EPA-454/R-93-047
LOCATING AND ESTIMATING
       AIR EMISSIONS
     FROM SOURCES OF
           TOLUENE
      Office Of Air Quality Planning And Standards
          Office Of Air, And Radiation
       U. S. Environmental Protection Agency
        Research Triangle Park,.NC 27711

             March 1994

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    ™    , ia!, bfen. reviewed by the Office Of Air Quality Planning And  Standards, U S
Environmental Protection Agency, and has been approved for publication  Any mention of trade'
names or commercial products is not intended to constitute endorsement or recommeSon for use
                                  EPA-454/R-93-047
                                         U

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                             TABLE OF CONTENTS
Section

DISCLAIMER  . . .
LIST OF FIGURES
LIST OF TABLES .
                                                                        Page
 1.0
2.0
3.0
4.0
5.0
PURPOSE OF DOCUMENT  .
1.1  Reference for Section 1.0
OVERVIEW OF DOCUMENT CONTENTS
2.1  References for Section 2.0 	,
BACKGROUND 	
3.1  Nature of Pollutant  	
3.2  Overview of Production and Use
3.3  References for Section 3.0 ....
  .  11
  . vi
  viii

  1-1
  1-5

  2-1
  2-5

  3-1
  3-1
  3-4
  3-7
EMISSIONS FROM TOLUENE PRODUCTION  	
4.1  Toluene Production from Petroleum Fractions	
     4.1.1  Hydrotreating	
     4.1.2  Catalytic Reforming	
     4.1.3  Secondary Hydrogenation (for Pyrolysis Gasoline)
     4.1.4  Toluene Recovery	
     4.1.5  Emissions	
     Toluene Production from Coal 	
     4.2.1  Process'Descriptions		
     4.2.2'  Emissions	
     Toluene Production from Styrene	 . . ...	
     4.3.1  Process,Description  .	
     4.3.2  Emissions	 .	
4.4- References for Section .4.0  .	
     4.2
     4.3
. 4-1
. 4-5
. 4-5
. 4-7
 4-10
 4-10
 4-14
 4-18
EMISSIONS FROM MAJOR USES. OF TOLUENE
5.1   Benzene-Production	
     5.2,.
    _ 511.1. Process;Description  ......
     5.1.2. Emissions.	 .	
     TolueneTDiisocyanate Production,,
     5.2.1 Process Description  	
     5.2.2 Emissions				.
     Trinitrotoluene Production  	
     513:1 Process Description  	
     5.3.2 Emissions	
 4-21
 4-21
 4_oo •
 4-22
 4-25

.  5-1
.  5-L
                                                                            .  5-8
                                                                            .  5-9'
                                                                            5-11
                                                                            5-11
                                                                            5-13
                                       111

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                         TABLE OF CONTENTS (Continued)
 Section
                                                                               Page
      5.4  Benzole Acid Production	5_14
           5.4.1 Process Description  	545
           5.4.2 Emissions	545
      5.5  Benzyl Chloride Production	5.15
           5.5.1 Process Description	5,47
           5.5.2 Emissions	5.47
      5.6  Other Toluene Derivatives  	5.43
      5.7  Paint and Ink Manufacturing	549
           5.7.1 Process Description-	5.24
           5.7.2 Emissions	5..2g
      5.8  Solvent Cleaning Operations		5-28
           5.8.1 Process Description	5..2g
           5.8.2 Emissions	.....>-	         5»29
      5.9  Other- Solvent Uses	" .	\	'  5.^0
      5.10  References for Section 5.0  	      5.32

6.0   EMISSIONS FROM THE USE OF TOLUENE-CONTAINING MATERIALS	6-1
      6.1   Surface Coating Operations  	54
           6.1.1 Process Description	    g_2
           6.1.2 Emissions	g_2
      6.2   Printing and Publishing 	g_5
           6.2.1 Process Description  	g.g
           6.2.2 Emissions	      g.g
    •  6.3   Gasoline and Automotive Emissions  	6-11
      5.4   Gasoline- Marketing  .	. ,	    542
           6.4.1 Toluene Emissions from Loading Marine Vessels  	6-15
           6.4.2 Toluene Emissions from Bulk Gasoline  Plants, BuJk Gasoline-
                Terminals and Service Stations	547
           6.4.3 Control Technology for Gasoline-Transfer ...	 6-22
           6.4.4 Control Technology for Gasoline Storage	6-26
           6.4.5 Control Technology for Vehicle Refueling-Emissions	 6-26
     6.5   Other Sources of Residual.Toluene.Emissions	6-28
     6.6   References for. Section 6.0  		. .,		         5,30

7.0  BY-PRODUCT'EMISSIONS:. PROCESSES: UNRELATED. TO PRODUCTION
     OR USE OF TOLUENE 	•_.	7^
     7.1   Coal Combustion		               -_!
     7.2  Hazardous and Solid Waste Incineration	  7:3
    . 7.3  Wastewater Treatment Processes	      7.4
     7.4  References for Section 7.0	_
                                        IV

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                    TABLE OF CONTENTS (Continued)
 Section
                                                                  Page
 8.0  AMBIENT AIR AND STATIONARY SOURCE TEST PROCEDURES          8-1
     8.1  EPA Method TO-1 	                   	o 2
     8.2  EPA Method TO-2 	'..'	'.'.'.'.'.'.	g~2
     8.3  EPA Method TO-3 	'.'.'.'.'.'.	  	s~5
     8.4  EPA Method TO-14 	'.'.'.'.'.'.	s'g
     8.5  EPA Method 0030	 .     " *"	8"8
     8.6  EPA Method 5040	'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.	g-10
     8.7  EPA Reference Method 18	                 	8 12
     8.8  EPA Method 0010	< . .       •	8"16
     8.9  EPA Method 8270	8"16
     8.10 NIOSH Method 1501 ...-.-	 '. . . . '.'.'.'.'.'  8-18
     8.11 References for Section 8.0	.'."	        8_2Q
                                        ^*
APPENDIX A  POTENTIAL SOURCE CATEGORIES OF
             TOLUENE EMISSIONS 	  A_!

APPENDIX B  LISTS OF PAINT, INK, AND PRINTING FACILITIES WITH
             ANNUAL SALES GREATER THAN $1 MILLION	B-l

APPENDIX C  TOLUENE SOURCE CATEGORIES IN SURFACE COATING
             OPERATIONS	    c.j

APPENDIX D  SUMMARY  OF EMISSION FACTORS LISTED IN
             THIS-DOCUMENT'			  D_{

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                                 LIST OF FIGURES
 Number

 3-1

 4-1

 4-2

 4-3

 4-4
                                                                                Page
 5-1

 5-2

 5-3

 5-4
6-1
6-3

6-4

8-1
8-7
         Chemical Use Tree for Toluene  	3.5-

         Process Flow Diagram for Hydrotreating	4.5

         Typical Reforming Unit	,	    4_g

         Generalized Toluene Recovery Process Row Diagram	4-12

         Process Flow Diagram for Styrene Production by Ethylbenzene
         Dehydrogenation	            _
         Process Flow Diagram of a Toluene Dealkylation Unit .".,	5.4
                                                 *:           ;
         Basic Operations That May Be Used in Toluene Diisocyanate Production  .... 5-10

         TNT Production 	             5_12

         Usage of Toluene in the Paint and Coatings Industry	5-20
5-5     Flow Diagram of the Paint and Ink Manufacturing Process  	5-25
        Flow Diagram of a Surface Coating Operation	    g-3
6-2,,    The - Gasoline Marketing Distribution System-in: the-. United States	6-L4
        Bulk Plant Vapor,Balance, System . .  .	        5.94

        Service Station Vapor Balance System		                      (5.05
                                                                                 3-4.
                                                                                 .5-0
        EPA Method TO-1 Sampling System  	.'         3.3

8-2    • Tenax® Cartridge/Design	

8-3     Carbon:Molecular;Sieve-Trap (CMS) Construction:	

8-4     Automated Sampling and Analysis System for Cryogenic Trapping	8-7

8-5     Canister Sampling System	                 g_9

8-6     Schematic of Volatile Organic Sampling Train (VOST)	         g_H

        Schematic Diagram of Trap Desorption/Anaiysis.System	 3_13
                                         VI

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                         LIST OF FIGURES (Continued)



Number                                                                    Page



8-8    Direct Interface Sampling System	8-14




8-9    Integrated Bag Sampling Train	8-15'




8-10   Modified Method 5 Sampling Train	8-17



8-11   Method 1501 Sampling System	.-	8-19
                                      vu

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                                  LIST OF TABLES
 Number

 3-1

 3-2

 4-1
 4-3

 4-4
4-9
5-4.
>o
                                                                               Page

        Chemical Identification of Toluene	   3_2

        Physical and Chemical Properties of Toluene	*.	   3.3

        Toluene Production Locations and Capacities	   4_2
 4-2     Estimated Domestic U.S. Supply and Demand of Toluene	4.4
        World-Wide Toluene Production	      4.5

        Catalytic Reforming Processes	 4-9

4-5     Pyrolysis Gasoline Hydrogenation Processes . r.	4_U

4-6     Emission Factors for Toluene Production from Petroleum Fractions  	4-15

4-7     Average Emission Factors for Fugitive Equipment Leak Emissions	4-17

4-8     Control Techniques and Efficiencies Applicable to Equipment Leak
        Emissions	;	                  410
        Emission Factors for Toluene Production from Coal	4-21
4-10    Emission Factors for Toluene Production from Styrene Production	4-24

5-1     Benzene Producers -Using.Toluene Feedstock	  5.3


5-2     Toluene. Diisocyanate-Production Locations and Capacities  .  ,	  ^-7

5-3     Benzoic Acid Production Locations and Capacities	   5_14


        Estimated Consumption:of;Toluene-Derivatives.in.Paints and.Coannas

        Estimated, Consumption of Solvent in. Paints and Coatings, By Market	

5-6     Emissions from Miscellaneous Sources of Toluene	    5.31


6-1     Gravure Association of America Industry Survey Results	6-10

6-2   _ Emission Factors from Gasoline Use	, . .                  fi_19
                                                                               5-21

                                                                               5-22
                                       vui

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                           LIST OF TABLES (Continued)

Number                                                                       Page

6-3     Uncontrolled Volatile Organic Compound and Toluene Emissions
        from Loading Gasoline in Marine Vessels 	6-16
                                                    tf

6-4     Toluene Emission Factors for Gasoline Loading and Bulk Terminals
        and Bulk Plants  			6-18

6-5     Toluene Emission Factors for Storage Losses at a Typical Gasoline
        Bulk Terminal  	,	6-20

6-6     Uncontrolled Gasoline Vapor and Toluene Emission from a Typical
        Bulk Plant	6-21

6-7     Uncontrolled Gasoline Vapor and Toluene Emissions from a Typical
        Service Station  .	6-23

6-8     Residual Emissions from Miscellaneous Sources of Toluene	6-29

7-1     Toluene Emissions from Combustible Coal Refuse Material	7-3
                                        IX

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                                EXECUTIVE SUMMARY

       Emissions of toluene into the atmosphere are of special significance because of the Clean
 Air Act Amendments of 1990.  These amendments mandate that toluene emissions be subject
 to standards that allow for the maximum degree of reduction of emissions and that, by 1995, a
 list  of source categories be established that accounts for no less than 90 percent  of toluene
 emissions. This document is designed to assist groups interested in inventorying air emissions
 of toluene by providing a compilation of available information on sources and emissions of this
 substance.
                                  •
       Toluene is a man-made aromatic hydrocarbon produced mostly from petroleum.  In the
 U.S., the Virgin Islands and Puerto Rico, toluene is  produced by 21  companies at  30 plants.
 Most toluene produced is derived from petroleum fractions.  In 1991, 3,104,000 megagrams
 (944 million gallons) of toluene were recovered.  Growth in demand is expected to be very
 modest over the next few years.

      Toluene is used as a cleaning solvent in the coating, printing and leather industry and'in
the manufacturing of paints and coatings, inks, adhesives, resins, and Pharmaceuticals. It is also
used as an;intermediate in the production of benzene and toluene diisocyanate,,and.for gasoline
blending.
       At the time of publication of this document, estimates of nationwide emissions of toluene
were not available.  Updates to this document will attempt to incorporate any nationwide
emission estimates subsequently developed.

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                                    SECTION 1.0
                              PURPOSE OF DOCUMENT   .


       The Environmental Protection Agency (EPA) and State  and local air pollution control
agencies are becoming increasingly aware of the presence of substances in the ambient air that
may be toxic at certain concentrations.  This awareness, in turn,  has led to attempts to identify
source/receptor relationships for these substances and to develop control programs to regulate
emissions.  Unfortunately, very little information is available on  the ambient air concentrations
of these substances or on the sources that may be discharging them to the atmosphere.


       To assist groups interested in inventorying air emissions of various potentially  toxic
substances, EPA is preparing  a series  of  documents such as this  that compiles  available
information on sources and emissions of these substances.  Prior documents in the series are
listed below:
      Substance

      Acrylonitrile
      Carbon Tetrachloride
      Chloroform
      Ethylene Bichloride
      Formaldehyde, (Revised)
      Nickel
      Chromium
      Manganese
      Phosgene
      Epichlorohydrin
      Vinylidene Chloride
      Ethylene Oxide1
      Chloro benzenes
      Poiychlorinated .Biphenyls-(PCBs)
      Poiycyciic. Organic:Matter (POM)
      Benzene
      Organic:-Liquid Storage-Tanks
      Coal and Oil Combustion Sources
      Municipal Waste Combustors
      Perchloroethylene and Trichloroethylene
      1,3-Butadiene
      Chromium (supplement)
 EPA Publication Number

 EPA-450/4-84-007a
 EPA-450/4-84-007b
 EPA-450/4-84-007c
 EPA-450/4-84-007d
 EPA-450/2-91-012
 EPA-450/4-84-007f
 EPA-450/4-84-Q07g
 EPA-450/4-84-OQ7h
 EPA-450/4-84-007i
 EPA-450/4-84-007J
 EPA-450/4-84-007k
 EPA-450/4-84-007I
 EPA-450/4-S4-007m
 EPA-450/4-84-007n -
 EPAr450/4-84-007p
EPA-450/4-84-007q
EPA-450/4-88-004
EPA-450/2-89-001
EPA-450/2-89-006
EPA-450/2-90-013
EPA-450/2-89-021
EPA-450/2-89-002
                                     .   1-1

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       Substance
       Sewage Sludge
       Styrene
       Methylene Chloride
EPA Publication Number
EPA-450/2-90-009
EPA-450/4-91-029
EPA-454/R-93-006  .
       This document deals specifically with toluene.  Its intended audience includes Federal,
State, and.local air pollution personnel and others who are interested in locating potential emitters
of toluene, and making gross estimates of air emissions therefrom.

       Because of the  limited  amounts of data  available on  potential  sources  of toluene
emissions, and since the process configurations, control equipment, and operating procedures of
many sources will not be the same  as those described here, this document is best used as a
primer to inform air pollution personnel about (1) the types of sources that may emit toluene, (2)
process variations and release points that may be expected within these sources, and (3) available
emissions information indicating the  potential for toluene to be released  into the air from each
operation.

       The reader is strongly cautioned against using the emissions information contained in this
document to try to develop an exact assessment of emissions  from any particular facility.
Because insufficient data are available to develop statistical estimates of the accuracy of these
emission factors, no estimate can be  made of the error char could result when .these-factors"'"are
used to calculate emissions from any given facility.  It is possible, in some extreme cases, that
order-of-magnrtude differences could result between actual and calculated emissions, depending
on differences in source configurations, control equipment,.and.operating practices. Thus,  in
situations  where an accurate-assessment  of toluene  emissions  is necessary,.source-specific
information  should be obtained to confirm  the-existence of particular -emitting-, operations, the
types and effectiveness of control measures, and the impact of operating practices.  A source test
and in some cases  a material balance- should be considered as, the best means to determine-air..
emissions directly from an operation.
                                          1-2

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        Another potential source of emissions data for toluene is the Toxic 'Chemical Release
 Inventory (TRI) form required'by Section 313 of Title m of the Superfund Amendments and
 Reauthorization Act of 1986 (SARA 313).1  SARA 313 requires owners and operators of certain
 facilities that manufacture, import, process,  or otherwise use certain toxic chemicals  to report"
 annually their releases of these chemicals to any environmental media.  As part of SARA 313,
 EPA provides public access to the annual emissions data.  The TRI data include general facility
 information, chemical information, and emissions data.  Air emissions data are reported as total
 facility release estimates, broken out into fugitive and point components.  No individual process
 or stack data are provided to EPA. The TRI requires the use of available stack monitoring or
 measurement of emissions to comply with  SARA 313.  If monitoring data are unavailable,
 emissions are to be quantified based on best estimates of releases to  the environment.
                                                     V-

       The reader is cautioned that the TRI  will not likely provide facility,  emissions, and
 chemical release data sufficient for conducting detailed exposure modeling and risk assessment.
 Accidental releases are also accounted for in the TRI, but are not included in inventories  of toxic-
 air pollutants. In many cases,.the TRI data are based on annual estimates of emissions  (e.g., on
 emission factors, material balances, engineering judgement).  Although the TRI database was
 consulted during the development of this  report, it should be  referred to  as an  additional
 mforrnation-source to locate potential emitters of toluene, and to, make-preliminary estimates of
 air emissions from these facilities.   To obtain an  exact assessment of air emissions  from
 processes-at a specific facility, source tests or in some-cases detailed material balance calculations
 should be-conducted,,and detailed plant site information should, be compiled.
                                                                                   t
       Each- L&E document,, as, standard procedure, is sent, to government; industry, ana
 environmenial; .groups,, wherever; EE A: is. aware  of expertise:,   These: groups.; are  given - the -
 opportunity  to review: the-document, ..comment; and provide additional data where-applicable:.
Where necessary, the documents are then revised to incorporate these comments. Although these
documents, have- undergone: extensive- review, there- may stiff  be- shortcomings.   Comments
subsequent to publication are welcome and will be  addressed_ based on, available time and
resources. In addition, any information is welcome on process descriptions, operating parameters.
                                          1-3

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control measures, and emissions information that would enable EPA to improve the contents of
this document Comments and information may be sent to the following address:
             Chief, Emission Factor and Methodologies Section
             Emission Inventory Branch, (MD-14)
             U.S. Environmental Protection Agency
             Research Triangle Park, NC 27711
                                        1-4

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1.1    REFERENCE FOR SECTION 1.0


1.     Toxic Chemical Release Reporting:  Community Right-To-Know. 52 FR 21152  June
      4, 1987.
                                   1-5

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                                      SECTION 2.0
                        OVERVIEW OF DOCUMENT CONTENTS

       The purpose of this document is to assist Federal, State and local air pollution agencies
 and others  who are interested in locating potential air emitters of toluene and making gross
 estimates of air emissions therefrom.  Because of the limited background data available, the
 information summarized in this document does not and should not be assumed to represent the
 source configuration or emissions associated with any particular facility.

       This section provides an overview of the contents of this document.  It briefly outlines
 the nature, extent, and format of the material presented in the remaining sections of this report.
                                                    xV
       Section 3.0 of this document briefly summarizes the physical and chemical characteristics
 of toluene, and provides an overview-of its production and use.  This background section may
 be useful to someone who needs to develop a general perspective on the nature of this substance
 and how it is manufactured and consumed.

       Section 4.0 of this document focuses on major production source categories  that may
 discharge air emissions .containing:toluene.- Section 5.0 discusses the uses of toluene as industrial
 feedstocks and major solvent uses, particularly degreasing and coating operations.  Section 6.0
 addresses emissions as a, result of releases from, toluene-containing products after manufacture.
 Section:7.0 describes emissions sources from the manufacture:of products  other than toluene, or
 as a by-product of processes (e.g., burning of fuel oil). Example process descriptions  and flow
 diagrams are-provided in-addition-to available emission factor estimates for each major industrial
 source, category described .infections 4.0, 5:0, 6.0;.and7:0,. Individual companies involved with
 either the- production  or use- of toluene: are reported- throughout' the document  Information
reported is extracted primarily from trade publications.

      Section 8.0 of this document summarizes 'available procedures for source sampling and
analysis of toluene., The summaries provide an overview  of applicable sampling and analytical
                                          2-1

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procedures,'citing references for those interested in conducting source tests. Although a NIOSH
procedure is provided, no EPA endorsement of this method is given or implied.

       Appendix A identifies potential source categories  of  toluene emissions by Standard
Industrial Classification (SIC) code and associated description. These potential source categories
do not necessarily denote significant sources of toluene emissions.  The readers interested in cross
referencing SICs with Source Classification Codes (SCCs) and associated descriptions should
consult the Crosswalk/Air Toxic Emission Factor Database Management System, Version 1.2
(October 1991) and/or the Volatile Organic Compound (VOC)IParticulate Matter (PM) Speciation
Database Management System, Version 1.4 (October 1991).1-2  Appendix B lists paint and ink
manufacturing facilities and printing facilities with sales greater than $1,000,000. Appendix C
                                                     X'
contains a listing of some of the surface coating operations using toluene-containing coatings.
Appendix D summarizes, in table format, all the emission factors listed in this document.

       Each emission factor listed in  Sections 3.0 through 7.0 has been assigned an emission
factor grade based on the criteria  for assigning data  quality  and emission factor ratings as
required in the document Technical Procedures for Developing  AP-42 Emission Factors and
Preparing AP-42 Sections. These criteria for rating test data used to develop emission factors
are presented below.3 The data used to develop emission factors are rated as.-follows: •

       A -   Tests  performed by  a  sound methodology and reported  in  enough  derail for
             adequate validation.  These-tests are-not necessarily EPA reference  test methods,
             although such-reference methods are certainly to be- used as a. guide.
       B  -   Tests that are performed by a generally sound methodology but lack enough detail
             for adequate-validation:.
       C' -  Tests  that are*, based: on, a, nonvaiidated,; or" draff-methodology or: that: lack a
             significant amount: of background data..
       D  -   Tests that are based  on a generally unacceptable method but may provide an
             order-of-magnitude value1 for- the:; source:
       Because of the almost impossible task, of assigning a meaningful confidence limit to
industry-specific variables  (e.g.,  sample size- vs. sample population,  industry and  facility
                                          2-2

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 variability, method of measurement), the use of a statistical confidence interval for an emission

 factor is not practical.  Therefore, some subjective quality rating is necessary.  The following

 emission factor quality ratings are applied to the emission factor tables.
         if

        A - Excellent. The emission factor was developed only from A-rated test data taken from
        many randomly chosen facilities in the industry population.   The source  category* is
        specific enough to minimize variability within the source category population.

      '  B - Above average. The emission factor was developed only from A-rated test data from
        a reasonable number of facilities. Although no specific bias is evident, it is not clear if
        the facilities tested represent a random sample of the industries. As in the A rating, the
        source category is specific enough  to minimize variability within  the  source category
        population.

        C - Average. The emission factor was developed only .from A- and B-rated test data from
        a reasonable number of facilities. Although no specific bias is evident, it is not clear if
        the facilities tested represent a random sample of the industry. As in the A rating, the
        source category is specific enough  to minimize variability within  the  source  category
        population.

        D - Below average.  The emission factor was developed only  from A- and B-rated test
        data from a small number of facilities, and there may be  reason to suspect that these
        facilities do not represent a random sample of the industry.  There also may be evidence
        of  variability within the source category population.   Limitations on the use of the
        emission factor are footnoted in the  emission factor table.

        E'" Poor-  The-emission factor was  developed from C- and D-rated rest data,  and there
        may be reason, to  suspect that the facilities  tested do not represent a random sample of
        the industry.  There also  may be-evidence: of variability  within  the source -category
       population.  Limitations.on the use of these factors are always footnoted.

       U - Unrated or Unratable.  The emission factor was developed from suspect data with no
       supporting documentation to accurately apply an A through. E rating. A "U" ratine may
        be-applied in the: folio wing circumstances:4

              - a. gross- mass balance- estimation
              - QA/QC, deficiencies found with: C~ and1 D-rated test: data:
              - gross engineering judgement                    .      -      .      ~
              - technology transfer:
'Source category: A category in the emission factor table for which an emission factor has.been calculated; generally a single process.


                                           2-3

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       This document does not contain any discussion of health or other environmental effects
of toluene.  It does include a discussion of ambient air monitoring techniques; however, these
ambient air monitoring methods may require modifications for stack sampling and may affect
data quality.

       EPA recently acquired air toxics emissions information from the California Air Resources
Board (GARB) as part of the California Rule AB-2588.  The AB-2588 regulations allow for
facilities to perform pooled source testing. The tests may be used to derive emission factors for
all sources of the same. type.  Several of the pooled source test reports contain information  on
toluene emissions; however, the reports were unavailable when this document was prepared.5
                                                    N*
       Information from the Toluene section of the SRI Chemical Economics Handbook was also
unavailable. This source is believed to contain the most recent production information and would
be useful in confirming toluene facilities, capacities, and production processes.
                                         2-4

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2.1    REFERENCES FOR SECTION 2.0
1.
2.
3.
4.
5.
U.S. Environmental Protection Agency.  Crosswalk!Air Toxic Emission Factor Database
Management  System, Version 7.2.   Office of Air Quality Planning  and Standards.
Research Triangle Park, NC. October 1991.

U.S. Environmental Protection Agency.  Volatile Organic Compound (VOC)IP articulate
Matter (PM)  Speciation Database Management System,  Version 1.4.   Office of Air
Quality Planning and Standards.  Research Triangle Park, NC. October 1991.

U.S. Environmental  Protection Agency.  Technical Procedures for Developing AP-42
Emission Factors and Preparing AP-42 Sections, Draft Document. Office of Air Quality
Planning  and Standards.  Research Triangle Park, NC.  March 1992.

Group discussion meeting on applying "U" ratings emission factors.  Anne Pope, EIB;
Robin Baker Jones, Midwest Research Institute; Garry Brooks, Radian Corporation; and
Theresa Moody, TRC Environmental Corporation.

Memorandum from Theresa K. Moody and Candace R.  Blackley, Radian Corporation, to
Anne Pope,- EIB,  Office of Air  Quality Planning and Standards, U.S. Environmental
Protection Agency, "Evaluating California Air Toxics Emissions Data  for Air Toxics
Compounds," February 28, 1992.                                     -
                                       2-5

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                                      SECTION 3.0
                                     BACKGROUND

  3.1    NATURE OF POLLUTANT

        Toluene is a man-made aromatic hydrocarbon produced mostly from petroleum.  This
  chemical intermediate is the predominant feedstock in benzene production and a key octane-
  boosting component for gasoline blending.  Toluene is also used as a raw material in the
  production of other chemicals (e.g., toluene diisocyanate and benzoic acid) and as a solvent in
 paints and coatings, inks, adhesives, and Pharmaceuticals.1
                                                   «,-
        Toluene's molecular formula is C^CH,; its molecular structure is represented as:
       Table 3-1 summarizes, the chemical identification information for toluene, and Table 3-2
 presents-toluene's chemical andphysicaLproperties.  This colorless liquid is volatile, flammable,
 and explosive in air. Toluene will react .with airborne hydroxyl radicals (OH'), atomic oxygen
 (O), ozone (O3), and peroxy radicals (RQ,) where R is an aikyl or aryl group to form a variety
 of oxidation products.  Toluene-is not corrosive-and will not react with dilute acids or bases.
 Purified toluene (nitration grade) normally contains less than 0.01 percent'benzene,  while the
 industtial grader may-contain up  to 25 percent: benzene.2

       Toluene, is released/in: the environment-from several.man-made-sources;-including the
following:2

       inadvertent sources (65 percent), such as emissions from  motor vehicles and aircraft
       exhaust, .osses during gasoline marketing activities, chemical spills,  and cigarette smoke
                                         3-1

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                               TABLE 3-1.
           CHEMICAL IDENTIFICATION OF TOLUENE
  Chemical name
Toluene
 Synonyms
Methylbenzene; toluol;
phenylmethane; methacide;
methylbenzol
 Molecular formula
CSH5CH3
 Identification numbers:3
 CAS Registry
 NIOSH RTECS
 EPA Hazardous Waste
 OHM/TADS
 DOT/UN/NA
 NCI
 STCC
108-88-3
XS 5250000
U220
7216928
UN 1294;. Toluene (Toluol)
C07272
49 093 05; Toluene
aCAS (Chemical Abstract Services); NIOSH (National Institute of Occupational Safety and
 Health); RTECS (Registry of Toxic Effects of Chemical Substances); EPA (Environmental
 Protection Agency); OHM/TADS (Oil and Hazardous Materials/Technical Assistance Data
 System); DOT/UN/NA (Department of Transportation/United Nations/North America);
 NCI (National Cancer Institute); STCC (Standard Transport Commodity Code)

Source: References 3-5
                                   3-2

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                        TABLE 3-2.
   PHYSICAL AND CHEMICAL PROPERTIES OF TOLUENE
Property
Molecular weight (grams)
Melting point
Boiling point (760 mm Hg)
Density, g/cm3
at 25°C (77°F)
at 20°C (68°F)
Physical state (ambient conditions)
Color
Odor
Odor threshold:
Range
Solubility:
Water at 20°C (68°F)
Organic solvents
Partition coefficients:
Log,0 octanol/water
Vapor pressure at 20°C (68°F)
at 30°C (86°F)
at 40°C (104°F)
Auto ignition temperature
Flashpoint"
Conversion factors (Vapor weight to volume)
Value
92.14
-95 to -94J°C (-139 to -138.1°F)
110.63°C (231.13°F)
0.8623
0.8667
Liquid
Clear
Benzene-like
0.17 ppm
0.17 - 40 ppm
Very slightfy soluble (0.05 g/100 mL)
Miscible with absolute alcohol, ether, and
chloroform
Soluble in acetone
2.69 (at 20°C or 68°F)
21.9 mm Hg (2.92 kPa)
36.7 mm Hg (4.89 kPa)
59.3 mm Hg (7.91 kPa)
480°C (896°F)
4.4°C (40°F) (C.C.)
16°C:(60.8°F) (O.C.)
i ppnv = - 3.824 mg/m3 (at 20°C) ' j
C.C. (closed cup); O.C. (open cup)
Source: References 3-5
                          3-3

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 *      processes in which toluene is used (33 percent)
 •      toluene production (2 percent)

        It is estimated that 86  percent of the toluene produced is eventually released into the
 biosphere (primarily the troposphere), where its lifetime ranges from 4 days (at high-altitudes
 during the summer) to several months (at low-altitudes during the winter). The average toluene.
 half-life resulting from atmospheric  oxidation is estimated to be 12.8 hours.2

        Toluene released  to   water may  be  removed  by  activated  sludge  degradation,
 biodegradation, and/or volatilization. The expected evaporative half-life of toluene in water is
 approximately five hours in water one meter in depth (3.28 feet).2
                                                      N»
                                                      X»
 3.2     OVERVIEW OF PRODUCTION AND USE

       The total annual capacity of toluene  manufacturing facilities in the United States, the
 Virgin Islands, and Puerto Rico was 5,344,000 megagrams (1,625 miUion gallons) in 1989.6 The
 majority of toluene (99.5 percent) is produced from petroleum fractions.  Catalytic reformates,
 produced by catalytic reforming, account for approximately 94.5 percent of the production
 capacity feedstocks. Pyrolysis gasolines, another petroleum feedstock, account for an additional
 five percent of feedstock materials. Coke-oven light oil comprises the remaining 0.5 percent of
 production capacity. In 1989, 21 companies  produced toluene at 30  manufacturing sites.L6

       Toluene  is  manufactured for  use as an intermediate in  the production of benzene (50
 percent) and toluene diisocyanate (9 percent), for gasoline blending (34 percent), for solvents (5
 percent), and/rbr the-production, of miscellaneous chemicals (2. percent).1  As a, solvent: toluene
 :s used in paints and coatings,, inks,, adhesives,, resins,  Pharmaceuticals,, and other formulated
products requiring a solvent carrier.  Toluene is  also  used  as  a cleaning solvent in surface
coating,  printing, and the  leather industry.  In addition-to-benzene  and .toluene- diisocyanate,
toluene  derivatives  include  benzole acid,  benzyl chloride,  trinitrotoluene,  vinyl  toluene.
toluenesulfonic acid, benzaldehyde, and  toluenesjilfonyl chloride.1-3 Figure 3-1  illustrates some
                                          3-4

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of the end uses of toluene. These uses are discussed in detail in Sections 5.0 and 6.0.  A list of
all potential toluene emission sources organized according to SIC code and associated description
is presented in Appendix A.   It is important to note that these  source categories do  hot
necessarily denote significant sources of toluene emissions, but only that these sources have the
potential to  emit toluene.
                                          3-5

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Production  Feedstock
   Use
Percent
 Reformate (94.5%)
 Pyrolysis r
 Gasoline (5%)
 Coke—Oven
 Light Oil (0.5%)
                                  Benzene  Production
Toluene Dfisocyanate
Production
                                  Use  as  a Solvent
Miscellaneous
Chemical Production
                                  Gasoline
                                  Blending
             Figure 3-1. Chemical use tree for toluene1-3'6
                            50
                                                             100
                                3-6

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3.3    REFERENCES FOR SECTION 3.0

1.     Toluene Chemical Product Synopsis, Mannsville Chemical Products Corp., Asbury Park,
       NJ.  March 1990.
2.
3.
4.
5.
6.
International Programme  on Chemical Safety.   Environmental Health Criteria 52:
Toluene.  World Health Organization.  Geneva. 1985.

Kirk-Othmer Encyclopedia of Chemical Technology.  3rd edition. Toluene.  Volume 23.
John Wiley and Sons.  New York, NY. pp. 246-273.  1983.

Environmental Protection Service, Environment Canada.  Environmental and Technical
Information for Problem Spills: Toluene. Technical Services Branch.  Beauregard Press
Limited, Minister of Supply and Services Canada. 1984.

Sax, Irving N. and Richard J. Lewis, Sr., Dangerous Properties of Industrial Materials.
Seventh Edition. Volume ffl. Van Nostrand Reinftbld.  New York, NY.  p. 3287. 1989.

SRI International Directory of Chemical Manufacturers.  Chemical Economics Handbook
Menlo Park, CA.   1991.
                                       3-7

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                                      SECTION 4.0'
                      EMISSIONS FROM TOLUENE PRODUCTION

        Toluene production and the associated air emissions are described in this section. Process
 flow diagrams are included as appropriate, with specific streams or vents in the figures labeled
 to correspond with the discussion in the text Emission factors for the production processes are
 presented when available, and associated control technologies are described.  If a particular
 facility is being included in an inventory, the reader should contact the specific facility to verify
 the  nature of the processes used,  production  volume, and controls that are in place before
 applying any of the emission factors presented  in this document

        Toluene is currently produced by  21 companies Si 30 plants in the United States, the
 Virgin  Islands,  and Puerto Rico.   The production locations  and capacities are presented in
 Table 4-1.1   In  1991, 3,104,000 megagrams (944 million gallons) of toluene were recovered
 compared with  a  1989 total annual capacity of approximately 5,344,000 megagrams (1,625
 million gallons).1'2 In 1989 eight facilities, representing seven companies, had annual capacities
 exceeding 55 million gallons.  Collectively, Amoco, Exxon, BP, Sun, Amerada Hess, Phillips,
 Mobil, and Chevron accounted for 72 percent of the total toluene capacity in the United States,
 the-Virgin Islands, and Puerto Rico. The  capacities listed in Table 4-1 are approximations, as
 most aromatics  operations have some flexibility in the amount of toluene they recover.  Table
 4-1  also identifies the: feedstock (e.g.,  catalytic reformate (reformate),  coke-oven light-oil,  or
 pyrolysis gasoline) from which toluene is recovered.1

       Although the  domestic extraction and distillation  capacity  for  toluene  exceeds
 4,932, millions of kilograms (1.5 billion gallons), the projected domestic demand for 1992, is only
 2,795'millions^ kilograms  (850-million gallons) with growth:expected to be-very modest over
 the next few years.3 No growth or slight growth in toluene  demand is anticipated because of the
 trend, to remove aromatics from, gasoline: blending  in.- favor, of  adding  oxygenated octane
enhancers.   If significant amounts  of toluene  are removed from  the gasoline pool, toluene
surpluses win occur possibly resulting in lower prices and industry-wide containment difficulties.
Use-of toluene in most solvent and chemical applications has also slowed.  Using toluene to
                                          4-1

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                    TABLE 4-1.
TOLUENE PRODUCTION LOCATIONS AND CAPACITIES
Facility
Amerada Hess Corporation
American Petrofina Incorporated
Amoco Corporation
Ashland Oil, Inc.
Atlantic Richfield Company
BP America, Inc. (Sohio)
Champlin Petroleum Co.
Chevron Corporation
Dow Chemical U.S.A.
Exxon Corporation
Kerr-McGee Corporation
! Koch Industries, Inc.
Mobil Corporation
j
Occidental Petroleum Corp.
Location
SL Croix, WI "
Port Arthur, TX
Texas City, TX
Catiettsburg, KY
Channelview, TX
Houston, TX
Alliance, LA
Lima, OH
Corpus Christi, TX
Philadelphia, PA
Port Arthur, TX..
Ffeeport TX
Baytown, TX
Corpus Christi,. TX
Corpus Christi,,TX.
Beaumont, TX
Chaimette, LA
Chocolate Bayou, TX
1989 Capacity
Millions of
Kilograms
(Millions of
Gallons)
460 (140)
170 (52)
806 (245)
79 (24)
26 (8)
105 (32)
99 (30)
197 (60)
329 (100)
99 (30)
79 (24)
92 (28)
39 (12)
13 (4)
605 (184)
135 (41)
247 (75)
148 (45)
16 (5)
109 (33)
82 (25)
.
Feedstock
Reformate
Reformate
Reformate
Reformate
Coke-oven light.
oil
Pyrolysis
gasoline
ileformate
ileformate
ileformate
leformate
leformate
ileformate
Pyrolysis
gasoline
Pyrolysis
gasoline
i
Reformate
Reformate-
tj"
Reformate-
Reformate-
Pyroiysis
gasoline
ieformate
Pyrolysis
gasoline
                    (continued)
                      4-2

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                                     TABLE 4-1.
       TOLUENE PRODUCTION LOCATIONS AND CAPACITIES
It
Facility
Phillips Petroleum Company
Salomon Inc.
Shell Oil Company
Sun Company, Inc.
Texaco, Inc.
Unocal Corporation
USX Corporation (Marathon)
Location
Sweeny, TX
Guayama, PR
Houston, TX
Deer Park, TX
Marcus Hook, PA
Toledo, OH -
Tulsa, OK
Delaware City, DE
El Dorado, KS
Beaumont, TX
Lemont, EL
Texas City, TX
1989 Capacity
Millions of
Kilograms
(Millions of
Gallons)
95 (29)
243 (74)
46 .(14)
164 (50)
158 (48)
., 233 (71)
76 (23)
135 (41)
36 (11)
95 (29)
62 (19)
66 (20)
Feedstock
Reformate
Reformate
Reformate
Reformate
Reformate
Reformate
Reformate
Reformate
Reformate
Reformate
ieformate
leformate
Source: Reference 1

NOTE: This-listing is subject to change as marker conditions change, facility ownership changes,
plants  are closed down, etc.  The reader should, verify the existence of particular facilities" by
consulting current.listings and/or the-plants themselves.  The level of.toluene emissions from any
given facility is a function  of variables such as capacity, throughput and control measures, and
should be determined,through direct contacts with, plant personnel.  These-operating plants and
locations were current as of January 1989.
produce-benzene--via.hydrodeaikyiation is one. exception,, as benzene demand is expected to srow

at approximately three percent per year.3" Table 4-2 shows historical and projected figures for

domestic- toluene capacity, production, imporrs,.exports and: demand.  Similarly, other countries

anticipate a slow growth or decline in toluene production.  Table 4-3 shows historical production
in other industrialized nations.
                                         4-3

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                                     TABLE 4-2.
        ESTIMATED DOMESTIC U.S. SUPPLY AND DEMAND OF
                                     TOLUENE


Production
Petroleum
Coke "
Total
Imports
Exports
Demand
Millions of Kilograms (Millions of Pounds) By Year
1985
320 (705)
.45 (1)
320 (705)
71 (157)
13 (28)
379 (834)
1986
340 (749r)
340 (749)
63 (138)
12 (27)
391 (860E)
1987
439 (967)
439 (967)
43 (95)
62 (136)
421 (926)
1988
397 (874)
397 (874)
56 (123)
35 (76)
419 (921)
1989
365 (804B)
365 (804)
40 (87)
49 (108)
356 (783)
1990
'N/A
N/A
N/A
364



(800)
1992
N/A
N/A
N/A
386



(850)
   Since 1982 the United States International Trade Commission (USITC) has not reported
   toluene production by coke-oven operators. Coke-ovenvbutput has been insignificant since
   1986. Sales data for toluene produced by petroleum refiners include only high-purity (98
   to 100 percent) toluene. It is assumed that all indicated output is high purity.
   E - Estimated figure (Mannsville Chemical Products Corp.)3
   N/A - Not available
   Source:  Reference 3
       Most of the toluene produced annually is derived from petroleum fractions.  However, the
concentration of light aromatics [e.g., benzene,  toluene, and xylene (BTX)] in petroleum rarely
exceeds-one percent Through processing, petroleum, specifically crude oil, can be converted to
BTX streams.  Several petroleum fractions are used in aromatic conversion processing.  The
fraction most important to the toluene production process is "straight-ran light naphtha" which
Includes ail of .the crude-oil components heavier than pentanes and: up to. a, final boiling point
between 105°C and L70°C (2210;to.338°F).^ ft is from this stream-that the majority of toiaene
is produced by catalytic reforming via hydrorreating.  A second refinery stream, also used as a
feedstock in toluene production, is.the, naphtha that results from the-pyroiysis or "steam cracking''
(e.g., hydrocracking) of heavier distillate fractions.  Although the primary  goal of cracking
naphtha is to manufacture ethylene and propylene, secondary reactions also produce considerable
                                        4-4

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                                     TABLE 4-3.
                  WORLD-WIDE TOLUENE PRODUCTION

Country
France
Germany1'1'
Italy"
Japan
Canada
Millions of Kilograms (Millions of Pounds) By Year
1988
47 (104)
605 (1,330)
218 (480)
1,019 (2,242)
417 (917)
1989
34 (74)
538 (1,184)
152 (338)
1,075 (2,365)
397 (873)
1990
34 (74)
418 (919)
192 (423)
1,078 (2,372)
425 (935)
1991

460 (1,013)
165 (363)
1,119 (2,462)
364 (801)

% Change
1990-91
=—
10
-14
4
-14
   •*••' ***** **J.%C *.\S* bAAV .1. WJ. A A AVSJ. T T WO !• \J WJ.11 iCtll Y WliX J *
   bData for 1991 are Chemical &. Engineering News estimates based on nine months reporting
   N/A - Not available        '                       *:  ..
   Source:  Reference 2
amounts of "pyrolysis gasoline" rich in aromatics.3'5 Additional toluene production methods
include separation from coal tars and recovery as a by-product from styrene manufacture.3'5

4.1    TOLUENE PRODUCTION FROM PETROLEUM FRACTIONS

4.1.1   Hvdrotreating

       Hydrotreating, schematically illustrated in Figure 4-i, is the process by which the Quality
of liquid hydrocarbon streams is improved by subjecting them to ,mild or severe conditions  of
hydrogen pressure in the presence of a catalyst  Both'pyrolysis gasolines and straight-run. light
naphthas (e.g.;, catalytic reformer feeds) undergo hydrotreating prior TO subsequenrprocessing and
toluene recovery. The- liquid petroleum feed:is preheated (Step  1),.heated in a furnace (Step 2"),
and combined with  recycled hydrogen gas. The combined feed is passed through, a'reactor
containing a catalyst bed where the hydrogenation reaction takes place (Step 3).6  Upon leaving
the reactor, the, stream is cooled and moved to a separator vessel where recycle or net hydrogen
is removed (Step 4).  The- liquid, then moves to a stabilizer or stripper which removes  hydrogen,
hydrogen sulfide, ammonia,, water,, organic compounds  of arsenic, and  palladium,  and light
                                        4-5

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                                                             H2 RICH GAS
HYDROGEN
 KAPHTHA,
                                                   SEPARATOR
                                                                     KYDRCTOEA7ED
                                                                  J   STREAM  -^
                Figure 4-1.  Process flow diagram for hydrotreating4

 (Reprinted -with permission from Hancock, E.G., ed., Toluene, the Xylenes and their
            Industrial Derivatives. Elsevier Scientific Publishing Company.
                           New York. New York.  1982.)
                                       4-6

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 hydrocarbons dissolved in the separator liquid (Step 5).  The stripped, hydrotreated fraction is
 then routed to the next processing step, either catalytic reforming or secondary hydrogenation.7

 4.1.2  Catalytic Reforming

       Catalytic reformate  is  the  major  source  of toluene,  accounting  for  approximately
 87 percent of the toluene produced domestically and approximately 94.5 percent of the production
 capacity feedstocks.1-5 Catalytic reforming involves the catalytic dehydrogenation of straight-run
 light naphtha in the presence of hydrogen (which reduces coke formation) to yield a mixture of
 aromatic  hydrocarbons (e.g., benzene, toluene, and the xylenes).4'5   The catalytic reforming
 process is illustrated in Figure 4-2.                                 .      -
                                                      V-

       Prior to reforming,  the light naphtha, containing the three primary  toluene synthesis
 compounds dimethylcyclopentane, methylcyclohexane, and ethylcyciopentane,  is hydrotreated
 to  remove  compounds  that  would  act as catalyst poisons in  the reforming  step.4'6   The
 hydrotreated naphtha is fed to  the reformer  unit containing the following components:4'7
 •      reactors which contain 'fixed bed catalysts
       heaters to bring the naphtha and recycle gas to reaction temperature and to supply heats
       of reaction
       a product cooling system and: a gas-liquid separator:
       a,hydrogen-gas recycle system
 •      a stabilizer to  separate light hydrocarbons dissolved in the  receiver liquid
 The:.naphtha. is.combined, with-recycled-hydrogen: (Step-1),. preheated. (Step- 2),. heated to  me
reaction; cemperamre. in:, a... fired; 4ieater.:-(Step::3), and: then:: transferred; to-a; series-, of catalyst-
 containing, reactors, (Step 4)4:  Because:-: the-reaction-.is endothermic,. a series of three- or,four
reactors with inter-stage reheat furnaces may be necessary to achieve the required, conversion.
The'reactors normally contain increasing-amounts-of cataiysr in  each stage.4"6
                                           4-7'

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                            FURNACES
HYDROTREATED
NAPHTHA ft.

x-
	 -H^

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y
P
A
l^--1

(3
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)

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v^
J



RE
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:CYCLE

A
/^


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^
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HYI
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-^-
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k

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-^H
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CLE
iSSOR
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H2 RICH GAS
FUEL GAS
A©
N(S) STABILIZER
^ — COLUMN
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1 REFORMATE
DRUM-
              REACTOR 1    REACTOR 2,   REACTOR 3   REACTOR 4
                                      |A
                                      f •  DENOTES POTENTIAL LOCATION OF FUGITT^" EMISSIONS'
                       Figure 4-2: Typical reforming unit4

(Reprinted with permission from Hancock, E.G., ed., Toluene, the Xylenes and their
          Industrial Derivatives.  Elsevier Scientific Publishing Company.
                          New York, New York. 1982.)
                                       4-8

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       The effluent from the last reactor is cooled and transferred to a receiving unit (e.g., the
flash drum) where the hydrogen is separated from the liquid reformate (Step 5).  The hydrogen
gases are compressed and recycled to the reactors while the reformate is moved to a stabilizer
fractionator (Step 6).   The fractionator removes C4 and lighter hydrocarbons to produce a
                                   4                       ,
stabilized reformate.  The stabilized reformate is used as a feedstock in the toluene recovery
process (described in Section 4.1.4).4-7

       Most of the facilities that produce toluene by catalytic reforming have proprietary
processes. Table 4-4 lists the process licensor and the process name.  The primary differences
between  these  processes  involve solving  reforming  process problems such  as catalyst
regeneration.  The processes also differ in the methods used to extract aromatics depending on
the type and purity of the product desired.4

                                    TABLE 4-4.
                  CATALYTIC REFORMING PROCESSES
Licensor
Chevron Research Co.
Engelhard Industries
Exxon Research Engineering
Houdry Division, Air Products
Institut Francois du.
Petrole
Standard Oil Co. (Indiana)
UOP Process Division
Name of Process
Rheniforming
Magnaforming
Powerforming
Houdriforming
Aromizing
Catalytic Reforming
Ultraforming
Platforming
  Source:: Reference;4-
                                        4-9

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 4.1.3  Secondary Hvdrogenation (for Pyrolvsis Gasoline)

       Pyrolysis gasoline, a by-product of ethylene and propylene manufacture, accounts for nine
 percent of domestic toluene production and five percent of production capacity  feedstock
 materials.115 Because pyrolysis gasoline contains reactive compounds (e.g., diolefins and styrenes)
 which will polymerize if subjected to reactor conditions severe enough to saturate olefins and
 remove sulfur compounds, it must undergo an initial hydrogenation step described in Section
 4.1.1 to reduce the  reactives to olefins prior to storage or further  processing.  The resulting
 product can be used as a high octane gasoline blending component or treated further for aromatic
 (e.g. benzene, toluene, and xylenes) extraction.4

       Following initial  hydrogenation, the pyrolysis gasoline (containing 21 percent toluene)
 normally undergoes  second stage hydrogenation hi which olefins are saturated, organic  sulfur
 forms hydrogen sulfide, combined nitrogen is converted to ammonia, and oxygenated compounds
 are reduced to hydrocarbons and water.  After these parallel reactions have been completed, the
 gases and liquid are separated. The liquid (containing 38 percent toluene) is then stripped of
 gaseous impurities, such as hydrogen'sulfide, and remaining light hydrocarbons before  being
 transferred to toluene recovery units.4'7

       Most of the  world's facilities  that  produce toluene from pyrolysis gasoline have
 proprietary hydrotreating processes.  The primary differences between these processes involve
 operating parameters such as  temperature, pressure, catalyst composition, and reactor geometry.
Table 4-5 lists the process licensor and the process name.4

-.1.4  Toluene- Recovery
       The hydrotreated and/or catalytically reformed streams  are rich in aromatics such  as
toluene, benzene, and the xylenes, as well as nonaromatics of similar boiling points.  Therefore,
the most appropriate procedures for separating toluene (and other aromatics) from other process
streams are extractive distillation and liquid-liquid extraction.4-6  Liquid-liquid extraction is the
most commonly used extraction method.5 If only one aromatic (e.g., benzene, toluene, or xyiene)

                                         4-10

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                                     TABLE 4-5.
        PYROLYSIS GASOLINE HYDROGENATION PROCESSES
Licensor
British Petroleum (BP)
C-E Lummus
Engelhard Industries'
Houdry Division, Air Products
Institut Francais du Petrole
Lurgi GmbH/Bayer AG
UOP Process Division
Name of Process
BP Selective Hydrogenation Process
DPG Hydrotreating
HPN Process
HPG Process
IFP Selective Hydrogenation Process
Bayer Selective Diolefin Hydrogenation
Lurgi Olefln Hydrogenation and —•
De^sulphurisation
LT Unibon Process
   Source:  Reference 4
is to be recovered in pure form, extractive distillation is preferred as the capital and operating
expenses are less than those associated with liquid-liquid,extraction.4 Figure 4-3 shows a process
flow diagram for toluene recovery. The diagram.includes prefractionation, extraction/ distillation,
and,,benzene/toluene fractionarion.

       Liquid-liquid  extraction methods are  the most  commonly used processes to  recover
toluene.   Two compounds  commonly  used, in  liquid-liquid extraction  are sulfolane  and
tetraethyiene-glycol.. The suifolane: process was developed by Shell and is licensed.by Universal
Oil Products (UOE).  (Jnion,'Carbide:: developed and, licensed the- tetraemylene^glycoi method..
These-rwo processes have replaced the Udex process which  used diethyiene.giycoi as the
extractant,5  Another/ commonly, used,  liquid-liquid,, extraction, method. is dimethyisuifoxide-
(DMSO) extraction, commercialized by the Institut Francais du Petrole. This process is different
from  the  other processes  in that aromatics are  extracted twice,  the  first  time using
dimethyisuifoxide (DMSO) and the.second time using a .light hydrocarbon.4
                                        4-11

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                                           C  4J
                                           «  J£
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4-12

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        The  hydrotreated and/or catalytically  reformed streams (crude BTX)  are normally
 prefiractionated prior  to  the  recovery  of toluene  by liquid-liquid  extraction to reduce the
 throughput of the extraction step. The crude BTX stream is first depentanized (Step 1) to remove
. the majority of components lighter than benzene  (e.g., Cs and lower- compounds) and then
 distilled (Step 2) to remove  components heavier than o-xylene.  The C5 compounds are removed
 for gasoline blending, while the xylenes fraction is processed for xylene  recovery.  The
 benzene/toluene fraction is fed to a cut column where the top portion is separated and moved to
 the extraction unit (Step 3).  The bottoms are removed and further refined.  Nonaromatics (the
 raffinate phase) leave through the top of the extractor while a mixture of aromatics, solvent and
 light nonaromatics leave through the bottom.  The raffinate is sent to a water wash for removal
 of solvent. The aromatics/solvent and light nonaromatics stream is transferred from the extractor
 either directly to a stripper or  to an extractive distillation column where nonaromatics  are
 removed  to  be  used later.  The stripper removes solvent leaving an  aromatic stream rich  in
 toluene.  (If  only a stripper  is used, then it acts as both an extractive distillation column and a
 solvent stripper, thereby reducing capital expenditures but requiring the facility to install a water
 washer to further reduce solvent content).4

       Extractive distillation methods  are  preferred. when  only one aromatic  (e.g., benzene.
 toluene, or xylene)  is  to be recovered in pure form.  Extractive distillation methods separate
 components  by  introducing  a solvent to a mixture.  The solvent suppresses the relative- vapor
 pressure of some components compared to other components in the mixture allowing the desired
 component to be extracted.4
                                                                 •» -

       The:;en± result-of .the-; extractive distillation process, description's very similar to that of
 the liquid-liquid, extraction, process,. The crude: BTX stream and the- extractive  solvent, are fed
to an extractive distillation column where nonaromatics (the raffinate) are separated (Step 3).
The.aromatic/solvent scream is transferred-to a stripper which removes the solvent leaving the
aromatic.    Some  of the  solvents  commonly  used: in  extractive  distillation  units  are-
dimethylformamide, n-formylmorpholine, m-methylpyrrolidone, and sulfolane.4
                                         4-13

-------
       After a toluene-rich aromatic stream has been extracted from crude BTX by either liquid-
 liquid extraction or extractive distillation, it can be further processed by conventional distillation
 to produce pure benzene and toluene.  The benzene/toluene fraction is often moved through a
 clay treatment tower prior to further distillation to remove any trace olefins (Step 4).  Benzene
 is removed from the top of the first distillation column (Step 5) while the distillation bottoms are
 fed to the toluene column.  The purified toluene (99.8 percent) is taken from  the top of the
 second distillation column (Step 6).4

 4.1.5 Emissions

       Most air emissions associated with toluene production from petroleum fractions arise from
 loading operations, toluene storage, and equipment leaks. "Process vents may also contribute to
 air emissions.  Toluene emissions from  other sources,  such as waste treatment and disposal
 facilities are discussed in Section 7.0.
                               •
 Process Emissions--
       Figure 4-3 shows that during toluene production,  process vent discharges  (A) of toluene
 occur primarily from the vacuum column vents, the reactor process vents, and the reactor process
 recovery vent. The hydrogen separation venUs only, used during startup, shutdown, and during
recovery section outages.9'10 The vacuum column vents  remove air that leaks into the column,
 as well as light hydrocarbons and hydrogen that form  during dehydrogenation, noncombustibles
 dissolved in the column feed, and any entrained aromatics.. The majority of.toluene-emissions
 occur at the benzene and toluene columns in the distillation train.
                                                      *

       Other sources of process emissions from toluene-production are less likely  because of the
need to operate most processes  under a vacuum and because of the heating value of the-gases.
The available emission estimates for toluene  production are given in Table 4-6.   Little
information  was found on specific emission controls.- Several types of recovery devices are used
in the Synthetic Organic Chemical Manufacturing Industry (SOCMI) to recover  hazardous air
pollutants including toluene. These control methods  include condensers, absorbers,  adsorbers,
                                         4-14

-------
and incinerators.  Recovery devices are used to recover products or by-products for sale or re-
use.
    9,10
                                    TABLE 4-6.
      EMISSION FACTORS FOR TOLUENE PRODUCTION FROM
                          PETROLEUM FRACTIONS
Emission Source
Storage tank working losses,
Toluene recovery1
Storage tank breathing los.ses,
Toluene recovery3
Toluene recovery,
General process emissions"
Toluene recovery,
Storage"
Toluene recovery from catalytic
formate, cracking unit?
Fugitives from petroleum refining
with cracking and reforming1"'0
Fugitives from petroleum refining
without: cracking and;ref ormingb-d
Emission Factor
0.66 lb/1000 gallon (0.079 kg/1000
liter) throughput
3.6 lb/1000 gallon (0.43 kg/1000 liter)
throughput
1.7 x 10~*lb/lb toluene produced
4.65 x lO^lb/lb toluene produced
2.0 x 10"5lb/lb toluene produced
21 Ib toluene/ton (10.5 g/kg) total
hydrocarbon
21 Ib toluene/ton (.10.5 g/kg) total
hydrocarbon:
Quality
Rating6
U
U
U
U
U
U
II
U
    ""Reference 12
    "Reference-14, 15:.
    cAssumes fugitives are 1.05 percent toluene.
    dAssumes fugitives are 0.105-percent toluene.
    "Based on engineering;judgement.
S torage • Emissions-

      Other possible sources of toluene emissions are storage tank losses (B) and handling

losses (C) that occur during product loading into-drums, -tank trucks, tank cars, barges, or ships.
Storage, tank losses including working losses that occur while filling the  tank, and breathing
                                      4-15

-------
 losses due to expansion from temperature changes. The calculations to determine emissions from
 storage tanks are complex and require a knowledge of a number of factors which are plant
 specific. Equations for storage tank emissions are given in the U.S.  Environmental Protection
 Agency's report titled Estimating Air Toxics Emissions from Organic Liquid Storage Tanks (EPA-
 450/4-88-004)." In the absence of specific data on the storage tank, two emission factors were
 identified in the literature.12  Both emission factors are shown in Table 4-6. No information was
 available regarding the use of floating roof tanks or any other control techniques on storage tanks.

 Equipment Leak Emissions-
        Emissions occur from process equipment components whenever the liquid or gas streams
 leak from the equipment. Equipment leaks can occur from the following components:  pump
 seals,  process valves, compressor seals and safety relief valves, flanges, open-ended lines, arid
 sampling connections.  Emission estimates can be calculated in the five ways described in the
 EPA publication Protocols for Generating Unit-Specific Emission Estimates for VOC and VHAP
 (EPA-450/3-88-010).13 The methods differ in complexity; however, the more complex, the more
 accurate the emission estimate.
                                                                                 •

       The  simplest method requires that the number of each component type be known.
 Furthermore, for each component,  the toluene content of the,stream and the time the component
 is in service is needed.  This information is then multiplied by the EPA's average emission
 factors for  the  Synthetic Organic  Chemical Manufacturing Industries  (SOCMI)  shown  in
 Table 4-7. This method should only be used if no other data are available; as it may result in
 an overestimation of actual equipment leak emissions. For each component, estimated emissions
ore:13
      No. of.   i
  I  equipment  j   X
  L components j
  Weight; %'
   toluene
., in, the, stream..
X
  Component-
    specific-
, emission factor.
X
                              No. hrs/yrin...
                            ., toluene service
        More complex, methodologies may be used, to obtain, more accurate-equipment, leak
emission estimates.   However, these methodologies require  that some level of emission
measurements (leak concentrations) be made for the facility's process equipment components,
These methodologies are briefly described here, and the reader is referred to the EPA Protocols
                                        4-16

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                                     TABLE 4-7.
              AVERAGE EMISSION FACTORS FOR FUGITIVE
                        EQUIPMENT LEAK EMISSIONS
Equipment
Valves
Pump Seals
Compressor Seals
Pressure Relief
Seals
Flanges
Open-Ended Lines
Sampling
Connections
Service
Gas
Light Liquid
Heavy Liquid
Light Liquid
Heavy Liquid
Gas/Vapor
Gas/Vapor
All
All
All
Emission Factor
(kg/hr/source)
0.0056
0.0071
0.00023
0.0494
0.0214
0.228
0.104 xV
0.00083
0.0017
0.0150
Emission Factor
(Ib/hr/source)
0.0123
0.0157
0.00051
0.1089
0.0472
0.5027
0.2293
0.0018
0.0037
0.0331
Quality
Rating1
U
u
U
u
u
u
u
     "Based on engineering judgement.
     Source: Reference 13
 documentor Fugitive-Emission Sources of Organic  Compounds-Additional Information on

 Emissions, Emission Reductions, and. Costs for calculation details.13-14

                   *
       The. first method,,the .leak/no leak, approach,. Is  based on a, determination of the number

 of leaking and nonleaking components..  A ..leaking component is: defined, by a  measured: or

 estimated, leak, concentration: greater than or equal to 10,000 ppmv.13  Once  the number: of

-leaking/nonleaking equipment components have been determined, the fugitive equipment leak

 emissions are- estimated using me-., appropriates emission factors  and  the .equation identified;

 previously for the average  emission factor method.
                                       4-17

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       The second method differentiates fugitive equipment leak emissions into  three leak
 concentration ranges:  0 -1,000 ppmv; 1,000 - 10,000 ppmv; and greater than 10,000 ppmv. The
 number of components falling into a particular range is then multiplied by the component-specific
 emission factor for that range. The component-specific emission factors can be found in EPA's
 Protocols document13

       The third  method  uses  screening data hi correlation equations derived  by  EPA.
 Correlation equations are only available for flanges, pump  seals, and valves in light-liquid and
 gas service. Finally, the fourth complex method gives each  facility an option to develop its own
 correlation equations, but requires more rigorous  testing, bagging, and analysis  of equipment
 leaks to determine mass emission rates.14

       Although  no specific information on  emissions controls  used by the  industry was
 identified,  equipment components in toluene service typically have  some  type of control.
 Generally, control of fugitive emissions requires the use of low-emission or emissionless process
 equipment, an inspection and maintenance program, and routine replacement of chronic leaking
 components.  Typical controls for equipment leaks are listed in Table 4-8.14 In addition, other
 leakless process equipment  is available such as leakless valves and sealless pumps.

 4.2 TOLUENE PRODUCTION FROM COAL

       Toluene can also be recovered from coalproducts; although coal is no longer an important
 source of toluene.  When coal is carbonized (e.g., heated in the absence of air)  in coke ovens or
 horizontal retorts, it produces coke residue and. volatile matter consisting of gas, tar, and  water.
 Both the^coaL tar and.the-coaLgas:contain-small.amounts,  of..toluene•.• which  can, be-separated
 through extraction processes. The-coal gas is normally scrubbed with an oil of coal tar or an oil
of petroleum origin. These  oils absorb the hydrocarbons entrained in the coal gas. The oil can
 then be distilled and the aromarics recovered as* crude  benzene/-6

       Crude benzene can be refined either by acid washing or hydrorefining.   Hydrorefinins is
the  more commonly  used  method.   The  two  methods of  hydrorefining  are the  Lurgi

  -   '                                   4-18

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                                TABLE 4-8.
   CONTROL TECHNIQUES AND EFFICIENCIES APPLICABLE
                 TO EQUIPMENT LEAK EMISSIONS
   Equipment Component
     (Emission Source)
         Control Technique
 Percent
Reduction
  Pump Seals
    Packed and mechanical
    Double mechanical13
Seal area enclosure vented to a
  combustion device
Monthly LDARb
Quarterly LDAR
Semiannual LDAR
Annual LDAR
N/Ad
    100a
     61
     32
      0
      0
  Compressors
Vent degassing reservoir to combustion
  device
    100a
  Ranges
None available
      0
  Valves
    Gas
    Liquid
Monthly LDAR
Quarterly LDAR
Semiannual LDAR
Annual LDAR
Monthly LDAR
Quarterly LDAR
Semiannual LDAR
Annual LDAR
     73
     64
     50
     24
     59
     44
     22
      0
  Pressure Relief Devices
   Gas
Monthly LDAR
Quarterly LDAR
Runrure Disk
                                                                   50
                                                                   44
                                                                  100
  Sanrole Connections
Closed-purge sampling
                                                                  100
  Open-ended Lines -
Cans on ooen ends
    100
* Combustion devices approach 100 percent control efficiency.
 LDAR (Leak detection and repair program)..
c Assumes the seal barrier fluid is maintained at a pressure above the pump stuffing box
 pressure and the system is equipped with a sensor that detects failure of the seal and/or
 barrier. fluid, system.:
dN/A (Not applicable).  There are no VOCemissions from this component..

Source:.  Reference 14-
                                   4-19

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 Hydrorefining® process and the Houdry Litol Hydrorefining® process.4  Many of the process
 steps described in the next two paragraphs are the same as those encountered in the previous
 section, Toluene Production from Petroleum Fractions.  The reader should refer to Section 4.1
 for further detail.

 4.2.1  Process Descriptions

        Crude benzene, in the Lurgi Hydrorefining® process, is preheated, vaporized and passed
 through a reactor where hydrodesulfurization, saturation of hydrocarbons, and reduction  of
 oxygen- and  nitrogen-containing compounds  occurs.   The reactor products are cooled and
 condensed with the condensed hydrocarbon stream undergoing stripping of hydrogen sulfide. The
 clean hydrotreated stream, the raffinate, is fed  to an extractive distillation unit where a toluene
 mixture is separated from nonaromatics also in the raffinate.  The toluene mixture then passes
 to a recovery  column where high purity toluene is recovered.4

       In the  Houdry Litol Hydrorefining® process, the crude benzene is first prefractioned as
 described previously in Section 4.1.4 Toluene Recovery.  The prefractionated distillate, containing
 approximately 17 percent by weight toluene, is mixed with hot hydrogen gas and vaporized.  The
 stream  passes to a reactor where  olefins  are  saturated and hydrogen sulfide and  butane are
 produced.  The resulting process stream  moves to the Lithol reactor  where desulfurization,
 hydrocracking and dealkylation take place. The reactions in. the: Lithol  reactor are exothermic
 and must be moderated by heat exchangers. After leaving the Lithoi reactor, the stream moves
 to a flash drum where aromatic hydrocarbons are separated, condensed, and forwarded to a
 stabilizer, a ciay tower, and then, the-benzene-tower.. The- final ixactionation takes place in the
 toluene tower  which yields pure toluene.4"
       Several new methods have been developed by which toluene can be produced from coal.
Many  of these  new processes  come from  the- liquification of coal  and are still' in- the
developmental stages. One process, the South African Coal, Oil, and Gas Corporation (SASOL)
operation has proven commercially feasible in South Africa. These processes, if successful, could
                                         4-20

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 lead to coal refineries that manufacture many of the products currently available from petroleum
 refineries.4

 4.2.2 Emissions

       No information was located in the literature that discussed process emission sources from
 toluene production from coal feedstocks.  Emissions are expected to be similar to those occurring
 from petroleum feedstocks where the equipment in use is the same. An overall emission factor
 for coke manufacture is shown in Table 4-9.
                                    TABLE 4-9.  *
       EMISSION FACTORS FOR TOLUENE PRODUCTION FROM
                                       COAL
Emission Source
Coke manufacture,
Coke oven
Emission Factor
2.4 x Krtb/lb coke produced
Quality
Rating3
U
    "Based on engineering judgement
    Source: Reference 14.
4.3 TOLUENE PRODUCTION FROM STYRENE

      Toluene: is  a  by-product  in  the  production  of  styrene  from  ethylbenzene  by
dehydrogenation. Small amounts, of toluene-are-.:also produced as a styrene by-product; via. the
isothermal production process..  However, because;the.isothermal,method is not currently used
in the United States and, emissions of toluene  are minimal  from  this process, it will not be
discussed in this document  Additional information on the isothermal process can be found in
Locating and Estimating Air Emissions from Sources of Styrene (EPA-450/4-91-029).8
                                       4-21

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4.3.1 Process Description

       In the dehydrogenation process shown in Figure 4-4, purified ethylbenzene is preheated
in a heat exchanger (Step  1), and the resultant vapor is mixed continuously with steam at 710°C
(1310°F) in the dehydrogenation reactor (Step 2) that contains one of several catalysts.  The
reaction product exits through the heat exchanger and is further cooled in a condenser (Step 3)
where water and crude styrene vapors are condensed. The hydrogen-rich process gas is recovered
(Step 4) and used as a fuel and the process water is purified in a stripper (Step 5) and recycled
to the boiler.  The remaining crude liquid styrene goes to a storage tank (Step 6).  The liquid
consists of styrene  (37 percent), ethlybenzene (61 percent), toluene (1 percent), benzene (0.7
percent); and tars (0.3 percent). Benzene and toluene are removed from the crude styrene in the
benzene/toluene column (Step 7). They are then typically Veparated by distillation (Step 8). The
toluene is normally sold, while the benzene is returned to the ethylbenzene production section
or sold. In some facilities, an ethylbenzene/benzene/toluene stream is separated from the crude
styrene initially (at step  6) and processed separately.

4.3.2  Emissions

       Emission factors for the production  of toluene from styrene production are shown  in
Table 4-10.   These  emission factors  were based on engineering judgement, and are therefore
given ^ratings of  "U."  The emission  factor for styrene  purification  came  from engineering
calculations at one facility, while the two factors for production process and production fugitive
emissions were  based on typical composition  and design information from  two emission
sources.14
                                         4-22

-------
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                                                           *

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                                                          o
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                                                         ";>>
                                                         o
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                                                         c.
                                                         0)
                                                         2
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4-23

-------
                       TABLE 4-10.
  EMISSION FACTORS FOR TOLUENE PRODUCTION FROM
                 STYRENE PRODUCTION
Emission Source
Styrene production process
emissions*
Styrene purification process
emissions, Styrene production1
Styrene production fugitive
emissions*
Storage Tank working lossesb
Storage Tank breathing lossesb
Emission Factor
3.04 Ib/ton (1.52 g/kg) styrene produced
2.34 Ib/ton (1.17 g/kg) styrene produced
22,840 Ib (10,358 kg)/process unit,
annually
0.66 lb/1000 gallon (0.079 kg/1000 liter)
throughput
3.6 lb/1000 gallon (0.43 kg/1000 liter)
throughput
Quality
Ratingc
U
u
U
u
u
bReference 12
"Based on engineering judgement.
                        4-24

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4.4 REFERENCES FOR SECTION 4.0
1.

2.

3.


4.


5.


6.

7.


8.



9.



10.



11.



12.,



13...
 SRI International. Chemical Economics Handbook. Menlo Park, CA.  1991.

 Facts and Figures. Chemical & Engineering News 70(26). pp 35-39,  66r75.  1992.

 Toluene Chemical Product Synopsis. Mannsville Chemical Products Corp. Asbury Park
 NJ, March 1990.

 Hancock,  E.G., ed., Toluene, the Xylenes and  their Industrial Derivatives.   Elsevier
 Scientific Publishing Company.   New York, NY. 1982.

 Kirk-Othmer Encyclopedia of Chemical Technology. 3rd edition. Toluene. Volume 23.
 John Wiley and Sons.  New York, NY. pp. 246-273.  1983.

 Faith, Keyes, and Clark's Industrial Chemicals.  Fourth Edition. 1975.
                                             sV
 Considine, Douglas M., ed., Chemical and Process Technology Encyclopedia. McGraw-
 Hill, Inc. pp. 603-606, 975-979, 1104-1106.  1974.

 U.S. Environmental Protection Agency.  Locating and Estimating Air Emissions from
 Sources of Styrene, Interim Report, EPA-450/3-90-020;  Office of Air Quality Planning
 and Standards. Research Triangle Park, NC. 1991.

 U.S. Environmental Protection Agency.  Locating and Estimating Air  Emissions from
 Sources of Benzene, EPA-450/4-84-007q. Office of Air Quality Planning and Standards.
 Research Triangle Park, NC. 1988.

 U.S. Environmental Protection Agency. Reacror Processes in Synthetic Organic Chemical
 Manufacturing Industry - Background Information for Proposed Standard, EPA-450/3-90-
 016a:  Office of Air Quality Planning and Standards.  Research Triangle Park, NC. 1990.

 U.S." Environmental Protection Agency. Estimating Air Toxics Emissions from Organic
 Liquid Storage Tanks, EPA-450/4-88-004. Office of Air Quality Planning and Standards.
 Research Triangle Park, NC., 1988,

 U.S;.Erivironmentai.Protection-,Agency. Crireria.PoilumnfEmission Facwrs for [he 1985
 NAPAP Emissions inventory; EPA-600/7-87-015'. Air-and Energy Engineering Research
.Laboratory, Research-Triangle-Park, NC 27711.  1987.

 U.S..Environmental Protection Agency.; Protocols-far Generating Unit-Specific Emission
 Estimates for Equipment Leaks of VOC and VHAP, EPA-450/3-88-010. Office of Air
 Quality Planning and Standards,  Research Triangle.Park, NC, 198$.
                                       4-25

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14.    U.S.  Environmental  Protection Agency.   Fugitive  Emission Sources  of Organic
    .  Compounds-Additional Information on  Emissions, Emission Reductions, and Costs.
      EPA-450/3-82-010.  Office of Air Quality Planning and Standards.  Research Triangle
      Park, NC. April 1982.

15.    U.S. Environmental Protection  Agency.  Toxic Air Pollutant Emission Factors - A
      Compilationfor Selected Air Toxic Compounds and Sources, EPA-450/2-88-006a,  Office
      of Air Quality Planning and Standards.  Research Triangle Park, NC. 1988.
                                       4-26

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                                      SECTION'5.0
                    EMISSIONS FROM MAJOR USES OF TOLUENE

       This section discusses emissions from major industrial processes that use toluene as a
 solvent  or  feedstock.   The processes  described are  the  production  of benzene,  toluene
 diisocyanate (TDI), trinitrotoluene (TNT), benzoic acid, and benzyl chloride.  In addition, product
 and process descriptions are provided for uses of toluene in solvent applications, such as paint
 and ink manufacturing and solvent cleaning operations.  The application of toluene containing
 paints, coatings, and inks will be discussed in Section 6.0.  Process flow diagrams are included
 as  appropriate, with specific streams or vents in the figures labeled  to correspond with the
 discussion in the text.
       Emissions of toluene are expected from all facilities involved in the previously mentioned
operations.  However, insufficient  information is available to develop emission factors for
fugitives or process emission sources. Available information is provided in each subsection. The
reader is encouraged to contact  the Toxic Chemical Release Inventory (TRI)  and specific
production facilities for information on toluene emissions and control technologies. It should be
noted, however, that TRI emission  estimates may be based upon engineering estimates, may
include-.accidental, releases,, and... therefore,- may not be reliable.-

       Residual emissions from  toluene-containing materials  are  discussed  separately  in
Section.6.0.   Toluene' emissions  resulting, as-a  by-product of another process-.(by-producr
emissions) are discussed in Section 7.0.
                                                            «

5.1.    BENZENE" INDUCTION

       Benzene can be produced from catalytic reformate, pyrolysis gasoline, coke-oven light oil,
or from toluene by hydrodealkylation (HDA) and dispropomonation. Benzene production direcriy
from toluene: accounts -for approximately 25, percent, of the. total, benzene produced.1  Major
derivatives of benzene, accountingfor 98 percenLof. benzene end.uses,  include ethylbenzene (for
styrerie),  cumene (for phenol), cyclohexane, nitrobenzene  (for aniline), chlorobenzene, and
                                          5-1

-------
 alkylbenzenes (for detergents).2  In addition, approximately two percent of the benzene produced
 is used as a solvent or feedstock in the following industries and products:  laboratories, metal
 degreasing, Pharmaceuticals manufacture, alcohols production, textiles, and miscellaneous small
 volume chemicals.24

       Thirteen  companies  at  eighteen   facilities  currently  produce  benzene  by  toluene
 hydrodealkylation or disproportionation. These facilities and their 1989 production capacities are
 listed in Table 5-1.1 The manufacture of benzene accounts for 50 percent of toluene end use.4

 5.1.1 Process Description

       Benzene  may  be  produced  from  toluene  through   HDA  or  disproportionation.
 Hydrodealkylation of toluene can be accomplished through thermal or catalytic processes.  The
 total dealkylation capacity is almost evenly distributed between the two methods. As shown in
 Figure 5-1, pure toluene (92 to 99 percent), or toluene  (85 to  90 percent) mixed  with other
 aromatics or paraffins is heated to 730°C (1,346°F) at  a specified pressure (Step 1) and is
 charged to the reactor (Step 2) in the presence of excess hydrogen.1-3  Toluene reacts with  the
 hydrogen, either by thermal initiation or contact with a dealkylation catalyst, to yield benzene arid
 methane.  The benzene may be separated from the.methane-in a low pressure separator  (Step 3)
 by flashing off the methane-containing gas.  The product is then stabilized (Step 4) and benzene
 is recovered by distillation (Step  5).  Benzene is sent to storage (Step 6).  Unreacted toluene arid
 some heavy by-products are recycled  (Step 7).  Approximately 70 to 85 percent conversion of
toluene  to benzene is accomplished per pass through the system, and the ultimate yield is
                                                 t
95 percent of the theoretical yield.3 Many.facilities that produce benzene from petroleum sources
also have the ability to produce- benzene:-fronr toluene- via HDA.,  The-HDA-.process is reported
EO be economically feasible-when low-cost hydrogen is available-and. when benzene is valued at
approximately 30 cents per gallon more than toluene.1-2
                                          5-2

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                          TABLE 5-1.
     BENZENE PRODUCERS USING TOLUENE FEEDSTOCK
Facility
Amerada Hess Corporation
American Petrofina
Incorporated
Arochem International
BP America, Inc. (Sohio)
Chevron Corporation
Coastal Refining and
Marketing
Dow Chemical U.S.A.
Hoechst Celanese
Koch Industries, Inc.
Lyondell Petrochemical Co.
	 __.,,. i
Occidental Petroleum Corp.
Phillips Puerto Rico Core-
Inc.;
Sun, Company, Inc.
Location
St. Croix, VI
Port Arthur, TX
Penuelas, PR
Alliance, LA
Lima, OH
Philadelphia, PA
Port Arthur, TX
Corpus Christi, TX
Freeport, TX
Plaquemine, LA
Bayport,.TX
Corpus Christi, TX
Houston, TX •
Chocolate Bayou,TX
Corpus Christi, TX
Guayama,, PR
Marcus Hook, , PA
Tuisa, OK
1989
Capacity
millons of
kilograms
(millions of
gallons)
N/A
109 (33)
- 115(35)
155 (47)
263 (80)
46 (14).
164 (50)
53 (16)
82 (25)
395 (120)
49 (15)
197 (60)
49 (15)
132 (40)
99 (30)
161 (49)
- 36-(ll)
66 (20)
Production
Method
Disproportionation
Disproportionation
HDA
HDA
HDA
HDA
HDA
HDA
HDA
HDA
HDA. '
HDA
DisproDortionation
HDA
HDA
HDA
'1
Disproportionation
HDA *
Source: Reference 1
N/A = Not Available ..
HDA = hydrodealkylation
                             5-3

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       HEATER        REACTOR
SEPARATOR       STABILIZER        BENZENE
                                COLUMN
MAKEUP
  GAS
    j     "fi
                                                   iA
                                                       DENOTES POTENTIAL LOCATION CF- EMISSIONS,
                                                       FUGITIVE EMISSIONS
              Figure 5-1.:  Process flow diagram of a toluene dealkylation- unit3
                                             5-4

-------
        Toluene disproportionation, or transalkylation, catalytically converts two molecules of
 toluene to.one molecule each of benzene and xylenes, as indicated by the reaction:5
                                                              CH.
                Toluene
Benzene
Mixed Xylene Isomers
The transalkylation process is similar to that of toluene HDA but occurs under less  severe
conditions (e.g., the transalkylation process operates at lower temperatures and consumes less
hydrogen).  Toluene is heated, combined with hydrogen, and sent to the reactor. The reacted
material is moved to a separator for removal of off-gases.  The product is stabilized and moved
through.clay towers.  Benzene,.toluene.:and xylenes are recovered by distillation and  unreacted
toluene is recycled.2'3 Toluene disproportionation is used when; the desired product  is xylene.
If benzene is the  only product required, then HDA is a more  economical and feasible process.1

5.1.2 Emissions

       Facilities manufacturing benzene emictoiuenefronrprocess equipment vents, open orocess
equipment; equipment leaks,.storage- tank, vents,  secondary .sources,, and. transfer: and; handling
operations.  No specific,emissions data for any of these sources are available:  however, it has
been estimated that 5.0 x 10°" pounds of toluene are emitted for every pound of toluene used in
the benzene manufacturing process.6
                                          5-5

-------
        Process equipment sources include heaters, reactors, separation tanks,  stabilization
, columns,  distillation columns, and the toluene recovery system.  The emissions will  vary
 according to the type of process used (e.g., HDA or disproportionation) and the percentage of
 toluene in the raw material feed stream.

        To control process vent emissions, the process streams can be  routed to a flare  or
 blowdown tank. Recovered toluene emissions from the distillation column are recycled with the
 reactor feed stream.  Where feasible, open equipment may be enclosed.

        Sources of fugitive emissions  and emission estimation procedures  are  discussed  in
 Section 4.0.  Also included in Section 4.0 is a table of emission control options and efficiencies.
                                                     X*

        A significant source of toluene air emissions occurs from toluene transfer during the
 loading and  unloading of trucks, tank cars, and barges and the filling of toluene storage tanks.
 Losses of toluene from storage tanks may also occur due to normal tank working and breathing
 losses. Toluene emissions from storage tanks are discussed in Section 4.1.5 under the topics of
 Storage and  Fugitives.

 5.2   TOLUENE  DIISOCYANATE PRODUCTION
       Toluene diisocyanate (TDI)  is produced  by a reaction sequence in which toluene is
 dinitrated to form dinitrotoluene.  Dinitrotoluene is hydrogenated  to form 2,4-diaminoroiuene
 which is treated with phosgene to yield two isomers of toluene diisocyanate 2,4-TDI and 2,6-TDI.
 Commercial toluene diisocyanates  are-available in three • isomer • ratios..   The majority  of
 commercially used TDI is a.rnixture;of 80 parts of the;2,4-TDI isomer and,20 parts of the-2.6-
 TDI isomer. A 65:35 mixture-of the,2,4- and 2,6-TDI isomers'is also available; as is pure TDI
 (greater than 99.5 percent 2,4-TDI).5-7  Either nitration-grade toluene or highly refined toluene
 (99.95-r percent)  is used as the* basic-feedstock by most TDI manufacturers.3

       Toluene diisocyanates are industrial intermediates used in the. production of polyurethane
 foams, paints, varnishes, elastomers, and coatings.  Rigid polyurethane foams, accounting for

                                          5-6

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about five percent of TDI demand, are used as insulation in refrigeration equipment.9 Flexible
polyurethane foams, used in furniture cushioning, transportation (e.g.,  automotive seating),
bedding, packaging, and carpet underlay, account for approximately 90 percent of the use of
toluene diisocyanates.7  Little or no growth in production of TDI is expected for several reasons.
Methyl diphenyl diisocyanate (MDI) is replacing TDI in many polyurethane foam applications.
TDI can react violently with compounds containing an active hydrogen atom.7

      Toluene diisocyanate is currently produced by five companies at six facilities in three
States.  These  facilities and  their   1990  production capacities are listed  in  Table 5-2.9
Manufacture of toluene diisocyanates accounts for nine percent of toluene end use.4

                                   TABLE 5-2.   „
    TOLUENE DHSOCYANATE PRODUCTION LOCATIONS AND
                                  CAPACITIES
Facility
BASF Corp,
Dow Chemical
ICL Americas
Mobay
Mobay
Olin
Location
Geismar, LA
Freeport, TX
Geismar, LA
New Martinsville, WV
Baytown, TX
Lake Charles, LA
1990 Capacity
Millions of Kilograms
(Millions of Pounds)
73 (160)
63 (140)
32: (70)
45 (100)
61 (135)
88 (195)
  Source: Referenced
                                       5-7

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5.2.1' Process Description            ,

      The manufacture of commercial toluene diisocyanates is based on the phosgenation of
primary amines.  Most commercial TDI plants also produce the intermediates dinitrotoluene
(DNT), toluene diamine (TDA) and phosgene.8

      TDI is produced by the following chemical reactions:
Reaction 1:
                        2HN03
                                    H2S04
                                                               N0
                                                                    -f- 2H2O
                                                       NO2
           toluene    nitric acid   sulfuricacid     2,4-dinitrotoluene       water
Reaction 2:
              CH<
                                                        CH,
                     NO
                          6H      Catalyst
                                                               NH2
                                                                         4H_0
        2,4-dinitrotoluene   hydrogen
Reaction 3:
                                                        NH2.
                                                  2,4-toluenediamine      water
                                                        GH'<,
                                                               NCO;
                       •f  2COC1-?
                                      Heat
                                                                     -p- 4HC1
                                                       NCO
       2,4-toluenediamine   phosgene        2,4-toluenediisocyanate   hyrogen chloride
                                        5-8

-------
       Figure 5-2 illustrates the basic operations that may  be used in toluene diisocyanate
 production.  The first step in the manufacture of TDI is the nitration of toluene  (Step  1).
 Nitration grade toluene is reacted with nitric acid to form DNT.  The reaction takes place at 65°
 to 80°C(149° to 176°F) in a well-agitated reactor equipped with cooling coils using sulfuric acid
 (60 to 70 percent) as the catalyzing agent10  The spent sulfuric acid is separated from the DNT
 reaction mixture, concentrated in a direct contact evaporator, and recycled to the nitration reactor
 (Step2).8

       The DNT is washed in a wash tank (Step 3) and then reacted with hydrogen in catalytic
 reduction reactors (Step 4), using precious metal, nickel, or carbon catalysts, to form crude TDA.
 The hydrogenation of DNT normally  occurs in an inert diluent  (e.g., an alcohol)  to avoid
 explosion hazards and to control the heat resulting from die exothermic process. The crude TDA
 is purified  by filtration and distillation (Step 5).8'10

       TDA   is  reacted  with  phosgene  in  a  solvent,  usually  o-dichlorobenzene   or
 mono-chlorobenzene to  form crude TDI and hydrogen chloride (HC1) (Step 6).  Phosgene is
 condensed  out of the HC1 by-product -and recycled to the reactor.  Crude TDI is sent to a
 distillation  column for the removal of residual phosgene (Step 7).  After  a series of distillation
 and condensation steps, the phosgene,  (from the  crude TDI)  is recycled.to the phosgenation
 reactor. The crude TDI still contains some of the chlorobenzene solvent in which it was reacted.
 This mixture  (TDI and solvent)  is transferred to  a vacuum distillation column .where  the solvent
 is. recovered .and  recycled (Step 8).  The: remaining crude. TDI - is vaporized by vacuum flash
 distillation  to separate TDI from any polymeric isocyanates that may have formed (Step 9). The
 TDI is then condensed and sent to  a vacuum distillation column-from which purified TDI is
removed  (Step-10).. THe-purified: TDI1 scream undergoes a. final-condensation step-before-being.:
 transferred, co product storage-(Step-11).3-1?.

5.'2i2: Emissions
       Typical emission sources at TDI manufacturing facilities include process equipment vents,
open process equipment, equipment.leaks, storage tank vents, secondary sources, and transfer and
                                          5-9

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 handling operations. No-specific emissions data for any of these sources are available; however,
• it has been estimated that 7.7 x 1CT4 pounds of toluene are emitted for every pound of toluene
 used in TDI manufacturing. An additional 1.9 x 10"4 pounds of toluene are released from fugitive
 sources per pound of toluene used.6                          »

        Process equipment  sources include nitration reactors, evaporators, the DNT wash tank,
 TDA reactors, filtration units, stabilization columns, and the condensation and distillation units.
 The emissions will vary according to degree of agitation of the reactors and the level of control
 on the equipment.                                     .

 5.3   TRINITROTOLUENE PRODUCTION
                                                    V-
       At one time, the production of trinitrotoluene (TNT) for explosives was the major end use
 of  toluene.  Although TNT is no longer  a primary  toluene derivative, it is  still a modern
 explosive used mainly for military purposes,  but also with commercial applications.  TNT
 provides low manufacturing cost, excellent chemical and thermal stability, and favorable physical
 properties to allow usage as a bursting-charge in sheUs, bombs, and grenades and as an ingredient
 in binary explosives, metallized explosives, propellant compositions and commercial blasting
 explosives.10

       Once manufactured by private companies, TNT is now produced by government facilities.
 It is.  not. likely, that, private-manufacture-o£ TNT will resume  as less  expensive, competitive
 industrial explosives are now available.11

 5.3". 1   Process Description3-10
       The production of TNT can be accomplished in two or three stage processes and in batch
or. continuous fashion;,  The: chemical, process- is the same: for- both. the- continuous and batch
methods.  Figure 5-3 illustrates the TNT manufacturing process. TNT is normally produced by
the nitration of toluene in three distinct mononitration stages each consisting of the addition of
one nitro (NOj) group into the aromatic ring.  The first nitro group can be introduced easily, but
                                         5-11

-------
                        A
                      '  (NOX.SOX.
                        •TOLUENE.
                        »TRINrTROMETHANE)
(«NOX.»SOX)
TO MIXED ACID
 PREPARATION
                                                            TO  DISPOSAL  TO DISPOSAL  TO STORAGE
                           H2SO<.  OR
                           Mg(N03J2
                   NfTRIC ACID
                 CONCEKTRATION
                                                 \  .DEMOTES' ?OTENT!AL,.LOCATION Or  EMISSIONS'.

                                                 'A
                                                 |    FUGITIVE EMISSIONS

                                                 IB'
                                                 |  STORAGE EMISSIONS

                                                 1C:
                                                 J   LOADING LOSSES


                                                 *' INDICATES NEGLIGIBLE AMOUNT
                            Figure 5-3.  TNT production12
                                             5-12

-------
 the second and third nitration steps require reaction forcing conditions using various mixtures of
 nitric and sulfuric acids in water.  Increasing amounts of sulfuric acid (and decreasing amounts
 of nitric acid)  are used with each  successive mononitration step.

       The mixed acids and the toluene are fed into a series of cooled, agitated reactors (Step 1).
 The  sulfuric  acid catalyzes  the  reaction producing 97  to 98 .percent  mononitrotoluene,
 approximately 0.2 percent DMT, 1 percent unreacted toluene, and some nitrocresols.10  Once the
 reaction has gone to completion, the spent acid and the mononitrotoluene separate into  two
.phases (Step 2).  The mononitrotoluene is purified by a water wash foUowed by an alkali wash
 and a second water wash (Step 3).  The spent acid (primarily sulfuric acid) is concentrated  in a
 direct contact evaporator using gases from a natural gas burner, recycled to the nitration reactor,
 and mixed with additional virgin acids to provide nitration acids of the desired strength.

       The crude mononitrotoluene is topped to remove unconverted toluene (Step 4) and then
 separated by fractional distillation  into a 2-nitrotoluene (2-NT) stream and a distillation residue
 which can be further distilled and crystallized  (Step 5) to recover the 3- and 4-NT isomers.
 (End  uses for these isomers are discussed in Section 5.6.)  The basic nitration process is repeated
 two additional  times to produce DNT and then TNT.

 5.3.2  Emissions

       Typical emission sources arTNT manufacturing facilities include process equipment vents,
 open process equipment, equipment leaks, storage tank vents, secondary sources, and transfer and
 handling operations.  No emissions data: for- any  of these: sources.were, available- during the
 preparation- of this- document.,

       Process  equipment sources include  nitration reactors, separation columns, wash tanks,
 evaporators,,filtxation,units,,and distiUation:units; 'The emissions:will vary according to the type
of process used (e.g., two or three  stage operations or, batch or continuous processing) and  the
strength of the nitration acid: mixture.
                                          5-13

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5.4  BENZOIC ACID PRODUCTION

       Benzoic acid is manufactured  from  toluene by  continuous liquid-phase oxidation.
Approximately 52 percent of the benzoic acid produced from toluene is converted to phenol by
the only U.S. phenol producer, Kalama Chemical.  Phenol, in turn, is used  to manufacture
phenolic resin for use in adhesives, hi plywood, binders for insulation, and laminating agents.
Other end uses for benzoic acid include plasticizers (20 percent), sodium and potassium benzoate
(12  percent), benzoyl  chloride (6 percent),  alkyd  resins (3 percent), and  butyl benzoate
(2 percent). Miscellaneous uses account for the remaining five percent of benzoic acid end uses.
Sodium and potassium benzoate, benzoic acid salts, are used mainly as food and beverage
preservatives  in the United States.  European countries and Japan  use sodium benzoate as a
corrosion inhibitor in antifreeze.13                    v-  -;

       Benzoic acid is currently produced by three companies.  These facilities and their 1990
production capacities are listed in Table 5-3.13

                                    TABLE 5-3.
   BENZOIC ACID PRODUCTION LOCATIONS AND  CAPACITIES
Facility
Kalama Chemical
Pfizer
Velsicol
Location
Kalama, WA
Terre Haute, IN
Chattanooga, TN
1990 Capacity
Millions of Kilograms
(Millions of Pounds)
63 (140)
4.5 (10)
29 (65)
  Source: Reference 13
                                       5-14

-------
 5.4.1  Process Description

        Benzoic acid is manufactured from toluene in the presence of cobalt catalysts  by
 continuous liquid-phase oxidation according to the following reaction:1
          CH
                                     COOH
        Toluene
                    +  1.5  O2
Oxygen
                                                +
Benzoic Acid
Water
 Approximately 0.87 pounds of toluene are required per pound of benzoic acid produced, with a-
 40 percent toluene conversion per pass.12

       Although many of the process details are proprietary, the basic reaction mechanisms are
 presented.  Toluene, the catalyst, and air (the source of oxygen) are fed  continuously into  a
 reactor maintained at 150°  to 250°C (300° to 480°F) and at a pressure of  5  to 50 atm.11  The
 temperature and the catalyst concentration determine the reaction rate. The reaction is complete
 when. 40 percent-of-.the toluene has been oxidized to. yield-crude-benzoic  acid.11  The reactor-
 effluent moves from  the oxidation reactor to an atmospheric stripping column heated by  a
 circulating hot oil  reboiler.  The unreacted toluene and other intermediates/by-products &.»..
 benzaldehyde (one  to two percenr) and benzyl benzoate (ten percent)] boning below benzoic acid
 are removed from the column and recycled.10  Crude benzoic acid is extracted from the column
                                                                                «
 using water and moved to• a, small, finishing column-where-pure:.benzoic  acid.is removed
 overhead,. The-finishing, column- bottoms are-returned:to the..stripping-coiurnn..

      - Vent gases  from the oxidation reactor are cooled by exchange with incoming air, then
 with-cooling.waier, and.finally, by ammonia refrigeration.. The ventgases are then expanded and
vented tQ the atmosphere through a carbon scrubber.  Much of the toluene in  the vent gases' is
recovered for recycle through the cooling process.
                                         5-15

-------
 5.4.2  Emissions

       Typical  emission sources at benzoic  acid  manufacturing facilities include process
 equipment vents, open  process  equipment, equipment leaks,  storage tank vents,  secondary
 sources, and transfer and handling operations.  No specific emissions data for any of these
 sources are available; however it has been estimated that 1 x 10'3 pounds of toluene are emitted
 for every pound of toluene used in benzoic acid manufacturing. An additional  1 x 10"4 pounds
 of toluene are released from fugitive sources.6

       Process equipment sources include reactors, stripping columns, wash tanks, and distillation
 units.  The emissions will  vary  according to  the type of process used (process details  are
 proprietary) and the temperature of the oxidation reactor.v~

 5.5  BENZYL CHLORIDE PRODUCTION
                                             e
       Benzyl chloride is produced commercially by the direct chlorination of boiling toluene.
 Two facilities in the United States produce benzyl chloride.  As of January 1,.1990, Monsanto
 in Bridgeport, New Jersey, had a  capacity of approximately 45 million kilograms (100 million
 pounds").  Akzo Chemical in Edison, New Jersey operated a facility with an 11" million kilogram
 (25 million pound) capacity.  The primary end use  of benzyl chloride (69  percent)  is as an
 intermediate in the production  of butyl benzyl phthaiate which is a plasticizer  for vinyl flooring
 and poiyvinyl acetate emulsion adhesives used in packaging. Sixteen percent of benzyl chloride
 is used in the production of quaternary ammonium compounds (quats).  Quats are used in
 sanitizers, disinfectants, deodorants, fungicides and algicides applied in food' production, dairies,
 bottling plants, restaurants;, swimming, pools, and,industrial.water treatment bacrericides.. Other
 uses of benzyl chloride-inciude-the production of benzyl alcohol, benzyl acetate, butyl benzoate.
and benzyl salicylate. Some of the end products of these chemicals are perfumes, cosmetics, and
 flavorings.'5  The annual growth  rare of benzyl, chloride in, the Unites States  is expected to
increase by no more than 1.0 percent from 1988 to 1993.1
                                         5-16

-------
 5.5.1 Process Description
        Benzyl chloride is produced by the direct chlorination of boiling toluene according to the
 following reaction:1
                                                                       -5-  HCl
           .  Toluene     Chlorine                      Benzyl Chloride
 Toluene is heated to 65° to 100°C (150° to 212°F) and chlorinated in the dark (or in an alternate
 process by photochlorination) until the mixture increases in weight by 37.5 percent.1'14  The
 reaction mixture  is agitated with a  mild alkali and then distilled.  Benzal chloride  and
 benzotrichloride are by-products of the chlorination reaction and occur in ratios with benzyl
 chloride of 1:0.1:10."  Excess toluene is recovered and recycled to the chlorinator while the
 resulting hydrogen chloride gas is absorbed in water forming muriatic acid. For every pound of
 benzyl chloride produced, 0.8 pounds of toluene are consumed.1

 5.5.2  Emissions

       Typical, emission sources .at benzyl chloride-- manufacturing facilities include process
 equipment vents,  open process  equipment,, equipment leaks,, storage tank vents, secondary'
 sources, and transfer and'handling operations.  No. specific-emissions data for any of these
 sources are available; however, it has been-estimated that 5.5 x 1QT4 pounds of toluene are-emitted
 for every pound of toluene used in benzyl chloride production. An additional 1.5 x W4 pounds
 of toluene are, released  from.fugitive sources.6

       Brocess  equipment-sources: include,,heaters, chlorinarion reactors,, and wash tanks. The
emissions will vary according  to the, type  of process -used   (e.g., dark  chlorination  or
photochlorination).
                                         5-17

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 5.6 OTHER TOLUENE DERIVATIVES

        Other toluene derivatives include mono- and dinitrotoluene, vinyl toluene, benzaldehyde,
 toluenesulfonyl chloride, chlorotoluenes, and toluenesulfonic acid.  End uses for these chemicals
 are discussed below.5-10

        The mono- and dinitrotoluene isomers can be hydrogenated to amines and then used as
 dye intermediates. The 3-nitrotoluene isomer is used in the production  of red-violet dyes for
 polyester fibers,  while 4-nitrotoluene is used in. fluorescent brightening agents for cellulosic
 materials.10
       Benzaldehyde is a by-product of toluene in the manufacture of benzoic acid. The primary
 use of benzaldehyde is as a chemical intermediate in the production of specialty chemicals used
 for food flavoring, Pharmaceuticals, herbicides, and dyestuffs.

    f  The production of vinyl toluene is accomplished by reacting ethylene and pure toluene
 in the presence of aluminum chloride  and hydrogen chloride.  Dow Chemical  currently  holds
 several patents for this manufacturing process. Vinyl toluene is used in unsaturated polyester and
 alkyd resins and as a co-polymer with butadiene. The end uses of these chemicals are normally
 paints, adhesives, and printing inks.5'10

       Toluene can be suifonated with suLfuric acid or sulfur trioxide to form toluene suiforiic
 acids.  Sulfonation with chlorpsulfonic acids yields toluene sulfonyl chloride.  The largest use
 of mixed toluene suifonic acids is in the production of cresols.  One of the isomers of "toluene
 iulfonic acid, p-toluene suifonic acid.(PTSA), is" used*,ln:the.production'-of resins, dyes, adhesives.,
 antidiabetic drugs, and as an additive in electroplating baths. Toluene-sulfonyi chlorides are used
 in disinfectants and in the manufacture of saccharin.5-10

       Mono-, di-, and  trichlorotoluenes are'prepared by  the ring-chlorination of  toluene.
Toluene is reacted with elemental chlorine in the presence of catalysts such as chlorides of iron.
 aluminum,  tin, titanium, and zirconium to yield ortho- and para-chiorotoluene.  These isomers

                                          5-18

-------
are used as solvents and in paint and rubber stripping formulations and dye carrier formulations.
Other eventual end uses include dyestuffs, Pharmaceuticals, and preservatives.5'10

5.7  PAINT AND INK MANUFACTURING

       Toluene is one of the solvents used as a raw material in the manufacture  of paints and
inks. In 1989, toluene accounted for 15 percent of the 1,977 kilograms (4,358 million pounds)
of solvent consumed in paints and coatings.15 Consumption in paints and coatings accounts for
approximately 45 percent of total toluene solvent sales.  A breakdown of the consumption of
toluene and its  derivatives  as  they are  used in paints  and coatings is  given in Table 5-4.
Figure 5-4 is a flow diagram indicating the uses of toluene in the paint and coatings industry.15
Section 6.0  discusses the application of toluene containing paints (surface coating) and inks
(printing).

       Paints and inks are made by blending pigments,  solvents, resins (or binders), oils (for
some inks), and other additives. The fluid component of the paint or ink, made of binders (oils
and/or resins) and solvents, is called the vehicle.  Vehicles transfer the pigment/binder mixture
to a surface in a thin, uniform film and normally play no role in film formation. (In the case of
reactive diluents and two- and three-component coatings, the vehicle becomes part of the coating
film.)  When a paint or ink is deposited on a substrate, the vehicle  soivent(s) should evaporate
completely.  Toluene is only one of the vehicle solvents used by paint and ink manufacturers/'5
Total toluene consumption in paints and coatings has increased since-1980.  One explanation for
this increased consumption is that toluene is priced lower than other commonly used solvents like
ketones. and-esters.15

       In 1987, Paint and Allied Products facilities-were-composed of 1,123'companies operating
1,426 plants, two-thirds of which were located in ten states.  The 1987 Census of Manufactures
shows that the 504-ink manufacturing facilities in the United,States are owned,by 224 companies
in nineteen States and the District of Columbia.  Ward's Business Directory lists 364 paint and
allied products facilities in SIC 2851  with 1990 sales greater than $1,000,000.17 Ward's also lists
                                         5-19

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                                    TABLE 5-4.
    ESTIMATED CONSUMPTION OF TOLUENE DERIVATIVES IN
                        PAINTS AND COATINGS, 1988

Derivative
Solvent
Toluene Diisocyanate
Benzyl Chloride
Benzoic Acid
Other3
Total Toluene
Millions of Kilograms (Millions of Pounds)
Derivative
Production from
Toluene
-
329 (725)
29 (63)
91 (200)
-

Toluene
Consumption
636 (1,400)
227 (500)
23 (50)
76 (168)
278 (612)
1,241 (2,730)
Derivative
Consumed in
Paints and
Coatings
287 (635)
9 (20)
1 (2)
3 (7)
16 (35)

Toluene Equivalents
for Paints and
Coatings
287 (635)
6 (14)
1 (2)
3 (6)
11 (25)
310 (682)
     Includes  TNT, vinyl toluene,  cresols, benzaldehyde, toluene sulfonic acids, toluene
     sulfonates, benzotin chloride, toluene diamine (other than the amount consumed for
     TDI), nitrotpluenes, chlorotoluenes, p-tert-butyl benzoic acid, toluene sulfonyl chloride,
     and as a denaturant. Excludes fuel use and benzene/xylenes production.

  Source: Reference 15
56 ink'manufacturing facilities in SIC 2393 with 1990 sales greater than $1,000,000. These lists
are. provided, in. Appendix B, Table B-1 and 'Table B-2,


      One method used to categorize the-products of the paint manufacturing .industry is by end-
user(e?.g:,. markets' served).  The-use-categories:. are: architectural coatings, product, coatings for

original equipment manufacturers (OEM), and special purpose coatings.  A summary of toluene
consumption in the paint use divisions by use category and subcategory is found, in Table 5-5.

No toluene was consumed, in-architectural coatings in 1988 or 1989. Toluene-is commonly used

in OEM product coatings such as those for wood furniture andfixtures, containers and closures,
automotive finishes,. and machinery and equipment.15
                                       5-21

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                     TABLE 5-5.
ESTIMATED CONSUMPTION OF SOLVENTS IN PAINTS AND
               COATINGS, BY MARKET
ft
Product Finishes
Wood Furniture and
Finishes
Wood Flat Stock
Metal Furniture and
Fixtures
Containers and Closures
Sheet, Strip and Coil
Major Appliances
Other Appliances
Automotive
Topcoat
Primer
Underbody Components
and Parts
Trucks and Buses
Railroad
Other TransDortarion
Machinery and Equipment
Electrical Insulation
Paper, Foil, and Film
Other Product Finishes
PRODUCT-OEM TOTAL
Total Solvents
Millions of Kilograms
(Millions of Pounds)
1988
127 (280)
3 (7)
39 (85)
86 (189)
32 (71)
19 (41)
10 (23)
_
28 (61)
16 (35)
16 (35)
16 (35)
4 (8)
6 (13)
70 (155)
27 (59)
18 ' (40)
116 (255)
633 (1.392)
1989
123 (270)
3 (6)
39 (85)
87 (191)
32 (71)
19 (41)
10 (23)
_
28 (61)
16 (35)
16 (35)
15 (33)
3 (7)
6 (13)
72 C159)
27 (59)
18 (40)
116 (256)
635 (1.398)
Total Toluene
Millions of Kilograms
(Millions of Pounds)
1988
33.7 (74.1)
0.4 (0.8)
3.8 (8.3)
10.4 . (22.8)
2.6 (5.8)
1.5 (3.3)
1.2 (2.7)
—
4.5 (10.0)
2.5 (5.6)
2.0 (4.5)
1.8 (3.9)
0.9 (2.0)
l.l (2.4)
7.9 (17.3)
—
2.6 (5.8)
11.4 (25.0)
37.7 (193)
1989
32.5 (71.5)
0.3 (0.6)
3.8 (8.3)
10.4 (22.9) *
2.6 (5.8)
1.5 (3.3)
1.2 (2.7)
—
4.5 (10.0)
2.5 (5.6)
2.0 (4.5)
1.7 (3.7)
0.8 (1.7)
LI (2.4)
8.0 (17.7)
__
2.6 (5.8)
11.4 (25.0)
87.3 (1921
                      (continued)
                       5-22

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                         TABLE 5-5.
  ESTIMATED CONSUMPTION OF SOLVENTS IN PAINTS AND
             COATINGS, BY MARKET (Continued)

Special Purpose Coatings
Maintenance ,
Marine
Pleasure
Commercial and
• Maintenance
Auto Refinishing
Traffic Paints
Aerosol
Other
TOTAL
SPECIAL PURPOSE
TOTAL
THINNER AND MISC.
TOTAL
PAINTS AND
COATINGS
Total Solvent
Millions of Kilograms
(Millions of Pounds)
1988
54 (118)
_
1 (3)
15 (33)
74 (162)
59 (130)
42 (93)
53 (117)
298 (656)
488 (1,073)
1,975 (4,345)
1989
59 (121)
—
1 (2)
15 (33)
74 (162)
59 (ISO)
42 (93)
54 (118)
300 (659)
764 (1,982)
1,977 (4,349)
Total Toluene
Millions of Kilograms
(Millions of Pounds)
1988
10.5 (23.1)
• •«• «
« —
2.0 (4.4)
9J (21.0)
. 28.3 (62.3)
6.2 (13.7)
5.5 (12.1)
62.0 (136.6)
138.6 (305)
288.6 (635)
1989
10.9 (23.9)
-
--
2.0 (4.4)
9.5 (21.0)
283 (62.3)
. 6.2 (13.7)
5.5 (12.2)
62.4 (137.5)
141.4 (311)
290.0 (640)
Note: Totals may not add due to rounding.
Source: Reference 15
                           5-23

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        No specific information was available relating the amount of toluene consumed in inks.
 However, toluene (and other organic solvents) are most often used in inks that employ a solvent
 carrier such as flexographic and rotogravure inks.  The other two  primary ink classifications,
 letterpress, and lithographic and offset inks, are of an oil or paste base.16

 5.7.1  Process Description

        Paint and ink facilities use similar manufacturing processes to produce  their respective
 products in batch scale production fashion. Most small plants (e.g., facilities employing less than
 20 people) produce paint in 40 to 2,000 liter (10 to 500 gallon) batches, while larger facilities
 produce paint in 800 to 11,000 liter (200 to 3,000 gallon) batches with stock items made in
 40,000 liter (10,000 gallon) runs.  Inks  are produced in ^batches ranging from  4 liters to over
 4,000 liters  (1 to 1000 gallons).15

        In most cases, manufacturing facilities purchase raw materials (e.g., pigments,  solvents,
 resins,  and  other additives) and  then formulate, or blend, a finished product.   Normally, no
 chemical  reactions take place during the process. Batch process production of paint and  ink
 involves four major steps:

 *      preassembly and premix
 •      pigment grinding/milling
       product finishing/blending
       product filling/packaging

 The manufacturing process is summarized, in: Figure 5-5.16

       The first step in the manufacturing process is preassembly and premix. In this  step,  the
 liquid raw materials (e.g., resins, solvents,,oils,  alcohols,.and/or water) are-"assembled" and
mixed in containers to form a viscous material to which pigments are added. The premix  stage
results in the formation of an intermediate product which  is referred  to as the base or mill, base.
                                          5-24

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5-25

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 With further processing, this base with high pigment concentration may become any one of a
 variety of specific end products.16

    .   The incorporation of the pigment into the paint or ink vehicle to yield a fine particle
 dispersion is referred to as pigment grinding or milling. The goal of pigment grinding is to
 achieve fine, uniformly-ground, smooth, round pigment particles which are permanently separated
 from other pigment  particles.  The degree  to  which this is realized determines the coating
 effectiveness and permanency of the paint or ink. Some of the more commonly used types of
 dispersion (milling) equipment are roller mills, ball and pebble mills, attritors, sand mills, bead
 and shot mills, high-speed stone and colloid mills, high-speed disk dispersers, impingement mills,
 and horizontal media mills.16
                                                     \»
       Final product  specifications are achieved in the product finishing step which consists of
 three intermediate stages: thinning,  tinting and blending.  Material letdown, or thinning, is the
 process by which a completed mill base dispersion is let down or reduced with solvent and/or
 binder to give a coating which is designed to provide a durable, serviceable film that is easily
 applied to the substrate. Tinting is  the process of adjusting the color of completed mill base
 dispersions.  Various combinations  of pigments, solvents, resins,  and  pastes are added to  the
 material  to meet the color requirements.  Blending is the process of incorporating the additions
 into the material in order to meet the desired product specifications.16

       The final  step in paint and ink manufacturing is product  filling operations.  After  the
 material  has been blended,  it is transferred from the blend tanks into containers for product
 shipment.  The transfer step normally involves product ^ filtration.16

 5.7.2  Emissions

       The primary factors affecting  the^ emission of toluene are the-types of solvents and resins
used in the manufacturing process, the temperature at which these compounds are mixed, and the
methods  and materials used  during cleanup operations.16
                                          5-26

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       Toluene is released from- several types of equipment and handling operations throughout
 the paint and ink manufacturing process and during cleanup operations.  During the preassembly
 and premix stage, emissions may come from equipment such as mix tanks or drums while resins
 are being thinned and materials are being added.  Toluene emissions also occur during the
 pigment grinding step when materials are added to the dispersion equipment The emissions that
 occur during  the product finishing step are mainly a result of material additions during the
 thinning and tinting stages.  Toluene emissions from product filling operations occur during
 material transfer and free-fall into the receiving container. Another emission source is product
 filtering.  As product flows, through a filtering device, it is often exposed to the air, resulting in
 releases  of  the incorporated toluene.  Toluene  emissions during filling operations result from
 product free-fall ancTmaterial splashing.  Fugitive emissions also result from flanges, valves, and
 pumps used to transfer material from equipment for one manufacturing stage to equipment for
 the next  stage.16 Emissions occurring'during-the manufacturing stages may be reduced by using
 equipment and process modifications such as tank lids or closed-system milling  equipment.

       In addition to emissions from process operations, toluene is also released from a variety
 of cleaning  operations following  the manufacture of solvent based products.  In many facilities,
 manufacturing  equipment is cleaned manually (with  solvents, brushes, and /or rags) on  the
 production,floor on an, as-needed-basis..  The standard, method of cleaning  .grinding eauipment
 involves  emptying the mill of product and then adding solvent to the vessel to capture remaining
 product residue. Emissions occur during.cleaning solvent addition and removal as well as during
 the cleaning process/6  Emissions from-cleaning, equipment'may be-reduced  by using ruober
 wipers, high-pressure spray heads, Or automatic tub washers.16

       There is little emission factor-information available-for the manufacmre.-of paints and inks.
 Estimates range-from: process, solvent:  losses • of one: to  nvo percent under  well controlled.
conditions to much higher percentages.  The process solvent losses vary significantly from facility
 to:facility, and therefore, chose emissions should be.evaluated: on:a.case-by-case-basis.- Many
paint and ink manufacturing facilities calculate total plant VOC emissions based on raw material
consumption, rather than calculating emissions  from processes or equipment by  an alternative
                                         5-27

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 method.   Total emissions  therefore reflect solvent losses  during manufacturing, cleaning
 operations, and storage.16

 5.8 SOLVENT CLEANING OPERATIONS

        Surface cleaning or degreasing operations include  solvent cleaning  or conditioning of
 metal surfaces  and parts,  fabricated plastics, electronic and electrical  components  and other
 nonporous substrates.  These cleaning processes .are designed to remove foreign materials, such
 as grease,  waxes,  and moisture in  preparation for  further  treatment  such  as painting,
 electroplating, galvanizing, anodizing or applying conversion coatings.
         _n
        The three categories  of solvent cleaning operations are cold cleaning, open-top vapor
 degreasing, and conveyorized degreasing which  can employ either cold  cleaning or vapor
 degreasing as its major cleaning process.  When toluene is  used, it is typically in cold cleaning
 operations.

 5.8.1 Process Description
       Cold cleaning  is a  batch  process  operation in which solvents  are  applied at room
temperature or slightly above room temperature, but always below the solvent's boiling point.
The mechanical or industrial parts or tools  to be cleaned axe placed in a basket inside the coid
cleaner and immersed in the solvent. Parts  too large for immersion may be sprayed or- brushed.
The solvent tank is often-agitated to enhance its cleaning action.  After cleaning, the pans are
removed from the tank and allowed to dry.

       Cold cleaners are usually the-simplest-and least expensive-of "the. three types of solvent
cleaners. The two basic types of cold cleaners are maintenance cold cleaners and manufacturing
coid cleaners.13 Maintenance cold cleaners are normally-simpler, less expensive, and smaller than
manufacturing  cold  cleaners.  They  are used  primarily for automotive  and general plant
maintenance cleaning.  Manufacturing cold cleaners are  larger, more specialized cleaners which
perform a higher quality of cleaning than maintenance cleaners.19 Coid cleaners may incorporate

                                          5-28

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 covers and freeboards to limit the evaporative loss of solvents.  Freeboard is the distance between
 the solvent level and the top edge of the unit.18

 5.8.2  Emissions
       Cold cleaning can result in both direct and indirect atmospheric emissions of toluene.
 Cold .cleaners are estimated to result in the largest total emissions of the three types of solvent
 cleaners, primarily due to the large numbers of these units and the high degree of evaporative
 losses:  Emissions from cold cleaners can occur through bath evaporation, solvent carry-out,
 solvejit agitation, waste solvent evaporation, and  spray evaporation.  These typical sources of
 emissions from cold cleaners are discussed below.19-20

       Bath evaporation from  cold cleaners  is simply evaporation from an uncovered  solvent
 tank. This  form of solvent loss can be reduced by covering the tank with a lid, increasing the
 freeboard height  of the tank  over  the  level of  the solvent,  and decreasing the amount of
 ventilation over an uncovered  tank.  Of these options, covering an open tank with a lid will
 usually render bath evaporation insignificant.  Bath evaporation accounts for approximately
 20 percent of the total organic  emissions from cold cleaners.18  Solvent carry-out emissions are
 due to evaporation of the solvent residue from the-part that was cleaned. Several factors regulate
 the amount  of emissions from carry-out sources.  Porous or absorbent materials (cloth, leather,
 wood) absorb the solvent and keep it retained for,extended periods of time.  The size of the load
 to be cleaned  must be..manageable in order to keep the-solvent from splashing our of the
degreasing unit. Proper drainage racks or shelves need to be employed to provide a place where
 the-:parts can dry off.  It is recommended that all  cold cleaned  parts dry for a minimum of  15
seconds while:in_the-drainage-faciJity.i9-2a

       Emissions from the agitation of the solvent depends on use of the cover, agitation system
adjustments, and  volatility of the solvent.. If the-.cover is kept closed,, then usually emissions
from agitation are kept low; however, when the tank is left open, emissions due to agitation  of
the  solvent increase dramatically.  Poor adjustment of the agitation  system, especially  the, air
flow, may lead to increased emissions.

                                          5-29

-------
        Waste solvent evaporation is the largest source of atmospheric emissions  from cold
  cleaners, accounting for between 50 and 75 percent of the total organic emissions.18  The degree
  of evaporation depends  on the size of the cold cleaner, the frequency of disposal, and the
  method(s) of disposal. If the cold cleaning removes large amounts of contaminants, or the parts
  require a high degree of cleanliness, then the solvent will need replacement more often and
  emissions will generaUy be greater. Disposal methods also influence the degree of evaporation
  from the waste solvent Some acceptable methods include proper incineration, distillation, and
  chemical landfilling, and emissions from these methods will vary depending on environmental
  and operational factors. Some disposal methods will  result in total release of the waste solvent
  into the atmosphere. These methods include flushing  the waste solvent into sewers or bodies of
  water, spreading  the  waste  solvent for  dust control, land-farming,  and landfilling  where  the
  solvent can easily leach into the soil  or evaporate into the- air.

        Evaporative  emissions  from  spraying the solvent over the part to be cleaned vary
 depending on the pressure of the spray, the fineness of the spray, and the tendency of the solvent
 to splash and overspray out of the  tank.  Evaporation is also increased when the spray is used
 continuously and  when the solvents are highly volatile.  GeneraUy, however, emissions from
 spray evaporation can be prevented through careful operation and equipment design.19-20

•5.9    OTHER SOLVENT USES

        In addition to-the previously discussed solvent,end uses, toluene is used  either alone or
 as a component of a multi-solvent system, in adhesives, rubbers, photographic film, agricultural
 sprays, and  other  chemical derivatives.    Available,  emission  factors  for some  of these
 miscellaneous  uses are included in Table 5-6.,
                                          5-30

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                        TABLE 5-6.
 EMISSIONS FROM MISCELLANEOUS SOURCES OF TOLUENE
Process
Neoprene Manufacture
Potential Source
Blend Tank
Solution Makeup Tank
Batch Polykettie
Stripper
Wash Belts
Dryer Exhaust
Emission Factor
0.05 g/kg neoprene
0.04 g/kg neoprene
0.018 g/kg neoprene
0.019 g/kg neoprene
0.015 g/kg neoprene
2.0 g/kg neoprene ,
Quality
Rating
E
E
E
E
E
E
Source: Reference 21
                          5-31

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5.10   REFERENCES FOR SECTION 5.0

1.     SRI International.  Chemical Economics Handbook.  Menlo Park, CA.  1991.

2.     Benzene Chemical Product Synopsis, Mannsville Chemical Products Corp., Asbury Park
       NJ. March 1992.

3.     U.S.  Environmental Protection Agency. Locating and. Estimating Air Emissions from
       Sources of Benzene, EPA-450/4-84-007q. Office of Air Quality Planning and Standards.
       Research Triangle Park, NC. 1988.

4.     Toluene Chemical Product Synopsis,  Mannsville Chemical Products Corp., Asbury Park
   •   NJ. March  1990.
5.
6.
7.
8.
9.
10..
  Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edition. Toluene.  Volume 23.
  John Wiley and Sons. New York, NY.  pp. 246-273. 1983.
                                              V-

  U.S. Environmental Protection Agency. Air Pollutant Emission Factors - A Compilation
.  for Selected Air Toxic Compounds and Sources, EPA-450/2-88-006a.   Office of Air
  Quality Planning and Standards. Research Triangle Park, NC.  1988.

  International Programme on  Chemical  Safety.  Environmental Health Criteria  75:
  Toluene Diisocyanates. World Health Organization.  Geneva. 1987.

  U.S. Environmental Protection Agency. Organic Chemical Manufacturing.  Volume 7:
  Selected Processes, Report 4: Toluene Diisocyanate, EPA-450/3-80-028b.  Office of Air
  Quality Planning. and Standards.  Research Triangle Park, NC. 1980.

  Toluene Diisocyanate Chemical Product Synopsis, Mannsville Chemical Products Corp.,
  Asbury Park, NJ.  October 1990.

  Hancock, E.G., ed., Toluene, the Xyienes: and- their- Industrial Derivatives.  Elsevier
  Scientific Publishing Company. New York, NY.  1982.
11.    Lowenheim, Fredrick A. and Moran, Marguerite/K., Faith, Keyes, and Clark's Industrial
12:
13.
14.

         emicals. Fourth. Edition.  1975.
  U.S., Environmental Protection Agency. , Compilation of Air Pollution- Emission Factors.
  AP-42; Fourth Edition' and Supplements. Office -of Air Quality Planning and Standards
  Research Triangle Park, NC. 1985.

  Benzole Acid Chemical Product Synopsis, Mannsville Chemical Products Corp., Asbury
  Park, NJ., March 1990.

  Benzyl Chloride Chemical Product Synopsis, Mannsville Chemical Products Corp  As bury
  Park, NJ,  January- 1990.


                                   5-32

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 15.


 16.



 17.


 18.


 19.



20.



21.
 SRI International.  U.S. Paint Industry Database.  Prepared for the National Paint and
 Coatings Association. Washington D.C.  1990.

 U.S. Environmental Protection Agency. Control ofVOC Emissions from Ink and Paint
 Manufacturing Processes, EPA-450/3-92-013.   Office  of Air Quality Planning  and
 Standards. Research Triangle Park, NC.  1991.

 Gale Research, Inc. Ward's Business Directory ofU.S. Private and Public Companies-
 1992, Volume 4.  Detroit, MI.  1991.

 U.S.  Environmental Protection  Agency.  Organic Solvent Cleaners  -  Background
 Information on Proposed Standards, EPA-450/2-78-045a. 1979.

 U.S. Environmental Protection Agency.  Control of Volatile Organic Emissions from
 Solvent Metal  Cleaning, EPA-450/2-77-022.   Office of Air  Quality Planning arid
 Standards.  Research Triangle Park, NC.  1977.
                                             N« •.                             •
 U.S. Environmental Protection Agency. • Alternative  Control Technology Document -
Halogenated Solvent Cleaners, EPA-450/3-89-030.  Office of Air Quality Planning and
 Standards.  Research Triangle Park, NC.  August 1989.

 U.S. Environmental Protection Agency. Source Assessment: Polychloroprene, State of the
Art, EPA-600/2-77-1070. Industrial Environmental Research Laboratory. Cincinnati OH
 1977.
                                        5-33

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                                     SECTION 6.0
        EMISSIONS FROM THE USE OF TOLUENE-CONTAINING MATERIALS

       As discussed in Section 3.0, toluene is present in many materials, including paints and
 coatings, inks, adhesives, resins, Pharmaceuticals, gasoline and other formulated products using
 a solvent  carrier. This section examines residual emissions from the use of toluene-containing
 materials.  Toluene may be emitted when toluene-containing products such as paint, ink and
 gasoline release small amounts over time.  Such releases are described in this section as residual
 emissions.

       The production  descriptions and emissions data presented in this section represent the
 most common and relevant processes and products.  Because of toluene's widespread use, all
 processes  cannot be included in this document

 6.1    SURFACE COATING OPERATIONS

       Surface coating operations involve the application of paint, varnish, lacquer or primer for
 decorative, functional, or protective purposes.   In 1989, 290 million kilograms (640 million
 pounds) of,toluene were consumed, in paints and coatings.1 Consumption of toluene in specific
 end-use markets was presented in Section 5.7, Table 5-5.  Appendix C contains a listing of some
 of the surface-coating, source-, categories-in. which, toluene: is used: Appendix C also indicates
 associated-SIC codes, potential toluene emission points,, and emissions reduction opportunities.
References are provided for additional information.

      The--general--application, methods-ton surface:, coating : operations* are'-discussed" below.
 Because-surf ace-coating is a very broad': category, detailed process-descriptions and process .flow'
diagrams for each category are not included in this document; however, the reader is encouraged
to review-the. references mentioned, at.the end of: this section and,in Appendix C.
                                         6-1

-------
 6.1.1   Process Description.

        Industrial surface coating operations use several different methods to apply coatings to
 substrates^ Some of the more commonly used techniques include spraying, dipping, rolling, flow
 coating, knife coating, and brushing.  Li addition to the application of coatings to substrates,
 many surface coating operations also include surface preparation  steps (e.g., cleaning and
 degreasing), drying and curing stages.  Spraying operations are normally performed in a spray
 booth using one of the following spray application methods:  air atomization, airless atomization,
 air-assisted airless, high-volume, low-pressure (HVLP), and electrostatic methods. Dip coating
 involves briefly immersing the substrate in a tank containing a bath of paint.  The object is
 slowly removed from the tank allowing excess paint to drain back into the tank. Roller coating
                                                      X'
 is used to .apply coatings and inks to  flat surfaces.  A typical roUer coating machine contains
 three or more power driven rollers, one of which is partially immersed in the coating material.
 The paint is transferred to a second, parallel roller by direct contact.  The sheet to be coated is
 run  between the  second and third rollers, and is coated by  transfer  of paint from the second
 roller. Flow coating is used on articles which cannot be dipped due to their buoyancy, such as
 fuel oil tanks, gas  cylinders, or pressure  bottles.  In this operation the coating material is fed
 through overhead nozzles which causes the paint to flow in a steady stream over the article to
 be coated.  Excess  paint is allowed to drain, from the coated,object and is then recycled.  Knife
 coating is used primarily to coat paper or fabric webs. The adjustable blade or "knife" distributes
 a liquid coating evenly over a moving surface.

 6.1.2  Emissions2'3
       Figure:6-i is a.generic-schematic-fibw diagram-of.a;.surface:.coaring'operation.  Process
operations, auxiliary facilities, and, emission  points are  illustrated.  Note that, this,is a generic
figure and may differ significantly from any specific coating operation.  The  operations shown
include degreasing, surface  coating,  and drying  and curing.   Auxiliary  facilities  include
degreasing solvent  storage, and surface- coating storage-. and blending.   Industrial categories,
specific operations  and-emission points. resulting in expected, toluene-emissions from, surface
coating operations are presented in Appendix A and in Appendix C.

                                           6-2,

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        Streams 1, 2, 3, 4 depict the flow of products through the plant.  Stream 1 represents the
 input of uncoated products to the surface coating system.  Stream 2 represents the flow of
 degreased or scoured products to the surface coating operation.  The type of surface coating
 operation used will depend upon the product-type coated, coating requirements, and the method
 of application.  Stream 3 represents the product flow to the drying and curing operation.  Stream
 4 represents the flow of coated finished products from the  surface coating section of a
 manufacturing  plant

        Streams 5 through 10 represent the flow of degreasing solvent through the surface coating
 section of a manufacturing plant  Streams 5 and 6 depict the flow of solvent into the plant and
.to the degreasing unit  Streams 7 and 8 represent the flowsof solvent vapors from the degreasing
 unit through the fume handling system.  Uncontrolled and controlled emissions are represented
 by streams 9 and 10, respectively.
                                             e
       Streams 11 through 21 represent the flow of surface coating raw materials through the
 plant  Streams 11, 12, 13, and 14 represent the flow of solvent, pigment, resin, and additives to
 the surface coating blending tank.  Stream 15 is the flow of coating  to the surface coating unit.
 For those operations that use spray painting, stream 16 is the-flow of compressed air/ Streams
 18 and 19 represent the flow of solvent and resin from the surface coating unit through the fume
 handling equipment. Uncontrolled and controlled emissions are depicted by streams 20 and 21.
 Potential release sources  are identified in Appendix C,
                                                                     1
       In Figure-6-L streams 22 through 25 represent the flow of gases (e.g.,  fuel,  steam or
 electrically heated, air) to the:drying-and, curing operation.  Drying and. curing,operations  occur
 in flash-off areas and curing ovens.  Flash-off areas are the places between application areas, or
 between an application area and an  oven, in which  solvent is allowed to volatilize from the
 coated piece. Ovens are  used between some coating  steps'to cure the coating prior to. the next
 step  in the finishing  sequence.  Streams  24 and 25 represent uncontrolled  and controlled
 emissions.  No  emission factor data were found in the literature.
                                          6-4

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       Facilities with surface coating operations may purchase and apply ready-to-use coatings,
 or  they  may  dilute their purchased coatings  to  decrease the coating viscosity and  improve
 performance and ease of application.  Toluene is used in solvent based coating formulations
 either as part of the coating vehicle or as a thinner. If a coating formulation is to be diluted in-
 house, several factors (e.g.,  temperature, humidity,  and type of coating) can determine the
 required dilution ratio. Consequently, the amount of toluene used may vary ,2*4'6  Emissions from
 the mixing and blending of surface coatings are discussed in Section 5.7.2.

       Toluene  may also be used in clean-up operations.  Clean-up solvent is used  to clean
 application equipment, piping, spray booths, coating storage and distribution equipment, and to
 strip cured coatings from wood parts or machinery.1
                                                    x»
                                                    •y-

       One method of reducing toluene emissions from surface coating operations is to modify
 the surface coating  formulation.  Conventional coatings normally contain at least 70 percent by
 volume solvent (either one solvent  or a mixture of solvents) to permit easy handling  and
 application. Minimizing or eliminating the use of these solvents in surface coating formulations
 is the most effective way to reduce VOC emissions. Alternatives to these conventional coatings
 include water-based coatings, high-solids  coatings,  powder  coatings, and  radiation  curable
 coatings.2

       Large surface-coating facilities  may use-add-on control devices to  capture and control
 solvent emissions.  Some-commonly used-.capture-devices include  covers, vents, hoods,  and
 partial or total enclosures.  Adsorbers, condensers and incinerators, with control efficiencies of
 95 to 98'percent are the most common control devices used in surface coating operations."4'5

 6.2- PRINTING AND. PUBLISHING..
       The printing and publishing-industry encompasses publishing, commercial printing, and
trade services.7  The trade services group includes typesetting, photoengraving, electrotypine and
stereotyping,, and platemaldng services.  The- trade  services group is not; examined in this
document because data, on solvent, use and emissions from these services are not available. Ink
                                          6-5

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 consumption in these groups has been apportioned to the four printing processes according to the
 type of ink consumed (e.g., gravure ink consumption assigned to gravure printing).  Process
 descriptions, however, will only be provided for the commercial printing processes.  Attention
 is given to the gravure and flexographic processes  as end uses of toluene.  Toluene emissions
 from off-set lithography processes have not been measured and are thought to be minimal.  The
 reader is encouraged  to explore toluene consumption and emissions in all facilities reporting
 under the SIC code 27 as solvent use is an inherent aspect of the operations in printing and
 publishing facilities.

        The publishing and printing groups are concentrated in four States, California, New York,
 Pennsylvania,  and Illinois.   The majority of establishments are small facilities  that employ
 between 1 and 20 people.7'8 Appendix B, Table B-3 presents the companies in the printing and
 publishing SIC codes grossing $1,000,000 or greater in annual sales.9

 6.2.1  Process Description

       The production of a printed product consists of five steps.  First, the artwork and/or copy
 (text)  is developed.  Next, a printing plate is made.  The plate is then  tested in the  press
 adjustment step.  The actual printing of the product is the second to the. last step  in the printing
 process, and the main source of toluene emissions.  The final step is cutting and finishing10.

       Printing ink composition varies among printing methods as.well as among jobs using the
 same printing press and method. Printing inks in general can be described as heat-set or non-
 heatser.  Heatset inks require the application of heat  to drive off the ink  solvent, and set the ink
 10 the  substrate.  Non-heatset: inks dry by oxidation: or adsorption to  the- substrate: and. do not
 require heat. Other, less common;  ink, cypes  include radiation and thermally cured inks.  All
evaporative inks consist of three basic components: pigments, binders, and solvents.2  Printing
processes using heatset inks that dry• through evaporation  of-the solvent are the major concern
for VOC (including toluene) emissions.  Only the gravure and flexography printing processes are
described here because specific emissions of toluene  were  not identified.from the  other printing.
methods.
                                          6-6

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 Gravure Printing Process Description—
        The configuration of the image surface makes the gravure process unique.  The printing
 cylinder is etched or engraved, creating tiny cells which comprise the image surface. The depth
 of each cell may vary and regulates the quantity of ink received by the substrate.  The average
 rotogravure press has eight printing units, each printing one color.  The paper position, speed,
 and tension through the printing unit is regulated by  a series of rollers.  A substrate dryer,
 equipped with heated air jets  to evaporate the solvent  from the  substrate and set the ink, is
 located  at the top  of each printing  unit.   The  dryer  air is exhausted from the unit by  a
 recirculation fan. The fan directs a portion of the solvent laden air to a control device, such as
 a carbon adsorption system.  The remaining portion of the air flow is recirculated over a steam
 heating coil and  back through the dryer.11
                                                     N»
                                                      X*
    •   Each printing unit has a self-contained inking system. The ink system consists of an ink
 fountain, a circulation pump, and a mix tank.  Solvent, and occasionally extenders or varnishes,
 are added to  the ink concentrate in  the mix tank.  Additional ink,  solvent, varnishes, and
 extenders are  automatically added to the mix tank.  The additions are monitored by level and
 viscosity control  devices.11

       A low viscosity ink is required for the gravure printing process... Raw ink concentrate
 generally contains 50 percent solvent by  volume.  The two most  commonly used  solvents in
 gravure printing and inks are toluene and a^xyiene-toiuene-lactoi spirit mixture (naphtha). Lactol
 Spirit is a petroleum, solvent component, of naphtha used  in mixture to hasten evaporation.
 Toluene  is known to  produce a higher  quality product and dissolves the ink resins well.
 However, toluene has a. limited.supply and is more expensive-than naphtha. The ink concentrate
is diluted at press .side with; additional, solvent at: a volume  ratio of approximately  1:1.  Since
solvent is also added, automatically to. the: inking- system to replace  evaporative  losses, the
resultant ink mixture may contain as much as 80 percent solvent by volume and 20  percent by
volume inland varnish solids.11
                                          6-7

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 Hexographic Printing Process Description--
        Flexographic printing is used to print flexible packaging, milk cartons, gift wraps, folding
 cartons, paperboard, paper cups and plates, and labels, tapes, and envelopes.  The majority of
 flexographic printing is done with a web-fed substrate.2
                                                                     x   *
        Solvent-based  flexographic  inks   typically   consist of  alcohols,   glycols,  esters,
 hydrocarbons, and ethers.  These inks may contain as much as 75 percent solvent by volume.
'Water-based and steam-set inks are also used in flexographic printing. Water-based inks contain
 approximately 25 percent by volume solvents.12  About 15 percent of all flexographic inks used
 are water-based.13  Steam-set inks use glycol solvents but do not contribute significantly to air
 emissions.
          14
 6.2.2  Emissions
 Gravure Printing Emission Points-
       Emissions from the rotogravure press occur from the ink fountain, the press, the dryer,
 and the chill rolls.2 The' dryer vent is the most typical point of control.  The  other emission
 sources are considered fugitive.  Emissions are influenced by press and job variables,  solvent
 concentration in  the ink, and solvent added as make-up during printing.  Approximately 2.5
 percent to 7 percent of the solvents used are retained in the printed product   The remaining
 solvents are reclaimed for reuse, recycled, and sold back  to  suppliers, or lost as  fugitive
 emissions.IUS'16 Typical ink formulations contain approximately 50 percent to 35 percent solvents
 by volume. Water  based inks, used in packaging and product printing, contain approximately 5
 percent to 30 percent solvents by volume and account for 30 percent to 40 percent of all inks
 used.  Water-iased inks; account for approximately 15 percent, of all inks used in all. gravure
 printing processes
£3.17
       Although specific emission estimates  of toluene  are  not available,  ink  and solvent
consumption numbers have been published and are reported below. Additionally, VOC emission
factors and rates are available.  A local survey may provide the needed information ©n the
percentage of toluene used relative to total solvent consumption.  Toluene emissions may then
                                          6-8

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 be estimated by multiplying the percentage of toluene by the ink consumption rate and solvent
 content of the ink.

        The Gravure Association of America (GAA) conducted a survey of their membership
 which reported solvent purchased, reused, and recovered in the various segments of the industry
 during 1987.18  Table 6-1 presents a summary of these statistics for publication, folding cartons,
 flexible packaging, and  product gravure printing.  The GAA membership  reported a total of
 41.4 million pounds of virgin solvent purchased, 246.2 million pounds of solvent recovered, and
 179.3  million pounds of solvent reused.  More solvent is recovered than bought due to solvent
 recovery from ink formulations. The portion of solvent that is recovered but not reused is sold
 back to the manufacturers, lost as fugitive emissions, or destroyed by incineration.  Projected to
 the  entire  gravure industry, these figures total 622.3  million pounds  of solvent purchased or
 reused, and 606.7 million  pounds  of solvent recovered.   The GAA projected total gravure
 publication plants' solvent consumption and fate based upon the percentage (by sales) of this
 segment responding to the survey.18  EPA projected solvent consumption and fate  for the folding
 carton and flexible packaging  segments based upon the same principle. The estimated ratio of
 solvent recovered to ink consumed for the publication segment of the industry was 73 percent.18

       Carbon adsorption and  incineration systems have  traditionally been employed co conrroi
 VOC emissions from the gravure printing process. The package printing sector has also achieved
 significant VOC reduction through the use of water-based printing inks.

       Rotogravure package printing plants may use water-based inks.  The use of water-based
1
 inks may contribute to an overall VOC'reduction of 65 to 75 percent, if the solvent content of
 the,inks is  maintained, below 25'percent.by volume.12

       One recent study has  demonstrated that  capture  and control systems have  been
 successfully applied to gravure  printing presses that achieve greater than 90 percent overall. VOC-
 control.19 The average VOC control efficiency at these facilities ranged from 94 to 99.5 percent
                                          6-9

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                                  TABLE 6-1.
          GRAVURE ASSOCIATION OF AMERICA INDUSTRY
                            SURVEY RESULTS
        MILLIONS OF KILOGRAMS (MILLIONS OF POUNDS)

Printing Process
Publication Plants
Folding Cartons '
Flexible Packaging
Product Gravure
Reported Results
Solvents Purchased
1 (2.2)
2.9 (6.4)
7.2 (15.9)
7.7 (16.9)
Solvents
Recovered
101.3 (222.9)
0.7 (1.6)
2.8 (6.2)
. 7.0 (15.5)
Solvents Reused
73.8 (1623)
0.7 (1.6)
1.9 (4.1)
5.1 (11.3)
Projected Gravure Industry
Estimates
Solvents
Purchased or
Reused
182.3 (401)
22.2 (48.8)
78.4 (172.5)
-
Solvents
Recovered
247.1 (543.6)
4.4 (9.7)
24.3 (53.4)
-
  aSurvey results scaled up to make projections for industry segments.
  Source: Reference 18
The facilities included in the study used total enclosure capture systems and one of the following
add-on destruction devices:
•     Catalytic Incineration
•     Regenerative Incineration
•     Thermal Incineration
•     Carbon Adsorption.
The Environmental Protection Agency (EPA) has developed and published standard criteria for
the design and operation of permanent total enclosure (PTE) systems.  The PTE criteria have
been published in the following sources:
      Guidelines for Developing a:Staie.Prorocol for the Measurement:, of Capmre Efficiency.
      Environmental Protection Agency. Policy Statement; April 16, 1990.
      Polymeric Coating of Supporting Substrates - Background Information for Promulgated
      Standards (EPA-450/3-85-022b)20
      Magnetic Tape Manufacturing  Industry - Background: Information for Promulgated
      Standards (EPA-450/3-85-029b)21
                                     6-10

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 Capture efficiency may be estimated at 100 percent if all the EPA PTE criteria are met.19

 Flexographic Printing Emission Points-
       Sources of emissions from flexographic printing operations are similar to the sources
 encountered from gravure operations. Emission control strategies are also similar.  Incineration
 and carbon adsorption emission control techniques  are available for use in the flexographic
 printing process.  However, it is often difficult to install effective hooding and ducting devices
 on the presses. Therefore, overall control efficiencies approximate only 60 percent.12 Alternative
 emission control techniques include the use of water-based inks and microwave driers.14

       Recent studies have indicated that flexographic printing presses controlled by catalytic and
 regenerative incineration may achieve a 95 percent overalfVOC reduction efficiency.13-22 A metal
 oxide catalyst is used  on flexographic printing presses to avoid poisoning  by chlorinated
 solvents.22
                                                                                      •
 6.3  GASOLINE AND AUTOMOTIVE EMISSIONS

       Aromatic hydrocarbons including toluene are added to gasoline to raise the octane rating,
 thereby suppressing engine knock, increasing power,.and;providing smoother running engines.
 Toluene and other hazardous components may then be emitted in automotive exhaust. One study
 estimates the global release rate of toluene from automobile  exhaust to be in the range of 3 to
 8 metric tons (6,600 to 17,600 pounds) per year.Z3  Automotive emissions  have been related to
photochemical smog and ozone formation for many years.  Atmospheric models recently became
 sophisticated enough, to accommodate-compositional, variations.2*'"

       One. recent, study involving automotive-emissions used 46 vehicles to provide detailed
composition of organic emissions under various driving conditions.24   Another study used  a
mobile-TAGA 6000  EM tandem, mass  spectrometer system to-obtain time resolved data for
selected aromatic compounds.25 Both of these studies present possible protocols to perform tests
that  would  better characterize emissions and  eventually  estimate  emissions of various VOC
                                         6-11

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 species, including1 toluene.  However, the information presented in these studies was not*
 sufficiently comprehensive for emission factor development

        Table 6-2 lists the existing emission factors for toluene as a result of gasoline use. These
                           *
 emission factors were based on engineering estimates and are therefore given a quality rating of
 "U."
                                       TABLE 6-2.
                 EMISSION FACTORS FROM GASOLINE USE
Emission Source
Evaporation from automobile
fuel tank
Automobile exhaust
Emission Factor
N»
2.22 x 10'5 Ib/vehicle mile traveled
(1.0 x 10'2 g/vehicle mile traveled)
8.46 x 104 Ib/vehicle mile traveled
(3.8 x 10'1 g/vehicle mile traveled)
Quality
Rating3
••••^•••^••MB
U
U
     "Based on engineering judgement. .
     Source: Reference 26
6.4  GASOLINE MARKETING

       Gasoline storage  and  distribution  activities represent  potential  sources  of toluene
emissions.  The toluene content of whole gasoline ranges from less than 1 to almost 16 percent
(premium gasoline) by weight, but typical concentrations  are around  15 percent by  weight.27
Therefore, totalhydrocarbon emissions resulting from storage tanks,.materiaLtransfer. and,vehicle
fueling include emissions of toluene. This section-describes sources of toluene emissions from
gasoline marketing operations.  Because the sources of these emissions are so widespread,
Individual locations are not identified in  this section:  Instead, emission "factors are presented,
along with a general discussion of the sources of these emissions.  The discussion is taken from
Reference 28.
                                        6-12

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        The transportation and marketing of petroleum liquids involve many distinct operations,
 each of which represents a potential source of toluene evaporative losses.  Crude petroleum
 products are  transported from production operations to a refinery by pipelines, water carriers
 (e.g.t  barges), tank trucks,  and rail tank  cars.  The  refined products  are conveyed to fuel
 marketing terminals and petrochemical industries by these same modes.  From fuel marketing
 terminals, the fuels are delivered by tank trucks to service stations, commercial accounts and
 local bulk storage plants.29

        As  shown in Figure 6-2, typical components of gasoline marketing include refinery
 storage, gasoline terminals, gasoline bulk plants, service stations, and ground transportation. The
 gasoline terminals and gasoline bulk plants are large facilities for the wholesale marketing  of
 gasoline, kerosene, and fuel oil. They receive these petroleum products from refineries or other
 terminals,  mostly by pipeline, tanker, or barge, and store the products  in large tanks.   The
 primary function of marine and pipeline terminals  is to  distribute products to other  terminals.
 Tank track loading terminals distribute products by tank trucks to  bulk plants, retail outlets  or
 final consumers. The typical bulk gasoline terminals have a daily throughput of 950,000 liters
 (250,000 gallons) of gasoline.28

        Service stations  receive gasoline* by tank truck from terminals or bulk plants or directly
 from refineries, and usually store the gasoline in.underground tanks.  Gasoline.service stations
 are establishments primarily selling- gasoline and automotive lubricants.

       Gasoline is by far the largest volume petroleum product marketed in the U.S., with a
 nationwide consumption of 419 billion- liters:(l 11. billion .gallons) in-199 L30 There are presently
 an; estimateda,700. bulk: terminals' storing: gasoiine-.in-the-U;s;31: A bout half; of these-terminals
 receive-products from refineries^by pipeline,  and half receive products by ship or barge delivery.
Most of the terminals (66 percent) are located,,along the east, coast-and in the Midwest.  The
remainder are  dispersed throughout the country, with locations largely determined by population
patterns..
                                          6-13

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       Ship, Rail, Barge
         Service.  Stations
                                Refinery Storage
                                       I
                                 Bulk Terminals
                                  Tank Trucks
                                Automobiles, Trucks
 Pipeline
                                                           Bulk Plants
                                                                T
                                                             Trucks.
                                                                I
                                                                T
Commercial',.
Rural: Users:
Figure 6-2.  The gasoline marketing distribution system in the United States22


                                     6-14

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       Evaporative emissions from the transportation and marketing of petroleum liquids may
 be separated, by storage equipment and mode of transportation used, into four categories.
       Rail tank cars, tank tracks and marine vessels:  loading, transit and ballasting losses
 •      Service stations:  bulk fuel drop losses and underground tank breathing losses
 •      Motor vehicle tanks:  refueling losses                                     -
 •      Large storage tanks:   breathing, working and standing storage losses
       The  emission  factors  presented  in  the following  discussions were  derived  from
 References 2, 28 and 32.   A recent EPA memorandum describing  speciated motor vehicle
 emissions  identified-diurnal, base  gasoline  evaporative organic  emissions  as  consisting of
 10.6 percent toluene. This reference defined  a base gasoiine (i.e., an industry average summer
 fuel) as having 32 percent arorhatics.32 Diurnal losses occur over a 24-hour period due to normal
 temperature changes. Although these losses refer to emissions from vehicles when the vehicle
 is stationary for an extended period with the engine switched off, the diurnal losses also approach
 the mechanisms that occur during  the loading, unloading, and storage of gasoline.33 To calculate
 an. emission factor for toluene, the 10.6  (0.106) percent toluene factor was applied to the VOC
 emission factors for evaporative emissions presented in EPA documents.2-28'32

 6.4.1   Toluene Emissions From Loading Marine Vessels

       Volatile organic  compounds (VOC) can  be: emitted  as  crude oil and refinery products
 (gasoiine, distiilaie  oil,  etc.) and are loaded and transported  by marine tankers and  barges.
 Loading losses are the primary, source of evaporative emissions from marine vessel operations.28
 These emissions occur as vapors  in "empty"  cargo, tanks, are expelled inio  the atmosphere as
 kquid:is added-, to'the.-cargo tank;. The-vapors: may'be-, composed of residual material left in the
 "empty" cargo tank and/or the material being added to the tank. Therefore,  the exact composition
 of the: vapors emitted during the loading process is difficult-to determine.,

      Assuming an  average  toluene/VOC ratio  of 0.106 (Reference 32), emission'factors for
toluene from marine vessel loading were calculated  and  are given in.Table 6-3.  Factors  are
                                         6-15

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                              TABLE 6-3.
    UNCONTROLLED VOLATILE ORGANIC COMPOUND AND
      TOLUENE EMISSIONS FROM LOADING GASOLINE IN
                         MARINE VESSELS
Emission Source
Ship/Ocean Barge:d
Uncleaned; volatile
previous cargo .
Ballasted; volatile
previous cargo
Cleaned; volatile
previous cargo
Gas-freed; -volatile
previous cargo
Any condition;
nonvolatile previous
cargo
Typical situation; any
cargo
Barge:d
Uncleaned; volatile
previous cargo
Gas-freed: any cargo
Typical situation; any
cargo
Volatile Organic
Compound Emission
Factor (mg/L
Transferred)"

315
205
180 .
X*
85
85
215

465
245
410
Toluene
Emission
Factor (mg/L
Transferred)11

33.4
21.7
19.1
9.0
9.0
22.8

49.3
25.9
43.5
Quality
Rating0

U
u
U
u
u
u
*
u
U 1
u
 » .^..v^o uav/ j.uj. injiuiH5iuaiiG-uuucu.icUic Y wv~. emissions.
"Based on an average toiuene/VOC ratio of 0.106 (Reference 32).
jjBased on engineering judgement.
 Ocean barge is a vessel with tank compartment depth of 40 feet; barge is a vessel with
 compartment depth of 10-12 feet.                 '
Source: References 2 and 32,
                                6-16

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 available for crude  oil,  distillate  oil,  and other fuels.2*28  However, reliable estimates  of die
 toluene content of these fuels were not found. Therefore, it was not possible to provide toluene
 emission factors for marine vessel loading of fuels other than gasoline.
                          *
 6.4.2  -Toluene Emissions from Bulk Gasoline Plants, Bulk Gasoline Terminals and Service
       Stations

       Each operation in which gasoline is transferred or stored is a potential source of toluene
 emissions.  At bulk terminals  and  bulk plants, loading and unloading  gasoline and storing
 gasoline are sources of toluene, emissions.  The gasoline that is stored in above ground tanks is
 pumped  through loading racks that measure the amount of product. The  loading racks consist
 of pumps, meters, and piping to transfer the gasoline or other liquid petroleum products. Loading
 of gasoline into tank trucks can be accomplished by one of three methods: splash, top submerged,
 or bottom loading.  In splash loading, gasoline is introduced into the tank truck directly through
 a compartment located on the top  of the truck.28 Top submerged loading is done- by attaching
 a downspout to the fill pipe  so that  gasoline is added to the  tank truck near the bottom  of the
 tank. Bottom loading is the loading of product into the truck tank from the bottom. Because
 emissions occur when the  product being loaded displaces vapors in the tank being  rilled, top
 submerged loading and bottom loading reduce-the amount of material (including toluene)  chat is
 emitted.28
       Vapor: balancing-systems,, consisting, of- a, pipeline between the vapor spaces of the crack
and the storage tanks, are closed systems. These  systems allow the transfer of vapor displaced
by liquid  in ..the-storage tank into, the transfer track, as  gasoline is put into the storage- tank.23
Table*6-4-lists emission: factors.for gasoline, vapor and.toluene: from gasoline loading, jacks at.
bulk-  terminals and, bulk: plants.1.   The-gasoline vapor emission,  factors'  were- taken from
Reference 28. The toluene factors were obtained by multiplying the gasoline vapor factor by the
average toluene content of the' vapor (0:106-percent).32-

       A typical bulk terminal may have four or five above ground storage tanks with capacities
ranging from 1,500-15,000 m3.23  Most tanks in gasoline service have an external floating roof
                                          6-17

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                                     TABLE 6-4.
       TOLUENE EMISSION FACTORS FOR GASOLINE LOADING
                 AT BULK TERMINALS AND BULK PLANTS
4
Loading Method
Splash
Submerged*1
Balance Service :
Gasoline Vapor
Emission Factor1
mg/L
1430
590
980
Toluene Emission
Factor1' mg/L
151.6
62.5
103.9
Quality
Rating*
U
U
u •
     aFrom Reference 28.  Gasoline factors represent emissions of nonmethane-nonethane
      VOC. Factors are expressed as mg gasoline vapor per liter gasoline transferred.
     ''Based on an average toluene/VOC ratio of 0.106 (Reference 32).
     °Based on engineering judgement
     Submerged loading is either top or bottom submerged.
     Source:  References 28 and 32
 to prevent the loss of product through evaporation and working losses. Fixed-roof tanks, still
 used in some areas to store gasoline, use pressure-vacuum vents to control breathing losses,
 Some tanks  may use vapor balancing or processing, equipment  to control working losses. A
 breather valve (pressure-vacuum valve), which is commonly installed on many fixed-roof tanks,
 allows -Jie tank to operate at a slight internal pressure or vacuum.

       The major types of emissions from fixed-roof tanks are breathing  and working losses.
 Breathing loss is the expulsion of vapor from a tank vapor space that has expanded OF contracted
 because of daily changes in. temperature and. barometric pressure:. The: emissions occur. in,:he
 absence of any liquid level change in the tank.  Combined filling and emptying losses are called.
 "working losses." Emptying losses occur when the air that is drawn into the tank during liquid
 removal saturates with hydrocarbon vapor and expands, thus exceeding the fixed capacity-of the
vapor space and overflowing through the pressure vacuum valve.28
                                       6-18

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       A typical external floating-roof tank: consists of a cylindrical steel shell equipped with a
 deck or roof that floats on the surface of the stored liquid, rising and falling with the liquid level.
 The liquid surface is completely covered by the floating roof except in the small annular space
 between the roof and the shell. A seal attached to the roof touches the tank wall (except for
 small gaps in some cases) and  covers the remaining area.  The seal slides against the tank wall
 as the roof is raised or lowered.  The floating  roof and  the  seal system serve to reduce the
 evaporative loss of the stored liquid.28

       An internal floating-roof tank-has both a permanently affixed roof and a roof that floats
 inside the tank on  the liquid surface (contact roof), or supported on pontoons several inches
 above the liquid surface (noncontact roof). The internal  floating-roof rises and falls with the
                                                     •-V
 liquid level, and helps to restrict the evaporation of organic liquids.28

       Losses from floating-roof tanks include standing-storage losses and withdrawal losses.
 Standing-storage  losses, which result  from causes  other than a  change in the  liquid  level,
 constitute the major- source of emissions from external floating-roof tanks. The largest potential
 source of these losses is an improper fit between the seal and the tank shell (seal losses).  As a
 result, some liquid  surface is exposed to  the atmosphere. Air flowing over the tank creates
 pressure  differentials around  the, floating roof.  Air flows into  the annular vapor space on the
 leeward side and an air-vapor mixture flows out on the windward side.28

       Withdrawal loss is another source-of emissions from, floating-roof tanks.  When liquid is
 withdrawn from a tank., the  floating roof is lowered and a' wet  portion of the  tank  waU is
 exposed.  Withdrawal loss is  the vaporization of liquid from the wet tank-wall.28

       Table 6-5  presents emission factors for  toluene, from  storage-tanks at  a  typical bulk
terminal.  The emission factors were based on EPA (Reference 28) factors and the average
 weight fraction of toluene in  the vapor of 0.106.32

      The two basic types of gasoline-loading into tank trucks at bulk plants. are the same, as
those used at terminals. The first is the splash filling method, which usually results in high levels
                                          6-19

-------
                                     TABLE 6-5.
       TOLUENE EMISSION FACTORS FOR STORAGE LOSSES AT
                 A TYPICAL GASOLINE BULK TERMINAL
Storage Method
Fixed Roof
Working Loss
Breathing Loss'
External Floating Roof d
Working Loss
Storage Loss
Gasoline Vapor
Emissions Factor
(Mg/yr/Tank)

34.2
8.8 '
•
!•£• N"-*
9.6
Toluene
Emission Factor
Mg/yr/Tanka

3.6
0.9

1
1.0
Quality
Rating"1

U
U

U
U
     Terminal with 950,000 liters/day (250,000 gallons/day) with four storage tanks for
     gasoline.
     bBased on engineering judgement
     "Typical fixed-roof tank based upon capacity of 2,680 m3 (16,750 barrels).
     Typical floating-roof tank based upon capacity of 5,760 m3 (36,000 barrels).
     'Emission factor = 9.89 x 10'7 Q) Mg/yr, where Q is the throughput through the tanks in
     barrels (References 28 and 32).
     Source: References 28 and 32".
of vapor generation and loss. The second method is submerged filling with either a submersed
fill pipe or bottom filling, which significantly reduces liquid turbulence and vapor-liquid contact
resulting in much lower emissions. Table 6-6 shows the uncontrolled emission factors for toluene
from a typical bulk plant,

       Gasoline tank trucks have been demonstrated to be major sources of vapor leakage. Some
vapors may leak uncontrolled to the atmosphere firom. dome-cover; assemblies, pressure-vacuum
(P-V) vents, and vapor collection piping and vents.  Other sources of vapor leakage on tank
trucks  that  occur less  frequently include tank shell flaws, liquid and vapor  transfer hoses,
improperly installed or loosened overfill protection sensors, and vapor couplers.  Since terminal
                                       6-20

-------
                                      TABLE 6-6.
           UNCONTROLLED GASOLINE VAPOR AND TOLUENE
                EMISSION FROM A TYPICAL BULK PLANT
Emission Source"
Storage Tanks - Fixed Roof
Breathing Loss
Filling Loss
Draining Loss
Gasoline Loading Racks
Splash. Loading
Submerged Loading
Submerged Loading
(Balance Service)
Gasoline Vapor
Emission Factor
mg/L

600
1150
460
N»
N*
1430
590
980
Toluene
Emission Factor6
mg/L

63.6
121.9
48.8

151.6
62.5
103.9
Quality
Rating6

U
u
U

u"
u
u
     ^Typical bulk plant with'a gasoline throughput of 19,000 liters/day (5,000 gallons/day)
     Based on gasoline emission factor and toluene/vapor ratio of 0.106 (Reference 32).
     °Based on engineering judgement.
     Source:  References 28 and 32
controls are usually found in areas where-trucks-are required to collect vapors after'delivery of
product: to bulk plants or service stations (balance  service),, the-gasoline vapor emission factor
associated with uncontrolled truck leakage was assumed to be 30 percent of the balance service
truck loading-factor (960 mg/liter x-0.30 = 288 mg/liter).23' Thus, the.emission factor for toluene
emissions: from:uncontrolled,truck,leakage:.-is 30.5"ma/liter,.based-:on a. toluene/vapor ratio of
0.106.32:

      The-discussion on service'station-operations-is divided into two-areas:  the filling of the
underground storage tank (Stage I) and automobile refueling (Stage II).' Although terminals and
bulk, plants-also have..two distinct, operations (tank-filling, and truck loading), the-filling of the
underground- tank at  the service station ends the  wholesale gasoline marketing chain.   The
                                        6-21.

-------
  automobile refueling operations interact directly with the public and control of these operations
  can be performed by putting control equipment -on either the service station or the automobile.28

  Toluene Emission from Service Stations-
        Normally, gasoline is delivered to service stations in large tank trucks from bulk terminals
  or smaller account trucks from bulk plants.  Emissions are generated when hydrocarbon vapors
  in the underground storage tank are displaced to the atmosphere by the gasoline being loaded into
  the tank.  As with other loading losses, the quantity of  the service  station tank loading loss
  depends on several variables, including the quantity of liquid transferred, size and length of the
  fill pipe, the method of filling, the tank configuration and  gasoline temperature, vapor pressure,
  and composition. A second source of emissions from service station tankage is underground tank
                                                      X-
  breathing.  Breathing losses  occur daily and are attributed to temperature .changes, barometric
  pressure changes, and gasoline evaporation.28

        In addition to service  station tank loading  losses,  vehicle  refueling operations  are
  considered to be-a major source of emissions.   Vehicle refueling emissions are attributable to
 vapor displaced from the automobile tank by dispensed  gasoline and to spillage.  The major
 factors affecting  the  quantity of emissions are gasoline  temperature, auto tank temperature,
  gasoline Reid vapor  pressure (RVP),  and  dispensing rates.  Table 6-7  lists the uncontrolled
 emissions from a typical gasoline service station. The gasoline vapor emission factors presented
  in Table 6-7 are from EPA documents.22

 6.4.3   Control  Technology for Gasoline Transfer  ,

        At bulk terminals and., bulk  plants, toluene emissions from gasoline transfer may be/
 controlled  by  a  vapor processing system  in conjunction with a  vapor, collection system.:3
 Figure 6-3 shows a Stage I control vapor balance system at a bulk plant. These systems collect
.and recover gasoline vapors from empty, returning-tank, trucks as- they are filled with gasoline
 from storage tanks.28
                                           6-22

-------
                             TABLE 6-7.
      UNCONTROLLED GASOLINE VAPOR AND TOLUENE
       EMISSIONS FROM A TYPICAL SERVICE STATION
Emission Source3
Underground Storage Tanks
Tank Filling Losses
Submerged Fill
- Splash Fill
Balanced Submerged
Filling
Breathing Losses
Automobile Refueling ,
Displacement Losses
Uncontrolled
Controlled
Spillage
Gasoline Vapor
Emission Factor
mg/L


880
1380
40
120

,
1320
132
84
Toluene
Emission Factor11
mg/L


93.3
146.3
4.2
12.7


139.9
13.9
8.9
Quality
Rating0


'U
u
U
u


u
u
u
Typical service station has a gasoline throughput of 190,000 liters/month
 (50,000 gallons/month).
"Based, on gasoline vapor emission-factor and toluene/vapor ratio of 0.106
 (Reference 32).                             ^    .
°Based on engineering judgement.

Source:  References 28 and 32
                               6-23

-------
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                               JC

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                                                        C
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-------
o
O
C3
a-

33
.2
a
 a
O,
 a
 -•a.;
s
                                                                              o


                                                                              JS
                                                                              S3
                                                                              O
                                                                              c.
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                                                                             _0

                                                                             '>
                           6-25

-------
        At service stations, vapor balance systems contain the gasoline vapors within the station's
 underground storage  tanks  for transfer to empty gasoline tank trucks returning to the bulk
 terminal or bulk plant  Figure 6-4 shows a diagram of a service station vapor balance system.

 6.4.4  Control Technology For Gasoline Storage

        The control technologies for controlling toluene emissions from gasoline storage involve
 upgrading the type of storage tank used or addition of a vapor control system.  For fixed-roof
 tanks, emissions are most readily controlled  by installation of internal floating roofs.28  An
 internal floating roof reduces the area of exposed liquid surface on the tank and, therefore,
 decreases evaporative loss.  Installing an internal floating-roof in a fixed-roof tank can reduce
 total emissions by 68.5 tor 97.8 percent28

       For external floating-roof tanks, no control measures have been identified for controlling
 withdrawal losses and emissions.28  These emissions are functions of the turnover rate of the tank
 and the characteristics of the tank shell. Rim seal losses in external floating-roof tanks depend
 on the type  of seal.  Liquid-mounted seals are more effective than Vapor-mounted seals  in
 reducing rim seal losses.28 Metallic shoe seals  are more  effective than vapor-mounted seals but
 less effective than liquid mounted seals.23

 6-4.5  Control Technology For Vehicle Refueling Emissions

       Vehicle refueling emissions are attributable to vapor displaced from the automobile taak
 by dispensed gasoline and to spillage. .The quantity of displaced vapors is dependent on gasoline
 temperature, vehicle; tank size and: temperature,  fueI-level,.gasoiine-Ryp; and. dispensing/rates.,^3

       The two basic refueling vapor control alternatives are control systems on service station
equipment  (Stage IT controls), and control systems on  vehicles (onboard controls). Onboard
controls are basically limited to the carbon,canister..
                                          6-26

-------
        There are currently three types of Stage E systems in limited use in the United States: the
 vapor balance, the'hybrid, and the vacuum assist systems. In the vapor balance system, gasoline
 vapor in the automobile fuel tank is displaced by the incoming liquid gasoline and is prevented
 from escaping to the atmosphere at the fillneck/nozzle interface by a flexible rubber "boot." This
 boot is fitted over the standard nozzle and is attached to a hose similar to the liquid hose.  The
 hose is connected to piping which vents to the underground tank. An exchange is made (vapor
 for liquid)  as the liquid displaces  vapor to  the  underground storage  tank.  The  underground
 storage tank assists this transaction by drawing in a volume of vapor equal to the volume of
 liquid removed.28       •
        The vacuum assist system differs from the balance system in that a "blower" (a vacuum
 pump) is used to provide an extra pull at the nozzle/fillneck interface. Assist systems can recover
 vapors effectively without a tight seal at the nozzle/ffflpipe interface because only a close fit is
 necessary.  A slight vacuum is maintained at the nozzle/fillneck interface  allowing air to be
 drawn into the  system and not allowing the vapors to escape.  Because  of this assist,  the
 interface "boot" need not be as tight fitting as with balance systems.  Further, the vast majority
 of assist nozzles do not require interlock mechanisms.  Assist systems generally have vapor
 passage valves located in the vapor passage somewhere other than in the nozzles, resulting in a
 nozzle which is  less bulky and cumbersome than nozzles employed by vapor balance systems.23

       The hybrid  system borrows from the concepts of both  the balance and vacuum assist
 systems.  It is designed to enhance vapor recovery at the nozzle/ffflneek interface by vacuum,
 while keeping the vacuum low enough so that a minimum level of excess vapor/air is returned
 to; the underground storage  tank.

       With the- hybrid system,  a  small amount of the liquid gasoline. (less-.than-10 percent)
pumped  from the storage tank is  routed (before metering) to a restricting nozzle called  an
aspirator. As the gasoline goes through this restricting nozzle; a small vacuunvis generated. This
vacuum is used to draw vapors into the rubber boot at the interface. Because the vacuum is  so
small, very .little excess air, if any,  is drawn into the boot, hose, and underground storage tank,
and thus there is no need for a secondary processor,, such as the vacuum assist's incinerator.^
                                          6-27

-------
       Onboard vapor control systems consist of carbon canisters installed on the vehicle to
control refueling emissions. The carbon canister system adsorbs, on activated carbon, the vapors
which are displaced from the vehicle fuel tank by the incoming gasoline.  Such a system first
adsorbs the emissions released during refueling and subsequently purges these vapors from the
carbon to the engine carburetor when it is operating.  This system is essentially an expansion of
the present evaporative emissions control system used in all new cars to minimize breathing
losses from the fuel tank and to control carburetor evaporative emissions. However, unlike the
present system, a refueling vapor recovery system will require a tight seal at the nozzle/fillneck
interface during refueling operations to ensure vapors flow into  the carbon canister and are not
lost to the atmosphere.28
                                                                             •

6.5    OTHER SOURCES OF RESIDUAL TOLUENE EMISSIONS

       Toluene can be emitted during the use of toluene-containing materials in manufacturing
another product Emissions from some of these miscellaneous sources are presented in Table 6-8.
                                         6-28

-------
                            TABLE 6-8.
   RESIDUAL EMISSIONS FROM MISCELLANEOUS SOURCES
                          OF TOLUENE
Source
Particle board with carpet3
Mineral wool used as thermal
insulation15
Building materials
(particle board, plywood, sealing
agents, wallpaper, floor coverings,
paint foam, and concrete)0
Clear acrylic latex caulk
with siliconed
Synthetic rubber adhesive
(for walls and ceilings)15
Synthetic rubber adhesive
(for vinyl carpet)6
Unspecified polymer adhesive
(for subflooring)8
Building materials'"
vinyl, cove-- molding
telephone, cable
urethane insulant
Concentration
in Air
•N/A
13-90 ug/m3
~ ,39.7 pg/m3
; • vV
Detected
N/A
N/A
N/A
detected
detected
detected
Emission
Rate
0.061 pg/m2/hour
N/A
N/A .
N/A '
0.59 jig/g/hour
62 ug/g/hour
2.4-2.6
ug/g/hour
N/A
N/A
N/A
Quality
Rating
E
D
.D
Ug
E
E
E
Us
" Ug
Ug j|
N/A - Not available
a - Reference 34
b - Reference. 35
cr- Reference- 3 6
d;-- Reference- 37
e - Reference 38
f - Reference,39
g — Nbfenough available information1 to apply a rating.
                               6-29

-------

-------
 6.6

 1.


 2.


 3.



 4.


 5.


 6.


 7.

 8.


 9.


 10..



 11.
 i



 12."
13.
 REFERENCES FOR SECTION 6.0

 SRI International.  U.S. Paint Industry Database. Prepared for the National Paint and
 Coatings Association. Washington D.C.  1990.
                        t
 U.S. Environmental Protection Agency. Compilation of Air Pollutant Emission Factors.
 AP-42, fourth edition and supplements. Research Triangle Park, NC. 1985.

 U.S. Environmental Protection Agency. Source Assessment: Prioritization of Air Pollution
from Industrial Surface Operations, EPA-650/2-75-019a.  Research Triangle Park NC
 1975.

 Bridgewater, A.V. and CJ. Mumford, Water Recycling and Pollution Control Handbook.
 Van Nostrand Reinhold Company. 1979.

 Godish, Thad, Air Quality.   Director of the Indoor Air Quality  Research Laboratory
 1985.                                       v.   ,:

 U.S. Environmental Protection Agency.   VOC Pollution Prevention Options for the
 Surface Coating Industry. Research Triangle Park, NC. 1991.

 7957 Census of Manufacturers. U.S. Department of Commerce, Bureau of Census.

The NAPL Printer's  Almanac.  The Printing  Economic Research  Center.  National
Association of Printers and Lithographers.  Teaneck, New Jersey.   1990.

Gale Research Inc., Ward's Business Directory of U.S. Private and Public Companies-
 1991.  Volume 4.  Detroit, MI., 1991.

U.S. Environmental Protection Agency. Guides to Pollution Prevention: The Commercial
Printing Industry, EPA/625/7-90/008.  Office of Research and Development. Washington
DC. August 1990.                      '                     '-.*"'

U.S. Environmental Protection Agency. Publication Rotogravure Printing - Background
Information/or Proposed.Standards, EPA-450/3-80-031a. Office of Air Quality Planning
and,Standards. Research/Triangle Park,.NC.' October,1980.

U.S. Environmental Protection Agency.  Control of Volatile Organic Emissions from
Existing Stationary Sources.   Volume VIE: Graphic Arts• Rotogravure and Flexograph,
EPA-450/2-78-033. Office of Air Quality Planning and  Standards. Research Triansle
Park,:NC.. December 1978.

North  Carolina Department  of Natural  Resources  and  Community  Development
Companion Document for the Conference on Waste Reduction for Industrial Air Toxics
Emissions. Pollution Prevention Pays Program. Greensboro, NC.  April 24, 1989.
                                       6-30

-------
 14.    Office  of Toxic Substances.   Carpenter, Ben H. and  Garland K. Milliard.   U.S.
       Environmental Protection Agency, Overview of Printing Process and Chemicals Used.
       Conference Proceedings: Environmental Aspects of Chemical Use in Printing Operations.
       Volume 1:  King of Prussia, PA. Washington, DC.  September 1975.

 15.    Neal, Barry and Robert H. Oppenheimer.  "Environmental Regulations and Compliance
       in the Gravure Industry," Tappi Journal,  p. 121.  July 1989.

 16.    Burt, Richard, Radian  Corporation.   NSPS for VOC Emissions from Publication
       Rotogravure Printing Industry. National Air Pollution Control Techniques Advisory
       Committee Meeting Minutes. December  12-13, 1979.

 17.    U.S. Environmental Protection Agency.  Control of Volatile Organic Emissions from
       Existing Stationary Sources.  Volume IE:  Graphic Arts - Rotogravure and Flexography,
       EPA-450/2-78-033. Emission Standards Engineering Division, Chemical and Petroleum
       Branch. Research Triangle Park, NC.

 18.    Profile Survey of the U.S. Gravure Industry. Gravure Association of America, New York,
       'NY.  1989.

 19.    U.S. Environmental Protection Agency.  Best Demonstrated Control Technology for
       Graphic Arts.  EPA-450/3-91-008.   Office of Air Quality  Planning and Standards.
       Research Triangle Park, NC. February 1991.

20.    U.S. Environmental Protection  Agency. Polymeric Coating of Supporting Substrates-
       Background Information for Promulgated Standards, Final EIS,  EPA-450/3-85-022b.
       Office of Air Quality Planning and Standards.  Research Triangle Park, NC. April 1989.

21.    U.S. Environmental  Protection Agency.  Magnetic Tape Manufacturing Industry--
       Background Information for Promulgated Standards, Final EIS,  EPA-450/3-S5-029b.
       Office of Air Quality Planning and Standards.  Research Triangle Park, NC.  July 1988.

22.    Michael Kosusko and  Carlos M.  Nunez.    Air  Waste- Management  Association.
       Destruction of Volatile Organic Compounds Using Catalytic Oxidation. Volume 2.  pp.
       254-259.  February 1990.

23.,    fsaksen; IvarS.. A.,, eral,, "Model: Analysis of. the Measured, Concentration of. Organic
       Gases in the Norwegian Arctic," Journal of Atmospheric Chemistry. 3(l):3-27.  1985.

24.    Sigsby,  Jr., John E., Tejada, Silvestre, and Roy, William, "Volatile Organic Compound
       Emissions from 46 In-Use  Passenger Cars," Environmental Science Technology:. 21(5)-
       466-475. 1987.
                                        6-31

-------
 25.
 26.
 27.
 28.
 29.
30.
31.
32.
33.


34.


35.,


36.


37.
 Mo,  S.H., Gibbs, R.E., Hill, B.J., Johnson, R.E.,  Webster, W.J., and Whitby, R.A.
 Relationships Among Time-Resolved Roadside Measurements of Benzene, Toluene, Xylene
 and Carbon Monoxide, Presented at the 80th Annual Meeting of APCA.  New York NY
 June 21-26, 1987.

 U.S.  Environmental Protection  Agency.  Toxic Air Pollutant Emission Factors - A
 Compilation for Selected Air Toxic Compounds and Sources, EPA-450/2-88-006a. Office
 of Air Quality Planning and Standards.  Research Triangle Park, NC. 1988.

 Bartok, William and Sarofim, Adel R, ed.,'Fossil Fuel Combustion:  A Source Book.
 John  Wiley & Sons, Inc/ New York,  NY.  1991.

 U.S. Environmental Protection Agency. Evaluation of Air Pollution Regulatory Strategies
for Gasoline Marketing Industry. EPA-450/3-84-012a. Washington, DC.  1984.

 U.S.  Environmental Protection Agency. Development of VOC Compliance Monitoring
 and Enforcement Strategies:  The Wholesale Gasoline Marketing  Chain  -  Volume II,
 EPA-340/l-SO-01-013a. Office of Air Quality Planning and Standards. Research Triangle
 Park, NC.  July 1980.

 Energy Information Administration.    Petroleum  Supply Annual 1991   Volume 1
 DOE/EIA=0340(91)/1.

 Telecon.  George Woodall, TRC" Environmental Corporation to Bonnie Ayotte of the
 Computer Petroleum Company, St. Paul, MN. September  22, 1992.

 Memorandum from Chris Lindhjem,  et al, U.S. Environmental Protection Agency to
 Record,-U.S. Environmental Protection Agency, "Speciation for SAT Runs " ^ori! M-
 1992.    ;                   ,          "                            '  "*

 Owen,' Keith and  CoLey, Trevor,.Automotive. Fuels Handbook.  Society  of Automotive
 Engineers, Inc.., Warrendale;  PA.  1990.

Colombo, A., et al, "Chamber Testing  of Organic Emissions  from Building and
Furnishing Materials," The Science of the Total. Environment. 91:, 237-249.   1990.

van:der:Wal,Jan:F;r,,etai.,''Thermai,Insulation-asa,Source^of Air Pollution," Environment-
International. 15: 409-412;  1989.'.

Molhave, Lars,, "Indoor Air  Pollution due to  Organic Gases and Vapors of Solvents in.
Building Materials," Environment.International.  8(1-6):: 117-127. 1982:

Tichenor, BrucevA., Jackson,, Merrill D.,  and Merrill, Raymond G., "Measurement  of
Organic Emissions from Indoor Materials - Small Chamber Studies," Proceedings of the
1986 EPA/APCA Symposium on Measurement of Toxic Air'Pollutants.
                                        6-32

-------
38.    Girman, J.R., et al,  "Emissions of Volatile Organic Compounds from Adhesives with
       Indoor Applications," Environment International.  12(1-4): 317-321.  1986.

39.    Sheldon, Linda S., et al, "Volatile Organic Emissions from Building Materials," Presented
       at the 79th Annual Meeting of the Air Pollution Control Association. Minneapolis, MN.
       June 22-27, 1986.                           ,   *
                                        6-33

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                                     SECTION 7.0
                              BY-PRODUCT EMISSIONS:
          PROCESSES UNRELATED TO PRODUCTION OR USE OF TOLUENE

       Toluene and other pollutants can be emitted to the atmosphere as the result of product
 manufacturing or from the burning of fossil fuels. Processes that release toluene as.by-product
 emissions are described in this section.  These processes include coal combustion, hazardous and
 solid waste incineration, and wastewater treatment processes. Data pertaining to emissions from
 fossil fuel  combustion in boilers and heaters were unavailable and therefore are not included in
 this section.

 7.1    COAL COMBUSTION                       °"      .

       Two coal combustion studies are briefly described in this section.  The first study
 analyzed samples  collected from a gasifier.   The second coal combustion study analyzed
 emissions from a burning coal refuse pile.1'2

       A coal combustion study was performed to collect data on the chemical composition of
 fugitive aerosol emissions at a pilot-scale gasifier using lignite coal. Sampling  was conducted
 at the Grand Forks Energy Technology Center  gasifier, Grand Forks, North Dakota.  From the
 gas chromatography (GC) and.gas. chromatography/mass spectrometry (GC/MS) analyses  that
 were performed, it, was determined that-toluene existed at the gasifier.  However, no data were
 reported.1
       Another air-monitoring study was performed,on,a,burning coaLreruse (gob) pile-in Oak
HUT, West, Virginia,  The West Virginia Air Pollution Control Commission requested assistance
from EPA to perform a study of the heavy metal and organic chemical emissions from a burning
gob pile.-   Carbon: monoxide emissions are expected from  these burning gob  piles,  while
emissions  of other compounds such  as toluene  are suspected.  Under the direction of EPA,
CCA/Technology Division performed a study on the types and quantities of emissions from the
gob pile.2
                                        7-1

-------
       The gob pile studied was similar to many of the hundred known to exist in coal mining
 areas in the country. This coal waste pile was created as the result of a nearby deep mining
 operation.  The emissions have  been generated  for decades  as a  result of the  spontaneous
 combustion of low grade, yet combustible coal refuse material.2

       Red dog, the solid matrix remaining after the combustible fractions are burned out of the
 coal waste is a popular fill and highway construction material. The two major results of mining
 red dog are increased gaseous emissions and an increased fugitive paniculate emission rate due
 to the excavation and loading of the red dog into trucks.  The slow natural combustion process
 presents a difficult situation for effective pollution control. Due to cost and the large amount of
 material involved, emission control of such a large area source is usually restrictive, although not
                                                    X*
 impossible.2                                      •    N

       GCA's investigative study was a two-phase approach in order  to maximize the quality of
 results.   The first phase was  a preliminary assessment,  followed by a more comprehensive
 quantitative emissions program. The preliminary assessment assisted in identifying pollutants
 present in the gob pile emissions and their approximate concentrations. The second phase of the
 investigation began with the siting of GCA's Mobile Laboratory and the startup of the analytical
 instrumentation. In addition, two meteorological monitoring stations were erected and calibrated,
 one at approximately 10 feet elevation directly at the test area and  one slightly downwind at
 approximately 200 feet  in elevation  above the  test area to measure  overall regional  wind
 conditions."  -

      Samples were collected  at the centerpoint;of each  of 24 equal area grids.  All samples
 were; collected from- within  10-inch  diameter ductwork, positioned  over; the- sample- poini to
 minimize dilution, mixing,  and variable wind  conditions.  After  all sample analyses  were
completed, a calculation was performed to convert measured concentrations (ppm, ppb, ug/m3)
 co average  emission rates (Ib/hr) for each parameter. An extrapolation of the average emission
rate from the sampled area to that of the total pile was then performed.. Also,  due  to, the large
range of values for  most, parameters,  a standard error calculation  was used  to describe the
                                          7-2

-------
 variability of each compound specific average rate.  Table 7-1 lists the emission rate and the
 emission factor for toluene resulting from this study.2

                                    TABLE 7-1.
     TOLUENE EMISSIONS FROM COMBUSTIBLE COAL REFUSE
                                   MATERIAL
Parameter
Toluene
Total Emission Rate
4.3 ± 3,6 kg/hr
(9.4 + 8.0 Ib/hr)
Emission Factor
4.1 x 10'5 kg/hr/m3 (2.5 x 10"6 lb/hr/ft3)
of burning refuse material
Quality
Rating
••OMBI^
D
 Source:  Reference 2.
       In summary, the investigative study resulted in calculated emission rates and emission
 factors for various parameters. This study concludes that the possibility of downwind exposure
 to toxic and suspected toxic airborne contaminants from the burning coal refuse pile exists.2

 7.2    HAZARDOUS AND SOLID WASTE INCINERATION

       Tne.-majority of atmospheric emissions of pollutants from the various hazardous and solid
 waste, disposal methods  comes from, incineration.  In  addition  to particulate  matter,  other
 pollutants, such as  volatile organic compounds (including  toluene) and carbon monoxide are
 frequently emitted as a result of incomplete combustion.of the waste due to improper combustor
 design  or poor operating conditions.

       Several, methods'are-used, to incinerate: municipal waste;.  These-inciude.massrbum excess
 air' combustion,, starved  air  or modular.; combustion,, and, refuse-derived  fuel combustion.
Approximately 70 percent of the total municipal solid waste is incinerated in.mass burn units.
More information on the methods of municipal waste combustion can be found in the document,
Characterization of the Municipal Waste Combustion Industry.3  Similarly, hazardous waste can
                                       7-3

-------
 be incinerated  by several methods  including thermal, catalytic and regenerative incineration.
 Toluene emission factors from incineration sources were not found.

       Open-air burning presents a particularly unique source of atmospheric emissions of
      t
 pollutants.  This method  of solid waste incineration allows for exposure to many variables
 including wind, ambient temperatures, and other environmental parameters such as rain and
 humidity, degree of compactness of the refuse, and composition and moisture of the refuse. In
 general,  lower temperatures are  achieved in open-air  burning than in closed combustion.
 Therefore, this allows for increased emissions of particulate matter, carbon monoxide, and volatile
 organic compounds  (including toluene)  with decreased emissions of nitrogen  oxides.  Other
 important regulating factors for open-air burning are fuel loading (how much refuse  material is
                                                    •\»
 burned per unit of land area) and arrangement of the refuse (in rows,  piles, or spread out).4
 Although specific toluene emission factors are unavailable, data indicate that emissions of volatile
 organic compounds from non-agricultural materials are approximately 25 percent methane, 8
 percent other saturates, 18  percent olefins,  and 42 percent other compounds  (oxygenates,
 acetylene, and aromatics, including toluene).4

7.3    WASTEWATER TREATMENT PROCESSES

       Atmospheric emissions of volatile organic compounds such as toluene can occur at any
 wastewater treatment process where the wastewater comes  into contact  with the surrounding
 ambient air. An estimated 5  million kilograms (11 million pounds) of toluene are discharged tb
 the environment annually as a constituent in wastewater.5 A study conducted at two Chicago-area
 wastewater treatment facilities estimated  that approximately 94 percent of the  toluene in the
 influent  waters  biodegraded  in activated sludge-systems while only 3 percent "volatilized.,
 However, if ail of the influent toluene at the two facilities were to volatilize, it  wouidL account
for nearly 29,000 kilograms (64,000 pounds) per year.6 Another study conducted in  California
estimated total air emissions of toluene-from statewide-municipal wastewater treatment plants :o
be approximately 250,000 kilograms (550,000 pounds per year).7
                                          7-4

-------
        The majority of air emissions from wastewater treatment facilities usually comes from the
 initial physical processes (e.g., screening, sedimentation, floatation, and filtration) due to both a
 higher pollutant concentration in the influent and a greater surface area caused by turbulence and
 mixing. Other sources of emissions include equalization and aeration basins and clarifiers.
        Because of the many factors that may affect emissions of volatile organics, including
 toluene, from wastewater treatment processes, calculating actual emissions estimates must be
 performed on a chemical-by-chemical, process-by-process basis.  Several  models have been
 developed that estimate emissions from wastewater treatment processes.  A brief description of
 some appropriate models are presented below; however, further information should be consulted
 in the appropriate reference(s).

       The SIM-S model (Surface Impoundment Modeling System), developed by the Control
 Technology Center of the U.S. Environmental Protection Agency, is a personal computer-based
 software program designed to  estimate atmospheric emissions from surface impoundments and
 wastewater collection devices.8'9 The Tsivoglou and Neal Reaeration model can be-used with the
 SIMS  model to  estimate VOC emissions from the devices that comprise the headworks of a
 POTW (since the SIMS  model does  not  account for  emissions  from  these  devices or for
 adsorption onto solids).10

       Several inherent problems exist with using these models.  First, the VOC concentrations
 in the wastewater  axe highly variable: among  the  influent, effluent, and  sludge-partitions:
 therefore, a single emission estimate would be-highly questionable.-  Second, the estimates-are
 usually based on constant behavior of relatively pure  compounds, so  mixing and variable
 chemical concentrations would.render the-emission factors less-useful. Finally, these estimates.
 are generally on-.the conservative-side,.and actual.emissions wiU often tend to.be:higher than the
 estimates.
       A major process resulting in the emission of wastewater pollutants is the separation of the
lighter organic phase from the main body of wastewater and the heavier inorganic solid phase.
A top organic layer consisting of many volatile organic and oil-based compounds is formed, and
exposed to ambient air.  Factors  affecting-volatilization of organic compounds  from the top
                                         7-5

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organic layer include characteristics of the wastewater and oil layers, the ambient wind speed,
design characteristics of the wastewater treatment operation, the concentration of pollutants in
the wastewater, detention time in the treatment system, and partition coefficients of the pollutants.
EPA has published several guidance documents and reports regarding emissions from wastewater
treatment systems which are referenced here.7'8
                                         1-6

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 7.4

 1.



 2.




 3..


 4.


 5.



 6.



7.



8.



9.



10.,
 REFERENCES FOR SECTION 7.0

 Joseph R. Stetter, Richard D. Flotard, and Elizabeth Gebert. Environmental Monitoring
 and Assessment in International Journal, Characterization of Airborne Particles at a
 High-BTU Coal-Gasification Pilot Plant. 1(4). 1982.

 Seely, Douglas E. and Engle, Ronald J. Investigative Air Monitoring Study at a Burning
 Coal Refuse Pile in Oak Hill, West Virginia. Presented at the 77th Annual Meeting of
 APCA.  San Francisco, CA.  June 24-29, 1984.

 Radian Corporation.   Characterization of the Municipal  Waste Combustion Industry,
 Appendix A. Research Triangle Park, NC.  October 1986.

 Gerstle,  R.W.,  and  D. A. Kemnitz.  "Atmospheric  Emissions from Open Burning,"
 Journal of Air Pollution Control Association.  12:324-327.  May 1967.

 U.S. Environmental Protection Agency. Development Document for Effluent Limitations
 Guidelines and Standards for the Plastics Molding and Forming Point Source Category,
 EPA-450/l-84-069b.  Effluent Guidelines Division.  Washington DC.  1984.

 Rittman, Bruce  E.  and Namkung,  Eun.   "Estimating Volatile  Organic  Compound
 Emissions from'Publicly Owned Treatment Works," Journal of The Water Pollution
 Control Federation, 59(7):670-678.  July 1987.

 Corsi, Richard L. "Emissions of Volatile and Potentially Toxic Organic Compounds from
 Municipal Wastewater Treatment Plants."  Presented at the 80th Annual Meeting of
 APCA. New York, NY. June 21-26, 1987.

 U.S. Environmental Protection Agency. Guidance Services, Control of Volatile Organic
 Compound Emissions-from-Industrial Wastewater, Volume I, Preliminary Draft. Office .of
 Air Quality Planning and Standards,  Research Triangle Park,  NC.  April 1989.

 U.S. Environmental Protection: Agency. Surface Impoundment Modeling System (SIMS)
 Version 2.0 User's Manual, EPA-450/4-907019a. Control Technology Center.  Research
Triangle Park, NC. 1990.

Tsivogiou,.E.C.,.and.L.A.. Ne'ai.; "fracer,.Measurementof Reaeration, JOT. Predicting the
Reaeration Capacity: of Inland. S treams," Journal, of Water Pollution Control,Federation
48(12):2669.  1976.
                                        7-7

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                                   SECTION 8.0
          AMBIENT AIR AND STATIONARY SOURCE TEST PROCEDURES

      Toluene emissions can be measured from ambient air and stationary sources utilizing the
test methods presented below. If applied to stack sampling, the ambient air monitoring methods
may require adaptation or modification.  If ambient air methodology is applied to stationary
source testing, appropriate precautions must be  taken to ensure  that the  capacity of the
methodology is not exceeded so that results will be quantitative.  Ambient methods which require
the use of sorbents are susceptible to sorbent saturation if high concentration levels exist. If this
happens, breakthrough will occur, and quantitative analysis is not possible.

      EPA Method TO-1: Determination of Volatile Organic Compounds in Ambient Air Using
      Tenaxu Adsorption and Gas  Chromatography/Mass Spectrometry (GC/MS)
      EPA Method TO-2: Determination of Volatile Organic  Compounds in  Ambient Air by
      Carbon Molecular  Sieve  Adsorption and  Gas  Chromatography/Mass  Spectrometrv
      (GC/MS)                                                                  y
      EPA Method TO-3: Determination of Volatile Organic Compounds in Ambient Air Using
      Cryogenic Preconcentration Techniques and Gas Chromatography with Flame lonization
      and Electron Capture Detection
      EPA Method TO-14: Determination of Volatile Organic Compounds (VOCs) in Ambient"
      Air  Using  SUMMA® Passivated Canister Sampling and Gas Chromatographic (GC)
      Analysis
      EPA Method 0030: Volatile Organic Sampling Train (VOST) with EPA Method 5040-
      Analysis of Sorbent Cartridges from VOST
      EPA Reference Method 18: Measurement of Gaseous Organic Compound Emissions by
      Gas. Chromatography
      EPA Method 0010: Modified: Method 5 Sampling Train: with EPA Method 8270:  Gas
      Chromatography/Mass Spectrometry for Semi-volatile. Organics:   Capillary  Column
      Technique
      NIOSH Method 1501: Aromatic Hydrocarbons
                                      8-L

-------
The following subsections briefly describe the recommended sampling and analytical methods
for determining toluene emissions.

8.1    EPA METHOD TO-11
      *
       Ambient air concentrations of toluene can be measured using EPA Method TO-1 from
the Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air.
This method is used to collect and determine volatile nonpolar organics (aromatic hydrocarbons,
chlorinated hydrocarbons) that can be captured on Tenax® and determined by thermal desorption
techniques. The compounds determined by this method have boiling points in the range of 80°
to 200°C (180° to 390°F).
                                                   %•
                                                   X-
       Figure  8-1 presents a schematic of the sampling system and Figure 8-2 presents a
schematic of typical Tenax®  cartridge designs.
                                                      e
       Ambient air is drawn through the cartridge which contains  approximately 1-2 grams
(0.035 to 0.07  ounces) of Tenax®.  Toluene is trapped on the Tenax® cartridge which is then
capped and sent to the laboratory for analysis utilizing purge-and-trap gas chromatography/mass
spectrometry (GC/MS) according-to the procedures specified in EPA Method 5040 (see Section
8.6). The recommended GC column is a 50 meter capillary, type SE-30 with an internal diameter
of 0.3 mm.

      The exact run time, flow rate and volume sampled varies from source to source depending
on the expected concentrations and  the required detection limit.  Typically, 10 to 20 L (0.3 to
0.7 ft3) of ambient air are sampled.  Analysis should be conducted/within 14  days of sample
collection.

3.2   EPA METHOD TO-21-
      Ambient air concentrations of toluene can be measured using EPA Method TO-2 from
the Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air.
                                         8-2

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                                     8-3

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                                     8-4

-------
 Compounds which can be determined using this method are nonpolar and highly volatile organics
 that can be captured on carbon molecular sieve (CMS) and determined by thermal desorption
 techniques. The compounds to be determined by this method have boiling points in the range
 of -15° to 120°C (5° to 250°F).  Toluene can be determined using this method.

       In summary, ambient air is drawn through a cartridge containing approximately 0.4 grams
 (0.01 ounces) of CMS adsorbent. Toluene is captured on the adsorbent while major inorganic
 compounds pass through.  The sample is then capped and sent to the laboratory for analysis.

       Prior to analysis, the CMS cartridge is purged with 2 or 3 L (0.07 to 0.1 ft3) of pure dry
 air to remove any moisture. The cartridge is then heated to 350° to'400°C (660° to 750°F) under
 a helium purge, and the desorbed toluene is collected in a Specially designed cryogenic trap. The
 collected toluene is then flash evaporated onto a capillary column (SE-30) and quantified using
 a GC/MS system.

       The exact run time, flow rate and volume sampled varies from source to source dependina
 on the expected concentration and the required detection limit. Typically, Method TO-2 is used
 when ambient air concentrations are expected to be high.  CMS has the ability to adsorb large
 quantities of organics before breakthrough occurs.

       Figure  8-1 is  representative  of both Methods TO-1 and TO-2  sampling  systems.
 Figure 8-3 illustrates a  CMS trap.   '

 8.3    EPA METHOD TO-31
       Ambient air concentrations of toluene-can be measured directly at the source using EPA
Method TO-3 from the Compendium Methods for the Determination  of Toxic Organic
Compounds in-Ambient Air:  This-method: is designed,for the-determination of highly volatile
nonpolar organic compounds having boiling points in the range of -10° to 200°C (14° to 390°F).
Figure 8-4 presents a schematic of a. typical on-line GC sampling system using cryogenic
trapping.

                                         8-5

-------
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                              8-6

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       The ambient air sample is" collected in the cryogenic trap using a vacuum pump equipped
 with a mass flow controller.  The GC oven is then chilled to a subambient temperature. The
 sample valve is then switched and the sample  is carried  onto the cooled GC  column.
 Simultaneously, the cryogenic trap is heated to assist in the'sample transfer process.  The GC
 column is then heated to the desired  temperature and the eluting peaks are identified and
 quantified using a flame ionization detector (FID).

 8.4    EPA METHOD-TO-141

       Ambient air concentrations of toluene can also be measured using EPA Method TO-14
 from the  Compendium of Methods for the Determination of Toxic Organic Compounds in
 Ambient Air. This method is based on collection of a whole air sample in SUMMA® passivated
 stainless steel canisters and is used  to determine semi-volatile and volatile organic compounds.
 The compounds  are separated by gas chromatography and measured by mass-selective  detector
 or multidetector  techniques such as FID, electron capture detection (ECD), and photoionization
 detection (PHD).  The recommended column for Method TO-14 is an HP OV-1 capillary with
 0.32mm ID. x 0.88 pm cross-linked methyl silicone coating or equivalent Samples should be
 analyzed within  14 days of collection.

       This method is applicable to specific semi-volatiles and volatile organic compounds that
 nave been tested and determined co be  stable  when stored in  pressurized and subatmospheric
pressure canisters.  Toluene can be successfully measured at the parts per  billion  by  volume
 • ppbv) level using this method.
                                   •
       Figure 8-5 presents a diagram of the canister  sampling system.

3.5    EPA METHOD 00302   -
      The volatile organic sampling train (VOST) from SW-846, (third edition) is designed for
die collection of volatile organic compounds from the stack gas effluents of hazardous waste
                                         8-8

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                8-9

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 incinerators. The VOST method was designed to collect volatile organics with boiling points in
 the .range of 30° to 100°C (86°  to 212°F).  Many compounds with boiling points above 100°C
 (212°F) may also be effectively collected using this method.   Toluene concentrations can be
 measured using this method. Figure 8-6 presents a schematic of the principle components of the
 VOST.

        In most cases, 20 L (0.7 ft3) of effluent stack gas are sampled at an approximate flow rate
 of 1 L/rninute (0.04 ftVmin) using a glass-lined heated probe. The gas stream is cooled to 20°C
 (68°F) by passage through a water-cooled condenser and the volatile organics are collected on
 a pair of sorbent resin traps.  Liquid condensate is collected in the impinger located between the
                      •
 two resin traps. The first resin  trap contains about 1.6 g (0.06 ounce) Tenax® and the second
 trap contains about 1 g (0.04 ounce) each of Tenax® and'petroleum-based charcoal.

        The Tenax® cartridges  are then thermally desorbed and analyzed by purge-and-trap
 GC/MS along with the condensate catch as specified in  EPA Method 5040. Analysis should be
 conducted within 14 days of sample collection.

 8.6    EPA METHOD 50402

        Principal organic  hazardous constituents  (POHCs) are  collected on Tenax®  and
 Tenax®/charcoal sorbent cartridges using a VOST, EPA Method 0030.  The contents of the
 sorbent cartridges are spiked with an intemai standard and thermally desorbed for 10 minuies a:
 80°C (176°F) with organic-free nitrogen or helium gas  [at a flow rate of 40 mL/min (2.4 in3)],.
 bubbled through 5 mL (0.3 in3) of organic-free: water, and trapped, on an analytical adsorbent trap.
 After the 10 minute desorption,, the-analytical adsorbent"trap-is rapidly* heated to  180°C (356°F),
 with the carrier gas flow reversed so that the effluent flow from the analytical  trap is directed
 into the GC/MS.   The volatile POHCs  are  separated  by  temperature-programmed  gas
.ehromatography and detected by low resolution mass spectrometry.  The concentrations .of che
 volatile POHCs are calculated using the internal standard technique.
                                          8-10

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       EPA Methods 5030 and 8240 may be referenced for specific requirements for the thermal
desorption unit, purge-and-trap unit, and GC/MS system.

       A diagram of the analytical system is presented in Figure 8-7. The Tenax® cartridges
should be analyzed within 14 days of collection.  The desired detection limit of this method is
0.1 ng/L (20 ng per Tenax® cartridge).

8.7    EPA REFERENCE METHOD  183

       EPA Reference Method 18  from 40 CFR Part 60, Appendix A, can be utilized for the
sampling and analysis of approximately 90 percent of the total gaseous organics emitted from
industrial sources. It does not include techniques to identify and measure  trace amounts of
organic compounds,  such  as those found in  room air and from fugitive sources.   Toluene
emissions can be measured from stationary sources using this method.   Method 18 can  be
conducted using either the direct interface method (on-line GC with FID) or by the collection of
an integrated Tedlar® or Mylar® bag with subsequent analysis by GC/FID.

       The direct interface method  draws a sample of the exhaust gas through a heated sample
line  directly into  a heated sample  loop and onto  the column of the GC. fined, with  an FID.
Figure 8-8 presents  a diagram of the  principle components of the direct interface sampling
system.

       Using the bag in drum technique as presented in Figure 8-9, a sample of the exhaust gas
is drawn into aTedlar® or Mylar® bag. The bag is placed inside a rigid leakproof container and
evacuated. Tne bag is then connected by a_Teflon® sample-line•• to a:sarhpling,:probe located at
the1 center of the  stack.. The sample is drawn into the- bag; by pumping- air- out: of the: rigid
container. The sample is then analyzed on-site or back at the laboratory by GC/FID.   The
Jtaoility  of  toluene- in a. Tedlar®  or Mylar® bag, is. currently unknown..   Therefore,  it: is
recommended that the analysis be conducted as soon as possible.
                                         8-12

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 8.8    EPA METHOD 00102

       EPA Method  0010 (Modified Method 5  Sampling Train) is  used to determine the
•destruction  and removal efficiency of semi-volatile principal organic hazardous constituents
 (POHCs) from incineration systems.  This  method  may  be used for determining toluene
 emissions.

       Gaseous and paniculate pollutants are withdrawn isokinetically from an emission source
 and collected in a multicomponent sampling train.  Figure 8-10 presents a schematic of the
 sampling system. Principal components of the train include a high-efficiency glass- or quartz-
 fiber filter  and a packed bed  of porous  polymeric adsorbent resin  (typically XAD-2   or
 polyurethane foam for PCBs). The filter is used to collect'organic-laden paniculate materials and
 the porous polymeric  resin to adsorb semi-volatile organic species (compounds with a boiling
point above 100°C (212°F)).  Comprehensive chemical analyses, using a variety of applicable
 analytical methodologies, are conducted to determine the identity and concentration of the organic
materials.

8.9    EPA METHOD 82702

       EPA Method  8270 is used, to  determine  the  concentration  of semi-volatile  organic
compounds in extracts prepared  from all types of solid waste matrices, soils, and ground water.
It is also applicable to an extract from sorbent media in conjunction with Method 0010.  Direct
injection of a sample may be used in limited applications.
         •

       Method 8270 can be-used to quantify most neutral, acidic, and, b'asic organic compounds
lhat are-soluble in metriylene chloride and capable of being-eiuted.without derivarizarion as sharp
peaks from  a  gas chromatographic fused-siiica capillary column coated with a slightly polar
silicone.   Toluene is  within the  boiling  point  range and, may  be-  determined, using  this
methodology.
                                         8-16

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       The-practical quantitation limit for Method 8270 is approximately 50 ug/mL of extract.
 The entire sorbent module with filter is typically extracted and concentrated to 1 mL (0.03 in3)
 (a final volume of 5 mL (0.2 in3)is used to avoid loss of volatile compounds), and this  final
 extract volume represents the entire volume of gas sampled.

 8.10   NIOSH METHOD 15014

       Ambient air and exhaust gas concentrations of toluene can also be measured using NIOSH
 Method 1501.  The levels of detection for NIOSH methods are usually much higher than the
 other procedures discussed. NIOSH methods are designed for worker exposure studies that are
 usually conducted over an 8 hour period.
                                                   x»
       Ambient air or exhaust gas samples are collected on a  solid  sorbent tube containing
 coconut shell charcoal with 100 mg on the front-half portion and 50 mg on the back-half. Two
 to 8 L (0.07 to 0.3 ft3) of air  are collected, depending on the expected concentrations, using a
 vacuum pump  set at an approximate  flow rate of 0.2  L/minute (0.007 ftVminute).   The
 breakthrough volume for toluene is 12 L (0.4 ft3).

       The samples are then capped, sent to the laboratory, desorbed with carbon disulfide (CSJ
 and analyzed by GC/FID. The column specified in NIOSH Method 1501 is a 3.0m x 2mm glass
 or stainless steel with 10 percent OV-275  on 100/200 mesh Chromosorb W-AW or equivalent
The stability of the sorbent sample is currently unknown, therefore analysis should be conducted
as soon as possible.

       Figure 8-ii presents a  schematic of the sampling,, system.
                                         8-18

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8.11  REFERENCES FOR SECTION 8.0

1.    U.S. Environmental Protection Agency. Compendium of Methods for the Determination
      of Toxic Organic Compounds in Ambient Air. EPA/600/4-89/017. June 1988.

2.    U.S. Environmental Protection Agency. Test Methods for Evaluating Solid Waste  Third
      Edition, Report No. SW-846.  Office  of Solid Waste  and Emergency  Response
      Washington, DC. November 1986.
3.
4.
40 CFR, Part 60, Appendix A, Method 18: Measurement of Gaseous Organic Compounds
by Gas Chromatography. pp 823 through 852.


NIOSH Manual of Analytical Methods, Third Edition, Volume 1 and 2. February 1984.
                                     8-20

-------

-------
                   APPENDIX A




POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
                      A-l

-------

-------
                                    TABLE A-l.
   POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
 SIC Code        Source Description
                 fammtammmmmmmm
 1011	Iron ores: taconite iron ore processing
 1099     Metal ores, NEC: aluminum ore (bauxite)
 1300     Oil and gas extraction fuel fired process heaters
 1311     Oil and gas production: crude oil production
 1321     Natural gas liquids
 1382     Oil and gas exploration services '
 1400     Nonmetallic minerals, except fuels (mining operations)
 L442      Mineral products: sand and gravel
 [475      Mineral products: phosphate rock
1499      Mineral products: salt mining
1611      Highway and street construction
1629     Heavy construction, nee
1781     Water well drilling
1791     Structural steel erection
1799     Special, trade contractors,, nee
2000     Food and agriculture fuel fired equipment: process heaters
201.1     Meat-packing plants••
2013     Sausages, and other prepared, meais
 :015     Food and kindred products: poultry slaughtering and processing
 '023	Dry, condensed,, evaporated  products
 02'6:
Fluid :mi1k-.
 032:     Organic-solvent-surface'coating: can.coating-
 033,     Canned, .fruits arid vegetables ,
 034     Dehydrated fruits, vegetables, soups
 037     Frozen fruits and vegetables
                                    (continued)
                                       A-2

-------
                      TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
                      (continued)
SIC Code
2043
2044
2046
2047
2048
2051
2052
2064
2076
2077
2079
2082
2084
2085
2086
2087
2091
2099
2111
"7 I'M
~
2200
2211
2221
2231
2241
Source Description
Cereal breakfast foods '
Rice milling
Wet com milling
Dog and cat food
Prepared feeds, nee ;
Bread, cake, arid related products
Cookies and crackers
Candy & other confectionery products
Vegetable oil mills, nee
Animal and marine fats and oils
Edible fats and oils, nee
Malt beverages
Wines, brandy, and brandy spirits
Distilled and blended liquors
Bottled and canned soft drinks
Flavoring extracts and syrups, necr
Canned and cured fish and seafoods . !
Food preparations, nee
Cigarettes
	 -n
C> •!
:gars ;
Organic solvent- textile: manufacturing:: knit fabric scouring.
Broadwoven fabric mills, cotton
Broadwoven fabric mills, manmade
Broadwoven fabric mills, wool
Narrow fabric mills
                      (continued)


                        A-3

-------
                                   TABLE A-l.
   POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
                                   (continued)
                         --- -  •   —
 SIC Code       Source Description
                ^••••MBMBMH
 2257     Weft knit fabric mills
 1261     Finishing plants,.cotton
 2262     Finishing plants, manmade
 2269     Finishing plants, nee
          Yarn spinning mills
 £282     Throwing and winding mills
 2284
 Thread mills
          Coated fabrics, not rubberized
  196
Tire cord and fabrics
         Nonwoven fabrics
2298     Cordage and twine
2299     Textile goods, nee
 2321     Men's and boys' shirts
2326     Men!s and boys' work clothing
2341
Women's and children's underwear
2353'     Hats, caps, and millinery.
2369-    Girls' and children's outerwear, nee
 381     Fabric dress and work gloves
2385"    Waterproof outerwear
 387:
Apparel-, belts"
2389     Apparel;and accessories; nee.
2392     House furnishings, nee
 394	Canvas and related products
2396     Automotive- and apparel teirnmings
 399     Fabricated textile products, nee
                                  (continued)
                                     A-4

-------
                       TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
                       (continued)
SIC Code
2421
2426
2429
2431
2434
2435
2436
2439
2449
2451
2452
2491
2493
2499
2511
2512
2514
2515
2517
2519
2521
2522
2531
2541
2542
Source Description
Sawmills and planing mills, general
Hardwood dimension & flooring mills
Special product sawmills, nee
Millwork
Wood kitchen cabinets
Hardwood veneer and plywood
Softwood veneer and plywood x.
Structural wood members,- nee
Wood containers, nee
Mobile homes
Prefabricated wood buildings
Wood preserving
Lumber and wood products: reconstituted wood products
Wood products, nee
Wood household furniture
Upholstered household furniture
Metal household furniture
Mattress.es and bedsprings
Wood TV and radio cabinets
Household furniture; nee
Wood office "furniture
Office furniture, except wood
Public building & related furniture
Wood partitions and fixtures
Partitions and fixtures, except wood
                        (continued)
                          A-5

-------
                       TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
                       (continued)
SIC Code Source Description
2585
2591
2599
2611
2621
2631
2652
2653
2655
2656
2657
2670
2670
2671
2672
2673'
2674
2675
2676-
^677-:
12679-
J2711
J2721
J2731
J2752'.
Refrigeration and heating
^
equipment
Drapery hardware & blinds & shades
Furniture and fixtures, nee
Pulp mills
Paper mills
Paperboard mills
Setup paperboard boxes

•

x»
Corrugated and 'solid .fiber boxes
Fiber cans, drums & similar products
Sanitary food containers
Paper and allied products:
Paper and .allied products:

folding paperboard boxes
miscellaneous converted paper products
Organic solvent surface coating: paper coating
Paper coated; &. laminated,
packaging
Paper coated and laminated, nee
Bags:, plastics, Jaminated., & .coated, I
Bags:- uncoated; paper & muitiwail !
Paper and allied products:
Sanitary paper products
Envelopes'
Paper, and allied products::
Newspapers
Periodicals
Book publishing
Book printing
^-^ 	 	 	
die-cut paper and board'

i
converted paper: products




                       (continued)
                         A-6.

-------
                                   TABLE A-l.
   POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
                                   (continued)
 SIC Code
       Source Description
 2741     Miscellaneous publishing
 2751     Printing/publishing: printing process
 2752     Commercial printing, lithographic
 2754     Commercial printing, gravure
 2759     Printing and publishing: commercial printing, nee
 2761
Manifold business forms
 2771     Greeting cards
 2782
Blankbooks and looseleaf binders
 2789     Bookbinding and related work
 2791      Typesetting
 2796     Printing and publishing: platemaking services
 2800    . Chemicals and allied products
2812
Alkalies and chlorine
2813
Industrial gases
2816     Inorganic pigments
2819      Industrial inorganic chemicals, nee
2821
Plastics materials and resins
2822     Synthetic rubber
*2S23
Cellulosic manmade fibers
         Organic-fibers,, nonceilulosKr
(2833
Medicinais and botanicals
2834     Pharmaceutical preparations
2835     Diagnostic substances
2836     Biological products exc. diagnostic
2841     Soap and other detergents
                                   (continued)
                                      A-7

-------
                      TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
                      (continued)
SIC Code
2842
2843
2844
2851
2861
2865
2869
2873
2874
2879
2891
2892
2893
2895
2899
2900
2911
2922
2951
2952:
2992
2999
3011
3021
3052
=====
Source Description
Polishes and sanitation goods
Surface active agents
Toilet preparations
Paints and allied products
Gum and wood chemicals
Cyclic crudes and intermediates
Industrial organic chemicals, nee >.
Nitrogenous fertilizers
Phosphatic fertilizers
Agricultural chemicals, nee
Adhesives and sealants
Explosives
Printing ink
Carbon black
Chemical preparations, nee
Petroleum and coal products petroleum industry i
Petroleum refining :
Petroleum Industry: Lube Oil Refining
Asphalt paving mixtures and blocks
Asphalt feits" and:, coatings - !
Lubricating oils and greases' j
Petroleum industry - petroleum refining: sludge converter
Tires and inner tubes
Rubber and plastics footwear
Rubber and plastics products: rubber and plastics hose and belting
(continued)
                        A-8

-------
                       TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
                       (continued)
SIC Code
3053
3061
3069
3079
3080
3081
3082
3083
3086
3087
3088
3089
3111
3131
3142
3143
3144
3149
?3172
3199
'3211
3221
3229
3231
3241
Source Description
Gaskets, packing and sealing devices
Mechanical rubber goods
Fabricated rubber products, nee
Organic solvent surface coating of plastic parts
Rubber and plastics products: miscellaneous plastics products, nee
Unsupported plastics film & sheet
Unsupported plastics profile shapes N-
Laminated plastics plate & sheet
Plastics foam products
Custom compound purchased resins
Plastics plumbing fixtures
Plastics products, nee
Leather tanning and finishing
Footwear cut stock
House slippers
Men's footwear, except athletic j
Women's footwear, except athletic
Footwear, except rubber, nee
Personal leather goods, nee •
Leather goods, nee - j
Flat slass
Glass containers
Pressed and blown glass, nee
Products of purchased glass
Cement, hydraulic j
                       (continued)
                        - A-9

-------
                                   TABLE A-l.
   POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
  	                           (continued)
 SIC Code
       Source Description
 3251     Mineral products: brick manufacturing
 3253     Ceramic wall and floor tile
 3255     Mineral products: castable refractory
 3261     Vitreous plumbing fixtures
 3263     Semivitreous table & kitchenware
 3264     Porcelain electrical supplies
 3271      Concrete block and brick
 3272     Concrete products, nee
 3274
 Lime
 3275     Mineral products: gypsum manufacturing
3291     Abrasive products
3292     Asbestos products
3295     Minerals, ground or treated
 •296
 Mineral wool
 297     Nonclay refractories
 299     Nonmetailic mineral oroducts. nee
 300
Secondary metals: misc. casting and fabricating
 312     Blast furnaces and steel mills
 313     Electrometailurgicai products.
3315'    Steel •. wire •: and ..related; pro ducts.
3316'     Cold, finishing of steel shanes
3317     Steel pipe and tubes
3320     Primary metal industries, iron and steel foundries
3321
Primary metal industries: gray and ductile iron foundries (gray iron)
         Steel investment foundries
                                     A-10

-------
                       TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
                       (continued)
SIC Code
3325
3331
3334
3339
3341
3351
3353
3354 ,
3355
3357
3360
3363
3364
3365
3366
3369
3398
3399
3400
3411
3^12
3421
3423
3425
3429
Source Description
Steel foundries, nee
Primaiy copper
Primary aluminum
Primary metal industries: primary nonferrous metals, nee (lead production)
Secondary nonferrous metals
Copper rolling and drawing
Aluminum sheet, plate, and foil v. -
Aluminum extruded products
Aluminum rolling and drawing, nee
Nonferrous wiredrawing & insulating
Primary metal industries: nonferrous foundries (castings)
Aluminum die-castings
Nonferrous die-casting exc. aluminum
Aluminum foundries
Copper foundries
Nonferrous foundries, nee j
Metal heat treating :
Primary metal products, nee
Fabricated metal products: -iron -and steel general processes jj
Metai cans i
Metal barrels, drums, and pails
Cutlery
Hand .and edge tools, nee
Saw blades and handsaws
Hardware, nee
                       (continued)

                         A-ll

-------
                                   TABLE A-l.
   POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
                                   (continued)
 3IC Code        Source Description
                •^•••MMMBi                              	
 '431     Fabricated metal products: porcelain enamel/ceramic glaze spraying
 3432     Plumbing fixture fittings and trim
 3433     Heating equipment, except electric
 5441
 Fabricated structural metal
 3442     Metal doors, sash, and trim
 5443     Fabricated plate work (boiler shops)
 5444
 Sheet metal work
 5446     Architectural metal work
 3448      Prefabricated metal buildings
3449
Miscellaneous metal work
3451     Screw machine products
 3452     Bolts, nuts, rivets, and washers
 5462     ton and steel forgings
 5463     Nonferrous forgings
 5465     Automotive stampings
 3466
Crowns and closures
3469     Metal stampings, nee
3471     Plating and polishing
3479' •   Metal coating and allied services
3482:
Small .arms ammunition -
3483     Ammunition;, exc; for small arms, nee
         Ordnance and accessories, nee
         Fluid power valves & hose fittings
        ~~                        ==
                                   (continued)
                                     A-12

-------
                       TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
                       (continued)
SIC Code
3493
3494
3496
3497
3498
3499
3511
3519
3523
3524
3531
3532
3533
3534
3535
3536
3537
3541
3542
3543
3544
3545
3546
3548
Source Description *
Steel springs, except wire
Valves and pipe fittings, nee
Misc. fabricated wire products
Metal foil and leaf
Fabricated pipe and fittings
Fabricated metal products, nee
Turbines and turbine generator sets
Internal combustion engines, nee
Farm machinery and equipment
Lawn and garden equipment
Construction machinery
Mining machinery
Oil and gas field machinery
Elevators and moving stairways
Conveyors and conveying equipment
Hoists, cranes, and monorails
Industrial trucks and tractors
Machine tools, metal cutting types
Machine tools, metal forming types
Industrial patterns
Special dies, Cools, jigs & fixtures
Machine tool accessories
i 	 i
Power-driven hand tools
Welding apparatus
                        (continued)
                         A-13

-------
                                  TABLE A-l.
   POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
  	               (continued)
                Source Description
SIC Code
••Mi
3549     MetalworMng machinery, nee
 3552    Textile machinery
 3553    Woodworking machinery
 3554    Paper industries machinery
 3555    Printing trades machinery
 3556     Food products machinery
 3559     Special industry machinery, nee
 3561	Pumps and pumping equipment
 3562     Ball and roller bearings
 3563     Air and gas compressors
 3564     Blowers and fans
3565     Packaging machinery
3566     Speed changers, drives, and gears
3567
        Industrial, furnaces and ovens
 569     General industrial machinery, nee
3571
        Electronic- comtiuters
 3572     Computer storage devices
3575     Computer terminals
 5577
         .omputer peripheral: equipment nee
3578:     Calculating: and accounting equipment:
3579^
        Office.machines, nee.
3581     Automatic vending machines
3582	Commercial laundry equipment
3585	Refrigeration and heating equipment
3586	Measuring and dispensing pumps
                                  (continued)
                                    A-14

-------
                       TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
                       (continued)
SIC Code
3589
3592
3593
3594
3599
3612
3613
3621
3624
3625
3629
3631
3632
3633
3634
3635
3639
3641
3643
3644
3645
3646
3647
3648
3651
Source Description
Service industry machinery, nee
Carburetors, pistons, rings, valves
Fluid power cylinders & actuators
Fluid power pumps and motors
Industrial machinery, nee
Transformers, except electronic
Switch gear and switchboard apparatus M.
Motors and generators
Carbon and graphite products
Electronic equipment: relays and industrial controls
Electrical industrial apparatus, nee
Household cooking equipment
Household refrigerators and freezers
Household laundry equipment
Electric housewares and fans
Household vacuum cleaners
Household appliances, nee
Electric lamps
Current-carrying wiring devices
Noncurrent-carrying wiring. devices'
Residential lighting fixtures. j
Commercial lighting fixtures
Vehicular lighting equipment
Lighting equipment, nee
Household audio and video equipment
                       (continued)
                         A-15

-------
                       TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
                       (continued)
SIC Code
3652
3661
3663
3669'
3671
3672
3674
3675
3676
3679
3691
3692
3694
3695
3699
3711
3713
3714
3715'
3716
3721
3724
3728
3731
3732
=^==
Source Description '
Prerecorded records and tapes
Telephone and telegraph apparatus
Radio & TV communications equipment
Communications equipment, nee
Electron tubes
Printed circuit boards
Semiconductors and related devices
Electronic capacitors
Electronic resistors
Electronic components, nee
Storage batteries
Primary batteries, dry and wet
Engine electrical equipment
Magnetic and optical recording media
Electrical equipment & supplies, nee
Motor- vehicles and car, bodies
Truck and bus bodies • j
Motor vehicle, parts and accessories
Truck, trailers
Mo tor: homes ;
Aircraft
Aircraft engines and engine parts
Aircraft parts and equipment, nee
Ship building and repairing
Boat building and repairing
                       (continued)
                        A-16

-------
                       TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
                       (continued)
SIC Code
3743
3751
3761
3764
3769
3792
3795
3799
3812
3820
3821
3822
3823
3824
3825
3826
3827
3829
3840
3841
3842
3843
3844
3845
3851
Source Description
Railroad equipment
Motorcycles, bicycles, and parts
Guided missiles and space vehicles
Space propulsion units and parts
Space vehicle equipment, nee
Travel trailers and campers
Tanks and tank components
Transportation equipment, nee
Search and navigation equipment
Instruments/related products - measuring/controlling devices:
Laboratory apparatus and furniture
Environmental controls
Process control instruments
Fluid meters and counting devices
Instruments to measure electricity
Analytical instruments
Optical instruments and lenses
Measuring & controlling devices, nee
Instruments and related products - medical instruments and suupiies: x-rav
Surgical and medical instruments
Surgical appliances and supplies
Dental equipment and supplies
X-ray apparatus and tubes
Electromedicai equipment
Ophthalmic goods
                       (continued)


                         A-17

-------
                                   TABLE A-l.
   POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
                                   (continued)
                Source Description
SIC Code
^mmm
3861     Photographic equipment and supplies
 3873     Watches, clocks, watchcases & parts
 3900    Miscellaneous manufacturing industries: process heaters
 3911      Jewelry, precious metal
 3914     Silverware and plated ware
 3915     Jewelers' materials & lapidary work
3931
         Musical instruments
3942     Dolls and stuffed toys
3944     Games, toys, and children's vehicles
3949     • Sporting and athletic goods, nee
3951     Pens and mechanical pencils
3952     Lead pencils and art goods
3953     Marking devices
3955     Carbon -paper and. inked ribbons
 961     Costume jewelry
3965
         Miscellaneous manufacturing industries:  fasteners, buttons, needles, and pins

         Brooms and brushes
 991
 '993     Signs and advertising specialties
 $995
        Burial caskets-
 996     Hard surface: floor coverings; nee
 999     Manufacturing industries, nee
4111
        Local and suburban; transit
 131     Intercity & rural bus transportation
 173     Bus terminal and service facilities
 212	Local trucking, without storage
                                   (continued)
                                     A-18

-------
                                   TABLE A-l.
   POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
                                   (continued)
SIC Code
       Source Description
4215      Courier services, except by air'
4226      Special warehousing and storage, nee
4231     Trucking terminal facilities
4491     Water transportation: marine cargo handling
4499     Water transportation; services, nee
4510     Air transportation: scheduled air transportation
4512     Air transportation, scheduled
4612     Crude petroleum pipelines
4741
Rental of railroad cars
4785     Inspection & fixed facilities
4789     Transportation services, nee
4900    • Solid waste disposal - commercial/institutional: landfill dump
4911
Anthracite coal
4922     Natural gas transmission
4923
Gas transmission and distribution
 1-925     Gas production and/or distribution
4941     Water supply
4952     Sewerage systems
4953
Refuse svstems
 -961     Steam and air-conditioning supply
 013     Motor vehicle- supplies and new parts
         Furniture
 '031     Lumber, plywood, and mUlwork
 040     Wholesale trade (durable goods):  professional equipment and supplies
                                   (continued)
                                      A-19

-------
                                  TABLE A-L.
   POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
  	                (continued)
 SIC Code       Source Description
     IMBBBH^HHl

 5044     Office equipment
 5045     Computers, peripherals & software
 5046     Commercial equipment, nee
5063     Electrical apparatus and equipment
5078     Refrigeration equipment and supplies
5084     Industrial machinery and equipment
5085     Industrial supplies
5092     Toys and hobby goods and supplies
5093     Scrap and waste materials
5113     Industrial & personal service paper
5130     Apparel, Piece Goods, and Notions
5169     Chemicals & allied products, nee
5171     Petroleum bulk stations & terminals
5172     Petroleum products,, nee
 182     Wine and distilled beverages
 191     Farm supplies
 194     Tobacco and tobacco products
)198     Paints, varnishes, and supplies
 211     Lumber and other building materials
 231;     Paint,: glass,, and, wallpaper, stores
 511
New and used, car dealers
 541
Gasoline service stations
 551
Boat dealers
 599     Automotive-dealers, nec~
 712
Furniture stores;
                                  (continued)
                                     A-20

-------
                      TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF TOLUENE EMISSIONS
                      (continued)
SIC Code
5984
5999
6141
6512
6513
6514 '
7215
7216
7218
7359
7372
7378
7389
7.514
7515
7532
7534
7538
7539
7540
7600
7629
7641
7694
7699
Source Description
Liquefied petroleum gas dealers
Miscellaneous retail stores, nee .
Personal credit institutions
Nonresidential building operators
Apartment building operators
Dwelling operators, exc. apartments
Coin-operated laundries and cleaning V.
Drycleaning plants, except rug
Industrial launderers
Equipment rental & leasing, nee
Prepackaged software
Computer maintenance & repair
Business services, nee
Passenger car rental
Passenger car leasing
Top & body repair & paint shops
Tire retreading and repair shops
General automotive repair shops
Automotive repair shops, nee
Auto repair, services, ancLparidng:: automotive services, except repair- j
Miscellaneous repair services:, eiecrricai equipment
Electrical repair shops, nee.
Reupholstery and furniture repair
Armature rewinding shops
Repair services, nee
                      (continued)


                        A-21

-------
                                   TABLE A-l.
   POTENTIAL SOURCE CATEGORIES OF TOLUENE EiMISSIONS
                                   (continued)
SIC Code
M1MBMHH
8062
8211
8244
8249
8331
8412
8711
8731
8732
8734
8740
8999
9199
9223
9224
9511
9711
9999
Source Description
General medical & surgical hospitals
Elementary and secondary schools
Business and secretarial schools
Vocational schools, nee
Job training and related services
Museums and art galleries
Engineering services
Engineering and management services: commercial physical research
Commercial nonphysical research
Testing laboratories
Engineering and management services: management and public relations
Services, nee
General government, nee
Correctional institutions:
Solid waste disposal - government: fire fighting
Air, water, & solid waste management ;
National security i
Nonclassifiable establishments
NEC.= Not elsewhere: classified.:.
Sources:-


Toxic Chemical Release Inventory (TR1), 1987-1990.  On-line access through the databases
National Library of Medicine, Bethesda, MD.

Crosswalk/Air Toxic Emission Factor Database Management System (XATEF), Version 12 US
Environmental Protection Agency, Office of. Air Quality Planning and Standards, Research
Triangle Park, NC. October 1991.


Volatile Organic Compound (VOC) Paniculate Matter (PM) Speciation Database Management
System,.Version 1.4.. U.S.-Environmental Protection:Agency, Office-of Air Qualirv Planning and
Standards, Research Triangle Park, NC. October 1991                     '
                                     A-22

-------

-------
                        APPENDIX B
LISTS OF PAINT, INK, AND PRINTING FACILITIES WITH ANNUAL SALES
                 GREATER THAN $1 MILLION
                           B-l

-------

-------
                     TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
      ANNUAL SALES GREATER THAN $1 MILLION
Name
Aervoe-Pacific Co. Inc.
AExcel Corp.
Agri-Blend Inc.
Akron Paint & Varnish Inc.
Akzo Coatings Inc. Reliance Universal Inc.
Akzo Coatings Inc. Akzo Resins & Vehicles
Akzo Coatings Inc.
AUentown Paint Manufacturing Co.
Also Indus Inc. Morton Paint Co.
Ameritone Paint Corp.
Ameron Inc. Enmar Finishes Div.
Ameron Inc. Ameron Protective Coatings
Div.
Amsterdam Color Works Inc.
Aspen Paints
Atlas Coating Corp.
Automotive Finishes Inc.
Baker Sealants & Coating
Barrett Varnish Co.
Bee Chem Co.
Behr Process Corp.
Address
PO Box 485, Gardnervffle NV 89410
7373 Production Dr, Mentor OH 44060
PO Box 957, Rowlett TX 75088
1390 Firestone Parkway, Akron OH 44301
1930 Bishop Ln, Louisville KY 40218
21625 Oak St, Matteson IL 60443
1600 Watterson Towers, Louisville KY 40218
PO Box 597, Allentown PA 18105
Box 6208, Canton OH 44706
PO Box 190, Long Beach CA 90801
PO Box 9610, Little Rock AR 72219
201 N Berry St, Brea CA 92621
1546 Stillwell Ave, Bronx NY 10461
1128 SW Spokane St, Seattle WA 98134
820 E 140th St, Bronx NY 10454
6430 Wyoming Ave, Dearborn MI 48126
234 Suydam Ave, Jersey City NJ 07304
1532 S 50th Ct, Cicero IL 60650
2700 E 170th St, Lansing DL 60438
PO Box 1287, Santa Ana CA 92702
=^==^==
Sales in
$ Millions
MIMMHMI
11
20
1*
4*
300
13
' 550*
4
3
40
15
112
7
4
7*
4
5
3
66
^3*
Benjamin Moore ac Co. 51 Chestnut Ridge Rd.. Montvaie NJ" 07645 ^Q* i
Bennette Paint Manufacturing Co.
PO Box 9088, Hampton VA 23670
Best Bros Paint ivlanufaciuring Co. ?O Box 2056, Sinking Spr PA 19608
Beverly Manufacturing Co. (Los Angeles)
BLrk Paint Manufactunns Inc.
Blue Ridge Talc Co. Inc.
Brewer Chem Corp.
Brod-Dugan Co.
5 j
i ii
9118 S Main St, Los Angeles CA 90003 2 ;
230 Keamv Ave, Jersey City NJ 07305 ->
PO Box 39, Henry VA 24102
PO Box 48, Honolulu HI 96810
2145 SchuetzRd. St. Louis MO 63146
9 1
50
15
i Brumng Paint Co., j .601 .3. Haven. ..Baltimore., MD 2'12'M. ! 
-------
                      TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
  ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Carboline Co.
Cardinal Color Co.
Cardinal Indus Finish Inc.
Century Chem Co.
Certified Coating Products
CF Jameson & Co. Inc.
Charles A Crosbie Labs Inc.
Chemical Technology Labs Inc.
Chemical Coating Corp.
Ciba-Geigy Corp. Drakenfeld Colors
Clement Coverall Inc.
CM Athey Paint Co.
Coatings & Chems Corp.
Colonial Refining & Chem Co.
Columbia Paint Corp.
Columbia Paint Co.
Colwell Gen Lie.
Commercial Chem Co. Inc.
Con-Lux Coatings Inc.
Cook & Dunn Paint Corp. Pure All Paint
Coatings Co.
Address
350 Hanley Indus Ct, St. Louis MO 63144
50-56 1st St, Paterson NJ 07524
1329 Potrero Ave, South El Mon CA 91733
5 Lawrence St, Bloomfield NJ 07003
2414 S Connor Ave, Los Angeles CA 90040
PO Box 197, Bradford MA 01835
PO Box 3497, Van Nuys CA 91407
12150 S Alameda St, Lynwood CA 90262
7300 Crider Ave, Pico Rivera CA 90660
PO Box 519, Washington PA 15301
PO Box 557, Cairiaen NJ 08101
1809 Bayard St, Baltimore MD 21230
3067 N Elston Ave, Chicago IL 60618
20575 Ctr Ridge Rd, Cleveland OH 44116
PO Box 2888, Huntington WV 25728
PO Box 4569, Spokane WA 99202
PO Box 329, Fort Wayne IN 46801
PO Box 2126, Santa Ana CA 92707 •
PO Box 847, Edison NJ 08818
700 Gotham Ave, Carlstadt NJ 07072
Cook ± Dunn Paint Corp. j 700 Gotham Parkway, Caristadt NJ 07072
Cook & Dunn Paint Corp. Adelphi
Coating
Cook Paint & Varnish Co.
Coronado Point Co. Inc.
Cosan Chem Corp.
Cotter & Co. Gen Paint & Chem Co.
Courtlauids Coarinss USA Inc.
Cowman «k Campbed
C? Inc.
Crest Chem Indus Ltd.
Crosby Coatings Inc.
CWC Indus Inc.
Daiys Inc.
Dampney Co. Inc.
Daniel Products Co.
Davis Paint Co.
700 Gotham Parkway, Carlstadt NJ 07072
PO Box 419389, Kansas Citv MO 64141
PO Sox 308, Sdgewater PL 32032
400 14th St, Caristadt NJ 07072
201Jandus Rd., Gary IL 60013
Sales in
$ Millions
65
7
18
5
1
1
1
3
3
28
4
6
5
3
5
17
20
'4
25
8*
20 !
3
100
23
10*
120
PO Box 1439, Louisville, KY 40201 i60*
PO Box 70328, Seattle WA 98107 3 j
PO Box- 333, Connersvule-lN 47331 | 5 j
PO Box 85, New Lenox IL 60451 i*
PO Box 1038, Chico CA 95927
2686 Lisbon Rd. Cleveland OH 44104
3525 Stone Way N', Seattle WA 98103
85 Paris St, Everett MA 02149
400 Claremont Ave, Jersey City NJ 07304
1311 Jron-St. Kansas City MO 64116
6
5 !
5 \
4
20
13 !
                       (continued)
                        B-3

-------
                     TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
  ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Davlin Paint Co. Inc.
DC Franche & Co.
De Boom Paint Co.
Dean & Bany Co.
Decratrend Paints
Deft Inc.
Del Paint Corp.
Delrac Manufacturers of Bisonite Products
Co. Inc.
DeSoto Inc.
Devoe & Raynolds Co.
Dexter Corp. Dexter Specialty Coatings
Div.
Diamond Products Co. Inc.
DJ Simpson Co.
Dover Sales Co. Inc.
Duncan Enterprises
Dunn Edwards Corp.
Dupli-Color Products Co.
Duralac Inc.
Duron Inc.
Dye Specialties Inc.
Egyptian Lacquer Manufacturing
Ellis & .Everard (US Holdings) Inc.
Prillaman Chem Corp.
Elpaco Coatings Corp.
Emco Finishing Products Inc.
Empire State Varnish Co.
Environmental Coatings Inc.
Epoca Co.
Epoxy Coatings Co.
Evans Paint Inc.
Everseai Manufacturing Co. Inc.
Fabrionics Inc.
Farboil Co.
Farwest Paint Manufacturing Co. Inc.
Federated Paint Manufacturing Co.
Ferro Corp. Coatings Div.
"
Address
700 Allston Way, Berkely CA 94702
1401 W Wabansia Ave, Chicago EL 60622
645 Texas St, San Francisco CA 94107-
296 Marconi Blvd, Columbus OH 43215
251 Mason Way, City of Didu CA 91746
17451 Von Karman Ave, Irvine CA 92714
3105 E Reno St, Oklahoma City OK 73117
PO Box 764, Tonawanda NY 14151
PO Box 5030, Des Plaines IL 60017
PO Box 7600, Louisville KY 40207
1 E Water St, Waukegan IL 60085
709 S 3rd Ave, Marshalltown IA 50158
PO Box 2265, South San Francisco CA 94080
PO Box 2479, Berkeley CA 94702
PO Box 7827, Fresno CA 93747
PO Box 30389, Los Angeles CA 90039
1601 Nicholas Blvd, Elk Grove Vi IL 60007
84 Lister Ave. Newark NJ 07105
10406 Tucker St, Beltsville MD 20705
PO Box 1447, Secaucus NJ 07096
PO Box 4449, Lafayette IN 47903
PO Box 4024, Martinsville -VA 24112
PO Box 447. Elkhart IN 46515
470 Cresent St. Jamestown NY 14701
38 Varick St, Brooklyn NY 11222
6450 Hanna Lake SE. Caledonia MI ^93 16
Sales in
$ Millions
mmmmmmmm
3*
3
5
15
17
- 15
4 .
3*
408
120*
80
18*
5
3*
30
150*
50
4
150
3 1
10 j
96*
S
i i
5
5
5 Lawrence- 3t, Sloomfieid NJ 07003 j ;
PO Box. 1035, Union City CA 94587 [
PO Box 4098, Roanoke VA 24015
475 Broad Ave,- Ridgefieid NJ 07657
Route 130 S, Camargo IL 61919
8200 FischerRd. Baltimore- MD 212^
PO Box 68726, Tukwila WA 98168
1882 S Normal St, Chicago IL 60616
PO Box 6550, Cleveland OH 44101
(continued)
.<*
I T
13
11
3
S*'
73*
======1
                       B-4

-------
                      TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
  ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Fiber-Resin Corp.
Fine Line Paint Corp.
Finishes Unlimited Inc.
Finnaren & Haley Inc.
Flecto Co. Inc.
Frank W Dunne Co.
Frazee Indus Inc.
Fredericks-Hansen Paint
Fuller O'Brien Corp:
Gilbert Spruance Co.
Given Paint Manufacturing Co. Inc.
GJ Nikolas & Co. Inc.
Glidden Co. Eastern Region
Glidden Co. Southwest Region
Glidden Co. Resin Div.
Gloss-Flo Corp.
Glyptal Inc.
Gordon Bartels Co.
Graham Paint & Varnish Co.
Grow Group Inc. US Paint Div.
Grow Group Inc. Natl Aerosol Products Co.
Grow Group Inc.
Guardsman Products Inc.
Guardsman Chems Inc.
H Behlen & Brother Inc.
Hancock Paint & Varnish
Hanna Chem Coatings Inc.
Harco Chem Coatings Inc.
Harrison Paint Corp.
Harnn Paint &. Filler
Hempel Coatings USA
Hentzen Coatings Inc.
Heresite Protective Coatings Inc.
Hofaoken Paint Co. Inc.
Hoffers Inc.
Hy-Klas Paints Inc.
Hydrosol Inc.
Address
PO Box 4187, Burbank CA 91503
12234 Los Nietos Rd, Santa Fe Spr CA 90670
PO Box 69, Sugar Grove EL 60554
2320 Haverford Rd, Ardmore PA 19003
PO Box 12955, Oakland CA 94608
1007 41st St, Oakland CA 94608
PO Box 2471, San Diego CA 92112
PO Box 5638, San Bernardino CA 92408
450 E Grand Ave, South San Francisco CA 94080
Richmond St & Tioga St, Philadelphia PA 19134
111 N Piedras St, El Paso TX 79905
2810 Washington Blvd, Bellwood DL 60104
PO Box 15049, Reading PA 19612
PO Box 566, Carrollton TX 75011
1065 Glidden St NW, Atlanta GA 30318
135 Jackson St, Brooklyn NY 11211
305 Eastern Ave, Chelsea MA 02150
2600 Harrison Ave, Rockford IL 61108
4800 S Richmond St, Chicago IL 60632
831 S 21st St, St. Louis MO 63103
2193 E 14th St, Los Angeles CA 90021
200 Park Ave, New York NY 10166
3033 Orchard Vista Dr, Grand Rapids MI 49501
13535 Monster Rd, Seattle WA 98178
Route 30 N Penh Rd, Amsterdam -NY 12010 '
109 Accord Dr, Norweil MA 02061
PO Box 147, Columbus OH 43216
208 DuPont St, Brooklyn NY 11222
Sales in
$ Millions
10
5
3
25*
20
7
100
12
140
10
7*
2
140
59
30
4
5
7
10*
30*
5
413 i
190 |
6
10 i
10
25
6
PO Box 8470, Canton OH 447 11 20 1
PO Box 116. Caristadt NJ 07072 3
20L Route 17 N, Rutherford NJ 07070
6937 W Mill Rd. Milwaukee WI 53218
PO Box 250, Manitowoc WI 54221
40 Endus Rd, Lodi NJ 07644
PO Box 777, Wausau WI 54401
1401 S 12th St, Louisville KY 40210
8407 S 77th Ave, Bridgeview IL 60455
15
12
15
17
47
6
30
                       (continued)
                         B-5

-------
                     TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
  ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
ICI Americas Inc. ICI Paints
Illinois Bronze Paint Co.
Indurall Coatings Inc.
Industrial Coatings Intl.
Insilco Corp. Sinclair Paint Co.
International Paint Co. USA Inc.
International Paint Co. USA Inc. Southwest
Div.
International Coatings Co.
Irathane Syss Inc.
IVC Indus Coatings Inc.
J Landau & Co. Inc.
James B Day & Co.
James Bute Co.
Jasco Chem Corp.
John L Armitage & Co.
Johnson Paints Inc.
Jones Blair Co. Oilman Paint &
Wallcovering Div.
Kalcor Coatings Co.
Kaufman Products Inc.
Keeier& Long Inc.
Keily-Moore Paine Co. Inc. Hurst Div.
Kelly-Moore Paint Co.
King Fiber Glass Corp. Hber Resin
Supply Div.
Komac Paint Inc.
Kop-Coat Co. Inc.
Kop-Coat Co. Inc. Pettit Paint Co.
Kurtees Coatings Inc. j
Kwal-Howeils Inc.
L & H Paint; Products Inc. .
Lasting Paints Inc.
Lenmar Inc.
Lilly Chem Products Inci,
Lilly Industrial Coatings Inc.
Lily Co. Inc.
Linear Dynamics Inc.
	 T
Address
925 Euclid Ave, Cleveland OH 44115
300 E Main St, Lake Zurich IL 60047
PO.Box 2371, Birmingham AL 35201
7030 Quad Ave, Baltimore MD 21237
6100 S Garfield Ave, Los Angeles CA 90040
6001 Antoine, Houston TX 77091
PO Box 920762, Houston TX 77292
13929 E 166th St, Cerritos CA 90701
PO Box 276, Hibbing MN 55746
PO Box 18163, Indianapolis IN 46218
PO Box 135, Carlstadt NJ 07072
Day Ln, Carpentersville IL 60110
PO Box 1819, Houston TX 77251
PO Drawer J, Mountain View CA 94040
1259 Route 46 E, Parsippany NJ 07054
PO Box 061319, Fort Myers FL 33906
PO Box 1257, Chattanooga TN 37401
37721 Stevens, Willoughby OH 44094
1326 N Bentalov St, Baltimore MD 21216
PO Box 460, Watertown CT 06795
301 W Hurst Bivd, Hurst TX 76053
987 Commercial St San Carlos CA 94070
366 W Nickerson St, Seattle WA 98119
1201 Osaae St. Denver CO 80204
480 Frelinghuysen Ave, Newark NJ 07114
36 Pine St. Rockaway NJ 07866
201 £ Market .St Louisville.. KY 40202 . i
PO Box- 39-R. Denver CO 80239
PO Sox 7311, San Francisco CA 94 PO
PO Box 4428, Baltimore -MD 21223
150 S Calverton Rd, Baltimore MD 21223
PO Box 188, Temnieton MA 01468
733 S West St, Indianapolis, IN 46225
PO Box 2358, High Point NC 27261
400 Lanidex Plz. Parsippany NJ 07054
(continued)
Sales in
$ Millions
843
25
8
14*
100*
50
18
5
8*.
9
4
8
3*
7
8*
9
38-
6
1*
10 i
15 j
230*
^ ',
10
15
11
16 i
	 — 	 	 : 	 j!
J. j
6
13
11
212
30
30
;
                       B-6

-------
                     TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
  ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Lyle Van Patten Co. Inc.
MA Bruder & Sons Inc.
Maas & Waldstein Co.
MAS Paints Lie.
Magmder Color Co. Inc. Radiant Color Div.
Major Paint Co.
Mansfield Paint Co. Inc.
Marteclnc.
Mamn-Senour Co.
Mautz Paint Co.
McCormick Paint Works Co.
McWhorter-McCIoskey Inc.
Mercury Paint Co. Inc.
Mid-States Paint Co.
Midwest Lacquer Manufacturing Co.
Midwest Paint Manufacturing Co.
Millmaster Onyx Group Inc. Mantrose-
Haeuser Co.
Mobile Paint Manufacturing Co.
Mohawk Finishing Products
Moline Paint Manufacturing Co.
Moling Paint Manufacturing
Monarch Faint Co.
Morton Ind Inc. Norris Paint/TMT
Muralo Co. Inc.
Muralo Co. Inc. Olympic Paint &. Chem
Co.
N Siperstein Inc.
National Paint Co. Inc.
National JLacquer & Paint Co.
Nelson *ech Coarinas Inc.
New York Bronze Powder Co. Inc.
Niles Chem Paint Co.
Norton & Son Inc.
Nu-Bnte Chem Co. Inc. Kyanize Painis
O'Brien Corp.
O'Brien Corp. Powder Coatings Div.
O'Brien Corp. Southeast Region
Address
321 W 135th St, Los Angeles CA 90061
PO Box 600, BroomaU PA 19008
2121 McCarter Highway, Newark NJ 07104 '
630 N 3rd St, Terre Haute IN 47808
PO Box 4019, Richmond CA 94804
4300 W 190th St, Torrance CA 90509
169 W Longview Ave, Mansfield OH 44905
760 .Aloha St, Seattle WA 98109
101 Prospect Ave, Cleveland OH 44115
PO Box 7068, Madison WI 53707
2355 Lewis Ave, Rockyille, MD 20851
5501 E Slauson Ave, Los Angeles CA 90040
14300 Schaefer Highway, Detroit MI 48227
9315 Watson Indus Park, St. Louis MO 63126
9353 Seymour Ave, Schiller Par EL 60176
2313 W River Rd N, Minneapolis MN 55411
500 Post Rd E, Westport CT 06880
4775 Hamilton Blvd, Theodore AL 36582
Route 30 N, Amsterdam NY 12010
5400 23rd Ave, Moline IL 61265
5400 23rd Ave, Moline EL 61265
PO Box 55604, Houston TX 77255
PO Box 2023, Salem OR 97308
PO Box 455, Bayonne NJ 07002
5928 S Garfield Ave, Los Angeles CA 90040
415 Montgomery St, Jersey City NJ 07302
3441 E 14th St, Los Angeles CA 90023
Sales in
$ Millions
3
140*
15
32
30
65
2
3
44*
19
18*
5
18
3
5
2
15
45
35*
17
125 !
29*
5,,, ,1
.12
i*
40
*"* !
7415 S Green St,. Chicago EL 60621 2 '
2147 N Tyler Ave,, South £1 Mon CA 91733 	 .- 2 	
519 Dowd Ave, Elizabeth NJ 07201
PO Box 307, Niles ME 49120
148 E 5th St Bayonne NJ 07002
30
16*
15*
2nd & Boston St, Everett MA 02149 i ' 20
450 E Grand Ave, South San Francisco CA 94080
5300 Sunrise Rd, Houston TX 77021
PO Box 864. Brunswick GA 31521
150*
40 j
11*
(continued)
                        B-7

-------
                     TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
  ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
i^MM^BEB^HMH^HHI^Mim^HI^^MM^HHH
Old Quaker Paint Co.
Orelite Chem Coatings
Pacific Coast Lacquer Co. Inc.
Palmer Paint Products Inc.
Pan Chem Corp.
Paragon Paint & Varnish Corp.
Parker Paint Manufacturing Co.
Parks Corp.
Parks Paint & Varnish Co. Inc.
Passonno Paints
Pave-Mark Corp.
PavePrep Corp.
Penn Color Inc.
Pentagon Chem & Paint Co.
Perfection Paint & Color Co.
Performance Coatings Inc.
Perry & Derrick Co.
Pervo Paint Co.
PFI Incorporated-Paints for Industry
Pierce & Stevens Corp.
Plasti-Kote Co. Inc.-
Plasticolors Inc.
Plextone Corp. of America
PMC Inc. Gen Plastics Div.
Ponderosa Paint Manufacturing Co. Inc.
Porter Paint Co.
Potter Paint Co. Inc.
PPG Indus Architectual Finishes Inc.
PPG Indus Inc. Automotive Products Grouo
Pratt &, Lambert Inc.
Pratt & Lambert Inc. Western Div.
Premier Coatings Inc.
Preservative Paint Co. Inc.
Pro-Line Paint Manufacturing Co. Inc.
Proctor Paint & Varnish
Progress Paint Manufacturing Co.
Pruett-Schaffer Chem Co..
^ — = ============irs:^^ES==
Address
2209 S Main St, Santa Ana CA 92707
62 Woolsey St, Irvington NJ 07111
3150 E Pico Blvd, Los Angeles CA 90023
PO Box 1058, Troy MI 48099
1 Washington Ave, Hawthorne NJ 07506
5-49 46th Ave, Long Island NY 11101
PO Box 1 1047, Tacoma WA 984 1 1
PO Box 5, Somerset MA 02726
660 Tonnelle Ave, Jersey City NJ 07307
500 Broadway, Watervliet NY 12189
PO Box 94108, Atlanta GA 30318
141 Central Ave, Westfield NJ 07090
400 Old Dublin Pike, Doylestown PA 18901
24 Woodward Ave, Ridgewood NY 11385
715 E Maryland St, Indianapolis IN 46202
PO Box 1569, Ukiah CA 95482
2510 Highland Ave, Cincinnati OH 45212
6624 -Stanford Ave, Los Angeles CA 90001
921 Santa Fe Springs Rd, Santa Fe Spr CA 90670
710 Ohio St, Buffalo NY 14203
PO Box 708, Medina OH 44258
2600 Michigan Ave, Ashtabula OH 44004
2141 McCarter Highway, Newark NJ 07104
55-T La France Ave, Bloomfield NJ 07003
PO Box 5466, Boise ID 83705
PO Box 1439, Louisville KY 40201
PO Box 265, Cambridge Ci IN 47327
2233 112th Ave NE, Bellevue WA 98004
PO Box 3510, Trov MI 48007
75 Tonawanda St. Buffalo NY 14207
Sales in
$ Millions
HMBMMM
31
4
3
7
5
14*
26
20
3*
10
20
14*
40
16*
6*
3 '
15
13
2
50
50
17 j
3
4 I
10 |
m ]
2* 1
110*
20*
246 !
PO Box 668, Marysville CA 95901 10
2250 Arthur Ave. Elk Grove Vi IL 60007
5410 Airport Way S, Seattle WA 98108
2646 Main St. San Diego CA 9211"
38 Wells Ave, Yonkers NY 10701
PO Box 33188, Louisville KY 40232
PO Box 4350, Pittsburgh PA 15204
(continued)
20
13
7*
20
10
4
=====
                       B-8

-------
                      TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
  ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Pyrolac Corp.
Quality Coatings Inc.
Raffi & Swanson Inc.
Randolph Products Co.
Red Spot Paint Varnish Co. Red Spot
Westland Lie.
Red Spot Paint Varnish Co.
Reliable Coatings Inc.
Republic Clear Thru Corp.
Republic Powdered Metals Inc.
Riley Bros Inc.
River Valley Coatings Inc.
Riverside Labs Inc.
RJ McGlennon Co. Inc.
Roymal Inc.
RPMInc.
Rudd Co. Inc.
Rust-Oleum Corp.
Rutland Fire Clay Co.
Sampson Paint Manufacturing Co.
Sampson Coatings Inc.
Sandstrom Products Co.
Saxon Paint & Home Care Centers Inc.
Dreeblan Paint Co.
Schalk Chems Inc.
Scott Paint Corp.
Seagrave Coatings Corp. Clover Leaf Paint
& Varnish
Seaside Inc.
Seibert-Oxidermo Inc.
SEM Products Inc.
Sentry Paint Technologies Inc.
Seymour of Sycamore Inc.
Sheboygan Paint Co.
Sheffield Bronze Paint Corp.
Sherwin-Williams Co.
Sherwin-Williams Co. Automotive Div.
Sherwin-Williams Co. Consumer Div.
Address
55 Schoon Ave, Hawthorne NJ 07506
1700 N State, Chandler IN 47610
100 Eames St, Wilmington MA 01887
Park Place E, Carlstadt NJ 07072
550 S Edwin St, Westland MI 48185
PO Box 418, Evansville IN 47703
13108 Euless St, Euless TX 76040
211 63rd St, Brooklyn NY 11220
PO Box 777, Median OH 44258
860 Washington Axe, Burlington IA 52601
PO Box 580, Aurora EL 60507
411 Union St, Geneva IL 60134
198 Utah St, San Francisco CA 94103
Route 103, Newport NH 03773
PO Box 777, Medina OH 44258
1630 15th Ave W, Seattle WA 98119
11 Hawthorne Parkway, Vemon Hills IL 60061
PO Box 340, Rutland VT 05702
1900 Ellen Rd, Richmond VA 23224
PO Box 6625, Richmond VA 23230
218, S High, Port Byron IL 61275
3729 W 49th St, Chicago IL 60632
2400 Vauxhall Rd, Union NJ 07083
5940 Palmer Blvd. Sarasota FL 34232
320 Paterson Plank Rd, Carlstadt N] 07072
PO Box 2809, Long Beach CA 90801
6455 Strong Ave, Detroit MI 48211
120 Senr.-Ln, Beimont CA 94002 .
237 Mill St. Darby PA 19023
917 Crosby Ave, Sycamore IL 60178
PO Box 417, Sheboygan WI 53082
17814 S. Waterloo Rd. Cleveland OH 44119
101 Prospect Ave NW, Cleveland OH 44115
101 Prospect Ave NW, Cleveland OH 44115
101 Prospect Ave NW, Cleveland OH 44115
Sales in
$ Millions
4*
2
15
9
15
56
14*
6
15 •
3
2*
3*
3 •
4
380
10
89
2
42
9
7'
15*
7 !
16* !
14*
3
11
.. .'/ 	 '
10
10
12
i
2,124
160
170*
                       (continued)
                         B-9

-------
                     TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
  ANNUAL -SALES GREATER THAN $1 MILLION (continued)
Name
Sherwin-Wilhams Co. Oakland
Sherwin-Williams Co. Chem Coatings Div.
Sigma Coatings Co.
Smiland Paint Co.
Snyder Bros Co.
Southern Coatings Inc.
Southwestern Petroleum Corp.
Spatz Paints Inc.
Specialty Coating & Chem
Spectra-Tone Paint Corp.
Spraylat Corp. Los Angeles
Stanchem Inc.
Standard Detroit Paint Co.
Standard T Chem Co. Inc.
Star Finishing Products Inc.
Star Bronze Co.
SiD Coating Corp.
Steelcote Manufacturing Corp.
Sterling Twelve Star Paint
Sterling-Clark-Lurton
Stevens Paint Corp.
Stonhard Inc.
Strathmore Products Inc.
Sullivan Coatings Inc.
Sunnyside Corp
Superior Varnish & Drier Co.
Superior Sealants Inc.
Supro Corp.
Technical. Coatings Laboratory Inc;
Technical Coatings Inc:
Technical Coatings Co.
Tenax Finishing Products
Tera Lite Inc.
Tester Corp.,
Thompson & i-ormby Inc.,
Ti-Kromatic Paints Inc.
Tnemec Co. Inc.
================================:====:==
' Address
1450 Sherwin Ave, Oakland CA 94608
11541 S Champlain Ave, Chicago IL 60628
PO Box 816, Harvey LA 70059
620 Lamar St, Los Angeles CA 90031
PO Box 760, Toccoa GA 30577
PO Box 160, Sumter SC 29151
PO Box 961005, Fort Worth TX 76161
1439 Hanley Industrial Ct, St. Louis MO 63144
7360 Varna Ave, North Hollywood CA 91605
9635 Klingerman St, South El Mon CA 91733
3465 S La Cienega,- Los Angeles CA 90016
401 Berlin St, East Berlin CT 06023
8225 Lyndon Ave, Detroit MI 48238
290 E Joe Orr Rd, Chicago Heights IL 60411
360 Shore Dr, Hinsdale IL 60521
PO Box 2206, Alliance OH 44601
461 Broad Ave, Ridgefield NJ 07657
3418 Gratiot St, St. Louis MO 63103
PO Box 791, Little Rock AR 72203
184 Commercial St, Maiden MA 02148
38 Wells Ave, Yonkers NY 10701
PO Box 308. Maple Shade NJ 08052
1970 W Fayette St, Syracuse NY 13204
410 N Hart St. Chicaso IL 60622
Sales in
$ Millions
32*
250
15
10
7
40
26
5
3
7
5
10
8
14*
15
11
3
4
15
9
15
62, i
6
o* -
225 Carpenter Ave, Wheeling IL 60090 id
PO Box 1310, MerchantvilleNJ 08109 I 7* ',
1135 Sylvan SW, Atlanta GA 30310
2650 Pomona Blvd, Pomona CA 91768
11*
4
PO Box 565, Avon CT 06001 • 6 :
PO Box/3337; Austin TX 78764 $ •,
1000 -Waish: Ave;. Santa. Clara- CA- 95050 : 6
390 Adams St, Newark NJ'071 14 5*
1631 S 10th St, San Jose Ca 95112
620 Buckbee St, Rockford IL 61106
825 Crossover Ln, Memphis TN 38117
2492 Doswell Ave, St. Paul MN 55108
PO Box 411749, Kansas City MO 64141 j
^^ — ^_ ]_
(continued)
3
43* !
«!,4* '
•3"
50 j
=====
                       B-10

-------
                      TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
  ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Touraine Paints Inc.
Tower Paint Manufacturing
Trail Chem Crap.
Triangle Coatings Lie.
United Paint & Chem Corp.
United Coatings Inc.
United Paint Co.
United Gilsonite Labs
Universal Paint Corp.
Universal Chems & Coatings Inc.
Universe Paint Co.
Valspar Corp. MCI Quality Coatings
Valspar Corp. Colony Paints Div.
Valspar Corp.
Valspar Corp. Masury Paint Co.
Vanex Color Inc.
VJ Dolan & Co. Inc.
Vogel Paint & Wax Inc. Marwin Paints Inc.
Vogel Paint & Wax Inc.
Voplex Corp. Allerton Chem Div.
Waterlox Chem & Coatings Corp.
Watson-Standard Co. Jordan Paine
Manufacturing Co.
Watson-Standard Co.
Wattyl Group Precision Paint Group
WC Richards Co. Inc.
Welco Manufacturing Co. Inc.
Wellborn Paint Manufacturing Co.
Western Automotive Finishes
Westrieid Coatings Corp.
Westingnouse Eiec Corp. insulating
Materials Div.
Whittaker Corp. Whutaker Decatur Coatings
William Zinsser & Co.
Wiltech Corp.
Wisconsin Protective Coatings Corp.
WM Barr & Co. Inc.
Yenkin Majestic Paint Corp.
Address
1760 Revere Beach Parkway, Everett MA 02149
620 W 27th St, Hialeah EL 33010
9904 Gidley St, El Monte CA 9173 1
1930 Fairway Dr, San Leandro CA 94577
24671 Telegraph Rd, Southfield M 48034
2850 Festival Dr, Kankakee EL 60901
404 E MaUory, Memphis TN 38109
PO Box 70, Scranton PA 18501
PO Box 1218, La Puente CA 91749
1975' Fox Ln, Elgin IL 60123
PO Box 668, Mary.sville CA 95901
6110 Gunn Highway, Tampa FL 33625
PO Box 418037, Kansas City MO 64141
1101 S 3rd St, Minneapolis MN 55415
1401 Severn St, Baltimore MD 21230
1700 Shawnee St, Mount Vemon IL 62864
1830 N Laramie Ave, Chicago IL 60639
2100 N 2nd St, Minneapolis MN 55411
Industrial Air Park Rd., Orange City IA 51041
763 Linden Ave, Rochester NY 14625
9808 Meech Ave, Cleveland OH 44105
7250 Franklin St, Forest Park JDL-60130
PO Box 11250, Pittsburgh PA 15238
5275 Peachtree, Atlanta GA 30341
3555 W i23rd St, Blue Island IL 60406
1225 Ozark St, North Kansas MO 64116
215 Rossmoor Rd SW, Albuquerque NM 87102
Sales in
$ Millions
17
10
4
5
11*
65
25
22*
20
10
3*
12
15
527
8
4
5
8*
100
1
4
, ,4
T
29*
if
15* !
10
15
1450 Ave R. Grand Prairi TX-75050 17-*
PO Box 815, Westfiied MA 01086 7 j
Route 993, Manor PA 15665
PO Box 2238, Decatur AL 35602
31 Belmont Dr, Somerset NJ 08873
PO Box 517, Longview WA 98632
PO Box 216, Green Bay WI 54305
PO Box 1879, Memphis TN 38113
PO Box 369004, Columbus OH 43236
i5 [
12*'
16
"i i
10
95
80
                       (continued)
                        B-ll

-------
                                  TABLE B-l.
    PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
      ANNUAL SALES GREATER THAN $1 MILLION (continued)
              Name
                                                Address

                                 3273 Casitas Ave, Los Angeles CA 90039
                                      Sales in
                                     $ Millions
                                        MM
                                         2*
  £olatone Process Inc.
3411 E 15th St, Los Angeles CA 90023
 ZPC Indus Coatings Inc.
120 E Minereal St, Milwaukee WI53204
 Synolyte Products Co.
PO Box 6244, Carson CA 90749
* Indicates an estimated financial figure.
Source: Gale Research, Inc. Ward's Business Directory of U.S. Private and Public Companies-1991  Volume 4
Detroit, MI. 1991.
                                    B-12

-------
                       TABLE B-2.
PRINTING INK MANUFACTURING FACILITIES (SIC 2893) WITH
       ANNUAL SALES GREATER THAN $1 MILLION
Name
Acme Printing Ink Co. Packaging Inc. Corp.
Acme Printing Ink Co.
AJ Daw Printing Ink Co.
American Inks & Coatings Corp.
Autoroll Machine Corp.
BASF Corp. Coatings & Colorants Div.
Bomark Inc.
Borden Inc. Coatings & Graphics Group
Braden Sutphin Ink Co.
Celia Corp.
Central Ink & Chem
Colonial Printing Ink Corp
Converters Ink Co.
Croda Inks Corp.
Custom Chem Corp.
Del Val Ink & Color Co. Inc.
Excello Color & Chem
Hint Ink Corp.
Flint Ink Corp. Capitol Printing Ink
Flint Ink Corp.
Gans Ink & Supply Co. Inc.
Gotham Ink &. Color Co. Inc.
Graphic Color Corp.
Handschy Ink &. Chems Inc.
Ink Masters Inc.
James River Corp. of Virginia CZ Inks Div.
JM Huber Corp. Carbon Div.
Kerley Ink Engineers Inc.
Kohl & Madden Printing Ink Corp.
Lakeland Laboratory Inc. Alfa Ink Div.
Lakeland Laboratory Inc.
Lawter Intl Inc.
Merit Printing Inc. Co.
Address
5001 S Mason Ave, Chicago IL 60638
165 Bond St, Elk Grove Vi IL 60007
3559 S Greenwood Ave, Los Angeles CA 90040
PO Box 803, Valley Forge PA 19482
11 River St, Middleton MA 01949
1255 Broad St, Clifton NJ 07015
601 S 6th Ave, City of Indu CA 91746
630 Glendale - Milford, Cincinnati OH 45215
3650 E 93rd St, Cleveland OH 44105
320 Union St, Sparta MI 49345
1100 N Harvester.Rd, West Chicago IL 60185
180 E Union Ave, East Rutherford NJ 07073
1301 S Park Ave, Linden NJ 07036
7777 N Merrimac, Niles IL 60648
30 Paul Kohner PI, Elmwood Park NJ 07407
1301 Taylors Ln, Riverton NJ 08077
1446 W Kinzie St, Chicago JJL 60622
25111 Glendale Ave, Detroit ME 48234
806 Channing PI ME, Washington DC 20018
1404 4th St, Berkeley CA 94710
1441 Boyd St, Los Angeles CA 90033
5-19 47th Ave, Long Island NY 11101
750 Arthur Ave, Elk Grove Vi IL 60007
120 25th Ave, Beilwood IL. 60104
2842 S 17th Ave, Broadview IL 60153
4150 GUT Ln. St. Louis MO 63119
9300 Needlepoint Rd, Baytown TX 77521
2839 -'19th Ave, Broadview EL 60153-
222 Bridge Plz Sq, Hackensack NJ 07601
655 Washington Ave, Carlstadt NJ 07072
655 Washington Ave, Carlstadt NJ 07072
990 Skokie Blvd. Northbrook IL 60062
1451 S Lorena St. Los Angeles CA 90023
Sales in
$ Millions
100
140*
13
15
12
105*
3
17*
25
15
9
17
16*
32*
40
5
84*
235
23
30*
18
4
18
30 j
3
28
18*
4* 	 !•
45
2* 1
•^
136
4*
                        (continued)
                         B-13

-------
                              TABLE B-2.
   PRINTING INK MANUFACTURING FACILITIES (SIC 2893) WITH
      ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Midland Color Co.
Miller-Cooper Co.
Morrison Printing Ink Co.
Naz-Dar Co.
Nor-Cote Intl Inc.
North American Printing Ink
Northern Printing Ink Corp.
Polypore Inc.
Polytex Color & Chem
PPG Indus Inc. PPG Ink Products Co.
Rexart Chem Corp.
Ron Ink Co. Inc.
Sicpa Indus of America Inc.
Sinclair & Valentine LP
Sun Chem Corp.
•Sun Chem Corp. Gen. Printing Ink Div.
Superior Printing Ink Co. Inc.
United States Printing Ink Corp. Leber Ink
Div.
United States Printing Ink Corp.
Van Son Holland Corp. of America
Vivitone Inc.
Walter W Lawrence
Wikoff Color Corp.
Address *
651 Bonnie Ln, Elk Grove Vi EL 60007 "
1601 Prospect Ave, Kansas City MO 64127
4801 W 160th St, Cleveland OH 44135
1087 N Northbranch St, Chicago IL 60622
PO Box 668, Crawfordsville IN 47933
1524 David Rd, Elgin IL 60123
8360 10th Ave N, Minneapolis MN 55427
4601 S 3rd Ave, Tucson AZ 85714
820 E 140th St, Bronx NY 10454
1835 Airport Exchange :Blvd, Covington KY 41018
1183 Westside Ave, Jersey City NJ 07306
61 Halstead St, Rochester NY 14610
8000 Research Way, Springfield VA 22153
2520 Pilot Knob Rd, St. Paul MN 55120
PO Box 1302, Fort Lee NJ 07024
135 W Lake St, Northlake IL 60164
70 Bethune St, New York NY 10014
PO Box 88700, Seattle WA 98138
343 Murray HilLPkwy, East Rutherford. NJ 07073
92 Union St, Mineola NY 11501
110.E 27th St, Paterson NJ 07514
9715 Alpaca St, South El Mon CA 91733
Sales in
$ Millions
85
6
14*
15*
5
14
8
10
3
15
6*
7
25
186
1,100
410*
50
6
65
42 j|
.- — !l
1
PO Box W, Fort Mill SC 29715 j 45* i
Source:  Gale Research, Inc. Ward's Business
Detroit, MI., 1991:
Directory of U.S. Private and Public Companies-!991, Volume 4.
                                B-14

-------
                    TABLE B-3.
PRINTING AND PUBLISHING FACILITIES
    ANNUAL SALES GREATER THAN $1
               (SIC 27) WITH
               MILLION
Company
(SIC 2711) Newspapers
Advance Publications Inc.
Affiliated Publications Inc.
Chicago Tribune Co.
Cox Enterprises Inc.
Dow Jones & Co. Inc.
EW Scripps Co.
Freedom Newspapers Inc.
Gannett Co. Inc. • •
Hearst Corp.
Ingersoll Publications Co.
Knight-Ridder Inc.
Media Gen Inc.
New York Times Co.
News America Publishing Inc.
Thomson Newspapers Corp.
Times Mirro Co.
Tribune Co.
*
Location

Staten Island, NY
Boston, MA
Chicago, IL
Atlanta, GA
Washington, DC
Wilmington, DE
N»
Irvine, CA-
Arlington, VA
New York, NY
Princeton, NJ
Miami, FL
Richmond, VA
New York, NY
New York, NY
Des Plaines. EL
Los Angeles. CA
Chicago. IL
Sales in
$ Millions

2,200*
542
500
1,970
1,444
1,266
500
3,518
1,900*
1,010*
2,268
606
1,769
3,000
550*
3.475
2.455
(SIC 2721) Periodicals j
ABC Publishing
Billboard Publications Inc.
BPI Communications Inc.,
Cahners Publishing Co. New York Magazine Div.
Chilton Co.
CMP Publications Fnc.
Conde Nast Publications Inc.
New York, NY
New York. 1NY
New York. NY
New York. NY
Radnor, PA
Manhasset. NY
New York, NY
310*
100
105 I
102' I
150
187*'
280*
(continued)
 B-15

-------
                    TABLE B-3.
PRINTING AND PUBLISHING FACILITIES (SIC 27) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Company
Grain Communicating Inc.
Diamonds Communications Inc.
Edgeil Communications Inc.
Forbes Inc.
International Data Group Inc.
Meredith Corp.
Meredith Corp. Ladies' Home Journal
National Enquirer Inc.
National Geographic Soc.
Newsweek Inc.
Official Airline Guides Inc.
Penthouse Intl. Ltd.
Penton Publishing Inc.
Peterson Publishing Co.
Playboy Enterprises Inc.
Reader's Digest Assn. Inc.
Reed Publishing (USA) Inc., Cahners Publishing
Co.
Reed Publishing (USA) Inc.
Rodale Press Inc.
Scholastic Inc.
Simon & Shuster Inc. Bur of Bus Practice
Standard & Poor's Corp.
Thompson Corp. Thompson Bus. Info.
Time Inc. Magazine Co.
Times Mirror Magazines Inc.
Location
Chicago, IL
New York, NY
Cleveland, OH
New York, NY
Framingham, MA
Des Moines, IA
New York, NY
vV-
Lantana, FL
Washington, DC
New York, NY
Oak Brook, IL
New York, NY
Cleveland, OH
Los Angeles, CA
Chicago, IL
. Pleasantville, NY
Newton. MA
Newton, MA
Emmaus, PA
New York. NY
Waterford, CT
New York; NY-
Stamford, CT
New York. NY
New York, NY
Sales in
$ Millions
145
470*
205
200
• 500
792
100
180
425
256
130*
160*
151 -
140*
160
1,832
430
600
150*
250*
100*
260*
160*
1.500*
470*
                     (continued)
                      B-16

-------
                    TABLE B-3.
PRINTING AND PUBLISHING FACILITIES (SIC 27) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Company
Trader Publications Inc.
US News & World Report Inc.
Warren Gorham & Lament Inc.
Whittle Communications Inc.
Ziff Communications Co.
Ziff Communications Co. Zif-Davis Publishing
Co.
Location
Clearwater, FL
New York, NY
New York, NY
Knoxville, TN
New York, NY
New York, NY
Sales in
$ Million:;
270*
140*
130
210*
340*
160*
(SIC 2731) Book Publishing
Addison-Wesley Publishing Co.
Bantam Doubleday Dell Publishing Group Inc.
David C. Cook Publishing Co.
Encyclopedia Britannica Inc.
Field Publications
Grolier Inc.
Harcourt Brace Jovanovich Inc.
Harper Collins Publishers Inc.
Houghton MiSlin Co.
Insilco Corp.
John Wiley & Sons Inc.
Lawyers Co-Operative Publishing Co. Inc.
Macmillan Inc.
Macmillan Inc. Info Svcs & Instruction
MacMillan Intl. Inc.
Macmillan-McGraw-Hill School Publishing Co..
School Div.
Reading, MA
New York, NY
Elgin, IL
Chicago, IL
Middletown, CT
Danbury, CT
Orlando, FL
New York, NY
Boston, MA
Midland. TX
New York, NY
Rochester, NY
New York, NY
New York, NY
New York. NY
New York, NY
120*
180*
100
624
100*
440*
1,341
450
370
450*
282
150*
950*
416
146*
200
                     (continued)
                       B-17

-------
                    TABLE B-3.
PRINTING AND PUBLISHING FACILITIES (SIC 27) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
»
Company
-••-•"—•—•••-•••—••——•«••••
Macmillian-McGraw-Hffl School Publishing Co.
McGraw-Hill Inc. McGraw-Hill Intl Book Group
Mosby Year Book Inc.
Prentice Hall Inc.
Putnam Publishing Group, Inc.
Rand McNally & Co.
Random House, Inc.
RR Donnelley & Sons Co. Willard Div.
Simon & Schuster Inc.
South- Western Publishing Co,
Sunday School Bd of the Southern Baptist
Convention
Time-Life Books Inc.
West Publishing Co.
Western Publishing Group Inc.
World Book Inc.
Zondervan Corp.
Location
— ——M— M— .^
Lake Forest, IL
New York, NY
St. Louis, MO
New York, NY
New York, NY
Skokie, EL
New York, NY
Willard, OH
New York, NY
Cincinnati, OH
Nashville, TN
Alexandria, VA
St Paul, MN
Racine, WI
Chicago. IL
Grand Rapids, MI
(SIC 2732) Book Printing
Arcata Graphics Co. Arcata Grannies Book Group
Banta Corp.
Bertelsmann Printing & Mfg. Corp.
Brown Printing Co. (Waseca Minnesota)
Great Lakes Color Printing Corp.
Harper & Row, Publishers
1 '
(cc
=^=^=^=
Sales in
$ Millions
i^mmmmmmmmm
390*
115
150
970*
100
430*
325
150
1,320
112
172
350
450* "
480
330*
100*

Kinesport, TN 17,')*
Menasha, WI
Berrwille, VA
568
10Q*
Waseca, MN 353 i
Brentwood, TN
New York, NY'
*=== i
ntinued)
210* |
450 ]
1
                     B-18

-------
                    TABLE B-3.
PRINTING AND PUBLISHING FACILITIES (SIC 27) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
>
Company
Jostens Inc. Printing & Publishing Div.
RR Donnelley & Sons Co.
Location
Minneapolis, MN
Chicago, IL
Sales in
$ Millions
121
3,122
(SIC 2741) Misc Publishing
Commerce Clearing House Inc.
Donnelley Directory
GTE Telephone Operations Inc. GTE Directories
Corp.
McGraw-Hill Info. Svcs. Co.
NYNEX Info Resources Co.
RL Polk & Co.
Simplicity Holdings, Inc.
Simplicity Pattern Co.
Southwestern Bell Yellow Pages Inc.
Southwestern Bell Publications Inc.
U.S. West Direct (U.S. West Marketing
Resources Group Inc.)
Wonderland Music Co. Inc.
Riverwoods, IL
New York, NY
Dallas-Fort, TX
New York,-NY
Middleton, MA
Detroit, MI
New York, NY
New York, NY
St. Louis, MO
St. Louis, MO
Aurora, CO
Burbank, CA
678
1,300*
360*
668
800
280
110*
101
240*
280*
160*
200*
(SIC 2752) Commercial Printing-Lithographic '
American Signature Graphics Foote & Davies
Div.
American Bank Stationary Co.
Avery Tntl Corp. Avery Label Co.
Graphic Controls Corp.
Graphisphere Corp.
HS Crocker Co. Inc.
Judd's Inc.
] NMG Inc.
Atlanta, GA
Baltimore, MD
Azusa, CA
Buffalo, NY
Des Plaines, IL
South San Francisco, CA
Washington, DC
Los Angeles, CA
195 • |
110*
no* i
140
110
140*'
114-
105 1
                     (continued) -
                       B-19

-------
                    TABLE B-3.
PRINTING AND PUBLISHING FACILITIES (SIC 27) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Company
""^ ^^••^^••••^•••••^••••IMBHBBi^Mii
Perry Printing Corp.
Quebecor Printing (USA) Inc.
Queens Group Inc.
Ringler America Inc.
KR Donnelley & Sons Co. Mattoon Mfg. Div.
RR Donnelley & Sons Co. Lancaster Mfg. Div.
Shea Communications Co.
Taylor Corp.
Treasure Chest Advertising Co. Inc.
Valassis Inserts Inc.
World Color Press Inc.
Location
^••BMBmMnBiMMnHHIiMM
Waterloo, WI
St Paul, MN
Long Island, NY
Itasca, IL
Mattoon, IL
Lancaster, PA
Louisville, KY
Mankato, MN
Glendora, CA
Livonia, MI
Effingham, IL
(SIC 2754) Commercial Printing-Gravure
All-State Legal Supply Co.
Arcata Graphics Co.
Beck Co. (Langhorne Pennsylvania)
Clark Printing Co. Inc.
ColorArt Inc.
Dennison Mfg. Co: IPC Dennison Co.
Dinagraphics Inc.
Golden Belt Mfg. Co.
Graphic Ctr. Cos. Inc.- Blake Printery
International Label Co.
JW Fergusson & Sons
Maxwell Communications Corp. Atglen
McCleery-Cumming Co.
Cranford, NJ
Baltimore, MD
W, Langhorne, PA
North Kansas, MO
St.,Louis, MO
Roaersville, TN
Cincinnati, OH
Durham, NC
St. San Luis Obi, CA
Clarksville, IN *
Richmond. VA
Atglen, PA
Washington, IA
Sales in
$ Millions
MMM^MMM
175
770
100
700
110*
190*
120
540*
550*
400*
650
•
43
500*
10
14*
30 '
60
20
70
11
30
34
50*
TT-
                     (continued)
                      B-20

-------
                    TABLE B-3.
PRINTING AND PUBLISHING FACILITIES (SIC 27) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Company
Meredith-Burda Corp.
Peny Printing Corp. Norway Div.
Printing House Inc. (Quincy Florida)
Ringier America Inc. Corinth Div.
Sheridan Press
Southern Gravure Svc. Inc.
Stevens Graphics Inc.
Technographic Inc. Decotone
World Color Press Inc. Salem Gravure Div.
Location
Des Moines, IA
Norway, MI
Quincy, FL
Corinth, MS
Hanover, PA
Louisville, KY
Atlanta, GA
Lexington/SC
Salem, IL
Sales in
$ Millions
500
25*
24
80
15
58*
150
30
80
(SIC 2759) Commercial Printing Nee
Alden Press Inc.
Avery Intl. Corp. Soabar Products Group
Bowne& Co. -Inc.
Curtis 1000 Inc.
Data Documents Inc. (Omaha)
Deluxe Corp.
Duplex Products Inc.
Graphic Indus. Inc.
John H. Hariand Co.
Maxwell Commun Corp.
Meehan-Tooker Inc.
Quad Graphics Inc.,
RR Donnelley & Sons Co. Warsaw Mfg. Div.
Webcraft Technologies Inc.
Williamhouse-Regency Inc.
Elk Grove Village, IL
Philadelphia, PA
New York, NY
Atlanta, GA
Omaha, NE
St. Paul, MN
Sycamore, EL
Atlanta, GA
Atlanta, GA
St. Paul, MN
East Rutherford, NJ
Pewaukee. WT *
Warsaw, IN
North Brunswick, NJ
New York,, NY
170*
100*
190
160*
200
1,316
327
310
345
720*
110
380
160* i
220*
230
                     (continued)
                      B-21

-------
                              TABLE B-3.
       PRINTING AND PUBLISHING FACILITIES (SIC 27) WITH
      ANNUAL SALES GREATER THAN $1 MILLION (continued)
Company
MI^BHIi^^^BI^^^BBI^BBI^M^^^^^^^^^^^^^^^_^^_
^^^^^^^^^^^^^^^^^^^^^^•^^^^^•^^^^^^^•••^^^••^^•••IM^BB
World Color Press Inc. Spartan Printing Co.
Location
••^^•••^^•^^^••fl^^^^^^^^^^^^^^^^^^^^^^^^^^^^
^^•^^^^^^^^^^^^^•^^^^^^^^^^^^^^^^^^^^^^•^^^^H
Sparta, IL
(SIC 2761) Manifold Business Forms
Allied Paper Inc. Allied-Energy Syss Inc.
American Bus Products Inc.
Arnold Corp.
CST Group Inc.
Ennis Bus. Forms Inc.
McGregor Printing Corp.
Moore Corp. Ltd. Moore Bus. Forms & Syss.
Div.
New England Bus. Svc. Inc.
Office Electronic Inc.
Standard Register Co.
Uarco Inc.
Vanier Graphics Corp. (American Bus. Products
Inc.)
Wallace Computer Svcs. Inc.
Dayton, OH
Atlanta, GA
Dayton, OH
Wheeling, IL
Ennis, TX
Washington; DC
Glenview, IL
Groton, MA
Itasca, IL
Dayton, OH
• Barrington, IL
Santee, CA
Hillside, IL
(SIC 2771) Greeting Cards •
American Greetings Corp.
American Greetings Corp. Seasonal Div.
Current Inc. (Colorado Springs Colorado)
Gibson Greetings Inc.,
Hallmark. Cards Inc. .
Hallmark Cards Inc. Topeka Products
-'• • ' ...-ii , .„,.. ., _ 	 ,_.,, , mm___
Cleveland, OH
Oscoola. AR
Colorado Springs, CO
Cincinnati, OH
Sales in
$ Millions
••n^HHMHHHM
100*

130*
387
200
110
130
125
1,675
226
105
709
520*
133
J.99

1,309
1 10
160
463 i
Kansas-Citv, MO ? -QO '
Topeka,, KS
=======:======================i====ri=====:
120*
^ —
* Indicates an estimated financial figure

EteteoT NflUeiSiearCfa' InC"  Ward'S 8usineSS Directory °f u-s: priva™ and Public Companies-1991, Volume
                                B-22

-------

-------
                     APPENDIX C
TOLUENE SOURCE CATEGORIES IN SURFACE COATING OPERATIONS
                         C-l

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-------
 REFERENCES FOR APPENDIX C
 1.
2.
3.
4.
       U.S. Environmental  Protection Agency.   VOC Pollution Prevention Options for the
       Surface Coating Industry.  Research Triangle Park, NC. 1991.

       U.S. Environmental Protection Agency.  Procedures from the Preparation of Emission
       Inventories for Carbon Monoxide and Precursors of Ozone, Volume I, EPA-450/4-91-016
       Research Triangle Park, NC.1991.

       U.S. Environmental Protection  Agency,  Stationary  Source Compliance Division.
       Recordkeeping Guidance Documentor Surface Coating Operations and the Graphic Arts
       Industry, EPA-340/1-88-003. Washington, DC.  December 1968.

       Ron Joseph and Associates, Inc.  Environmental and  Coatings Training Program.
       Workbook for presentation by Ron Joseph to EPA Region 1. September 2 and 3, 1987.

       The Bureau of  National Affairs, "Control Technologies" Air Pollution Control:  BNA
       Policy and Practice Series.  Washington, DC.  1992.

       Alliance Technologies.   VOC Control Policy in the United States:  An Overview of
       Programs and Regulations.  December 1991.

       U.S. Environmental Protection Agency.   Control of Volatile Emissions from Existing
       Stationary Sources.  Volume 11: Surface Coating of Large Appliances, EPA-450/2-77-
       034. Research Triangle Park, NC.  1977

       U.S. Environmental Protection  Agency.  Industrial Surface  Coating:  Appliances -
      Background Information for Proposed Standards (Draft Environmental Impact Statement)
       EPA-450/3-80-037A.  Research Triangle Park, NC.  1980.

      U.S. Environmental Protection Agency.   Control of Volatile Organic Emissions from
      Existing Stationary Sources.  Volume 11: Surface Coating of Magnetic Wire EPA-450/2-
      77-033. Research Triangle Park, NC.  1977.

      U.S. Environmental Protection Agency.  Control of Volatile Organic Emissions from
      Existing Stationary Sources.  Volume 11 :=Surface Coating of Cans, Coils, Paper, Fabrics,
      Automobiles and Light-Duty Trucks, EPA-450/2-77-088.  Research Triangle Park, NC
11.    U.S. Environmental Protection Agency.  Enforceability Aspects, of RACT for Factory
      Surface Coating of Flat Wood Paneling, EPA-340/1-80-005. Washington, DC.  1980.
6.
7.
8.
9.
10.
                                       C-6

-------
12.    U.S. Environmental Protection  Agency.  Automobile and Light Duty Truck Surface
      Coating Operations-Background Information for Promulgated Standards, EPA-450/3-79-
      030B.  1980.

13.    U.S. Environmental Protection  Agency.  Beverage  Can Surface Coating Industry -
      Background Information for Proposed Standards, EPA-450/3-80-036 A. Research Triangle
      Park, NC. 1980.

14.    U.S. Environmental Protection  Agency.  Beverage  Can Surface Coating Industry -
      Background Information for Promulgated Standards of Performance, EPA-450/3-80-036B.
      Research Triangle Park, NC.  1983.

15.    U.S. Environmental Protection  Agency.  Metal Coil Surface Coating  Industiy -
      Background Information for Proposed Standards, EPA-450/3-80-035 A. Research Triangle
      Park, NC. 1982.  .

16.    U.S. Environmental Protection  Agency.  Metai* Coil Surface Coating  Industry -
      Background Information for Promulgated Standards, EPA-450/3-80-035B.  Research
      Triangle Park, NC. 1982.

17.    U.S. Environmental Protection  Agency.   Pressure Sensitive Tape  and Label Surface
      Coating Industry-Background Information for Proposed Standards,EPA.-45Q/3-SQ-QQ3 A.
      Research Triangle Park, NC. 1980.

18.    U.S. Environmental Protection Agency. Final Environmental Impact Statement Pressure
      Sensitive Tape and Label Surface  Coating  Industry - Background Information for
      Promulgated Standards, EPA-450/3-80-003B:  Research Triangle  Park, NC.  1983.

19.    U.S. Environmental Protection  Agency.  Control  of Volatile Organic  Compound
      Emissions from Wood Furniture Coating Operations.  Draft CTG.  Research Triangle
      Park, NC. October 1991.

20.    U.S. Environmental Protection Agency.   Control of Volatile Organic Emissions from
      Existing Stationary Sources. Volume 11: Surface Coating of Flatwood Paneling, EPA-
      450/2-78-032. Research Triangle Park, NC. 1978.

21.    U.S. Environmental Protection Agency.   Control, of Volatile Organic Emissions from
      Existing  Stationary Sources.    Volume 11:  Surface Coating  of Metal  Furniture,
      EPA-450/2-77-032.  Research Triangle Park, NC. 1977.

22.    U.S. Environmental Protection Agency.   Control of Volatile Organic Emissions from
      Existing Stationary*Sources. Volume 11: Surface Coating of Miscellaneous Metal Parts
      and Products, EPA-450/2-78-015. Research Triangle  Park, NC.  1978.
                                        C-7

-------
23.
24.
25.
26.
U.S.  Environmental  Protection  Agency.   Surface  Coating  of Metal  Furniture -
Background Information for Proposed Standards, EP A-450/3-80-007 A. Research Triangle
Park, NC.  1980.

U.S.  Environmental  Protection  Agency.   Surface  Coating  of Metal  Furniture -
Background Information for Promulgated Standards, EPA-450/3-80-007B  Research
Triangle Park, NC. 1982.

U.S. Environmental Protection Agency.  Surface Coating of Plastic Parts for Business
Machines  - Background Information for Proposed Standards, EPA /450-3-85-019a
Research Triangle Park, NC.  1985.

U.S. Environmental Protection Agency.  Source Screening Study. Document summarizes
emission control technology for source categories including the surface coating of large
ships, large aircraft, and wood furniture.   1980.
                                        C-8

-------

-------
         APPENDIX D
SUMMARY OF EMISSION FACTORS
   LISTED IN THIS DOCUMENT
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-------
                                   TECHNICAL REPORT DATA
                            {Please read Instructions on the reverse before completing)
1. REPORT NO.
4. TITLE AND SUBTITLE
 Locating And  Estimating Air Emissions  From Sources Of
 Toluene
                                                            5. REPORT DATE
                                                             March 16, 1994
             6. PERFORMING ORGANIZATION CODE
                                                            3. RtCIP"=NT'S ACCESSION NO.
7. AUTHOR(S)
                                                            8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
 TRC Environmental  Corporation
 100 Europa Drive,  Suite 150
 Chapel Hill, NC  27514
             10. PROGRAM ELEMENT NO.
             11. CONTRACT/GRANT NO.
                                                                 68-D9-0173
12. SPONSORING AGENCY NAME AND ADDRESS
 U.S. Environmental  Protection Agency
 Office of Air Quality Planning And Standards
 Technical Support  Division (MD-14)
 Research Triangle  Park,  NC  27711
             13. TYPE OF REPORT AND PERIOD COVERED
                      Final
             14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
 EPA Project Officer:   Dennis Beauregard
16. ABSTRACT
 To assist groups  interested in inventorying  air emissions of various potentially
 toxic substances,  EPA  is  preparing a series  of documents such  as  this to compile
 available information  on  sources and emission  of these substances.   This document
 deals specifically with Toluene.  Its intended includes federal,  state and local
 air pollution personnel and others interested  in locating potential  emitters of Toluene
 and in making gross  estimates of air emissions therefrom.

 This document presents  information on (1) the  types of sources that  may emit Toluene,
 (2) process variations  and release points for  these sources, and  (3) available
 emissions information  indicating the potential for Toluene releases  into the air
 from each operation.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                              b.lOENTIFlERS/OPEN ENDED TERMS
                           c. COSATI Field/Group
 Toluene
 Air  Emissions, Sources
 Locating Air Emissions: Sources
 Toxic  Substances
 Emission Estimation
18. DISTRIBUTION STATEMENT


Unlimited
19. SECURITY CLASS (This Report)
  Unclassified
                                                                          21. NO. OF PAGES
2O. SECURITY CLASS (This page)

  Unclassified
                           22. PRICE
 EPA Form 2220-1 (Rov. 4-77)   PREVIOUS EDITION is OBSOLETE

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