3! x 7')
Doors (8* x 8') w/operator
Dock Levelers
Dock Seals
Dock Canopy
Dock Stairway
Ceilings
V.A. Tile
Toilet Fixtures
Toilet Partitions ง Screens
Lockers
Heat ง Vent
Lighting
Sprinklers (Calc. Syst.)
Quan.
580 C.Y.
80 C.Y.
500 C.Y.
45,000 S.F.
45,000 S.F.
382,000 Ib.
15,600 S.F.
4,800 S.F.
850 L.F.
4 ea.
14 ea.
11 ea.
9 ea.
9 ea.
9 ea.
1,500 S.F.
1 ea.
6,800 S.F.
6,800 S.F.
20 ea.
9 ea.
70 ea.
45,000 S.F.
45,000 S.F.
45,000 S.F.
Unit
Cost
1.36
90
8.90
.80
.81
.22
2.35
1.75
1.30
700
880
265
975
1,100
600
3.00
1,000
1.00
.50
400
100
40
.75
.90
.75
Total
Material
800
7,200
4,450
36,000
36,400
84,000
36,700
8,400
1,100
2,800
12,300
2,900
8,800
9,900
5,400
4,500
1,000
6,800
3,400
8,000
900
2,800
34,000
40,500
34,000
                                                             393,050





Contractors - Overhead ง Profit   - 25%



Chicago Area Adjustment           -  4%



Adjustment from Jan.  to Dec.  '72  -  5%



                                    34%                      153,650




                              Total                          526,700
                         A-25

-------
A-26

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                   APPENDIX B






PROCESS NARRATIVE OF PAINT AND VARNISH INDUSTRY

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                                      APPENDIX  B

            PROCESS  NARRATIVE  OF  PAINT AND VARNISH INDUSTRY
     The Paint and Varnish industry is one of the oldest manufacturing industries in the United
States. The industry is made up of about 1,600 companies operating 1,875 plants.'1'  It is well
distributed  geographically  throughout the country  and the number of plants  or  production
volume is definitely related to density of population. Even though about 27 companies account
for about  57% of the total sales, the industry  is one of the few  remaining which  contains
numerous small companies that specialize in a  limited product line to be marketed  within a
geographical region. There are fewer than 20 companies that sell paint nationwide.

     The industry is now emerging as a scientific business from its beginning as an art 50 years
ago. Even with rapid growth in technology, the industry processing techniques still are not well
defined and vary from one producer to another. To add further complication, the industry is
technically one of the most complex of the chemical industry. A plant that  produces a broad
line of  products  might utilize over 600 different raw materials and purchased  intermediates.
These  materials can be generally classified  in the following categories:  oils, metallic  driers,
resins, pigment extenders,  plasticizers, solvents,  dyes, bleaching agents, organic  monomers for
resins and additives of many kinds.

     The industry produces an equally large number of finished products which are generally
classified as trade sale finishes, maintenance finishes and industrial finishes.

     Trade sale products are stock-type  paints generally distributed through wholesale-retail
channels and packaged in  sizes ranging from 1/2  pint to 1  gallon. A subdivision of trade sale
products are maintenance  finishes which  are used for the protection and  upkeep of factories,
buildings  and structures such as  bridges and storage tanks.  Since they are usually stock type,
they come under the Department of Commerce definition of trade sales.

     The other major type of paint products are industrial finishes which  are generally defined
as those applied to manufactured products. These finishes such as automotive, aircraft, furniture
and electrical  are usually  specifically  formulated for the using industry. Within these major
product lines there are literally  thousands of  different products for many different applications
and types of customers. Trade sales finishes and industrial finishes are produced in almost equal
volume with the production for this year  estimated at 475 million gallons for each type. Trade
sales,  however, are expected to account for  55% of the  dollar sales or about $1,685 million
dollars.
                                          B-1

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                                PROCESS  DESCRIPTION

     Starting  with all  purchased  raw material,  the manufacturing process for pigmented
products is deceptively simple from a process  viewpoint.   Basically,  it consists of mixing or
dispersing pigment and vehicle to  give the final product. This is schematically illustrated in
Figure 1.

     The paint vehicle is defined as the liquid portion of the paint and consists of volatile
solvent and non-volatile binder such as oils and resins. The non-volatile portion is also called the
vehicle solid or film former. The pigment portion  of  the paint consists of hiding pigments such
as titanium dioxide (Ti02), extenders or fillers such as talc or barium sulfate, and any mineral
matter used for flatting or other purposes.

     The incorporation of the pigment in the paint vehicle is accomplished by a combination of
grinding  and dispersion  or dispersion alone. When  it is  necessary  to  further grind  the raw
pigment, the pebble or steel ball mills are normally used. With the advent of fine particle grades
of pigment and extenders, as well as the wide spread use of wetting agents, the trend is toward
milling methods  that  are  based  on dispersion  without grinding.  This dispersion consists of
breakup  of  the  pigment clusters  and  agglomerates, followed  by wetting of  the individual
particles  with the binder or vehicle.  Some of the more popular methods currently being used are
high speed disc impellers, high speed impingement mills and the sand mill.

     Aside from  this dispersion  step,  pigment paint manufacturing  involves  handling of raw
material  as well as handling and packaging of finished product. Operations of a typical  plant
may be summarized as a raw material and finished product handling  problem with a variety of
interdispersed batch operations. The inter-relationship of all  these operations is schematically
illustrated in Figure 2. The operations depicted  are those of a plant that makes its own resins
and produces both trade sale and industrial finishes.

     Many of the  larger  and  some of the medium  size manufacturers produce a significant
amount  of their formulation ingredients, including  pigments, resins, modified oils and  basic
chemicals.  Certain manufacturers  produce  these ingredients in  an  amount exceeding  their
requirements and sell the excess to other manufacturers. A significant number also produce only
a portion of their  resins and  purchase the remainder from their competitors or suppliers who
specialize in resin manufacturing.

     The manufacturing  of resins and varnishes is by far the  most complex process in a  paint
plant,  primarily as the result of the  large  variety  of different raw materials,  products and
cooking formulas utilized. The complexity begins  with the nomenclature used  in classification
of the final product. Originally, varnishes were all made  from naturally occurring material and
they were easily defined as a homogeneous solution of drying oils and resins in organic solvents.
As new synthetic resins were developed, the resulting varnishes were classified as resins rather
than varnishes. Examples of this are alkyd, epoxy and polyurethane resin varnishes.

     There are two basic types of  varnishes, spirit varnishes and oleoresinous varnishes. Spirit
                                           B-2

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varnishes are formed by dissolving a resin in a solvent. They dry by solvent evaporation. Shellac
is a good example of a spirit varnish. Another material that might fall in this category is lacquer.
Technically,  lacquers are defined as a colloidal dispersion or solution of nitro-cellulose, or of
similar film-forming compounds, with  resins and plasticizers, in solvent and diluents which dry
primarily by solvent evaporation.

     Oleoresinous varnishes,  as  the name implies, are solutions of both oils and resins. These
varnishes dry by solvent evaporation and by reaction of  the  non-volatile liquid portion  with
oxygen in the air to form a solid film. They are classified  as oxygen convertible varnishes and
the film formed on drying is insoluble in the original solvent. A summary of the various types of
material used in the production of classical varnishes is given in Table 1.

     Varnish is  cooked in both portable kettles and  large reactors. Kettles  are  used only to a
limited extent and primarily  by the smaller manufacturers. The very old, coke fired, 30 gallon
capacity copper kettles are no longer used. The varnish kettles which are used, have capacities of
150 to  375 gallons. These are fabricated of stainless steel,  have straight sides and are equipped
with  three  or four-wheel trucks.  Heating  is  done  with natural gas  or fuel  oil for better
temperature control. The kettles are fitted with retractable hoods and exhaust  pipes,  some of
which may incorporate solvent  condensers.  Cooling and  thinning  are  normally done in special
rooms. A typical varnish production operation is illustrated  in Figure 3.

     The manufacturing of oleoresinous varnishes is  somewhat more complex  than for spirit
varnishes. This manufacture consists of the heating or cooking of oil and resins together for the
purpose of obtaining compatability of resin and oil and solubility of the mixture in solvent, as
well as for development of higher molecular weight molecules or polymers.

     The time  and temperature of the cook  are the operating variables used to  develop the
desired end product polymerization or "body". The chemical reactions which occur are  not well
defined. The resin is a  polymer  before cooking and may or may not increase in molecular size
during the cook. This resin may react with the oil to produce copolymers of oil and resin or it
may exist as a homogeneous mixture or solution of oil homopolymers and resin homopolymers.

     It  is possible to blend resins and heat-bodied oil  and obtain the same varnish that can be
produced  by cooking the resin  and the unbodied oils. This indicates that copolymerization  is
not the fundamental reaction  in varnish cooking.

     Heat bodying or polymerization of an oil is done to increase its viscosity and is carried out
in a kettle in a fashion similar to  varnish cooking. The fundamental reaction  that occurs  is
polymerization of the oil monomers to form dinners with a small portion of trimers.

     There is a large variety of synthetic resins produced for use in the manufacture of surface
coatings. A listing  of  the more popular resins is given  below. They  are  listed by order of
consumption  by the coatings industry:(6>
                                          B-5

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                          Alkyd                  Styrene Butadiene
                          Vinyl                  Phenolic
                          Amino                 Polyester
                          Epoxy                 Urethane
                          Acrylic                 Silicone

     By  far  the  most  widely used  of  these resins are  the  alkyds and the vinyls. Alkyd
consumption is approximately five times that of the vinyl, which is approximately twice that of
the amino resins. Further discussion will concentrate on alkyd  resins.

     Alkyd  resins comprise a group of synthetic resins which can be described as oil-modified
polyester resins.  They  are  produced from  the  reaction  of polyols or  polyhydric alcohol,
polybasic acid and oil or fatty monobasic acid. A listing and  discussion of commonly used raw
materials will follow.

     1.   Oils or fatty acid (2)

                          Linseed                 Castor
                          Soybean                Coconut
                          Safflower               Cottonseed
                          Tall Oil fatty acid        Laurie Acid
                          Tall Oil                 Pelargonic  Acid
                          Fish                    Isodecanoic Acid
                          Tung (minor)
                          Oiticica (minor)
                          Dehydrated Castor (minor)

     The materials in the first column are oxidizing or drying types. The materials in the second
column are  non-oxidizing and  yield soft  non-drying  alkyds which are used  primarily as
plasticizers for hard film resins. The acids shown in this column are the only materials that are
strictly synthetic in origin.

     2.   Polyols

         Name                   Formula                    Form
                                     H
          Ethylene glycol            HC  - OH                 Liquid

                                    HC  - OH
                                     H

                               H    H        H    H
          Diethylene    HO-  C-  C-0-C-C-OH     Liquid
            glycol              H    H        H    H
                                          B-8

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         Propylene glycol
         Glycerine
           CP-95% glycerine
           Super-98%
H
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                                    H
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  OH

  OH

  OH


H2COH
                                                   Liquid
                                                    Liquid
                                                             White Solid
                                            H2COH
     Glycerol or glycerine was the first polyol used for alkyds.  It is also the most widely used
polyol for alkyds.

     The second polyol, based on usage, is pentaerythritol (PE), which came into common use
in the 1940's.  PE is supplied as "technical grade" material  and contains  mono, di,  tri and
polypentaerythritol.  The material consists  primarily of the mono form which was  illustrated
previously in the list of polyols.

     The important distinguishing feature of the various polyols is the number of potentially
reactive  hydroxyl groups  in the  molecule,  known as  functionality.  The glycols  with  a
functionality of two produce only straight chain polymers and their resins are soft and flexible.
The  resultant  products are  used primarily  as  plasticizers for  hard  resins.  Glycerine  has  a
functionality of three  and  is used primarily in short and medium oil alkyds. Pentaerythritol,
with a functionality of four, cross-links to a greater extent, forming harder polymers. It is ideal
for use in long oil alkyds.
     3.   Acids and Anhydrides

         Name

         Phthalic
           anhydride
           (ortho)
                                   Formula


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                                          B-9

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         Isophthalic                        /C*^                   White needles
          acid (meta)                  HC'
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       Terephthalic                          |                       white crystals
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         Maleic                                                     White solid
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                                          HC	C
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                                                    0

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    The acidic material can be used as an acid or anhydride. The anhydride is formed from two
molecules of acid minus a molecule  of water or removal of one molecule of water from a di
acid. It is preferred, since it reacts faster and yields less water for removal from the cook.

    For many years, phthalic anhydride  (ortho)  (PA)  was the only polybasic acid used in
substantial proportions in alkyds.  It still remains the predominant dibasic acid. PA is produced
from the catalytic oxidation of naphthalene or ortho-xylene.

    The chemistry  of alkyd resin  systems is  very complex. So much  so that  theoretical
considerations offer only a good starting point. Final formulae and variations are developed by
trial and error changes, based  on performance requirements and shortcomings  of previous
batches.
                                       B-10

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     Condensation  is the reaction basic to all polyester resins, including alkyds. This reaction
follows the elementary equation for esterification as shown below:
                  ,ฐ                            o

            RC        +    R.iOH^	* RC         +    HoO
               \                          \
                   OH                          OR!

            Acid       +    Alcohol              (Ester  -i-  Water) 	>



                                   For Alkyd Resins

                          PA  +  Glycerine $=*  Ester  + H20

     The ester monomer formed is very complex and further  reacts  to  form large polymers
called resins. The polymers formed are low in molecular weight by comparison to other resins.
For example alkyd resins have molecular weights ranging from 1,000 to 7,000 while some vinyl
and acrylic resins have average molecular weights in  excess of 100,000 and in some cases as high
as 500,000.

     The alkyd polymers also react with  oil  or fatty  acid and are generally classified by the
amount of oil or PA used in the formulation, as described below:

                                            % Oil              % PA
Short Oil
Medium Oil
Long Oil
Very Long Oil
33 to 45
46 to 55
56 to 70
71 up
35
30 to 35
20 to 30
20
    The resulting reactants of the PA, polyol and oil may be represented  in part as shown
below.
                       Phthalic Anhydride (PA)  + Glycerine  G(OH)3	)
                         G-PA-G-PA-G-PA-G-PA
                         0000
                         H                  |         H
                           HOOC-PA      PA - COOH
                                        B-11

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     This will then react with the long chain oil monoglyceride or fatty acid (FA) to yield:

         HOOC - PA - G - PA - G - PA - G - PA - G - PA - G - PA - G - OH
                       0
                       H
      O
      H
0
H
0
H
                                 F
                                 A
                          F
                          A
Short Oil Alkyd

     Alkyds can be manufactured directly from a fatty acid, polyol and acid or from the fatty
acid oil, polyol  and acid. The second  combination (oil,  glycerine and PA) produces glyceryl
phthalate which is insoluble in the oil and precipitates. This problem can be overcome by first
converting  the oil to a  monoglyceride by heating with a polyol in the presence of a catalyst.
This process is called alcoholysis of the oil. The basic reaction is shown below:
              C H2 OOCR

              CHOOCR      +

              CH2OOCR

              Triglyceride
 CH2OH

2CHOH

 CH2OH

 Glycerine
         CH2OH

        3CHOH
         CH2OOCR
         Monoglyceride
     This is an ester interchange reaction with no loss of water.
     When fatty acid rather than oil is used as the starting material, this is called the "one-stage"
process. In this process, the fatty acid and glycerine are  added to the kettle,  the agitator is
started and heat is introduced. When the batch reaches 440ฐ F, the PA  is slowly added and
cooking continued for another 3 to 4 hours until the desired body and acid number are reached.

     If the fusion process  is being used, a continuous purge of inert gas is maintained to remove
the water formed  in the reaction. This water may also be removed by what is known as the
solvent  process. It is similar  to the fusion process except that about 10% aromatic solvent
(usually xylene) is added  at the start. The vaporized solvent is passed into a condenser. The
condensate then flows to a decant receiver for separation of reaction water. Recovered solvent is
returned to the reactor.

     As discussed earlier, when oil is used rather than fatty acid, the alkyds are produced in a
two stage process.  In the first stage the monoglyceride is first produced from the linseed oil and
glycerol. Catalyst and oil  are  added and the  alcoholysis  of the  polyol and oil is carried out
between 450  and 500ฐ F  until the desired  end  point is reached. When  the alcoholysis  is
completed, any additional polyol needed is added.
                                         B-12

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     Following this, the required amount of PA and esterification catalyst are slowly added. If
solvent cooking is to be used, the solvent is also added at this time. Cooking then  proceeds as
before.

     A typical  manufacturing formula for a 50% oil-modified glyceryl phthalate alkyd using the
two stage process is given below.(4)

                                                               Ib

                      First stage

                        Linseed oil                             51.3
                        Glycerol (95%)                         12.8
                        Catalyst, Ca(OH)2                         0.026

                      Second stage

                        Glycerol (95%)                          6.2
                        Phthalic Anhydride                      39.7
                        Catalyst
                        Methyl p-Toluene SuIfonate               0.2
                                                              110.2

                         Approx. Loss                          10.2
                         Solids Yield                          100.0

     Alkyd  and other resins are  cooked in closed set kettles, more properly  called reactors.
They vary in size  in commercial production from  500 to 10,000  gallons. A typical reactor
system  is shown in Figure 4. They are generally fabricated of Type 304 or 316 stainless steel
with well polished  surfaces to  assure  easy cleaning. Design pressure is usually 50 psig.  These
reactors may be heated electrically, direct fired with gas or oil or indirectly heated using  a heat
transfer media such  as Dowtherm(R). They are also equipped with  a  manway, sight-glass,
charging and sampling line, condenser  system, weigh tanks, temperature measuring devices and
agitator. The  manway is used both for charging solid material and for access to the kettle for
cleaning and repair.

     The reactor may be  equipped with a variety of different condenser systems. The system
shown  in Figure 4 includes a packed fractionating column, a reflux  condenser and a main
condenser. The condensers are water cooled shell and tube type and  may be either horizontally
or vertically inclined. Vapors are processed  and condensed  on the tube side  and drain to a
decant receiver for separation and possible return of solvent to the reactor. A dual function
aspirator Venturi scrubber is often added to the system. It is used to ventilate the kettle during
addition of  solid materials and may also remove entrained unreacted or vaporized  solids and
liquids from the venting gases.

                                         B-13

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                         -SPRAY  TOWER
                                                               REFLUX
                                                              COMDEIXISER
                                                                            vEfxi T
                                        F RAC TICXSIAT IMG
                                         DISTILLATIOM
                                                                    PORTHOLE
                                                                    FOR  SOLIDS
                                                                 DIRECT  FIRED  OR
                                                                                FOR  MIQM
                                                                 TEMPERATURE  VAPOR
                                                                   R  LIQUID
TO RESIM
STORAC3E
                                     FIC3URE1
           MODEIRM  RESIN   PRODUCTION   SYSTEIfVI
                                          OF
                     SOLVENT  AND  FUSION  COOKS
                                           B-14

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     Thinning tanks are always included as part of the reactor system. They are normally water
cooled  and equipped  with a condenser  and agitator. The partially cooled finished alkyd  is
transferred from the reactor to the partially filled thinning tank. Since most alkyd resins are
thinned  to 50%  solids, the capacities of these  tanks  are normally twice the capacity of the
reactors. These tanks are also frequently mounted on scales so that  thinning solvents may be
accurately added.

     The final step in a reactor system is filtering of the thinned resin prior to final storage. This
is normally done while it is still hot. Filter presses are the most commonly used filtering device.

     The manufacturing procedures and equipment used  for the  production  of  other  resins
listed at the  beginning of  this  discussion are quite similar. The major differences are the raw
materials and the process steps utilized.  A detailed discussion of these other resins is beyond the
scope of this narrative.
                         NATURE  OF  GASEOUS DISCHARGE

     There are two  major types of emissions from a paint plant. These are non-fugitive and
fugitive. Non-fugitive emissions are those that are collected by and confined within an exhaust
system.  Fugitive emissions  are  those  that  escape into  the  plant  atmosphere from various
operations and  exit the  plant building through the  doors  and  windows  in  an  unregulated
fashion.

     In today's typical paint plant there are two types of fugitive emissions. These are pigment
particulate and paint solvents. In a small percentage of the plants an attempt is made to collect
these emissions. The incentive  for doing  so is based on insurance requirements as well  as
occupational health  and  safety  rather  than air pollution considerations or regulations. The
newly  passed OSHA regulations will have a dramatic effect on the paint industry practice and
necessitate the regulation of  fugitive emissions.
                           PARTICULATE  CONTAMINANTS

     Fugitive particulate emissions consist primarily of the various pigments used. As a general
rule, the pigments are received and stored in 25 to 50 pound paper sacks or fiber drums. Modern
pigment manufacturing has developed fine sized pigment, 0.05 to 0.25  microns, for ease  of
dispersion into the paint vehicle. Loading of these fine pigments into grinding equipment results
in fugitive particulate dust emissions into  the surrounding plant areas. This  dust  is either
collected by a ventilation and exhaust system or allowed to settle and later collected as part of
the general housekeeping requirements.

     A variety of resins are received as granular or flaked solids which are of large size and do
not result in a fugitive dust emission. The  manufacturer of these  solid resins,  however, does
encounter fugitive emission problems in his flaking or grinding operations.
                                          B-15

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                             GASEOUS CONTAMINANTS
     Solvent emissions occur in almost every phase of paint and varnish manufacturing and in
numerous locations throughout individual plants. A  listing of emission points is  given  below.
   Location            Operation              Temp., ฐF                Pressure

1. Resin Plant          Thinning               200 to 300ฐ F           Atmospheric
2. Resin Plant          Filtering               200 to 300ฐ F           Atmospheric
3. Resin Plant          Storage Tanks              100ฐ F              Atmospheric
4. Paint Plant          Blending Tanks           Ambient             Atmospheric
5. Paint Plant          Milling                   Ambient             Atmospheric
6. Paint Plant          Dispersion                Ambient             Atmospheric
7. Paint Plant          Holding Tank             Ambient             Atmospheric
8. Paint Plant          Filtering                 Ambient             Atmospheric

     The extent of these emissions vary with the type of operation and the effort extended to
control  atmospheric  losses. The  high temperature thinning  and  filtering results in the largest
emissions while packaging  in drums and cans contribute the smallest emission. Other operations
contribute intermediate emissions which vary depending on the degree of control exercised and
the vapor pressure of the solvent used.

     In  some cases, efforts are made to collect fugitive emissions by use of ventilation hoods
and a closed exhaust system. More frequently,  however, they are exhausted  from the building
by  general  building  exhaust  fans which  ventilate  areas having  the highest contaminant
concentration.

     Resin plants or  paint  plants producing resins and varnishes are likely to have a number of
regulated emissions.  These emissions consist primarily of gaseous hydrocarbons  in air or  inert
gas streams. The three major sources of these regulated emissions are:

         1.   Varnish cooking
         2.   Resin cooking
         3.   Thinning

     Other less concentrated streams that may or may not be regulated are:

         1.   Storage and rundown tank vent systems
         2.   Filter press  vent systems
         3.   Sandmill vent systems

     Considerable  effort  has  been  expended  to  identify  the  various  types  of  chemical
compounds emitted  during a varnish cook. The majority of this work was done in the 1950's
and is well summarized by R.  L. Stenburg131 in the H.E.W. Technical Report A58-4. A copy of
                                         B-16

-------
his summary is included here as Table 2. In general, one or more of the following compounds
are emitted, depending upon the  ingredients in the cook and the cooking temperature; water
vapor, fatty acids, glycerine, acrolein, phenols,  aldehydes, ketones, terpene oils and terpene.
These materials are mainly decomposition products of the varnish ingredients.

     Varnishes and oils are cooked or bodied at temperatures from 200  to 650ฐ F. At about
350ฐ F decomposition begins and continues throughout the cooking cycle  which normally runs
between 8 and 12 hours. The  quantity, composition and  rate of emissions depends upon the
ingredients  in the cook as well as the maximum  temperature, the  length,  the method of
introducing additive, the degree of stirring and the use of inert gas blowing.  In general, the
emissions will average between one to  three percent of the charge in oil bodying and three to six
percent in varnish cooking. Aside from academic interest, the exact chemical structure of these
emissions is  not too important. Of more importance  are the characteristics  of the emissions
related to ease of  removal by the applicable pollution control devices.

     Modern resin reactors and varnish cookers account  for the  majority of  clear coatings
production  in the paint and varnish industry. As described earlier, these products are cooked in
larger more carefully controlled reactors equipped with product recovery devices  which  also
help reduce atmospheric emission.

     As with the  old varnish  kettles, the amount of emissions vary  with the type of cook, the
cooking time, the maximum temperature, the initial ingredients as well as the type and method
of introducing ingredients.

     For solvent  cooking the quantity of emission does not vary significantly with  the size of
the reactor  but is rather more a function of the volatility of the solvent being used and the size
and/or efficiency  of the condenser. Since there is no sparge  gas used  in solvent cooking, exhaust
volumes  are small and consist  primarily of noncondensed  solvent fumes. Emissions will  run
from 0.1 to 0.5 pounds per hour and will be less cyclic in nature than for fusion cooks.

     Emissions during  fusion cooking run  much higher and vary with the size  of the reactor.
The total exhaust volume is  dependent  primarily on  the sparge  rate of inert gas. Dean H.
Parker'41  indicated typical  sparge rates of 0.04 ft3/min/gal  of charge during the first hour, 0.02
ft3 during the second,  and 0.01  ft3  during the remainder of the cook. The exhaust rate  will
average from 2 ft3/min/100 gallons of capacity  on small reactors to 1 ft3/min/100 gallons of
capacity on large  reactors. A  summary of source test results from a variety of  resin reactors is
presented in Table 3.(11'

     Since fusion  cooking is a cyclic batch process, the concentration of emission will vary from
the start to finish of the cook. Hydrocarbon concentration will vary  from 15,000 to 80,000
ppm as methane equivalent, depending on the time of the cycle and the type of cook. There are
at least 100 different emission curves  that could be encountered if one tried to cover all  of the
different cooking  formulas. Particulate phthalic anhydride (PA) is also emitted from the kettle
and concentration levels vary depending on cycle time, types of  cook, method of charging and
type of  PA  used. Charging of  liquid PA  rather than  dry solid  PA significantly reduces the
                                         B-17

-------
                  TABLE 2
COMPOSITION OF OIL  AND VARNISH  FUMES13'
Bodying Oils
Water vapor
Fatty acids
Glycerine
Acrolein
Aldehydes
Ketones
Carbon dioxide
Running Natural
Gums
Water vapor
Fatty acids
Terpenes
Terpene Oils
Tar


Manufacturing
Oleoresinous
Varnish
Water vapor
Fatty acids
Glycerine
Acrolein
Phenols
Aldehydes
Ketones
Manufacturing
Alkyd Varnish
Water vapor
Fatty acids
Glycerine
Phthalic anhydride
Carbon dioxide


                       Terpene Oils




                       Terpenes




                       Carbon dioxide
                     B-18

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emission rate.  However, if the linear velocity of the sparge gas is maintained below 150ft/min,
the carryover of PA is also significantly reduced. Entrained and sublimed PA will run between 1
to 3 pounds per hour  over a period of 50 to 70 minutes during and following the charging
period. Plots of hydrocarbon emission level vs. time for three of many possible cooks are given
as Figures 5, 6 and 7.(10) These emission concentrations  are those measured directly out of a
closed kettle or reactor.

     Figure  7 shows typical variations in emissions from one batch to another when cooking the
same product  in the same kettle. Variations twice as great as this are not uncommon. Emissions
increase dramatically and rapidly as indicated on Figures  5 and 6 whenever the loading hatches
are opened.  This is a result of forced exhaust of the kettle to prevent spillage of fumes  into the
room from the open hatch.

     The storage of liquid PA will  result in significant vaporization  losses from the storage tank
and an effort must be made to control these losses. The most widely used method consists of  an
inert gas blanketing in conjunction with a pressure  controlled unit. The tank is also equipped
with a water cooled condenser used to vent the tank during filling. After filling the condenser is
then heated  with steam to remove collected PA by melting.
                      POLLUTION CONTROL  CONSIDERATIONS

     Collection of particulate pigment or resin emission is a simple straightforward job. The
only practical control device is a  fabric filter, and  it is ideally suited for  this application.
Collection efficiency for the submicron pigment dust (0.05 to 0.25  microns) is in the range of
99.9%.  There  are  no  temperature problems since the  exhaust  system  runs at ambient
temperatures.  The grain loading is very low and baglife is extensive. Approximately 0.01% of
the loaded pigments are lost and collected. Grain  loadings to  the fabric filter  run around 0.19
grain/SCF. A  typical  collection system  is shown  in  Figure 8. The collection system can be a
fixed hood which can handle both dust and pigment bags or a flexible hose positioned above the
loading hatch or attached to the top of the tank.  The tank attachment provides the most
positive control of fugitive dust emission but also increases pigment and solvent losses slightly.

     The application  of control  equipment  to  this problem is quite simple and can be solved
with standard  off-the-shelf equipment from a host of suppliers.  For this  reason, detailed
equipment cost and installation bids will not be required.

     The control of hydrocarbon and odors from the various emission  sources listed earlier is
not quite as straightforward as the dust emission. There are three types of control equipment
that have been applied to  this problem. They are catalytic and thermal combustion devices, and
wet scrubbers.

     As a general rule, wet scrubbing does not provide a satisfactory solution for the following
reasons:
                                         B-20

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     1.    Removal efficiency of fine hydrocarbon aerosol is not good at economically practical
          pressure drops.

     2.    Noncondensible  hydrocarbon solvent vapors will not be removed.

     3.    Odor  removal without  the addition of  an  oxidizing agent  such  as potassium
          permanganate or sodium hypochorite is unsatisfactory. If an oxidizing agent is used,
          operating cost will be quite  high due to the high concentration of other oxidizable
          material such as phthalic anydride, resins and oil.

     4.    Mobile packing and high make-up water rates are required to prevent plugging of the
          scrubber beds and spray nozzles.

     5.    Correction of the.air pollution problem with wet scrubbing causes an equivalent water
          pollution  problem  which in many areas is more costly to correct than the original air
          pollution problem.

     The  only control  technique currently being used  that has proven effective for all cases is
combustion. Three  general methods  are employed to combust waste gases, as shown below.
          1.   Flame Combustion
          2.   Thermal Combustion
          3.   Catalytic Combustion

     All  of  the  above methods are oxidation  processes.  Ordinarily, each requires that the
gaseous effluents be heated to the point where oxidation of the combustible will take place. The
three methods differ basically in the temperature to which the gas stream must be heated.

     Flame combustion  is the easiest of the three to understand, as it comes the closest to
everyday experience. When a gas stream is contaminated with combustibles at a concentration
approaching the lower  flammable limit, it is frequently practical to add a small amount of
natural gas as an auxiliary fuel and sufficient air for combustion when necessary, and then pass
the resulting mixture through a burner. The contaminants in the mixture serve as a part of the
fuel. Flame incinerators  of this type are most often used for closed chemical reactors. They are
not used on resin reactors at present. They may be an ideal solution some day, however, when
methods of operating a closed, pressurized resin reactor are developed.

     It is far more likely that the concentration of combustible contaminants in an air stream
will  be  well below the   lower  limit of flammability. When this is  the  case, direct thermal
combustion  is  considerably  more economical  than  flame  combustion.  Direct  thermal
combustion  is carried out by equipment such as that illustrated in Figure 9. In this equipment, a
gas burner is used to raise the temperature of the flowing stream sufficiently to cause a slow
thermal reaction  to occur in a residence chamber.
                                         B-25

-------
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     Whereas  flame temperatures  bring  about  oxidation  by  free  radical  mechanisms at
temperatures of 2500ฐ F and higher, thermal combustion  of ordinary hydrocarbon compounds
begins to take place at temperatures as low as 900 to 1000ฐF. Good conversion efficiencies are
produced at temperatures in the order of 1400ฐ F with a residence time of 0.3 to 0.6 seconds.

     Catalytic combustion is carried out by bringing the gas stream into intimate contact with a
bed of catalyst. In this system, the reaction takes place directly upon the surface of the catalyst,
which is usually composed of  precious metals, such as platinum and palladium. While thermal
combustion equipment  brings about  oxidation at concentrations below the limits of flame
combustion,  catalytic combustion operated below the limits of flammability  and below the
normal  oxidation  temperatures  of the  contaminants.  The  reaction  is  instantaneous  by
comparison to thermal combustion and no residence chamber is required. Catalytic combustion
is carried out by equipment such as that illustrated  in Figure 10.

     In general, catalytic  afterburners are less expensive to operate,  however, they  depend
directly on the performance of the catalyst for their effectiveness. It will not function properly
if the catalyst become deactivated. Because of this, catalytic units are not inherently functional
when operated at design conditions.  In many areas, means for ensuring adequate performance of
the catalyst on a long-term basis will  be required by environmental control offices.

     The  basis for design of either  catalytic or thermal  combustion is the hydrocarbon
concentration of the exhaust gases handled by the incinerator. The maximum hydrocarbon level
is set by most insurance companies at one-quarter  of the lower explosive  limit (L.E.L.) which is
equivalent  to 13 BTU/SCF of exhaust gas. As outlined earlier, the quantity of emission may
vary  significantly with cooking time and the type of cook. There  is also likely to be a large
variety of  different hydrocarbons emitted. For this reason, theoretical calculations ofemissions
for design  purposes are not satisfactory. On site emission  measurements, as shown earlier on
Figures 5  and 6, are required.  Once the rate of emission is determined, it is then necessary to
calculate the dilution air required to meet 1/4 LEL and set up the duct work system to provide
for this dilution. When possible, dilution air should be utilized to help capture as many fugitive
fume emissions as possible.  For example this  can be accomplished by taking the dilution air
from  a  hood positioned over the resin filter press and venting the thinning tanks and product
rundown tanks into the same system.

     A concentration of 1/4 LEL or  13 BTU/SCF will  give a temperature rise of about 600ฐ F in
the afterburner. This is too high if  a heat exchanger  is to be used, and in these cases, we will
dilute to a maximum concentration of  12 BTU/SCF. In all  cases, the heat exchangers will be the
parallel  flow type having a thermal efficiency of 42%. This is required due to the high emission
concentration to assure temperature  balance and control.

     The major  problem with catalytic  or thermal afterburners  as applied to open  or closed
resin and varnish kettles is  the danger of fires and/or explosions. This has happened in numerous
occasions  in  the past due primarily to excessive hydrocarbon emission from kettles. These
problems have been all but eliminated on newer units by  assuring that the design was based on
actual emission measurements of the  highest emitting  cook  and the addition of some of the
                                         B-27

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following system safety features:

     1.    High limit temperature alarm to shut off burner and activate a diversion system.

     2.    High velocity  duct section to  assure gas flow to afterburner  substantially exceeds
         flame propogation velocity of hydrocarbons being burned.

     3.    Double  manifolding  or  hot   gas  recycle  to  prevent  condensation  of  heavy
         hydrocarbons or phthalic anhydride.

     4.    Diversion  system to  block off  hydrocarbon  emissions to unit, by-passing them
         directly out of separate exhaust and introduce fresh air to purge the unit.

     5.   Pneumatic operation of the diversion system to assure fast positive action and provide
         a fail-safe system in the event of either air or electrical failure.

     6.   Purging with inert gas in the event of power failure.

     The above general requirements are applicable to all types of afterburner control. Specific
details for each type of system will be given in the equipment specifications.
                                           B-29

-------
                                    REFERENCES
1.   Marketing Guide to the Paint Industry, Patricia Noble, Ed., Charles H. Kline & Co., Inc.,
     Fairfield, New Jersey, 1969.

2.   Federation Series on Coating Technology, Units
     1.   Introduction to Coating Technology, Oct., 1964
     3.   Oils for Organic Coatings, Sept., 1965
     4.   Modern Varnish Technology, May, 1966
     5.   Alkyd Resins, March, 1967
     12.  Principles of Formulation and Paint Calculation, June, 1969
     17.  Acrylic Resins, March, 1971
     19.  Vinyl Resins, April, 1972, Federation of Societies for Paint Technology, Philadelphia,
         Pennsylvania

3.   Stenburg, R. L, Control of Atmospheric Emissions from Paint and Varnish Manufacturing
     Operations, U.S. Department of Health, Education and Welfare,  Robert A. Taft Sanitary
     Engineering Center, Technical Report A58-4, Cincinnati, Ohio (June, 1958).

4.   Parker,  Dean  H.,  Principles  of  Surface  Coating Technology, John  Wiley  &  Sons,
     Interscience Publishers Division, New York, N.Y., 1965.

5.   The Technology of Paints, Varnishes and Lacquers,  Charles R. Martens, Ed.,  Reinhold
     Book Corp., New York, N.Y., 1968.

6.   Spence,  J.  W.  and Haynie, F. H., Paint  Technology and Air Pollution: A Survey and
     Economic  Assessment,  Environmental   Protection   Agency,  National  Environmental
     Research Center, Office of Air Programs Publication No. AP-103, Research Triangle Park,
     North Carolina, February, 1972.

7.   Hardison,  L. C., A Summary of  the Use of Catalyst for Stationary Emission Source
     Control, presented at Franklin Institute, Philadelphia, Pennsylvania (Nov., 1968).

8.   Hardison,  L. C., "Disposal of Gaseous Wastes", presented at East Ohio Gas Company
     Seminar on Waste Disposal, Cleveland, Ohio (May, 1967).

9.   Hardison, L. C., "Controlling Combustible Emissions",  Paint and Varnish Production, July,
     1967.

10.  Unpublished source tests of 11  different  kettles, Hirt Combustion Engineers, Montebello,
     California, August, 1971.

11.  Unpublished source tests of 10 different kettles, PPG Industries.
                                         B-30

-------
12.   Rolke,  R.  W.,  et  al, Afterburner Systems Study, Shell  Development  Co.,  Emeryville,
     California.
                                        B-31

-------
           APPENDIX C






CAPITAL AND OPERATING COST FORMS

-------
       APPENDIX  C
ESTIMATED CAPITAL COST DATA
     (COSTS IN DOLLARS)


Effluent Gas Flow
ACFM
ฐF
SCFM
Moisture Content, Vol. %
Effluent Contaminant Loading
gr/ACF (ppm)
Ib/hr
Cleaned Gas Flow
ACFM
ฐF
SCFM
Moisture Content, Vol. %
Cleaned Gas Contaminant Loading
gr/ACF (ppm)
Ib/hr
Cleaning Efficiency, %
( 1 ) Gas Cleaning Device Cost
(2) Auxiliaries Cost
(a) Fan(s)
(b) Pump(s)
(c) Damper(s)
(d) Conditioning,
Equipment
(e) Dust Disposal
Equipment
(3) Installation Cost
(a) Engineering
(b) Foundations
& Support
Ductwork
Stack
Electrical
Piping
Insulation
Painting
Supervision
Startup
Performance Test
Other
(4) Total Cost
LA Process Wt.
Small









































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                               TECHNICAL REPORT DATA
                         (Please read Instructions on the reverse before completing)
 1. REPORT NO.
  EPA-450/3-74-031
                                                    3. RECIPIENT'S ACCESSION-NO.
 4. TITLE AND SUBTITLE
  Air Pollution  Control  Engineering and Cost Study
  of the Paint and Varnish  Industry
                                                    5. REPORT DATE
                                                     June  1974 (date of issue)
                             6. PERFORMING ORGANIZATION CODE
 7. AUTHOR(S)

  Edward J. Dowd, Project Director
                                                    8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
                                                    10. PROGRAM ELEMENT NO.
  Air Resources,  Inc.
  800 E. Northwest Highway
  Palatine, Illinois  60067
                              11. CONTRACT/GRANT NO.

                              Contract  No. 68-02-0259
 12. SPONSORING AGENCY NAME AND ADDRESS
                                                    13. TYPE OF REPORT AND PERIOD COVERED
  EPA, Office of Air and Water Programs
  Office of Air Quality Planning & Standards
  Industrial Studies Branch
  Research Triangle Park, N.C.  27711
                              Final  Report
                              14. SPONSORING AGENCY CODE
 15. SUPPLEMENTARY NOTES
 16. ABSTRACT
  Under this  contract,  a  comprehensive study  was conducted of the  Paint
  and Varnish Industry  and its relationship to the pollution of  our
  environment.   The report presents  a description of  the industry,  its
  method of operation and the chemical processes utilized.  Also pre-
  sented are  comprehensive industry  statistics including type, size and
  location of present day plants  and past, present and  projected industry
  trends.  In addition,  the following environmental and economic informa-
  tion is presented:  types and quantities of air pollution emissions and
  their geographical distribution;  the effect of operations on air
  pollution emissions;  the impact  of emissions on air quality; the type
  and effectiveness of  existing control technology; performance  and costs
  of best control technology; the  economic impact of  the use of  best con-
  trol by the industry;  emission measurement  techniques and problems; in-
  spection procedures to  determine  compliance with air  pollution
  regulations;  and areas  of needed  research and development.  The
  manufacture of various  pigments  is included as part of the Paint and
  Varnish Industry study.   A three  page bibliography  is included in the
  report.  The manufacture of Ti02  was studied in detail.
 7.
                            KEY WORDS AND DOCUMENT ANALYSIS
                DESCRIPTORS
                                        b.IDENTIFIERS/OPEN ENDED TERMS
                                         c.  COSATI Field/Group
 Air Pollution
 Air Pollution Control  Equipment
 Scrubbers
 Condensation Resins
 Zinc Oxide
 Iron Oxides
 Titanium Dioxide
Cost Analysis
Hydrocarbons
Resin  Production
Paint  Production
Varnish Production
Particulates
Solvent Emissions
Cadmium Pigment
Chrome Pigment
Thprmal Aftprhurnpr<;. nathlvMr
                                           7/A,  7/B
                                          n/i
                                          13/B,  13/1
 8. DISTRIBUTION STATEMENT

  Release Unlimited
                  19. SECURITY CLASS (ThisReport)
                  Unclassified
                                                                21T NO. OF PAGES
                                        20. SECURITY CLASS (This page)
                                         Unclassified
                                                                22. PRICE
EPA Form 2220-1 (9-73)

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