PB84-102151
Alternative Treatment of Organic
Solvents and Sludges from Metal
Finishing Operations
Monsanto Research Corp., Day tori, OH
Prepared for

Industrial Environmental Research Lab.
Cincinnati, OH
Sep 83
                                                      ^

-------
                                   TECHNICAL REPORT DATA
                            /Please read Instnicr.ons on the retcne before
1  REPORT NO                   p
  EPA-600/2-83-094           |
4. TITLE ANOSUBTITLE

Alternate Treatment of Organic Solvents and Sludges
from Metal Finishing  Operations
F*"-i.]  Rpoorr
7  AUTHORIS)

William H. Hedley
9  PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research  Corporation
1515 Nicholas  Koad
Dayton, OH 45407
12. SPONSORING AGENCY NAME AND ADDRESS

 USEPA, lERL-Ci
 26 W. St. Clair
 Cincinnati, OH 45268

15 SUPPLEMENTARY NOTES
          •omplttingl
             3
               RECIPIENT'S ACCESSION NO-.
                  P33  4   10215!
             S REPORT DATE

             8. PERFORMING ORGANIZATION CODE


             8 PERFORMING ORGANIZATION REPORT NO.

                MRC DAI121

             10 PROGRAM EL'. jlENT NO.


             11. CONTRACT/JRANT NO.

                 63-03-3025

             13. TYPE OF REPORT AND PERIOD COVERED
                Final
             14 SPONSORING AGENCY CODE

                EPA-600/12
16. ABSTRACT

     A description of the metal finishing  industry and its  use of organic
     chemicals,  i.e. solvents,  oils, and coatings, is given.   The quantities
     and  composition of wastes  from these  processes is estimated, as well
     as current  technologies  used to recover or dispose of  them.   Recommendations
     for  improvements in techniques for recovery/reuse and  disposal of these
     wastes  are  included..
w.
                                 KEY WORDS ANO DOCUMENT ANALYSIS

                                               b.lDENTIFIEPS/OPEN ENDED TERMS  JC.  COSATI I-'lcld/C.fOUp
 18. DISTRIBUTION STATEMENT
            Release  co Public

 EPA Form 2220-1 (Rev. 4-77)   PHKVIOUS EDITION is OBSOLETE  ±
19 SECURITY Cl •<" (ThisKcpartl
   Unclassified
20 SECURITY ri < v (Tha page)
   Unclassified
21. NO OF PAGES
     363
22  PRICE

-------
                                             EPA-600/2-83-094
                                             September 1983

                                              P384-102151
ALTERNATIVE TREATMENT OF ORGANIC SOLVENTS AND SLUDGES
           FROM METAL FINISHING OPERATIONS
                    FINAL REPORT
                         by

                    Sam C. Cheng
                   Bharat 0. Desai
                   Carol S. Smith
                 Harlan D. Toy, Jr.
                  Tom E. Ctvrtnicek
                  William H. Hedley
            Monsanto Research Corporation
                 Dayton, Ohio  45407
           Contract No. 68-03-3025;  SDM-01
                   Project Officer

                Alfred B. Craig,  Jr.
    Industrial Environmental Research Laboratory
               Cincinnati, Ohio   45268
    INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
         OFFICE OF RESEARCH AND DEVELOPMENT
        U.S. ENVIRONMENTAL PROTECTION AGENCY
               CINCINNATI, OHIO   45268

-------
                      NOTICE

This document has been reviewed in accordance with
U.S. Environmental Protection Agency policy and
approved for publication.   Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
                       11

-------
                            CONTENTS
Figures	    iv
Tables	viii

   1.  Introduction	     1
   2.  Summary	     2
            Industry description 	     2
            Organic wastes 	     3
            Recovery and disposal	     3
            Conclusions	     5
   3.  Conclusions and Recommendations 	     6
            Conclusions	     6
            Recommendations	     7
   4.  Characterization of Metal Finishing Industry	    11
            Metal finishing industry categories	    11
            Metal finishing industry description 	    18
            Solvent cleaning industry description	    22
            Surface coating industry description 	    26
   5.  Description of Process Operations, Raw Materials, and
         Wastes	    35
            Metalworking 	    35
            Solvent cleaning 	    88
            Surface coating	103
   6.  Identification of Byproduct Utilization Schemes  . . .   132
            Disposal and reclamation of emulsified oils. . .   132
            Disposal and reclamation of straight mineral
              oils	174
            Disposal and reclamation of fatty oils	211
            Reclamation, treatment, and disposal of syn-
              thetic fluids	214
            Disposal and reclamation of organic solvents . .   217
            Disposal and reclamation of paints 	   254

References	257
Appendices

   A.  Oil  composition data	270
   B.  Solvent description and composition data	291
   C.  Composition data for new and waste surface coatings .   310
 0150-0153                      iii

-------
Number                                                       Faqe

   1   Geographic distribution of metal finishing plants by
         state	   17

   2   Geographic distribution of neta3 finishing plants
         with ?0 or more employees by states	   19

   3   Sale-3 of lubricating and industrial oils, by state:
         l'J77	   23

   4   Geographic distribution of cold cleaning operations  .   26

   5   Geographic distribution of vapor decreasing
         operations	   27

   6   Paints and allied products	   28

   7   Geographic distribution of nonautomotive product sur-
         face coating plants by state	   34

   8   Typical foundry production flow chart 	   37

   9   Jimplifie'.i typical foundry operation	   38
                i
  10   Steel manufacturing process flow diagram	   41

  11   Product f.(ow of typical steel mill operations  ....   43

  12   Process diagram for cold rolling oil application re-
         circulation system	   44

  13   Wire drawing	   47

  14   Forward extrusion/backward extrusion	   49

  15   Simplified typical machining operation	   51

  16   Cutting tool chip formation	   52

  17   The abrauive coated bel*-. for polishing  *,nd buffing.  .   $3

  18   Geographic distribution of waste oils generated by
         metal finishing plants in the United  States  ....   37
                                IV

-------
                       FIGURES (continued)

Number                                                       Faqe

  19   Cold cleaner	/.	   89

  20   Basic open top vapor degreaser	   91

  21   Ferris wheel degreaser	   93

  22   Vibra degreaser	   93

  23   Monorail degrsaser	   94

  24   Cross-rod degreaser 	   94

  25   Mesh belt conveyorized degreaser	   95

  26   Geographic distribution of waste degreasing solvents
         oenerated by metal finishing plants in the United
         States	104

  27   Air atc-mized spray	105

  28   Pressure atomized spray 	  106

  29   Electrostatic field assisted spraying painting. . .   .  106

  30   Centrifugal atomized spray	107

  31   Dip coating rigid, profiled merchandise 	  107

  32   Flow coating	•	108

  33   Roll coating	109

  34   Electrocoating	110

  35   Electrostatic fluidized bed 	  110

  36   Fluidized electrostatic powder spraying 	  Ill

  37   Raw materials flow diagram for the paint and allied
         products industry 	  112

  38   Geographical distribution cf coating wastes generated
         by metal finishing plants in the United States. .  .  131

  39   Fluid reclaiming	133

  40   API separator	138

-------
                       FIGURES (continued)
Number                                                      ' Page
  41   Disc-type centrifuge	'	140
  42   Decanter centrifuge 	  141
  43   Pressure filtration	,	143
  44   Vacuum filtration 	  144
  45   Coalescing gravity separator	147
  46   Typical emulsion breaking/skimming system 	  149
  47   Electrochemical oil removal/recovery cell: negatively
         charged oil droplets	151
  48   Typical dissolved air  flotation system.  . * 	  153
  49   Simplified ultrafiltration membrane module	156
  50   Semi-batch ultrafiltration system  	  157
  51   Evaporation unit for emulsified oil	163
  52   Acid/clay treatment 	  179
  53   IFF process	181
  54   Snamprogetti process	183
  55   BERT re-refining process outlite	184
  56   The Philips PROP process	186
  57   Recyclon process	187
  58   KTI process	188
  b9   Reclaiming of spent oils by ultrafiltration 	  189
  60   The Pfaudler test center process	190
  61   Oil is distilled in two stages using Luwa's thin film
         evaporator	191
  62   Resource Technology process  	  192
  *3   Bradley waste treatment  flow diagram	213
                               VI

-------
                       FIGURES (continued)
Number
  64   Reverse osmosis can be used to reduce the water con-
         tent of synthetics	216
  65   Carbon adsorption principle of operation	220
  66   Adsorption capital costs	222
  67   Schematic representation of degreaser with cold trap
         installed	 .  .  .   225
  68   Capital costs for refrigeration vapor recovery units.   227
  69   Annualized costs for refrigeration vapor recovery
         units	227
  70   Capital costs for packed tower absorbers	231
  71   Annualized costs for a cross-flow packed scrubber .  .   232
  72   Continuous fractional distillation column 	   234
  73   Distillation:  changes in total capital costs with
         scale	238
  74   Distillation:  changes in O&M requirements with
         scale	238
  75   Detail of single evaporator showing associated equip-
         ment included in the evaporator module	241
  76   Evaporation:  changes in total capital costs with
         scale	245
  77   Evaporation:  changes in operating requirements with
         scale	 .   245
                               Vll

-------
TABLES
Number
1

2

3

4

5

5

7
8


9

10

11

:i2
13

14
15
16
17
18

•*
r
SIC Codes Comprising the Metal Finishing Category
Industry 	 •'. 	
Plant Population for the Metal Finishing Industry by
SIC Codes and by State 	
Metal Finishing Processes and- Op'eTations Included in
the Study 	 '. 	
Metal Finishing Processes and Operations Excluded
from the Study. . . 	
Estimated 1979 U.S. Sales and Projected U.S. Demand
for Metalworking Oils, 1980-1990 	
Annual Degreasing Solvent Consumption, by Solvent
Type 	
Solvent Degreasing Operations ....;. 	
Comparison of Estimated Production of Product Coating
for Original Equipment Manufacture in "the U.S.,
1980 and 1990 	
U.S. Production of Product Coating for Original
Equipment Manufacture by End Use 	
Geographic Distribution of U.S. Automobile Assembly
Plant Production 	
Geographic Distribution of U.S. Light-Duty Truck
Assembly Plant Production . . . . 	
Polishing and Grinding with an Abrasive-Coated Belt .
Classification of Metalworking Fluids and Related
Materials 	
Report Classification Scheme for Metalworking Fluids.
Lubricant Additives 	
Chemical Categories of Cutting Fluid Preservatives. .
baste Types Generated by Metalworking Operations. . .
Effect of Oil-Water Ratio on Growth of Bacteria in an
Oil Emulsion 	
'age

12

15

20

20

21

24
25


29

29

31

33
54

64
66
72
76
77

81
   Vlll

-------
                       TABLES (continued)
Number                   '                                    Page
  19   Pollutant Concentrations Found in Emulsified Oils
         from Metal Finishing Plants 	    83
  20   BOD and COD Values for Synthetic Cutting Fluids ...    85
  21   Geographic Distribution of Waste Oils Generated by
         Metal Finishing Industry	    86
  22   Typical Applications for Vapor-Degreasing Solvents. .    96
  23   Properties of Commercially Available* Solvents ....    97
  24   Distribution of U.S. Degreasing Solvent Consumption .    98
  25   Waste Solvent Generation by Type of Degreasing
         Operation	101
  26   Boiling Points of Clean and Contaminated Solvents  . .   101
  27   Geographic Distribution of Waste Degreasing Solvents
         Generated by Metal Finishing Industry 	   102
  28   Resins Used by Paint Industry	115
  29   Oils Used by Paint Industry	'  116
  30   Pigments Used by ti:«* Paint Industry	117
  31   Solvents Used by Paint Industry	118
  32   Miscellaneous Materials Added to Surface Coatings  . .   119
  33   Properties of Water-Borne Coatings	121
  34   Solids and Solvent Content of Water-Borne Paints.  . .   122
  35   Advantages of Water-Borne Coatings	123
  36   Disadvantages of Water-Borne Coatings  	   123
  .37   Powder Coating Resin Groups	124
  38   Comparison of Powder Coatings to Solvent-Based
         Coatings	125
  39   Expected Transfer Efficiency	127
                                IX

-------

-------
                       TABLES (continued)

Number                          •                             Page

  60   Analytical Characterization of Sludges Collected
         From In-Plant Processing Equipment for Emulsified
         Oils	175

  61   Organic Components in Sludges Designated in Column 3
         of Table 60	176

  62   Summary of Waste Oil Processes	195

  63   Re-Refining Process Water Analyses	196

  64   Acid Sludge Analyses Composite	200

  65   Analysis of Re-Refining Caustic/Silicate Sludge .  .  .  200

  66   Re-Refining Process Hydrocarbor./Sludge/Clay Analyses.  201

  67   Biodegradation of Synthetic Fluids	215

  68   Working Bed Capacities	218

  69   Typical Components of Annualized Costs for Carbon
         Adsorption Systems. .  .	223

  70   Components of Annualized Costs for a Refrigeration
         Vapor Recovery Unit	223

  71   Summary of Capital Costs for Distillation  	  236

  72   Summary of First Year Operating Costs for
         Distillation	237

  73   Computation of Life Cycle  Average Cost for Implement-
         ing Distillation	239

  74   Summary of Capital Costs for Evaporation	243

  75   Summary of First Year O&M  Costs for Evaporation .  .  .  244

  76   Characteristics of Still Bottom Samples  Collected
         From Solvent Reclaiming  Operations	247

  77   Quantity of Solvent by Disposal Routes	251

  78   Disposal Charges of Organic Waste by  Incineration  .  .  253
                               XI

-------
                            SECTION 1

                          INTRODUCTION


Disposal of organic wastes from metal finishing is an increasingly
costly alternative to reprocessing and reuse.  Resulting in mate-
rials suitable for in-plant resue, use as fuel, or resale to and
reuse by other uses, secondary processing of these wastes could
conserve raw material consumption and thus reduce the amount of
waste that ultimately would enter the environment.  Under EPA
contract 68-03-3025 Monsanto Research Corporation (MRC) assembled
data on the nature of metal finishing industry, current practices
in using, recycling, and disposal of organic fluids, type and
quantity of organi- fluids used and organic wastes generated by
the metal finishing industry categories including metalworking
(metal rolling, cutting, grinding, and heat treating), solvent
cleaning 'degreasing),  and surface coating (painting and rust pre-
vention) (refer to Section 4.1 for further definition of those
metal finishing operations included and excluded from this study),
anc* technologies available for recovery, reuse, and dispose;- of
organic fluids and wastes.

To collect relevant information, a thorough literature search was
conducted followed by limited industry contacts and visits to envi-
ronmental regulatory agencies in several industrial states.  Waste
sampling and analyses were not included in the program scope.

The purpose of this report is to summarize program findings.  The
report is organized into six sections.  Following the summary, and
the conclusions and recommendations in Sections 2 and 3, Section 4
gives information on the size, growth, SIC code distribution, and
geographic distribution of the metal finishing industry.  In Sec-
tion 5, the metal finishing industry and operations are described
including raw materials used, and wastes produced.  Section 6
describes technologies for ref\ning, reclamation, reuse, and dis-
posal of metal finishing waste products.

Raw data on industry waste caracteristics collected from state
agent files are appended.

-------
                            SECTION 2

                             SUMMARY


Approximately 150,000 industrial plants in SIC Codes 25 and 33-39
comprise the United States metal finishing industry.  The purposes
of this study were (1) to describe the metal finishing industry
and its use of organic materials, (2) to describe the quantity
and composition of organic wastes from metal finishing, (3) to
describe the current technologies used to recover or dispose of
these materials, and (4) to draw conclusions and make recommenda-
tions as to future work that needs to be done to improve the ways
in which organic residues from the metal finishing industry are
reused or disposed of.

2.1  INDUSTRY DESCRIPTION

This study of the metal finishing industry focuses on processes
which use significant amounts of organic materials.  These are
(1) the metalworking processes,  (2) solvent cleaning, and
(3) product coating processes.

Metalworking processes use oils.  They are of four types:
(1) metal removal, (2) metal forming, (3) heat treating, and
(4) rust preventive coating.

Metal cutting operations, such as machining, require oils both as
lubricants and coolants.  Emulsified oils or soluble synthetic
fluids are sold as concentrates, then diluted with water before
use.  Metal forming operations use oils primarily for lubrication.
The hot and cold-rolling operations used for production of steel
and aluminum strip and sheet use many different types of oils.
Heat treating operations, such as quenching, use mineral and
emulsified oils to quickly reduce metal temperatures.  Straight
mineral oils are used to coat steel coil as a rust preventive.

Degreasing or solvent metal cleaning uses nonaqueous solvents to
clean surfaces of all of the common ferrous and nonferrous metals.
The four main types of organic solvents used for solvent metal
degreasing operations are:  alcohols, halogenated solvents, hydro-
carbons, and ketones.

Paints are classified in two major categories, as solvent-based
or water-borne paints.  The water-borne paints were developed to
decrease the total amount of volatile solvent emissions and are

-------
widely used as product coatings.  However, solvent-borne enamels
and lacquers remain the most widely used in the automotive
industry.  Six major methods are used for the application of
product coatings in the metal finishing industry:  (1) spray
painting, (2) dip coating, (3) flow coating, (4) roll coating,
(5) electrodeposition, and (6) powder coating.

2.2  ORGANIC WASTES

The annual quantities of organic materials used in metal finish-
ing, the amounts of organic waste currently collected, and the
estimated amounts that could be collected are shown below.




Use
Metalworking (oils)
Degreasing (solvents)
Product coatings (paints)
TOTAL

Annual
consumption,
10 6 kq/yr
760
670
VL.PBO
2,480

Waste
collected,
106 kq/yr
180
580
200
960
Waste
potentially
collectable,
106 kq/yr
480
630
200
1,310
The oils may be petroleum-based mineral oils  (used straight),
emulsified oils, or synthetic oils.  Commonly used additive types
include anti-oxidants, rust preventatives, extreme pressure
additives, viscosity index improvers, pour point depressants,
fatty oils, and emulsifiers.

Waste mineral oils may contain sulfur, chlorine, fluorides,
nitrogen, phosphates, metal chips and fines,  sediment, water,
PCBs, oxidation products, and phenolic compounds as contaminants.

Waste emulsified and synthetic oils may contain metal particles,
biodegradation products,  tramp oil, nitrosamines, and residues
from oil additives—including sulfur, phosphorus, chlorine, zinc,
lead, copper, and phenolic compounds—as  contaminants.

The waste solvents may be halogenated or  nonhalogenated  and may
contain oil, grease, wax, metallic particles, etc.

Waste coating may contain high concentrations of organic solvents,
resins, and heavy metals.

2.3  RECOVERY AND DISPOSAL

Environmental regulations usually prohibit the discharge of
untreated organic wastes  from the metal finishing industry into

-------
surface waters because they contain unallowable concentrations
of both organic and inorganic pollutants.

With increasingly restrictive environmental regulations, disposal
of waste oils is becoming expensive.  Therefore', refining/recla-
mation/alternate applications are viable options for waste oil
generators.

Refining/reclamation technology for waste straight oils is well
developed.  Independent re-refiners accept waste oils for refining
based on their composition and compatibility with refining tech-
nology used in their plants.

Waste emulsified oil treatment reclamation technology has been
well developed in recent years.  Economics of on-site or off-site
treatment or disposal for a plant will depend or the volume of
waste emulsified oil generated.  Larger plants generally treat
their waste prior to discharging wastewater to surface waters.
Smaller plants exercise off-site treatment or disposal options.
it is possible that some plants might still be illegally disposing
of waste emulsified oil into sewers.  The use of regional facili-
ties to treat waste emulsified oils from small plants has been
considered.

Synthetic fluids are expensive, so  fluid maintenance and manage-
ment programs in the plant are utilized to increase fluid life
expectancy.  Very limited technology is available at present to
reclaim spent synthetic fluids.  Synthetic fluids manufacturing
f;irms are developing water soluble  biodegradable synthetic fluids
to avoid costly disposal problems.  Disposal alternatives and
costs are highly dependent on the chemical formulations of syn-
thetic fluids, which are generally  treated as proprietary infor-
mation.  For this reason, very limited information is available
about treatment or disposal of spent synthetic  fluids.

Waste solvents have high potentials for recovery and reuse.  Also
the Resource Conservation and Recovery Act (RCRA) lists waste
solvents as hazardous waste, so they are to be  disposed of in
accordance with the regulations.

Recla'iation technology  for waste solvents is well developed.  Due
to RCRA regulations, disposal of waste solvents is becoming very
expensive.  For this reason more generators are starting to use
the? services of waste solvent reclaiming firms.  Waste  solvent
reclaiming firms have been growing  in number since RCRA regula-
tions came into effect.

The major  application method contributing to paint waste is the
spray coating method.   The waste is almost exclusively  disposed
of in either sanitary or secured landfills.  A  very small portion
is incinerated.

-------
Paint wastes have limited recovery or reuse potential.   Waste
coating may or may not be a hazardous waste depending on its com-
position.  The disposal practice will depend on whether the waste
is hazardous or nonhazardous.  RCRA testing will be required to
classify a waste coating as hazardous or nonhazardous.

2.4  CONCLUSIONS

Conclusions from this work and recommendations based upon them
are included.  Specific batch scale studies, engineering studies,
and economic studied which are needed are listed.

-------
                            SECTION 3

                 CONCLUSIONS AND RECOMMENDATIONS
3.1  CONCLUSIONS

 (1) The 150,000 metal finishing plants in the United States use
     2,480 million kilograms of organic materials per year.

 (2) At present approximately 40 percent of these materials are
     collected for reclamation or disposal by processes such as
     incineration, landfill, or using in road paving.  The other
     60 percent which is not collected, is disposed of by proc-
     esses such as vaporization losses, process losses on-site,
     and dumping.

 (3) The metal finishing industry is concentrated in ten heavily
     industrialized states:  California, Illinois, New York, Ohio,
     Michigan, Pennsylvania, Texas,  New Jersey, Massachusetts,
     and Indiana  (in order of number of large plants).

 (4) These states are the ones with"the most potential for setting
     up reclamation centers since they generate the largest amount
     of wastes.

 (5) The organic wastes from the metal finishing industry come
     primarily from the metalworking, solvent cleaning, and prod-
     uct coating processes.

 (6) The wastes from the metalworking and solvent cleaning proc-
     esses generally contain sufficient concentrations of organ-
     ic or inorganic contaminants to make them environmentally
     unacceptable for discharge to surface waters without
     treatment.

 (7) Paint wastes vary from innocuous to hazardous; hence, deci-
     sions must be made on each one individually to determine
     whether or not there are restrictions on the manner in which
     they are disposed of.

 (8) Waste oil compositions vary considerably, depending upon
     their initial composition, the process in which they are
     used, the severity of the operating conditions (temperature
     and pressure), and the degree of recycle or reuse.

-------
 (9) Waste mineral oil refining and reclamation technology is
     well developed technically,  but their economic practicality
     is in quection.   At present only a small  fraction of the oil
     which could be re-refined is processed for reuse.   The rel-
     atively small volume of oil being processed and its fluctuat-
     ing quantities produce uncertainty in the economic viability
     of this approach.  As long as there are few regulations
     requiring or strongly encouraging re-refining,  it will con-
     tinue to be a solution for only a small fraction of oil
     disposal problems.

(10) The costs of disposing of waste oil are increasing, making
     re-refining or reclamation more attractive economically.

(11) High-priced synthetic metalworking fluids are increasingly
     used in the industry.  The recovery potential for synthetic
     fluids is unknown at present.

(12) Few reclaimers handle waste oil water emulsions,  or synthetic
     or water-based metal working fluids.

(13) Solvent recovery is handicapped by the diversity of solvents
     available and the small quantities of specific solvents at
     some locations.   Some solvent recovery companies are not well
     qualified,  and they are frequently underfinanced.

(14) Some solvents are complex mixtures of chemicals that are
     difficult to recycle.

(15) Disposal companies are basically incinerating waste solvents
     at high cost.  Disposal costs are so high that waste solvent
     generators are reluctant to call them.

(16) Most solvent recyclers only process a limited number of sol-
     vents.  They may not provide a service to many small waste
     solvent generators.

3.2  RECOMMENDATIONS

3.2.1  Bench-Scale Studies

 (1) Establish a bench-scale or pilot-scale demonstration project
     for treatment or reuse of metalworking fluid wastes of the
     types and amounts that would be generated in small metal-
     working plants.   A study of an emulsion treatment process
     would be appropriate since this type of process currently is
     presenting problems.

 (2) Conduct a bench-scale or pilot-scale study to determine -the
     influence of oil additives on re-refining processes, and the
     feasibility of recycle or reuse of metalworking fluids after
     changing the additive composition.

-------
 (3)  Through laboratory analysis  and  bench-scale  studies,  inves-
     tigate the effects on fluid  performance  characteristics  and
     hazard potential  of increased  concentrations of .additives
     (as in repeatedly recycled or  reused  fluids).

 (4)  Conduct bench-scale studies  to determine effective  methods
     for breaking the  emulsions and oil/water separation.

 (5)  Investigate on a  bench-scale method for  removing  water from
     emulsified oils without breaking the  emulsion, reconditioning
     the oil, redilutiug with fresh makeup water, and  returning
     the oils to service with minimal treatment.

 (6)  Conduct a bench-scale or pilot-scale  study to determine the
     types of metalworking fluids most effectively re-refined.

 (7)  Conduct bench- or pilot-scale  studies to investigate the
     recovery potential of synthetic  metalworking fluids,  and
     identify appropriate recovery  technologies.

3.2.2  Engineering Studies

 (8)  Conduct a survey  of large metalworking plants (large-volume
     users of metalworking fluids)  to determine the present extent
     of metalworking fluid recycle  or reuse;  identify  and categorize
     by type of fluid, type of operation,  type of machine, type of
     metal, etc.  Conduct a study of plant metalworking operations
     to determine costs associated  wjth in-plant vs.  external anal-
     ysis and treatment of metalworking fluids, and cost-effective
     process improvements to conserve fluid usage.

 (9)  Identify alternative uses for  recycled metalworking fluids,
     degreasing solvents, and waste paints.

(10)  Investigate technologies for dewatering or concentration of
     metalfinishing sludges.

(11)  Identify alternative uses for  nonhazardous metalfinishing
     sludges, still bottoms, etc.

(12)  Investigate alternative disposal methods for hazardous
     metalfinishing sludges and still bottoms, such as burning
     paint sludges in a cement kiln.

(13)  Through an in-plant engineering study of metalworking opera-
     tions, recommend a preventive  maintenance program to prolong
     the working life of synthetic  metalworking fluids.

(.14)  Conduct a wastestream sampling program to establish pre-
     treatment standards for disposal of waste oil.

-------
(15) Based on the results of sampling,  desiqn a waste treatment
     system to increase the recoverable portion of waste metal-
     working fluids.

(16) Cond.'-Jwt an in-plant engineering study to improve the segre-
     gation of metalworking fluids preparatory to recycle,  reuse,
     or re-refining.

3.2.3  Economic Studies

(17) Investig?te small metalworking plants (<20 employees)  to de-
     termine v.he feasibility of metal finishing fluid reuse or re-
     cycle and identify economical alternatives for the small user;

(18) Initiate and demonstrate economic incentives (tax-sheltered,
     depreciation-acceleration) for these small metalworking
     plants to practice recycle or reuse as a cost-effective
     alternative to disposal.

(19) Investigate the effectiveness of financial incentives  on the
     establishment of regional metal finishing waste fluid recy-
     cling centers and waste exchangers in the more heavily indus-
     trialized areas of the United States identified in this
     report.

(20) Investigate the economic feasibility of emulsified,oil
     treatment or reclamation in small plants.

(21) Conduct an economic study of the oil re-refining and solvent
     and paint reclaiming industries.

(22) Conduct a study to identify the recoverable portion of metal-
     finishing wastes and determine the economic value and potentic
     uses for recovered materials.

(23) Identify present disposition of wastes and ascertain the
     degree of hazard presented for each, particularly if they
     are currently disposed of in improper ways.

(24) Aid both large and small manufacturers in complying with
     nonpolluting program by encouraging safe disposal, recycle,
     or re-refining in a practical and economic manner.  Essen-
     tially develop a handbook for metalworking fluid and clean-
     ing solvents recycle, re-refining, reclamation or disposal.
     It would present practical methods, economics of operation
     and provide the manufacturers with acceptable alternatives.

(25) Considering the disposal problems of different localities and
     size of industrial operations, set in motion a project to en-
     courage recyclers by demonstrating the market, suggesting
     processing alternatives and showing the economic advantages
     for the communities.

-------
(26)  Catalog present commercial  services,  listing  by  manufacturer,
     locality,  end types of solvent and oils  processed.   Note de-
     ficiencies and consider problems.   Frequently, it is difficult
     for a waste generator to find a recycler.   If inadequacies
     are identified and publicized,  private industry  may fill the
     void.

(27)  Investigate the available processes and  methods  for recy-
     cling solvents and metalworking fluids to  determine their:

          Effectiveness for EPA  Compliance
          Effectiveness of process economics
          Note deficiencies and  address research to correcting
          deficiencies so that acceptable processes will be
          available to control pollution.

(28)  Review present recycle and  disposal methods used by the in-
     dustry and compare them with present EPA regulations.  Note
     degree of environmental insult and injury  occurring and rec-
     ommend a practical approach to reducing  injury.   Consider the
     effect of more regulation,  improved recycling and disposal
     technology or economic incentives.  In effect,  develop a
     program to correct the problem .where it  exists.
                                10

-------
                            SECTION 4

          CHARACTERIZATION OF METAL FINISHING INDUSTRY


4.1  METAL FINISHING INDUSTRY CATEGORIES

Nearly half of the total industrial activity in the United States
is classified as metal finishing.  Metal finishing thus comprises
the largest single industry segment.  It spends .45 percent of
total dollars expended by industrial plants for materials, makes
40 percent of all capital expenditures, employs 47 percent of all
industrial workers, accounts for 53 percent of the total industry
payroll [1] and includes 148,719 plants [2].

The U.s metal finishing industry is classified into eight major
groups and 58 subgroups under Standard Industrial Classification
(SIC) codes 25 and 33 through 39, as shown in Table 1 [2],  Based
on the 1977 Census of Manufacturers [2], except for Alaska, the
metal finishing industry was found in all states and the District
of Columbia as shown in Table 2  [3].  Seventeen states and the
District of Columbia list plant population of less than 1,000.
California has the largest metal finishing plant population,
22,296, and is followed by New Yorl: with 12,888 plants.  An addi-
tional 7 states—Illinois, Massachusetts, Michigan, New Jersey,
Ohio, Pennsylvania, and Texas—have plant populations of more
than 5,000.  This is illustrated in Figure 1.

Although all plants use organic  fluids and produce organic wastes,
it is the larger plants that are likely to generate waste quanti-
ties significant enough for economic segregation, reprocessing,
    reuse.  Out of the total of  148,719 plants, 48,907 (one-third
[1] Richards, D. W.; and Suprenant, K. S.  Study to support new
    source performance standards for solvent metal cleaning opera-
    tions.  Appendix reports.  U.S. Environmental Protection Agency;
    1976 July 30.  Contract 68-02-1329, Task Order No. 9.
[2] Development document for effluent limitations guidelines
    and standards for the metal finishing point source category.
    Washington, DC; U.S. Environment?.! Protection Agency; 1980
    June; 557 p.  EPA 440/l-80-091a.
[3] 1977 Census of Manufactures, Geographic Area Series MC77-A-1
    through MC77-A-51.  Washington, DC; U.S. Department of Com-
    merce, Bureau of the Census; 1978.


                                11

-------
       TABLE 1.  SIC CODES COMPRISING THE METAL FINISHING CATCGORY INDUSTRY |2|


             SIC major group and subcategory of manufacture with definition	

Major Group 25 Metal Furniture,  Except Laboratory and Hospital Furniture

  251   Household Furniture
  252   Office Furniture
  253   Public Building and Related Furniture
  254   Partitions and Fixtures
  259   Miscellaneous Furniture  and Fixtures

Major Group 33 Primary Metal Products, Except Metal Forqings and Stampings

  331   Blast Furnace and Basic  Steel Products
  332   Iron and Steel Foundries
  333   Primary Nonferrous Metals
  334   Secondary Nonferrous Metals
  335   Nonferrous Rolling and Drawing
  336   Nonferrous Foundries
  339   Miscellaneous Primary Metal Products

Major Group 34 Fabricated Metal  Products, Except Machinery and Transportation Equipment

  341   Metal Cans and Shipping  Containers
  342   Cutlery, Hand Tools, and General Hardware
  343   Heating Equipment (except Electric and Warm Air, Plumbing Fixtures)
  344   Fabricated Structural Metal Products
  345   Screw Machine Products,  and Colts, Nuts, Screws, Rivets and Washers
  346   Metal Forgings and Stampings
  347   Coating, Engraving and Allied Services
  348   Ordnance and Accessories, except Vehicles and Guided Missiles
  349   Miscellaneous Fabricated Metal Products

                                                                            (continued)

-------
                                  TABLE 1 (continued)
	SIC major group and subcategory of manufacture with definition	

Major Croup 35 Machinery,  Except Electrical

  351   Engines and Turbines
  352   Farm and Garden Machinery and Equipment
  353   Construction,  Mining and Materials Handling Machinery and Equipment
  354   Metalworking Machinery and Equipment
  355   Special Industry Machinery, except Metalworking Machinery
  356   General Industrial Machinery and Equipment
  357   Office, Computing, and Accounting Machines
  358   Refrigeration and Service Industry Machinery
  359   Miscellaneous Machinery, except Electrical

Major Group 36 Electrical and Electronic Machinery, Equipment and Supplies

  361   Electric Transmission and Distribution Equipment
  362   Electrical Industrial Apparatus
  363   Household Appliances
  364   Electr.c Lighting and Wiring Equipment
  365   Radio ard Television Receiving Equipment, except Communication Types
  366   Communication Equipment
  367   Electronic Components and Accessories
  369   Miscellaneous Electrical Machinery, Equipment,  and Supplies

Major Group 37 Transportation Equipment

  371   Motor Vehicles and Motor Vehicle Equipment
  372   Aircraft and Parts
  373   Ship and Boat Building and Repairing
  374   Railroad Equipment
  375   Motorcycles, Bicycles, and Parts
  376   Guided Missiles and Space Vehicles and Parts
  379   Miscellaneous Transportation Equipment
                                                                            (continued)

-------
                                TABLE 1 (continued)
             SIC major group and subcategory of manufacture with definition
Major Group 38 Measuring, Analyzing and Controlling Instruments:  Photographic, Mt'-dica3
and Optical Goods; Watches and Clocks                                             •

  381   Engineering, Laboratory, Scientific, and Research Instruments and Associated
          Equipment
  382   Measurirg rnd Controlling Instruments
  383   Optical Instruments and senses
  38t   Surgical,  Medical, and Dental Instruments and Supplies
  385   Opthalmic Gooas
  386   Photographic Equipment and Supplies
  387   Watches, Clocks, Clockwork Operated Devices;, and Parts
                                  -4
Major Group 39 Miscellaneous Manufacturing Industries

  391   Jewelry, Silverware, and Plated Ware
  393   Musical Instruments
  394   Dolls
  395   Pens, Pencils, and Other Office' and Artists' Materials
  396   Costume Jewelry, Costume No/elt.ies, Buttons and Miscellaneous Notions, except
          Precious Metal
  399   Miscellaneous Manufacturing Industries.

-------
TABLE 2.  PLANT POPULATION FOR THE METAL FINISHING
          INDUSTRY BY SIC CODES AND BY STATE (3J
1977 SIC Code
25


With 20

State Total
alabaaa 169
Arisona 103
arkaiuaa 124
California 1,752
Co'oraJo 127
Connecticut 113
Delaware 9
Olatrict of
Coliabl*
Florida 546
Georgia 228
Havaii 30
Idaho 20
Illlr.oia 142
Indiana, 242
Iowa 65
Kansas 80
Kentucky 93
Loulaiana 77
Maine 35
Hirylanil 108
Massachusetts 295
Michigan 317
Minnesota • 133
Mississippi 159
Miaaouri 196
Montana 14
eea or
•ore
62
21
51
570
28
42
1

a*
122
94
6
5
55
128
23
20
38
13
12
30
81
132
38
76
70
4
33


34

With 20
cevloy-

Total
158
64
52
794
bl
229
9

-
110
85
-
10
583
283
77
56
U
42
13
62
249
581
112
36
140
16
can or
Bare
102
36
26
358
23
122
6

.
49
47
-
4
327
184
41
29
49
24
4
30
129
329
M
25
80
6

Total
437
261
216
4.366
318
1.007
47

19
976
464
36
73
2.647
931
293
290
304
282
86
310
1.195
2.439
609
161
620
44

With 20
employ-
ees or
acre
193
62
78
1.396
98
418
IS

6
268
ISO
9
20
1.148
449
118
107
146
96
27
111
440
1.060
250
70
240
10
35



Total
439
380
301
6,711
517
1,341
58

11
1,049
624
38
129
3,480
1,386
564
559
413
396
114
34C
1 634
3.983
1.112
233
693
51
All ei
With 20
employ-
ees or
•ore
112
'7
65
1.278
112
313
12

j
188
153
3
21
1,036
415
210
163
135
102
31
99
439
1,206
322
70
223
7
26
itebliehcd inotnx


Totil
115
159
90
3,047
158
423
12

.
506
165
.
a
1,080
329
95
110
110
70
43
179
6M
4-19
279
73
242
7
With 20
evploy-
eeo or
•ore
53
50
51
1,131
49
206
5

.
159
74
.
2
557
186
44
37
66
20
27
80
326
201
120
46
HO
1
37
•ents


With 20
ecploy-

Total
158
100
121
1,906
113
169
12

.
668
169
21
49
300
448
102
163
85
224
86
117
189
624
151
77
194
24
ees or
ax>r«
61
23
35
626
27
78
6

.
169
61
4
12
140
243
38
69
34
87
12
29
58
304
56
36
74
5
38



With 20
mploy-

Trtel
VI
78
27
1.4i8
121
209
13

.
246
75
.
.
484
129
51
41
39
31
22
107
435
261
145
25
10*
-
tea or
•ore
16
13
4
430
29
108
5

-
52
21
.
-
185
44
14
17
12
6
b
26
173
96
57
9
42
•
39

25, 33 thru 39
(total)

With 20
enploy-

Totnl
135
219
too
2.262
260
282
31

17
669
207
83
47
842
267
142
113
112
129
69
154
600
46
-------
TABLE 2 (continued)
19/7 SIC Code
25



State
hebraska
Nevada
Sew Haxpshire
Nev Jersey
New Mexico
Nev York
North
Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennrylvatiio
Rhode Island
South
Carolina
South Dakota
Tennessee
Texas
Utah
Vernonl
Virginia
Washington
West Virginia
Wisconsin
Wyomng
TOTALS



Total
32
24
61
324
34
1.028

664
- '
307
95
123
451
36

63
-
341
S12
67
27
175
144
22
169
-
9,879

With 20
eap'oy-
• ei cr
•ore
12
5
19
104
3
257

391
-
11!
16
31
186
6

29
-
132
164
20
16
85
45
11
74
-
3,461
33
34
35
36
37
38
39
All established instruments


Total
26
12
39
314
21
466

67
-
6S9
82
72
598
110

52
.
118
324
35
14
64
55
49
233
-
7,313
With 20
employ-
ees or
•ore
IS
3
22
159
7
223

45
-
403
44
33
355
36

27
.
68
151
15
7
34
10
28
144
-
3.9J5


Total
130
6j
133
1,055
74
2.S42

469
23
2.376
448
406
1,940
414

232
35
522
1.933
164
43
279
478
HI
83S
22
33.678
With 20
employ-
ees or
•ore
S3
10
38
532
13
780

192
4
1.113
171
122
838
.12

85
10
224
707
55
10
118
124
59
351
4
12,740


Total
263
68
225
2,173
148
2,871

841
92
3.683
, 650
560
2.497
319

382
75
587
2.794
193
as
414
642
227
1,512
52
48,117
With 20
eor.loy-
ees or
more
63
7
71
506
18
636

208
25
1.111
154
130
732
60

112
23
162
713
48
32
123
129
5°
520
9
12,455


Total
50
1 37
110
919
43
1,527

200
-
647
121
149
776
67

79
9
240
614
73
31
175
205
26
315
-
14,936
With 20
enploy-
ees or
•ore
28
9
51
390
12
581

98
.
357
47
46
382
35

41
5
104
220
20
11
68
S3
IS
157
-
6.333


Total
43
21
27
225
20
430

177
11
468
184
210
341
46

70
26
198
635
57
12
131
343
25
178
-
10.151
With 20
enploy-
eea or
•o**e
15
3
5
77
5
134

S3
3
224
59
56
154
17

27
6
81
198
16
5
49
89
U
75
-
3.649


Total
33
16
60
431
20
854

78
.
331
80
81
410
48

27
7
74
352
53
11
80
66
18
119
-
7.435
With 20
enploy-
ees or
arare
16
3
25
179
4
312

27
-
129
21
18
154
22

11
4
18
105
IS
4
27
17
6
50
-
3.531


Total
73
69
63
754
238
3.170

234
25
590
160
185
667
1,051

93
31
265
733
81
44
130
278
48
350
-
17,210
With 20
employ-
ees or
•ore
13
16
16
240
13
'21

49
6
146
20
10
173
274

27
4
77
130
14
7
29
47
9
96
-
3.793
25. 33 thru 39
(total)



Total
650
310
718
6.695
598
12.888

2.750
15!
9.061
1,820
1,786
7,683
2,0)1

998
183
2.345
7.957
713
267
1,448
2.231
549
3.711
74
14.879

With 2
eHploy
ees o
•ore
21
>
24
2.18
7
3.64

1.06
3
3.59
S3
45
2.97
5*

35
5
8fc
2.40
20
9
S3
53
19
1.46
1
48 90

-------
                                         NUMBER OF METAL FINISHING PLANTS
                                                 M  MORE THAN 10.000
                                                     5,000 -10,000
                                                     1,000-5,000
                                                     LESS THAN 1,000
Figure  1.   Geographic distribution of metal finishing plants by  state [3]

-------
of the total) employ 20 or more employees.   The majority of the
large plants (  75 percent), are concentrated in 14 states (Cali-
fornia, Connecticut, Florida,  Illinois,  Massachusetts,  Michigan,
New Jersey, New York, North Carolina,  Ohio,  Pennsylvania, Texas,
and Wisconsin)  with California, Illinois, Michigan," New York
and Ohio having the largest populations.  This is illustrated in
Figure 2.

The metal finishing industry may be categorized on the basis of
four factors:  (1) plant size (related to the amount of waste
produced); (2)  type of metal finishing operation(s) used (cutting,
cleaning,  coating, etc.);  (3) type of business association (inde-
pendent job shop versus in-piant, captive shop); and (4) type of
organic material used   Regardless of the size and type of
business association (factors 1 and 3),  the type of metal fin-
ishing operations in use will determine the type of organic
waste produced.  Metal finishing operations generate oil wastes,
solvent cleaning operations generate degreasing solvents, and
surface coating operations generate paint sludges.  The following
three subsections describe the metal finishing industry by these
three types of operations.

There are many metal finishing processes and operations but not
all of them are included in this study.   The following processes
are included:  (1) metal forming, (2) metal removal, (3) heat
treating,   (4) coating, and (5) cleaning.  These processes and
operations included in each process are listed in Table 3.  ThG
processes excluded from the study are all metal plating processes,
etching, and other chemical treatment processes.  These and their
respective operations are  listed in Table 4.  They are excluded
either because they are known not to use organic fluids and
produce organic wastes or because they have been included in other
studies.

4.2  METAL FINISHING INDUSTRY DESCRIPTION

Metal  forming operations are not ordinarily included in the metal
finishing category, but they are included within the scope of this
report because the metal rolling and stamping operations consume
an estimated 25 percent of all metal finishing oils [4,5].

Metal  finishing oils are also used in metal removal operations
(such  as cutting), heat treating and rust preventive coating
operations.  The metal removal operations, such as cutting and
grinding use half of all metal finishing oils  [4,5].  Heat treat-
ing oils and rust protective oils each account for approximately
 [4]   Sager, R. C.  Comparing lube demand data.  Hydrocarbon Proces-
      sing.  60(7):141-147, 1981 July.
 [5]   Helm, J. L.  Lube-supply problems to crop up in 1980s.  Oil &
      Gas Journal.  89-94, 1979 December 10.


                                18

-------
                                     NUMBER OF METAL FINISHING PLANTS
                                            M MORE THAN 3,000
                                                1,000-3,000
                                                LESS THAN 1,000
Figure 2,
Geographic  distribution of  metal finishing plants with
20 or more  employees by states |3).

-------
            TABLE  3.  METAL  FINISHING PROCESSES AND OPERATIONS INCLUDED IN THE STUDY

Process category
Forming
Rolling
Casting
Molding
Stamping
Blanking
Drawing
Extrusion
Removal
Cutting
Grinding
Polishing
Buffing
Barrel tumbling
Abrasive machining
Treatment
Quenching
Tempering
Coating
Rust protection (oils)
Undercoating
Wax coating
Painting
Cleaning
Solvent cleaning
Degreasing

N>
O
           TABLE 4.  METAL FINISHING PROCESSES AND OPERATIONS EXCLUDED FROM THE STUDY
. Process category
Alteration
Alloying
Welding
Brazing
Soldering
Removal
Shot blasting
Sand blasting
Coating
Rubber
Plastic
Ceramic
Chromating
Phosphating
Conversion
Cleaning . Plating
Acid Immersion
Alkaline Electroplating
Galvanizing
Chemical
Etching
Polishing
Acid pickling
Anodizing
Bright-dipping
Passive ting
Paint curing

-------
ten percent of the usage,  whila the remaining five percent is
for other miscellaneous metalwcrk applications [4,5].

4.2.1  Industry size

On the basis of NPRA and U.S. DOE data, total sales of metal
finishing oils in 1979 were estimated at 878 million liters
(232 million gallons) [4,5].

4.2.2  Growth Trends

Table 5 presents the 1979 sales estimates by metal finishing cate-
gory, as well as projected demand for metal finishing oils from
1980 to 1990 [4J.  Little growth is expected in the demand for
metal finishing fluids.  The ten-year growth rate for metal finish-
ing oils is expected to average less than one percer.t per year [4].
By 1982.a no-growth status is predicted for removal oils because of
the increased use of water base cutting and grinding fluids  [4].
Although the use of treating oils is expected to increase, improved
conservation practices are expected to extend fluid life.  Forming,
protecting, and other metal finishing oils are used in significant
quantity for ferrous and nonferrous metal stampings, forgings, and
extrusions in the automotive industry, and growth in these areas,
if any, should relate directly to automobile production rates [4].

 TABLE 5.  ESTIMATED 1979 U.S. SALES AND PROJECTED U.S. DEMAND FOR
           METALWORKING OILS, 1980-1990 [4], MILLIONS OF LITERS
Metalworking
category
Removal
Forming
Treating
Protecting
Other
TOTAL
Year
1979
462
219
72
98
27
878
1980
413
189
64
91
27
784
1981
416
189
64
95
27
791
1982
420
197
68
98
27
810
1985
424
204
72
102
27
829
1990
424
219
76
106
27
852
4.2.3   SIC Code Description

Metal  forming  (metal rolling) operations  are concentrated in SIC
Code 33  (metal rolling) and SIC Code 34  (metal  forging and stamp-
ing).   Metal removal operations,  associated with production of
finished or semi-finished products, are widespread in SIC Codes 25
and 34-39.  Rust preventative (oil) coatr.ng and heat treating
operations are conducted in all SIC categories.  Table 1 in
Section 4.1 provides a brief description  of the major three
digit  SIC Codes included in these eight 2-digit SIC Codes.
                                 21

-------
4.2.4  Geographic Distribution

Figure 3 depicts the nationwide geographic distribution of 1977
sales of all lubricating and j.ndustrial oils,  including automotive,
aviation, and all industrial'oils, including metal finishing oils
[6].  The metal finishing operations are widespread across tne
country, although specific regions of the United States have char-
acteristic industries; i.e., automotive production and assembly
industries in Ohio and Michigan, steelmaking industries in Illi-
nois and Indiana and aviation-related industries in California [4].

4.3  SOLVENT CLEANING INDUSTRY H^'CRIPTION
                            .S
Industrial cleaning processes can be classified as acid cleaning,
alkali cleaning or solvent clean:ng.  Acid cleaning and alkaline
cleaning processes are important in the metal finishing industry
but are not inclur!.-Jd within the scope of this study.  Those proc-
esses which gercrate significant amounts of organic waste/^'are
characterized as solvent metal cleaning or degreasing. /"'
                                                     ./
                                                    ^r
There are two basic processes for solvent cleanincu" (1) cold
cleaning (generally a simple soak, spray or wipe-'cleaning), and
(2) vapor degreasing (cleaning by condensing vaporized solvent
on a metal surface).

Degreasing or solvent metal cleaning employs nonaqueous solvents
to clean all of the common industrial metals, including malleable,
ductile, and gray cast iron; carbon and alloy steel; stainless
steel; copper; brass; bronze; zinc; aluminum; magnesium; tin; lead;
nickel; and titanium.  The degreasing process is adaptable to items
of a wide range of sizes and shapes, from transistor components to
aircraft sections.  The process is also used to clean metal strip
and wire at speeds from 45 m/min to 60 m/min [7J.

4.3.1   Industry Size

Based on manufacturer surveys and plant visits, the  segment of the
metal finishing industry performing solvent cleaning-degreasing
operations as an integral part of product manufacture is estimated
to be 49-51 percent of all industrial manufacturing  plants having
20 or more employees  [1,3].  The average total amount of organic
solvents consumed per year in metal cleaning is estimated at 670
million kilograms (1,500 million Ib) [3].
 [6]  Sales of lubricating and industrial oils and greases.  Current
     industrial reports series.  Washington, DC; U.S. Department of
     Commerce; Bureau of the Census.  1978 November.  16 p.

 [7] Hoogheem, T. J.; Horn, D. A.; Hughes, T. W.; and Marn, P. J.
    Source assessment:  solvent evaporation - degreasing opera-
    tion.  Cincinnati, OH; U.S. Environmental Protection Agency,
    1979 August.  133 p.  EPA-600/2-79-019f.  PB 80-128812.


                                22

-------
K)
W
              Figure 3.
                                         OILS (1,000 gallons)
                                         m  150,001  - ABOVE
                                         ED  40,001 - 150,000
                                         Q  10.001 - 40.000
                                         D  10.000 - BELOW
Sales  of lubricating and  industrial oils,  by state:
1977  (6).

-------
4.3.2  Growth Trends

The amount of solvent used for industrial cleaning is projected
to reach 1,043 million kg/yr (2,300 million lb/yr) by 1985 (3J.
Table 6 presents the amounts of degreasing solvents consumed per
year in the United States categorized by type of cleaning process
and solvent type [7].

         TABLE 6.  ANNUAL DEGREASING SOLVENT CONSUMPTION,
                   BY SOLVENT TYPE [7]


                Degreaser typeAverage solvent
        	Solvent used	consumption, kg/yr

        Cold cleaning:
          Butanol                                  53.6
          Acetone                          .       126.3
          Methyl ethyl ketone                     177.6
          Hexane                                  420.6
          Naphthas                                454.7
          Mineral spirits                         420.6
          Toluene                                 256.6
          Xylenes                                 420.6
          Cyclohexane                             420.6
          Benzene                                 420.6
          Ethers                                3,410.2
       -   Carbon tetrachloride                     68.2
          Fluorocarbons                            89.7
          Methylene chloride                    2,187.8
          Perchloroethylene                       249.2
          Trichloroethylene          .             292.8
          Trichloroethane                         568.2

        Open top vapor degreasing:
          Fluorocarbons                         3,806
          Methylene chloride                   24,518
          Perchloroethylene                    10,070
          Trichloroethylene                     7,165
          Trichloroethane                      16,394

        Conveyonzed vapor degreasing:
          Fluorocarbons                         9,403
          Methylene chloride                   60,053
          Perchloroethylene                    24,883
          Trichloroethylene                    17,780
          Trichloroethane                      40,468
                                24

-------
4.3.3  SIC Code Description

Eight SIC Codes (numbers 25 and 33-39) describe the industrial
categories utilizing metal degreasing operations.   The number of
degreasing operations for each SIC industrial code for 1972 was
estimated using percentages calculated from information presented
in Reference [1] and the information is presented in Table 7.
         TABLE 7.  SOLVENT DECREASING OPERATIONS  [7]



0

Industrial product category


Number
of
SIC plants
Estimated
number of
vapor
degreasing
operations
Estimated
number of
cold
cleaning
operations
  Metal furniture              25    9,233       492      23,869
  Primary metals               33    6,792     1,547      17,558
  Fabricated products          34   29,525     5,140      76,329
  Nonelectric machinery        35   40,792     5,302     105,456
  Electric equipment           36   12,270     6,302      31,720
  Transportation equipment     37    8,802     1,917      22,756
  Instruments and clocks       38    5,983     2,559      15,467
  Miscellaneous                39   15,187       886      39,262

  Subtotal                         128,584    24,145     332.417
  1972 data.
4.3.4  Geographic Distribution

4.3.4.1  Cold Cleaning--
In 19V2 more than half  (54 percent) of cold cleaning operations
were located in nine states:  California, Florida, Illinois,
Michigan, New Jersey, New York, Ohio, Pennsylvania, and Texas;
Figure 4 illustrates the geographic distribution of the locations
of these cold cleaning  operations  (7).  The remaining plants are
distributed throughout  all the other states [7].

4.3.4.2  Vapor Deqreasing—
In 1972 more than 63 percent of vapor degreasing operations were
found in nine states:   California, Illinois, Massachusetts, Michi-
gan, New Jersey, New York, Ohio, Pennsylvania, and Texas.  The
balance of the plants were located in 40 of the remaining 41 states
[7].  Figure 5 represents the geographic distribution of vapor de-
greasing operations  [7].
                                25

-------
                                        010 5000
                                        JOOOtoBCCO
                                        noootosoooo
                                        > soon
           Figure 4.  Geographic distribution of cold
                      cleaning operations [7].

4.4  SURFACE COATING INDUSTRY DESCRIPTION

The two categories of products manufactured by the U.S. coatings
industry "are:  (1) architectural coatings, such as exterior and
interior house paints,  and (2) industrial finishes, including
product coatings formulated specifically.for original equipment
manufacture and applied as part of the manufacturing process, and
special purpose coatings such as aerosol paints, roof coatings,
and refinish coatings.   Figure 6 illustrates the types of coatings
produced by the paint and allied products industry [8].

4.4.1  Industry Size

In 1980 the estimated U.S. production of industrial product coat-
ings for original equipment manufacture was over 1.7 billion
liters (450 million gallons)  19].  Of this total amount of paint
[8] Hughes, T. W.; Horn, D. A.; Sandy, C. W.; and Serth, R. W.
    Source assessment:  prioritization of air pollution from
    industrial surface coating operations.  Research Triangle
    Park, NC; U.S. Environmental Protection Agency; 1975
    February.  EPA-650/2-75-109a.

[9] Dean, J. C.  The U.S. coatings industry strategy for survival
    in the '80s.  Chemical Week.  1981 October 21.
                                26

-------
           Figxire 5.   Geographic distribution of vapor
                      degreasing operations [7].

and allied products,  an estimated 60 percent consists of volatile
compounds such as organic solvents and water.   If the volatile
portion of .the product coatings is disregarded for comparison
purposes, the 1980 production can be stated as 680 million dry
liters (180 million dry gallons) (40 percent of the proceeding
total quantities) [9].

4.4.2  Growth Trends

The production of these products is expected to increase at an
average annual rate of 1-1.5 percent for an estimated annual pro-
duction of 738 million dry liters (195 million dry gallons) by
1990 (9].  Air pollution regulations limiting volatile emissions
into the atmosphere will cause an increasing shift from conven-
tional solvent-based coating systems to water-based and high-
solids systems.  The volatile content of product coatings in 1990
wj11 average 40 percent, down from the present 60 percent [9].
The net result of this shift in product composition will be a
decrease in the total volume of product coatings produced in
1990, as indicated in Table 8 [9].  The distribution of product
coatings by product category is ptovided in Table 9 [9J.
                                27

-------
                                                     Interior
                                                    75! 1/820



— J
SPlvmt-BdV
321 HK6

Hiler-B.iv I


I Ml Wa'iraml
Vdrmin
l';imei .in)!ulir
6ihei '
ni'(hm tnamti
ii
12? ? 11



Miscellaneous

ill Ql 'It




•I



Product Finishes
996 6/1207








167 4/164
Thlnners
117 U991































































Silvenl-Bise
46C Ur.M



220 U237


























"





























Inimil S« i/51
I'riner «n.1 '
-------
TABLE 8.  COMPARISON OF ESTIMATED PRODUCTION OF PRODUCT COATING FOR
          ORIGINAL EQUIPMENT MANUFACTURE IN THE U.S., 1980 AND 1990


Total production, million liters
Total production, (nonvolatile ingredients),
million dry liters
Volatile fraction (organic solvents and water), percent
Norvolatile fraction (pigments, resins, etc.), percent
Year
1980
1,700
680
60
40

1990
1,230
738
40
60

    TABLE 9.  U.S. PRODUCTION OF PRODUCT COATING FOR ORIGINAL
              EQUIPMENT MANUFACTURE BY END USE  [9]

                                          Production, millions of
                                          	dry liters	
                                                    Year
          Product category
1980
1985
1990
Metal- coating
  Auto, truck, and bus          .          114       110       102
  Containers, closures, metal deco         83        83        80
  Machinery, equipment                     72        76        80
  Coil, sheet, strip  (prefinished)         42        53        68
  Appliances                               38        38       -38
  Metal furniture, fixtures                34        34        38

Nonmetal
  Wood furniture, fixtures                117       117       121
  Special substances, paper, plastic       72        80        95
  Wood and composition flat stock          38        34        34
  Other                                    72        76        83
  Total metal coating                    382       394       405
  Total nonmetal coating                  299       307       333
  Total production                        681       700       738
4.4.3   SIC Code Distribution

Organic product coatings  are used  in the metal  finishing industry
in  the  manufacture of prefinished  metal (coil coatings) and  for
finishing fabricated ferrous and nonferrous metal products such  as
transportation equipment  (auto, truck, and bus), metal containers,
electric equipment and nonelectric machinery, metal  furniture  and
household appliances and  miscellaneous metal products in SIC Codes
25  and  34-39, as  described  in Table 1 in Section 4.1.  Geographic
                                 29

-------
distribution by state of ruetal finishing industries in SIC Codes
25 and 33-39 is presented in Table 2 in Section 4.1.

4.4.4  Geographic Distribution

4.4.4.1  Automobile Coatings—
The automobile  industry is the largest manufacturing industry in
the United States.  Motor vehicle and allied industries account
for one-sixth of the Gross National Product.  Surface coating
is the final and most important automobile finishing process.

At the beginning of 1978, passenger cars and light-duty trucks
were being assembled at 45 and 24 locations, respactively, in
the United States.  Total reported outputs from these plants in
1977 and 1975, respectively, were over 9.1 million passenger cars
and over 1.7 million light-duty trucks [10].

Automobile assembly plants are located in 19 states and 43 cities,
as shown in Tables 10 and 11.  However, over 32 percent of all
automobiles and light-duty trucks produced in the United States
are manufactured in Michigan  [10].

4.4.4.2  Automotive Coatings—
In 1972, according to the Thomas Register of American Manufacturers,
there were approximately 8,700 nonautomobile, product-type surface
coating plants in the United  States each having a total sales
volume of 3500,000 per year or more.  More than 85 percent of the
plants were located in 19 states.  These states were:  Minnesota,
Wisconsin, Iowa, Missouri, Illinois, Indiana, Michigan, Ohio,
Pennsylvania, New York, Massachusetts, Connecticut, California,
Oregon, Washington, Tennessee, North Carolina, Texas, and New
Jersey.  The other 15 percent of the plants were located in the
remaining 31 states.  Only two of the states did not have product-
type surface coating plants;  these were Alaska and Wyoming  [8].

Figure 7 is a graphical presentation of the geographic distribu-
tion of these nonautomotive,  product surface coating plants,
based on 1972 data  [8].
 The term  "automobile industry" as used here includes both auto-
 mobile and truck production.

DThe term  "light-duty truck" is defined as "all vehicles with
- ratings of 8,500 pounds or less GVW."  Included in this classifi-
 cation are pickup trucks, vans, panel trucks, station wagons
 built on  pickup truck chassis, multistop trucks, and off-road
 vehicles.
 [10] Automobile and light-duty truck surface coating operations
     background information document.  Research Triangle Park, NC:
     U.S. Environmental Protection Agency; 1979 October.  301 p.
     EPA-450/3-79-030.  PB 80-123540.
                                30

-------
TABLE 10.  GEOGRAPHIC DISTRIBUTION OF U.S.
           ASSEMBLY PLANT PRODUCTION [10]
                       (Model Year 1977)
AUTOMOBILE
State
California





Delaware


Florida

Georgia



' Illinois


Kansas

Kentucky

Maryland

Massachusetts

Michigan










City
(Total)
Fremont
Los Angeles
San Jose
Souch Gate
Van Nuys
(Total)
Newark
Wilmington
(Total)
Sebring
(Total)
Atlanta
Doraville
Lakewood
(Total)
Belvirtere
Chicago
(Total)
Fairfax
(Total)
Louisville
(Total)
Baltimore
(Total)
Framingham
(Total)
Dearborn
Detroit
Flint
Hamtranck
Kalamazoo
Lansing
Pontiac
Wayne
Willow Run
Wixon
Percentage
8.1
1.8
1.4
0.7
1.4
2.8
4.0
2.5
1.5


6.6
2.0
2.7
1.9
4.5
1.9
2.6
2.9
2.9
1.1
1.1
2.7
2.7
1.5
1.5
32.3
1.4
6.4
4.6
4.2

4.4
3.6
3.0
2.8
1.9
Units
740,492
164,216
128,143
59,744
131,233
257,156
363,202
226,435
136,767
_
-
595,926
186,130
241,423
158,373
409,062
173,178
235,884
267,110
267,110
101,057
101,057
241,171
241,171
135,776
135,776
2,948,759
131,016
587,342
416,459
. 379,562
—
404,000
326,231
273,150
255,078
175,921
                                                  (continued)
                          31

-------
                       TABLE  10  (continued)

State
Minnesota

Missouri



New Jersey



New York

Ohio .




Texas

Wisconsin


City
(Total)
Twin Cities
(Total)
Kansas City
Leeds
St. Louis
(Total)
Linden
Mahwah
Metuchen
(Total)
Tarrytown
(Total)
Avon Lake
Lorain
Lordstown
Norwood •*
(Total)
Arlington
(Total)
Janesville
Kenosha
Percentage
1.3
1.3
11.1
1.0
2.8
7.3
6.6
2.7
2.9
1.0
?.5
2.5
7.3
0.4
2.7
1.8
2.4
2.5
2.5
5.0
3.0
2.0
Units
115,464
115,464
1,010,786
93,946
252,119
664,721
596,791
243,455
260,560
92,776
230,894
230,894
660,101
36,136
241,017
162,029
220,919
230,371
230,371
457,581
275,576
182,005
United States
TOTAL
100.0
9,104,543
                                32

-------
    TABLE  11.  GEOGRAPHICAL DISTRIBUTION OF U.S. LIGHT-DUTY
               TRUCK ASSEMBLY PLANT PRODUCTION
                            (Model Year 1975)

State
California
Georgia
Indiana
Kentucky
Maryland
Michigan
Missouri
New Jersey
Ohio
Texas
Virginia
Wisconsin
City
(Total)
Fremont
San Jose
(Total)
Atlanta
Doraville
Lakewood
Fort Wayne
South Bend
(Total)
Louisville
(Total)
Baltimore
(Total)
Detroit
Flint
Warren
Wayne
(Total)
Kansas City
Leeds
St. Louis
(Total)
Mahwah
(Total)
Avon Lake
Lorain
Lordstown
Toledo
Arlington
(Total)
Norfolk
(Total)
Janesville
Percentage
8
3
5
4
1
3

9
9
4
4
35
1
14
12
8
10
4
6
3
3
20
9
6
3

3
3
4
4
Units
130,829
53,000
77,829
61,925
13,228
48,697

153,404
153,404
72,175
72,175
601,456
10,543
250,050
212,033
128,830
181,377
67,946
113,431
42,925
42,925
357,502
143,895
102,763
110,844

54,777
54,777
62,153
62,153
United States
TOTAL
100
1,718,523
                                33

-------
w
f
JUMBER OF PLANTS PER








0-9 STATE

10-99

100 AND OVER

                   Figure  7.  Geographic distribution of nonautomotive product
                             surface  coating  plants by state   [8].
      aBased on distribution  of 8,700  nonautomotive  surface  coating operations  in  1972.
       geographic distribtuion of automotive  assembly  plants see Table  10.
For

-------
                            SECTION 5

               DESCRIPTION OF PROCESS OPERATIONS,
                    RAW MATERIALS, AND WASTES


This section describes metal finishing operations including metal
working, solvent cleaning, and surface coating, the raw materials
used, and the wastes generated.

5.1  METALWORKING

This section describes various metalworking operations, itfetalwork-
ing oils, and the waste oils generated.

5.1.1  Process Descriptions

The metalworking processes utilizing oils include metal forming,
metal removal, heat treating, and corrosion-preventive coating
processes.

5.1.1.1  Mei:al Forming—
Metal forming processes are of three major types:  (1) casting
and molding, (2) hot rolling and cold rolling, and (3) press form-
ing, drawing, and extrusion.  All three types of forming operations
are conducted on a large scale in metal foundries.  Foundries- in
the United States annually produce 17 million Mg (19 million tons)
of cast iron [11], 124 million Mg (137 million tons) of steel [12],
and 45 million Mg (50 million tons) of aluminum [13].

Examination of the basic iron casting and steel working processes
will illustrate forming, rolling, casting, and molding operations
commonly utilized in the production of otner metals as well.
 [11] Baldwin, V. H.  Environmental assessment of iron casting.
     Research Triangle Park, NC; U.S. Environmental Protection
     Agency; 1980 January.  171 p.  EPA-600/2-80-021.  PE 80-187545,

 [12] Draft development document for the iron and steel manufactur-
     ing point source category.  Vol. I, Draft document.  Washing-
     ton, DC;  U.S. Environmental Protection Agency; 1979 October.
     EPA-440/l-79-024a.  PB 81-184392.
 [13] Hotlen, B. w.  Bidenate oxygen compounds as boundary lubri-
     cants for aluminum.  Lubrication Engineering-.  398-403, 1974
     August.
                                35

-------
                     Reproduced by NTIS
                     National Technical Information Service
                     U.S. Department of Commerce
                     Springfield, VA 22161
 •o
 « .
 U «•-
       •*-
 r« >    «-
 ig!=°
 0)  Q.
          O
    —  ® "O
 s  i  *• S
 2!  | ~-g
 *-  E c  Sf
 S  o> *"'  c
 C  W —'  *•
 i-  «<::  «
 o     a»     w


 4) -Q  B! .^  "D
2  «•  g
gfeS

This report was printed specifically for your
order from our collection of more than 1.5

million technical reports.

For economy and efficiency, NTIS does not maintain stock of its vast
collection of technical reports. Rather, most documents are printed for
each order. Your copy is the best possible reproduction available from
our master archive. If you have any questions concerning this docu-
ment or any order you placed with NTIS, please call our Customer
Services Department at (703) 487-4660.

Always think of NTIS when you want:
• Access to the technical, scientific, and engineering results generated
by the ongoing multibillion dollar R&D program of the U.S. Government.
• R&D results from Japan, West Germany, Great Britain, and some 20
other countries, most of it reported in English.

 NTIS also operates two centers that can provide you with valuable
information:
• The Federal Computer Products Center - offers software and
datafiles produced by Federal agencies.
• The Center for the Utilization of Federal Technology - gives you
access to the best of Federal technologies and laboratory resources.

For more information about NTIS, send for our FREE NTIS Products
and Services Catalog which describes how you can access this U.S.
and foreign Government technology. Call (703) 487-4650 or send this
sheet to NTIS, U.S. Department of Commerce, Springfield, VA 22161.
Ask for catalog, PR-827.

Name	
Address	
                     Telephone
                              -Your Source to U.S. and Foreign Government
                               Research and Technology

-------
Newer technologies for metal forming will be discussed after con-
sideration of the most comnon processes.

Casting and Molding—Metal castings are produced from iron, steel,
alloys of aluminum, copper, brass, nickel, magnesium, or zinc.
The technologies for ferrous ant? nonferrous casting operations are'--
similar, therefore, the. discussion will concentrate on iron and
steel casting.

Figure 8 is the process flow chart for typical iron foundry cast-
ing operations  [11].  Figure 9 gives a simplified version of the
flow chart, indicating the types of waste expected in casting
operations.

In preparation  for casting," iron is melted in cupolas, electric
arc furnaces, or electric induction furnaces [11].  Various types
of processes are used for producing metal castings.

The basic method for casting metal involves pouring the molten
metal into a sand mold.  A metal casting is produced by filling
the cavity in a sand mold with the molten metal, allowing the
metal to cool and solidify, then breaking the mold, discarding the
sand, and removing the cast metal.

The sand mold is formed by placing a model of wood, metal, or
plastic in an appropriately sized container and packing with sand,
either by hand  or hydraulic press.  Clay or other chemical sub-
stances are added to increase the shape-retaining ability of the
sand.   In the next step of the operation, the model is removed
and the shaped  cavity filled with the molten metal.  After the
castings are cooled and removed from the molds, excess metal imper-
fections must be broken or ground off.   If the separate parts of
the mola did not mate perfectly, there may be a "flash1 or sharp
edge to be removed  [11].

In pressure casting, molds are rectangular blocks of graphite en-
closing a cavity of the desired size.  A ladle of molten metal is
placed  in a pressure chamber, which is then sealed.  Pressurized
air is  then directed into the pressure chamber and the molten
metal is forced into the graphite chamber through a ceramic pour-
ing tube.  The  pressure is released from the chamber and the filled
mold is removed and allowed to cool  [14].
 [14]  Proposed  development  document  for  effluent  limitations guide-
      lines  and standards for  the  iron and steel  manufacturing
      point  source  category.   Volume III  - Steel  making, vacuum
      degassing and continuous casting subcategories.  Washington,
      DC; U.S.  Environmental Protection  Agency; 1980 December.
      513 p.  EPA-440/l-80-024b.   PB 81-184418.


                                36

-------
to
-o
                                                    Reproduced Irom
                                                    best available copy.
                        Figure 8.   Typical  foundry production flow chart  [11].

-------
to
00
Flux

Coke




MptaK

-t»


Metal Melting
1n
Cupola
IS
I"

Metal
Pouring


                                                     Casting
Cooling,
Mechanical
Cleaning.
and Finishing


Finished
I/ va»nny

                                                                      J8Z-
                                                  Spent Sdnd, Dust, Sludge,
                                                      and  Slag to Open
                                                           Dump
                          Figure 9.   Simplified typical  foundry operation  [14].

-------
In the continuous casting process,  molten steel from the furnace
is forced through a water-cooled copper mold to produce a semi-
finished product.  As the semi-solidified (liquid .center) steel
emerges from the molds, it is sprayed with water.to further cool
and solidify the cast product.  The serai-finished product then
passes into the cut-off zone, where the product is cut to the
desired length, as bloom, billet, or slab.  One of three config-
urations is used for continuous casting:  vertical casting, ver-
tical casting with bending rolls, or a curved mold design with
straightening mechanism.  The latter design needs the smallest
area for production [14].

Shell molding using a two-piece plastic shell supported by iron
shot is employed for the production of high precision castings.
Permanent molds of steel, cast iron, or ceramic may be used, al-
though they are more expensive and time-consuming.  Physically
bonded molding is the newest technology for casting metal using
non-chemically-bound sand or powdered iron.  Applications of air
pressure, magnetic or vacuum molding processes are expected to
increase because of their lower potential for environmental
pollution [11].

Steelmaking—Basic raw materials for steelmaking axe hot metal or
pig iron, steel scrap, limestone, dolomite, fluorspar and iron
ores.  Iron is converted into steel ingots in either an open hearth,
basic oxygen, or electric-arc furnace.  Use of the slow process
open'hearth furnace is widespread'but declining.  The basic oxygen
furnace can handle a greater variety of raw materials, and the
electric-arc furnace is best suited for production of high quality
stainless steels [12].
                                              m
The molten steel either is cast continuously into products of the
desired shape or is cast into ingots for subsequent forming.  In
conventional casting, the molten steel is tapped into a refractory-
lined steel laddie.  The laddie is moved by an overhead crane to a
pouring platform where the steel is then poured  into a series of
molds of the desired dimensions.  Alloying materials and deoxidi-
zers may be added during the tapping of the charge or in the
molds.  The steel solidifies in each of the molds to form a cast-
ing called an ingot.   In the continuous casting  process, a laddie
of steel is brought and positioned over the tundish which is over
the water-cooled copper mold.  The laddie nozzle is opened and the
tundish is filled with molten steel to the desired depth.  Then
the tundish nozzles are opened to permit molten  steel to en^.er
the molds.  The casting then passes through a cooling ch£jnber,
straightening mechanism, and cutting device where it is cut into
the desired lengths  [15].

[15] Parsons, T., ed.  Industry profiles for environmental use:
     the iron and steel industry.  Research Triangle Park, NC;
     U.S. Environmental Protection Agency; 1977  February.  209 p.
     EPA-600/2-77-023X.  PB 266 226.


                                39

-------
Figure 10 presents the flow diagram for the basic steel manufac-
turing process [12].

Hot Rolling [12]—The temperature of steel ingots is raised in a
soaking pit furnace to prepare the steel for hot working (rolling).
In the furnace, the steel is heated until it is plastic enough for
rolling to the des-ired shape.

In the rolling of steel to reduce thickness, metal is deformed
but not cut.  In the rolling process, the same volume of metal
leaves the *olls as enters it and therefore the speed of exit cf
the metal from the rolls is greater than the speed of entry.  Some
slippage therefore occurs as the metal passes between the rolls.
The main properties desired of a rolling fluid are to control the
amount of slippage, withstand the high roll pressures, cool the
rolls and produce a good quality surface finish on the rolled strip.

The basic operation in a primary m:ll is the gradual compression
of the steel ingot between the surfaces of two rotating rolls and
the progression of the ingot through the space between the rolls.
The physical properties of the ingot prohibit making the total
required deformation of the steel in one pass through the rolls,
so a number of passes in sequence are always necessary.  As the
ingot enters the rolls, high pressure water jets remove surface
scale.  The ingot,is passed back and forth between the horizontal
and vertical rolls while manipulators turn the ingot from time to
time so that it is well worked on all sides.  When the desired ,
shape has been achieved in the rolling operation, the end pieces
or crops are removed by electric or hydraulic shears.  The semi-
finished pieces are stored or sent to reheating furnaces for sub-
sequent rolling into sheets, coils, or other shapes.          , ,

Ever increasing attention is being devoted to the conditioning of
semi-finished products as the requirements for high quality steel
products increases.  Ma3or elements in this area involve the need
for removing surface defects from blooms, billets, and slabs prior
to shaping, as by rolling into a product for the market.  Such
defects as rolled seams, light scabs, checks, etc., generally retain
their identity during subsequent forming processes and result in
products of inferior quality.  These surface defects may be removed
by hand chipping, machine chipping, grinding, mailing, and scarfing.
Scarfing removes defects with an oxyacetylene torch, either by a
manual process or with a production machine.

Merchant-bar, rod, and wire mills produce a wide variety ot" prod-
ucts in continuous operations ranging from shapes of small size
through bars and rods.  The designations of the various mills as
well as the classification of their products are not very well
defined within the industry; in general, a small cross-sectional
area and a very Icng length distinguish the products of these
mills.  Raw materials for these mills are reheated billets.  Many
older mills use hand looping operations in which the material is


                                40

-------
                                                Sltll PKXXJCT HAm»M:lU*HlO
                                             _   „-  - , . -„-,>_._ • - '^'^- * -
                                             ««»>rr/rvj     |	L

                                                 1     I     r
IGURC ra-i
Figure 10.  Steel manufacturing process flow  diagram  [12].

-------
passed from mill stand to mill stand.  As with other ;rolling oper-
ations, the billet i;> progressively squeezed and shaped to the
desired product dimensions in a series of rolls.  Water sprays
are used throughout the operation to remove scale.

The continuous hot strip mill utilizes slabs which are brought to
rolling temperatures in continuous reheating furnaces; the condi-
tioned slabs pass through scale breakers and high pressure water
sprays which dislodge the loosened scale.  A series of roughing
stands and a rotary crop shear produce a section that can be
finished to a coil of the proper weight and gauge.  The second
scale breaker and high pressure water sprays precede the finish-
ing stand train in which the final size reductions are made.
Cooling water is applied through sprays on the run-out table, and
the finished strip is coiled.  Such a mill can turn a 6-foot thick
slab of steel into a thin- strip or sheet a quarter of a mile long
in three minutes or less.  The product of the modern hot strip mill
may be sold as produced, or used within the mill for further proc-
essing in cold reduction mills, and for plated or coated products.

Welded tubular products are made from hot-rolled skelp with square
or slightly beveled edges, the width and thickness of the skelp
being selected to suit the various sizes and wall thicknesses to be
made.  The coiled skelp is uncoiled, heated, and fed through form-
ing and welding rolls where the edges are pressed together at high
temperature to form a weld.  Welded pipe or tube can also be made
by the electric weld process, where the weld is made by either
fusion or resistance welding.

Seamless tubular products are made by rotary piercing of a solid
round bar or billet, followed by various forming operations to
produce the required size and wall thickness.                " "

The product flow of typical steel mill operations is illustrated
in Figure 11.
 Cold Rolling  [lb] — Cold rolling is that operation where unheated
 metal  is passed  through a pair of rolls to reduce its thickness,
 to produce  a  smooth dense surface, and to develop controlled
 mechanical  properties of the metal.

 Direct application, recirculation, or combination systems are
 used for oil  application at cold rolling mills.  A general process
 diagram of  the recirculation system is shown in Figure 12.
 [16]  Proposed  development document  for effluent limitation guide-
      lines  and standards for  the  iron and  steel manufacturing
      point  source  category.   Volume VI.  Cold  forming, alkaline
      cleaning.   Washington, DC; U.S. Environmental Protection
      Agency; 1980  December.   604  p.  EPA-440/l-80-024b.
      PB  81-184442.
                                42

-------
*>
u>
                                                                 ^ SUIT WUO
                                                                I    Plpt
                                                                         HCCL IMOU»T«» SlOOt
                                                                            HOT  rOKMiMO
                                                                         rmctss »to
                                                                                   FIGURE JH-t
                    Figure  11.  Product flow of "typical  steel mill operations  [12]

-------
                                   Reproduced from
                                   best  available copy.
                                                                                                loll"-. 01' tmtvati.
                                                                                                ctly «toito maiw fr
                                                                                                ail
                                        Muc oil> »atl* walo Itom
                                        ail (lorag* unit handling,
                                        pint momunonc* ihop-ioll
                                        lacing, tic
Figure  12.   Process diagram  for  cold rolling oil application  recirculation  system  [16]

-------
There are various types of cold rolling processes.  Cold reduc-
tion is a special form of cold rolling in which the thickness of
the product is reduced by relatively large amounts in each pass
through tha rolls.  In the production of most cold rolled mate-
rials, the cold reduction process is used to reduce the thickness
of the hot rolled breakdown between 25 percent and 90 percent.

Cold rolled strip, cold rolled sheet, and cold rolled flat bar are
the principal cold reduced flat products.  Carbon, alloy or stain-
less steels are used, depending on the end use of the products.

Most rolled products are carbon steel in sheet form and are used
as base material  for such coated products as long terne sheets,
galvanized sheets, aluminum coated sheets, tin-plate, or tin-free
steel.  Hot rolled coils called "breakdowns" are the base material
used in the cold  rolling operation.  Prior to rolling, however,
they must be descaled and pickled, usually in a continuous pick-
ling operation.

There are several types of cold reduction mills which vary in de-
sign from single  stand reversing mills to continuous mills with
up to six stands  in tandem (in series).  In the single stand re-
versing mill, the product is rolled back and forth between the
w&rk rolls until  the desired tnickness and mechanical and surface
characteristics are achieved.  In the single stand nonreversing
mill, the material makes a single pass through the rolls and is
recoiled.  If additional roiling is required, the coil is returned
to the head of the mill and reworked.  The single stand nonrevers-
ing mill is generally used for tempering operations.

Most cold reduced flat steel is rolled on continuous three, four,
or five stand tandem mills.  In these mills, the material con-
tinually passes from roll to roll until the desired thickness is
attained.  The continuous rolling mills represent modern technol-
ogy and is the type of equipment installed in new mills.

A typical modern  cold rolling shop contains a continuous pickling
operation (sulfuric or hydrochloric acid) to remove scale and
rust  from the hot rolled breakdown coil.  As it leaves the pickler
the strip is oiled to prevent rusting and to act  as a lubricant
in the cold rolling mill.  The coil is then fed into a continuous
cold  rolling reducing mill that can contain up to six rolling
stands in tandem.  Each stand contributing to the reduction in
thickness of the  material, the first contributes  the greatest re-
duction while the last stand acts as a straightening, finishing,
and gauging roll.  Unlike hot forming, no scale is formed during
this  operation.

The properties of hot rolled seamless pipe can be improved by
cold  wording the  product.  Cold working the pipe  increases its
yield strength and generally improves the product.  One method of
cold  working is the  seamless pipe method, in which the hot rolled


                                45

-------
pipe is dropped into an expander trough and clamped with one end
held firmly against a backstop.  A long ram is positioned at the
opposite end of the pipe, and an expander plug is forced through
the pipe by extreme pressure.  The plug is lubricated through the
ram head with a water soluble oil.  After cold expansion, the
seamless pipe enters a rotary straightener and then is hydro-
statically tested  [16].

Drawing—While most quality requirements for seamless pipe and
tubing products can be met by the hot rolling processes, some pipe
and tube specifications require closer tolerance, enhanced physical
and surface properties, thinner walle, and smaller diameters than
can be met by cold drawing the hot rolled tubes in a finishing
operation.

The process consists of pulling a cold tube through a die, the
hole of which is smaller than the outside diameter of the tube
being drawn.  At the same time, the inside surface of the tube is
supported by a mandrel anchored on the end of a rod, so that the
mandrel remains in the plane of the die during the drawing opera-
tion.  Another method involves using an internal bar rather than
a stationary mandrel.  This bar travels along with the tube, as
it is drawn through the die.  The hot rolled tubes are crimped
and pointed on one end, so that the pipe section can pass through
the die and permit the jaws of the puller mechanism to grip the
end of the tube.   Some tubes of certain steel grades are annealed
prior to the cold  drawing operation.  All tubes are pickled to
remove scale and oxides, rinsed, and then dipped into a lubricant
tub (flour, tallow and water, or a special oil emulsion foi a
bright finish) prior to the cold drawing operatior  [16].

Wire Drawing--Wire drawing bears some similarity to cold rolling,
in that the same volume of met£.i leaves the die as enters it and
metal deformation  takes place with some slippage in the die  .  The
speed of exit of the metal from the die is greater than the speed
of entry, because  the wire drawing operation reduces the cross-
sectional area of  the wire.  The exit speed may be several hundred
•feet per minute, many times the entry speed into the initial die.
In a wire drawing  train, the wire is pulled through a series of
dies so that the diameter of the wire is progressively reduced.
Between each die,  the wire is passed around rollers to obtain the
desired tension.   The art of wire drawing is a complex phenomenon
and much depends upon the skill of the operators.  The  lubrica-
tion of the wire during  its passage through the die plays an im-
portant role, particularly with regard to lessening the  amount of
die wear  [17].  Figure 13 presents a representation of the process
for wire drawing.
 [17]  Billett,  M.   Industrial  lubrication.   New York, Pergamon
      Press,  1979.   136  p.
                                 46

-------
                 Figure 13.  Wire drawing [17].

Press Forming and Extrusion—The term press work is used by the
metals industry TC.O embrace almost all press operations including
stamping, blanking, forming, and related processes.  Blanking is
a process accomplished with dies in presses in which desired shapes
are cut from flat or preformed stock.  A blank is usually the work-
piece for subsequent forming or machining, but may.constitute a
finished product in some cases.  A number of processes are used
in press forming, the choice depending on the type of shape needed.
These include drawing, bending, stamping, and coining.  Although
cold forming is most common, hot forming is used for very heavy
stock.  Some forming operations are dry and in others a lubricant
is used [18].  For hot forging on a hydraulic press, adequate
lubrication of dies is essential, due to longer contact times in
this type of forging.  Although a lower sliding friction is desir-
able at the die-workpiece interface, one of the main functions of
the die lubricant is to act as an intermediate layer between the
die and the workpiece.  This prevents seizing on the die and reduces
die wear.  Further, the axial motion of the dies causes radial flow
of metal on the die surface.  This tends to wipe the lubricant off
the die surface.  Thus, hot-forging lubricants should  withstand
high temperatures under high pressures and sliding contact [19].
 [18] Levin, J.; Beeland, G.; Greenberg, J.; and Peters, G.
     Assessment of industrial hazardous waste practices special
     machinery manufacturing industries.  Washington, DC; U.S.
     Environmental Protection Agency; 1977 March.  328 p.  EPA-
     530/SW-141C.  PB 265 981.
 [19] Lahoti, G. D.; Nagpal, V.; and Altan, T.  Selection of lubri-
     cants in hot forging and extrusion.  First international
     conference on lubrication challenges in metalworking and
     processing.  Chicago,  ITT Research Institute, 1978, 52-59.
                                47

-------
Extrusion—There are two alternative methods,  forward or direct
extrusion and backward or indirect extrusion.   In the process of
forward extrusion,  the metal is pushed through a die, when it is
required to form it into a desired component shape (Figure 14).
It thus differs from wire drawing, where metal is continuously
being pulled through a die.  However, as with wire drawing, the
pres&ures involved in the cold extrusion process are extremely
high as are the resulting temperatures.  Most attempts to avoid
the necessity to phosphate the metal surface of the component to
be extruded and to use only a lubricant, without an underlying key,
have not been successful.  A similar lubrication situation exists
with backward extrusion, in which a punch is used to cause metal
flow back over the punch tool surface to form the component shape.
In contrast to forward extrusion, the metal is not pushed forward
through a die (Figure 14)  [17].

Titanium alloys, alloy steels, stainless steels, and tool steels
are extruded on a commercial basis using a variety of graphite and
glass base lubricants.  In the patented Sejournet process, the
heated billet is commonly rolled over a bed of ground glass, or
it is sprinkled with glass powder which supplies a layer of low-
melting glass to the billet surface.  Prior to insertion of the
billet into the container, a suitable die glass lubricating system
is positioned immediately ahead of the die.  This may consist of
a compacted glass pad, glass wool, or both.  The prelub::icated
billet is quickly inserted into the container followed by appro-
priate-followers or a dummy block, and the extrusion cycle is
started.  The unique features of glass as a lubricant are its
ability to soften selectively during contact with the hot billet
and, at the same time, to insulate the hot-billet material from
the tooling, which is usually maintained at a temperature con-.,
siderably lower than that of the billet [20].

5.1.1.2  Metal Removal —
Metal removal or machining processes are of four major types:
(1) cutting,  (2) grinding, (3) polishing and buffing, and  (4) mass
finishing and barrel tumbling.

Machining, according to the definition of the metalworking indus-
try, is the removal of material in the form of chips from metal
parts, usually through the use of a machine tool.  The factors
involved in machining are the workpiece, machine tool, cutting
tool, and cutting fluid.  Grinding is a form of cutting in which
abrasive grains in a grinding wheel act as the cutters.

The machine shop equipment used in plants for metalworking in-
cludes: engine and turret  lathes, milling machines,  drill presses
and electric  drills, grinders of  several types, boring mills,
 [20]  Cook, C. R.  Lubricants  for high temperature extrusion.
      28:199-218,  1971  June.
                                48

-------
                                                                Cottln* will ItoUl Kortlnd
vO
                        Figure  14.  Forward extrusion/backward extrusion [17].

-------
planers and hand and cut-off saws.  These tools are capable of
functions with a wide variety of nomenclature but they all fall
within the general category of cutting and shaping.  Several
machining operations are often carried out in conjunction with
each other and many pieces of equipment are capable of rsrforming
more than one machining function.  A typical machining process is
shown schraatically in Figure 15  [18].

Examples of the machining operations which are common to many
metalworking establishments include:  milling, facing, turning,
grinding, boring, drilling, reaming, sawing, and planing.  All of
them remove metal which may be in the form of chips, turnings,
grindings, borings, etc.

When metal is cut by any of the  above methods, heat is generated.
Continuous cooling and lubrication are usually necessary to pro-
tect both the tool and the workpiece from damage and to facilitate
cutting action .  These functions are accomplished by the use of
cutting fluids, or coolants, which also flush away metal chips,
reduce strain hardening of the mstal, and prevent rust.  Cast iron
and some nc::ferrous materials do not require the use of cutting
fluids [18].

Cutting  [17]—In a metal cutting operation, a tool shears the metal
and the sheared metal removed from the workpiece forms into either
continuous or discontinuous chips (Figure 16).  The energy result-
ing from the shearing of the metal is dissipated through the work-
piece' and tool, in the form of heat.  Additional frictional heat is
also produced by the flow and rubbing of the metal chips, as they
are formed, over the surface of  the cutting tool.  The total heat
released may cause the building  up of some sheared metal on the
tool surface, a phenomenon known as a built-up edge.  This weld-
ing of tool to workpiece can be  avoided by the rapid removal of
the heat evolved and also by decreasing the total amount produced,
by reducing the frictional heat  component.

A copious, well-directed supply  of cutting fluid can remove suffi-
cient heat by metal surface cooling, as the fluid can penetrate
fairly well into the region where the formed chip is rubbing over
the tool, producing the frictional heat.  The fluid can also lub-
ricate the passage of the chip over the tool.  The two main require-
ments for cutting  fluids are, therefore, the ability to maintain
the tool and workpiece at acceptable temperature levels and to
reduce the frictional heat formed during the cutting operation.

In all cutting oil applications, whether with neat or water-based
fluids,  it is important to maintain a copious supply of fluid to
the cutting zone.  This is especially important when ceramic or
cemented carbide tools are used.  An interruption in fluid flow
will allow large temperature variations in the tool, with the
possibility of cracking of the tool tip and its early breakdown.
                                50

-------
Metal
Parts
    Machining,
Milling. Drilling,
 Grinding, Sawing
        Scrap Metal
       By-Product to
        Reclamation
ft
V
Parts
Cleaning
K
If
Finished
Ketal
Parts
             Spent Coolants,
          Sweepings & GrindIngs
Spent Cleaning
  Solvents
          Figure  15.  Simplified typical Machining  operation (18)

-------
          Figure 16.  Cutting tool chip formation [17].

The correct use of cutting fluids allows increased rates of pro-
duction to be achieved in workshops.  This is due to the increase
of tool life obtained by reducing the tool wear, improving the
stock removal rate, making power savings and obtaining better corr-
ponent surface finish, with more accurate dimensional tolerances.
A further advantage of using a cutting fluid is that with ferrous
components, the residual fluid remaining on the surfaces after
the machining operation prevents rusting occurring.

Grinding—Grinding is the application of abrasives to a workpiece
to effect the removal of surface material.  In metal,finishing shops,
grinding may be performed to achieve a desired surface finish, to
remove undesirable material *"rom the surface, to remove huirrs or
sharp edges, or to achieve close dimensional tolerance.

Grinding equipment include? belts, disks, or wheels consisting of
or covered with various abrasives; e.g., silica, alumina, silicon
carbide, garnet, alundum, or emery.  Grinding equipment may be
portable or stationary.  Grinding may be with or without the use
of lubricants or coolants such as water or water-based mixtures,
solutions, or emulsions containing cutting oils, soaps, deter-
gents, wetting agents, or proprietary compounds.  Auxiliary equip-
ment associated with grinding operations includes hoods, vents,
ducts, and dust collectors, and in the case of wet grinding,
tanks, pumps, and pipes for the supply, collection, and recycle
of lubricants or coolants  [21].

Polishing and Buffing—Polishing operations are performed for the
purpose of achieving an intermediate surface which can be refined
further, normally by buffing, prior to plating or surface coating.
The purpose of buffing is to smooth and brighten the surface with-
out much metal removal.
 [21] Hollowell, J. B.; Valter, L. E.; Gurlis,  J. A.;  and Layer,
     C. H.  Assessment of  industrial hazardous waste  practices  -
     electroplating  and metal  finishing  industries  -  job shops.
     Washington, DC; U.S.  Environmental  Protection  Agency; 1976
     September.  516 p.  PB  264  349.


                                 52

-------
Polishing is carried out on hard-faced wheels varying in diameter,
thickness, and material depending upon the part that is being
processed, the finish, and the material-removal rate desired.
Wheels are constructed of woven cotton fabrics, canvas, felt, or
leather discs g]ued or sewn together, or a combination of glued
and sewn discs.  Felt wheels are used where true surfaces are
required or where a contoured shape is being finished.  Leather
wheels produce a finer finish, and wood wheels covered with
leather are normally used for flat surfaces.

Abrasives are generally applied to these belts or wheels with
synthetic adhesives or cements which have generally replaced the
hide glue formerly used.  The ratio of abrasive to glue used in
the facing of the wheels changes with grit size [21].

The power is generally transmitted to the coated abrasive belt
through a contact wheel, which is a multi-purpose component and
plays a crucial role in stock removed per time interval, finish
generated and belt life, hence, cost of operation.

Figure 17 illustrates a typical design for an  abrasive-coated
polishing belt [22J.
             Figure  17.  The  abrasive  coated  belt  for
                        polishing  and buffing  [22].

 Table  12  provides a listing  of typical specifications  for polish-
 ing and grinding various  metals with  ar. aiirasive-coated  belt  [22].

 Mass Finishing  and  Barrel Tumbling—Mass finishing  is  a  process  of
 deburring,  edge and corner radiusing,  and surface finishing a quan-
 tity of components  in bulk by mechanical means.   Improvement  of
 surface includes removal  of  rust and  scale,  reduction  of surface
 [22]  Leggett,  R.   The coated belt:   a production tool.   Metal
      Finishing.   75(12) :9-15,  1977  December.
                                 53

-------
               TABLE  12.   POLISHING  AND  GRINDING WITH AN ABRASIVE-COATED BELT \22\
Ul

Material
Hot and cold
rolled steel



Stainless
steel



Aluaimn




Copper and
copper
alloys


Monferroua die
castings



Cast iron


Titaniun



Operation
Grinding
Polishing

Fine Polishing

Grindino
Polishing

• Fine Polishing

Grinding
Polishing

Fine polishing

Grinding
Polishing

Fine polishing

Grinding
Polishing

Fine polishing

Gi inding
Polishing
Fine polishing
Grinding
Polishing
Fine polishing

Abrasive
7A or A/0
ZA or A/0

A/0

ZA or A/0
ZA or A/0

A/0 or S/C

ZA or A/0
A/0 or S/C

A/0 or S/C

A/0 or S/C
A/0 or S/C

A/0 or S/C

ZA or A/0
A/0 or S.C

A/0 or S/C

iA or A/0
ZA or A/0
ZA or A/0
ZA or S/C
S/C
S/C

Grits
24-60
80-150

180-J4I.

36-60
80-150

180-240

24-80
100-180

220-320

36-80
100-150

180-320

24-80
100-180

220-320

24-60
80-150
150-240
36-60
80-120
150-240
Belt
speed
4000-7000
4000-7000

1000-7000

3000- SOuO
3000-5000

3000-5000

4000-7000
4000-7000

4000-7000

3000-7000
3000-7000

3000-7000

5000-7000
5000-7000

5000-7000

2000-5000
2000-5000
2000-5000
1000-2500
1000-2500
1000-2500

Lubricant
Dry
Dry or light
grease
Heavy grease or
polishing oil
Dry
Dry or light
grease
Heavy grease or
polishing oil
Light grease
Light grease

Light grease or
heavy grease
Light ij'.«te
Light greate

Light grease or
heavy grease
L'ght grease
Light grease

Light grease or
heavy grease
Dry
Dry
Light grease
Dry
Light grease
Light grease

Contact wheel type
Cog tooth or serrated
Plain face rubber, canvas

Plain race rubber, canvas, cloth

Cog tooth or serrated
Plain face rubber

Plain face rubber, canvcs, cloth

Cog tooth or serrated
Plain face rubber

Plain face rubber, canvas, cloth

Cog tooth or serrated
Plain face rubber, canvas, cloth

Plain face rubber, canvas, cloth

Serrated or plain
Plain face rubber, canvas, cloth

Plain face rubber, canvas, cloth

Cog tooth or serrated
Serrated or plain
Plain rubber
Cog tooth or aei rated
Serrated or plain
Plain face rubber, canvas, cloth
"DuT^cTeT?
har iirbC
70-9S
40-79
Hcdiua
Soft

70-95
40-70

Soft

70-9S
40-70
Hediua
Soft

70-95
40-70
Medim
Soft

70-95
40-70
Hediun
Soft

VO-SJ — •
40-70
30-50
70-95
40-70
Soft.

-------
profile and generating suitable surface textures for decorative
reasons or subsequent paint or chemical coatings.  All mass finish-
ing techniques are based on the principle of loading components to
be finished into a container together with media, the media being
natural stones, manufactured nuggets, or abrasives bonded into
various ceramic and plastic shapes.  Media can also include steel
shapes, wood pegs, leather pieces and, on occasion, the components
themselves can act as their own media for what is commonly called,
"part on part" processing.  Generally, water and some form of com-
pound are also added to the container during operation.  Some form
of action is applied to the container to cause the med^a to rub
against component surfaces, edges, and corners [22].

The basic limitations of mass finishing are that, generally, ac-
tion will be effective on all the surface edges and corners of the
part, and it is not normally possible to give preferential treat-
ment to one area compared with another.  Action will be greater on
corners than on similarly exposed surfaces.  Action in holes and
recesses is significantly less than on exposed areas and, in small
deep recesses, it is unusual to be able to do any significant work
at all [23].

In rotating barrel finishing the drum is loaded approximately 60
percent full with the mixture of parts and media.  For normal
operations, loading higher than 60 percent slows down the action,
and lesser loading is wasting space.  For most operations, water
is added about level to the top of the load.  Increasing amounts
of water provide gentle action but slow down the process, reducing
the water level c£.n increase the action, but can also produce
problems with maintanance of clean]mess and consistency.  Com-
pounds are usually added as a means -of increasing acrading or
polishing action, and to keep components and media clean, inhibit
corrosion, soften the water, etc.

The finishing action within a tumbling barrel results from parts
and media sliding down the slope formed by barrel rotation and,
hence, rubbing against each other.   It is possible to automate
barrel tumbling equipment.  This process incorporates its own
material handling system.  The drum rotates in a clockwise direc-
tion for finishing the parts.  Then,  at the end of the process,
the drum's rotation is reversed and parts are fed out through a
screener [23].

Centrifugal barrel finishing, like tumbling, uses abrasive nedia,
compound and water to deourr and surface finish a variety of com-
ponents, but the centrifugal action results in very fast, highly
controllable deburring, radius, and  finishing operations, together
 [23] Hignett, B.  Mass finishing.  Metal Finishing.  76<7):17-21,
     1978 July.


                                55

-------
'-.'ith the capability of imparting very high compressive stresses in
the surface of components.

In the operation of centrifugal barrel finishing, a number of
drums ar^ mounted on the periphery of a turret.  The.turret ro-
tates at  i high speed in one direction while the drums are rotated
in a slower speed in the direction opposite to that of the turret.
Drums are generally loaded in a manner similar to that for normal
tumbling o_- vibratory operations, that is, with parts, media, water,
and some  .irm of compound.  Turret rotation creates a high centri-
fugal fore :, up to as much as 50 gravities, compacting the load
within the drums into a tight mass.  Rotation of the drums causes
the media to slide against the work load, removing burrs and re-
fining the surfaces [231.

Vibratory deburring equipment is faster and more convenient than
tumbling barrels. It also has the capability of getting more action
in recesses of components.  In addition, vibratory machines can
process  larger components than those that can be handled in normal
barrels, without fixtures and with less likelihood of damage.  Mod-
ern tub  type vibrators are nade long enough to process components
up to about 9 meters (30  feet) long, such as wing spars,  with the
long tub-type VibraLoia,  it is possible to have fully automated,
continuous processing of  small parts loading at one end of the tub,
with unloading at the far end through a separator where media can
be returned to the load end on a conveyor.

Round style or donut vibrators are driven by a vibratory motor' "
mounted  directly under the center of the tub with a vertical
shaft.   Parts and media move around the donut-shaped barrel as
they are vibrated against one another.  Most donut-type vibrators
have simple integral separating systems.  Of somewhat more gentle
action,  donut style machines are easier and more economical to
handle than tub-type units for most smaller-sized components [23].

Spindle  machines comprise a circular, rotating tub which holds
loose abrasive media, and a rotary spindle to which the part is
fixed.   The workpiece mounted CA the spindle is immersed into the
rapidly  moving abrasive slurry, causing the abrasive to flow swiftly
over rough edges and over the surface of components.  Process cycles
in spindle equipment rarely exceed 5 minutes and are frequently
less than 30 seconds.  This equipment is clearly very well suited
for parts such as gears,  sprockets, and bearing cages where fix-
turing is straightforward and action of the abrasive will be abso-
lutely uniform over all significant areas.  Equipment can deburr,
edge radius, and produce  very fine surface finishes and, because
parts are  fixtured, there is no possibility of part-on-part impinge-
ment during the process or at reload time.  The limitations result
primarily  from the need to fixture the workpieces.  Where parts
can be handled entirely satisfactorily in bulk in vibrators, cen-
trifugal barrel machines  or conventional barrels, then probably
those machines will be more economical  [23].


                                 56

-------
5.1.1.3  Heat Treating
Heat treatment of metals is defined as the process of heating and
cooling of a solid metal or alloy in such a way as to obtain
desired conditions or properties.  Heat treating processes include
annealing and normalizing, used to reduce or control hardness in
hot or cold worked metals; hardening by heating and quenching of
certain metals, principally steels; carburizing, in which carbon
is introduced into the surface of low carbon steels by heating
them in carbon-rich media followed by quenching; and tempering or
drawing in which metals are heated at low temperatures for stress
relieving or to modify the hardness of quenched steels.  Although
steel is the principal metal which is heat treated, the process
is also applied to some grades of cast iron, aluminum alloys,
copper alloys, and magnesium alloys.

Heat treating operations always involve heating of metals under
controlled conditions to a prescribed temperature, followed by
cooling at a rate required to result in the desired physical
property in the part being heat treated.  Heating operations are
performed in a variety of batch or continuous furnaces in which
reducing or oxidizing atmospheres may be present to control the
rate of carbon introduction or elimination from the metallic sur-
faces; or they may be performed in liquid heating media such as
molten salts or lead.  The type of heat treating process used
depends on the type cf metal involved and the specific properties
to be rendered.  Quenching media-include such liquids as water,
-brine, 'oil, molten salt, and molten lead.  For some operations,
cooling is done in still air, or in the furnace by reducing the
temperature at a controlled rate.  Parts to be heat treated are
often cleaned by washing in alkaline solutions before heating,
and are generally cleaned after heat treatment by washing, sh'b't
blasting, or pickling in acids  [18].

Quenching—In a typical quenching operation, baskets of hot metal
parts are dipped into an oil bath or quench oil is sprayed on metal
parts too large for smaller batch operations.   In this application,
the oil acts as a cooling medium rather than as a lubricant  [24].

Annealing  [16]—During cold rolling, the steel becomes quite hard
and unsuitable for most uses.  As a result, the strip must usually
undergo annealing to return its ductility and to effect other changes
in mechanical properties.  This is done in either a batch or con-
tinuous annealing operation.

In batch or box annealing, a large stationary mass of steel is
subjected to a long heat treating cycle and allowed to cool slowly.
In continuous annealing, a single strip of cold reduced product
 [24]  Bigda,  R.  J.   Review of all  lubricants  used  in  the U.S.  and
      their re-refining potential.   Bartlesville,  OK; U.S. Depart-
      ment of Energy;  1980 June.   86 p.   DOE/BC/30227-1.
                                 57

-------
passes through a furnace in a relatively short period of time.
The heat treating and cooling cycle in the furnace is determined
by the temperature gradient"within the furnace as well as the
dimensions and rate of travel of the steel.  To prevent, oxidation
and the formation of scale, inert atmospheres are maintained in
these furnaces at all times.   Prior to annealing, t'he material
must be cleaned of all dirt and oil from the pickling operation
to prevent surface blemishes.  In the case of the continuous an-
nealing furnaces, the material is uncoiled and passes through a
continuous cleaning operation prior to entering the furnace.
Upon leaving the furnace, the material is oiled and recoiled and
is then ready to be tempered.

Tempering  [16]—After cleaning and annealing, a considerable amount
of product is tempered.  In tempering, the thickness of the mate-
rial is reduced only a few percent to impart desired mechanical
properties and surface characteristics.

The temper mill is a single stand cold rolling mill designed to
produce a slight reduction in thickness of the steel.  This reduc-
tion develops the proper stiffness or temper by cold working the
steel at a controlled rate.  The end use of the material dictates
the degree of tempering to be performed.

An oil-water emulsion lubricant is sprayed on the matarial before
it enters the rolls of a cold rolling mill and the material is
coated with oil prior to recoiling..  This oil prevents rust while
the material is in transit or in storage and must be removed be-
fore the material can be further processed or formed.

5.1.1.4  Corrosion Prevention [17]—
The role of temporary corrosion preventive coatings in the indus-
trial oil  field is to give short-term protection to metallic com-
ponents or equipment.  This protection may be during storage, or
transportation, or between manufacturing processes.  The word tem-
porary implies the products are easily removable, when required,
from the metallic surfaces.  This is usually done by solvent or
alkali degreasing.  The products are therefore not designed for
the same duties as the permanent protectives, such as paints and
metal coatings, which are not intended to be removable after
application.

The chief  destructive mechanism is the atmospheric rusting of
iron.  Rusting is an electrochemical process and proceeds in the
presence of air - providing oxygen - and water.  Small differences
in electrochemical potential are usually present on iron surfaces
and these  set up local anodes and cathodes.  In  the presence of
air and water, which acts  as an electrolyte, the cathodic reaction
which takes place on the surface produces  rust.  Rust consists of
oxides, and hydroxides of  iron, and its hygroscopic nature allows
moisture to be trapped, encouraging further rusting.
                                 58

-------
Mechanisms other than rusting can also cause the corrosive de-
struction of unprotected iron and steel surfaces.  The presence of
sulfur dioxide and pollutants in the atmosphere can lead to the
formation of acidic corrosion.  Wood acids, exuding from wooden
packing cases in contact with metal, can also cause a similar form
of attack.  Even mineral oils, used as a protective, can be oxi-
dized when in thin films to form organic corrosive acids.  Bac-
terial colonies present on the metallic surface can also set up a
corrosive mechanism by the formation of oxygen concentration cells.
The metal under the colony exists under anaerobic conditions and
locally corrodes when it becomes anodic with respect to the colony
edges.  The edges have a higher concentration of oxygen and are
cathodic.  These forms of acidic corrosion are normally combated
by the inclusion of basic inhibitors in the protective, to neu-
tralize the acids as they form.

The temporary corrosion preventives are predominantly designed for
the protection of ferrous materials under indoor or outdoor short-
term sheltered storage.  They may be classified into three main
types: soft film, hard film, and oil protectives.

Soft Film--The soft film types frequently contain a solvent for
ease of application of the protective  film.  When the solvent
evaporates, the soft film is left evenly distributed on the metal
surface.  The film often consists of hydrocarbon material and nat-
ural products such as lanolin.  Sometimes, these solvent-deposited
products possess dewatering properties in addition, so that metal
components do not have to be dried before being dipped into the
product.  The dewatering grades have surface-active agents incor-
porated in them, so that any water on  the metal surface is dis-
placed and the surface .Becomes preferentially wetted by the
hydrocarbon material.  The displaced water falls to the bottom
of the dipping bath where it is drained away at intervals.

In addition to the solvent-deposited grades, there  are also the
non-solvent-deposited soft film grades, such as the petrolatums .
ana greases   Sometimes, the petrolatums have corrosion inhibitors
incorporated  in them to neutralize  acidic corrosion.  The petro-
latums ars normally heated before trie  components to be protected
are dipped in them.  The type of film  formed is soft, thick, and
malleable.  The exact thickness will depend upon the dipping
temperature.

The thick  film petrolatums can be used for the long-term storage
of components, under indoor conditions.  They can also be utilized
for storage under outdoor conditions,  as long as a  further protec-
tive wrapping layer is employed.  This is  ideally a grease-proof
paper.  The additional wrapping protects the film from contamina-
tion  and  reduces the risk of mechanical damage.  Roller and ball
bearings  are  frequently protected during storage by the use of
petrolatums.  The thick film can easily be removed, when required,
                                 59

-------
from the protected component.  Besides wiping and solvent degreas-
ing, a dip in a hot oil bath can also be used to remove the pro-
tective film.

Hard Film—The hard film protectives are the second type of tem-
porary corrosion preventives.  They are solvent deposited grades
which yield, as the name implies, a hard rather than a soft film,
after application.  These products are frequently based on hard-
film-forming ingredients, such as bitumen, contained in a solvent.
They protect metal surfaces for much longer periods than the soft
film types, because the hard film is tougher and more resilient.
They are used in such applications as car underbody sealants and
for the protection of certain deck areas of ships.

Oils—The third type of temporary corrosion preventives are the
oil protectives.  These do not contain solvents and consist of
mineral oil with corrosion inhibitors to combat acidic corrosion.
They are used mainly for the protection of small components.  Due
to the relatively low viscosity of mineral oil, the films formed
tend to ce of a thin nature because of the oil drainage which
occurs from a co-.nponent after dipping.  They give, therefore, less
protection than the soft and hard film protectives.  A special
class of temporary oil protective is used for the filling or gear
boxes and crankcases of internal combustion engines.  These oils
are used for protection during transportation of the units, and
are designed also for the units to be run for a short time on the
oils, before filling with the service oil.         •     •       ',

In the field of steel rolling, special sheet coating oils are used
for the protection of the rolled strip after tempering.  These
oils aretused to protect the coiled.strip during its transportation
from the steel mill to the customer.  These types of oils are
usually formulated to suit the specified requirements of the cus-
tomer.  A motor manufacturer may require special degreasing prop-
erties for the oil, so that it can readily be removed by the
established process used at the  factory.  Ease of removal of the
.coating oil is of prime importance in this case, so that the proc-
ess of metal phospha'cing and the application of permanent protec-
tive paint coats can be readily carried out when desired.  Before
the transportation of the oiled coils of strip from the steelworks,
it  is normal practice to treat the exposed edges of the coils with
additional protective.  Edges are particularly prone to corrosion
and are subject to rubbing during handling and transit.  As in extra
precaution during transportation, the coils of strip may also be
protected with a wrapping of waxed paper.

5.1.2  Raw Materials

Each segment of the metalfinishing industry demands oils specifi-
cally formulated for its requirements.  The following widely used
oils illustrate the variety of products needed by the industry:
rolling oils, cutting oils, quenching oils, and rust preventative


                                 60

-------
oils.  The following section describes the purposes of metalvork-
ing fluids, the classification of metalworking fluids, metalwork-
ing oil descriptions, and process applications for "specific types
of fluids.

5.1.2.1  Requirements—The basic functions of metalworking fluids
are lubrication and/or cooling.

Lubrication

Three types of lubrication, differentiated on the basis of lu>ri-
cating film thickness, are hydrodynamic lubrication (bulk or thick
film), boundary or extreme pressure lubrication (thickness of
molecular level), and thin film lubrication (an intermediate
thickness film) [25].  When moving parts are separated by a film
of fluid greater than 0.25 micrometer (1 x 10"6 in.),  the surface
load is supported entirely by the hydrostatic pressure built up
in the film [25].  In this type of lubrication, friction and
temperature rise are due entirely to the viscosity of the fluid
and are not affected by the chemical composition of the fluid or
the metal surfaces with which it comes in contact  [25].

As long as hydrodynamic lubrication is maintained, metal surfaces ^ .-
do not come in contact and surface wear is negligible.  When the
load on the surface increases or the viscosity of the fluid de-
creases, the film decreases to a thickness measured in molecules,
and the lubricant film is characterized as boundary or extreme
pressure lubrication.  Boundary lubricant films are formed by a
surface chemical reaction or physical absorption of a component
of the. fluid.  In boundary lubrication, moving surfaces may ,c,ome
into contact, causing surface wear or metal transfsr  [25].

Thin film lubrication is intermediate between the first two types.
In this type of lubrication, both viscosity of the fluid and chem-
ical composition are important to metalworking fluid performance
[25].  The type of ir.etalworking operation, and the type of lubri-
cation will determine the choice of metalworking fluid.

Cooling—In metalworking operations such as cutting and quenching
the cooling properties of a fluid are more important than the lubri-
cating properties.  A good coolant must have a high specific heat,
a high thermal conductivity, and a high heat of vaporization.  The
cooling ability of a fluid is also influenced by its ability to
penetrate to the work zone and effectively wet the tool, die, and/or
workpiece  [25].  OiJSbased fluids have good wetting and penetrat-
ing properties, while water-based systems vary from poor to good.
The specific heat and thermal conductivity of oil is approximately
 [25] Ackerman, A. W.  The properties and classification of metal-
     working fluids.  Lubrication Engineering.  7:285-291, 1969
     July.


                                61

-------
one-third that of water.  Therefore,  oil-based systems generally
cool less effectively than water-based coolants [25].   In addition,
all metalworking fluids must fulfill  one or more of the following
requirements [26]:

     Friction Reduction - The most common purpose of metalworking
     lubricants is the reduction of friction by the naintenance of
     a film separating metallic surfaces, thus reducing force and
     power requirements.

     Heat Removal - In many instances, especially if the metalwork-
     ing operation is of the continuous type, the lubricant is
     required to cool the dies and/or the workpiece material.  The
     lubricant must remove both heat generated during •the plastic
     deformation of the workpiece material, and heat generated at
     the interface of tool and workpiece.

     Thermal-Insulation - Lubricants employed in hot working oper-
     ations must provide thermal insulation between die and work-
     piece surfaces, partly to reduce heat loss from the hot stock
     and partly to protect the die from excessive heat.

     Wear Reduction - Effective metalworking lubrication reduces
     the surface erosion wear on dies and rolls by forming a film
     to minimize metal-to-metal contact.  Wear may also be decreased
     through removing suspended metal fines and debris in recircu-
     lating lubrication systems.

     Metal Pick-up Prevention - A metalworking lubricant prevents
     metal pick-up on the tool surface by preventing the metal-to-
     metal contact that can result in spot welding of tool and •
     workpiece.  Lubrication failure can cause rapid scoring of
     the softer material or gradual surface deterioration.

     Improving Surface Finish - Elimination or reduction of sur-
     face defects by proper lubrication in metalworking operations
     results in an improved surface on finished metal products.

     Corrosion Prevention - In ferrous and nonferrous metalwork-
     ing, the oxidation and corrosion preventive properties of the
     metalworking oils are extremely important.  The metalworking
     fluid must protect the surface against oxidation and scale
     formation.

In  addition, the metalworking fluid must remain stable in use, be
unaffected by temperature or bacteriological attack, and protect
against  formation of corrosive breakdown products.
 [26] Schey, J. A.  Purposes and attributes of metalworking
     lubricants.  Lubrication Engineering.  23:193-198, 1967
     May.
                                62

-------
5.1.2.2  Classification—The ASTM has adopted a standard classi-
fication of metalworking fluids which divides fluids into five
groups.  Table 13 provides the current ASTrt standard classification
of metalworking fluids and related materials [21].

For the purposes of this report, metalworking fluids are classi-
fied into three groups and will be discussed in the following
order:

     (1)  straight oils (mineral and fatty),
     (2)  emulsified oils,
     (3)  synthetic fluids.

A fourth section discusses metalworking fluid additives.  Table 14
presents the classification scheme for metalworking fluids used
in this report, based on information in Reference 24.

5.1.2.3  Description—This section describes the three main types
of metalworking fluids and the  additive utilized therein.

Straight oils with no water phase  (neac oils) are of two types,
mineral oils and fatty oils.  Approximately  forty-five percent of
all metalworking oils are straight mineral oils  [24].  The neat
cutting oils are used for the slower and more difficult machining
operations, such as gear cutting,  screwing and broaching.  The
main  ability required is lubrication to reduce fnctional heat  and
thus  decrease tool wear.  Complicated  tool  form  regnnding can  be
an expensive operation  and therefore reduced tool wear can be a
key  factor  in the economy of  the machining operations.  The neat
oils  fall  into  two main  classes, straight mineral oils  and mineral
oils  blended with tatty  oils  [17]'.

Straight Mineral Oils—Mineral  oils  used as  metalworking  fluids
are  produced  from petroleum base stocks.  After  the lower boiling
components  have been  removed  by distillation from  the crude oil,
the  remaining  complex mixture of hydrocarbons  is fractionated under
vacuum conditions to  prevent  the cracking  or decomposition  of the
higher molecular weight hydrocarbons.   In  the  vacuum fractionation
process,  lubricating  oils  are separated and collected in fractions
of various boiling  ranges.  The separated  fractions are  refined and
may  then be blended together  to make a long series  of viscosity
 grades for use  as  industrial  mineral oils.

Mineral oils  are mixtures of  vast numbers  of hydrocarbons,  al-
 though small  amounts  of sulfur and traces  of nitrogen and oxygen
 compounds m?.y also  be present.   The composition of the  hydrocaibon
 [27] Standard classification of metalworking fluids and related
      materials.  In:  1976 Annual Book of ASTM Standards.  Part 24.
      Philadelphia,  PA, American Society for Testing and Materials.
      1976.  ANSI/:VSTM D 2281-73.


                                 63

-------
  TABLE 13.   CLASSIFICATION  OF  METALWORKING  FLUIDS
             AND RELATED  MATERIALS  [27]
 I.   Oils and oil  base  fluids
     A.   Minerals  oils  -  uncompounded
     B.   Fatty oils
         1.   Uncompounded
         2.   Fatty oils containing chlorinated compounds
         3.   Fatty oils containing sulfurized compounds
         4.   Fatty oils made by combining B2  and B3
     C.   Mineral oils - compounded
         1.   Blends  of mineral  oil and fatty  oil
         2.   Sulfurized and/or  chlorinated mineral oil
         3.   Mineral oils containing sulfurized fatty
             compounds  and/or sulfurized nonfatty
             compounds
         4.   Mineral oils containing chlorinated fatty
             compounds  and/or chlorinated nonfatty
             compounds
         5.   Mineral oils containing sulfo-chlorinated
             fats or sulfo-chlorinated nonfatty
             compounds
         6.   Mineral oils made  by combining C3 and C4
         7.   Mineral oils and/or fatty oils containing
             nitrogen or  phosphorus compounds or solid
             lubricants,  etc.,- in addition to, compounds
             from the groups described in Cl  through C6

II.   Aqueous emulsions  and dispersions
     A.   Oil-in-water emulsions (soluble oils)
         1.   Mineral oil  - emulsions of Class 1-A
         2.   Blends  of mineral  oil and fatty oil -
             emulsions of Class I-B1 or I-C1
         3.   Heavy duty or extreme pressure - emulsions
             Class I-C2 through I-C7
     B.   Water-in-oil emulsions
         1.   Mineral oil  - emulsions of Class I-A
         2.   Blends  of mineral  oil and fatty oil -
             emulsions of Class I-B1 or I-C1
         3.   Heavy duty or extreme pressure - emulsions
             of Class I-C2 through I-C7
     C.   Colloidal emulsions
         1.   Regular - emulsions of Class I-A
         2.   Fatty - emulsions  of Class I-B1 and T-C1
         3.   Heavy duty or extreme pressure - emulsions
             of Class I-C2 through I-C7
     D.   Dispersions
         1.   Physical dispersions of liquid (Class  I)
             materials
         2.   Physical dispersions of solid (Class IV)
             materials


                          64

-------
                  TABLE 13 (continued)
III.   Chemical solutions (true and colloidal solutions)
      A.   Organic - water-soluble organic systems giving
          clear,  transparent solutions of low surface
          tension
      B.   Inorganic
      C.   Mixtures - blends of organic and inorganic
          solutions
          1.   High surface tension (45 dynes or over)
          2.   Intermediate surface tension (36 to 44
              dynes;
          3.   Low surface tension (35 dynes and under)

 IV.   Solid lubricants
      A.   Powders
          1.   Crystalline, such as graphite, lead sul-
              fide, mica, molybdenum disulfide, talc,
              calcium oxide, calcium carbonate, zinc
              oxide, and zinc sulfide
          2.   Polymeric, such as polyethylene and PTFE
              (polytetrafluoroethylene)
          3.   Amorphous, such as soaps and waxes
          4.   Mixtures of Classes IV-A1,  IV-A2, and
              IV-A3
      B.   Vitreous materials
          1.   Borates
          2.   Glasses
          3.   Phosphates
   ,.,  C.   Greases and pastes
      D.   Dry films
          1.   Particle bonded
          2.   Resin bonded
          3.   Vitreous bonded
              a.   Salts
              b.   Glasses
      E.   Chemical conversion coatings
          1.   Phosphate
          2.   Oxalate
  V.   Miscellaneous
      A.   Chlorinated nonoil type materials, neat
      B.   Sulfurized nonoil type materials, neat
      C.   Combinations of Classes V-A and V-B
      D.   Organic materials not otherwise specified,
          such as alcohols, glycols, polyols, esters,
          phosphorus compounds, etc.; and dispersion of
          solid lubricants  (Class IV) in such organic
          materials
                           65

-------
             TABLE  14.   REPORT CLASSIFICATION SCHEME
                         FOR METALWORKING FLUIDS [24]
  Type of fluid
                Usage,
                                 Additives
          Base stock
                   Percent
              Type
 Straight oils

 Mineral oils
45
 Fatty oils
 Emulsified oils
50
     Naphthenic petroleum
     Paraffinic petroleum
     Animal or fish oils
     Vegetable oils
High viscosity
  petroleum
2-10    Extreme pressure (EP)

2-15    Friction reducing
         animal fats
<18    Chlorine
<22    Sulfur
       Corrosion inhibitors
         detergent/dispersant
       Biocide

       Used to formulate
         mineral oil
         additives

       Emulsifiers
       Corrosion inhibitors
       Biocide
 Svnthetic oils
     Nonpetroleum   • •
       chemical fluids
                           Used to formulate
                             mineral oil
                             additives
mixture depends largely upon which part of the world  the  crude
oil originated.  However, most  oils are mixtures of paraffins,
naphthenes  and aromatics.  The  paraffinic oils are more resistant
to oxidation than the aromatic  oils,  but when oxidation is not a
problem,  the unsaturated ring-type structures of the  aromatics
allows them to absorb greater quantities of energy before break-
down occurs.   This specific advantage of aromatic oils is exploited
in the field of high temperature  heat transfer where  the  better
thermal stability of the aromatic-type oils becomes advantageous.
However,  when the oxidation stability of the oil is more  important
than its  thermal stability, for example, in a quenching oil bath,
then the  paraffin-type oils ao.e preferred to the aromatics [17].

An especially important characteristic for the straight mineral
oil class is the viscosity level  chosen for a particular  applica-
tion.  Although the oil must be able to lubricate effectively, the
use of a  lc^ viscosity oil will improve the cooling ability which,
of course,,  is advantageous.  On the other hand, higher viscosity
                                  66

-------
oils would have better retentive properties on the tool and work-
piece in the region of the cutting zone.  This is an important
advantage in the slow speed cutting of the tougher metals.

Mineral oils, blended with fatty oils, are sometimes used when
additional lubrication characteristics are desired.  The fatty
component has good friction reduction properties, due to the
tenacious films it forms on metal surfaces.  The compounded oils
are also useful in the machining of metals, where staining by the
cutting fluid may be a problem.  Examples are the yellow metals
(copper alloys) and aluminum alloys, which can be machined with
compounded oils to give excellent surface finishes and minimal
tool wear.  The main disadvantage of compounded oils is that the
fatty component is prone to oxidation, with the result that the
viscosity and acidity of the oil may increase [17].

Fatty Oils—The sources of the fatty acids are frequently veoe-
table, animal, or fish oils.  These naturally derived oils provide
the vast majority of the fatty compounds used in the general com-
pounding of mineral oils for many industrial purposes.  We have
already mentioned their use in modifying the fnctional character-
istics of mineral oils.  They are also employed in mineral oils
which have to operate in wet environments.  The fatty oil, in the
same case, acts as a surface active agent.  It tends to take the
water into the body of the oil, in the form of a water-in-oil
emulsion, thus preventing the lubricant film from being washed off
the surface to be lubricated.

Selected fatty oils "-.uch as rape seed, lard, tallow, arachis,
sperm, olive, palm «. r»  castor have been frequently used for many
industrial lubrio-  . •• i purposes.  -Some have also been utilized.
for the manufacture ol fatty additives which have incorporated
in their extreme pressure agents such as sulfur and chlorine.

The various fatty oils possess different compositions.  They are
a source of both saturated fatty acids, such as palmitic  and
stearic, in admixture with unsaturated fatty acids, such  as cleic
and linoleic acids.  Castor oil is rather unique, in the  fact that
it contains an appreciable quantity of ricinoleic acid and hardly
any saturated fatty acids.  Ricinoleic acid is an unsaturated hy-
droxyoleic acid which has practically no action on rubber, unlike
the other fatty oils and also, for that matter, mineral oil.  This
makes the use of castor oil especially advantageous in industrial
applications, where it may come into contact with rubber  compon-
ents.  However, one of the great disadvantages of castor  oil is
that it possesses a very high viscosity at low temperatures.  This
considerably reduces its potential field of activity.

The various fatty oils have different solubility characteristics
in mineral oils.  Castor oil has only a limited solubility of
about 2 percent.  Other fatty oils are much more soluble  and ara
                                 67

-------
frequently used in the 10 to 20 percent weight range for the com-
pounding of mineral oils.  The solubility is affected by the
hydrocarbon types present-in the .mineral oil ar.d,  of course, the
temperature.

The main disadvantages of fatty oils, for industrial lubrication,
are lack of stability and high price.  They tend to decompose and
form gummy deposits at elevated temperatures.  They possess, there-
fore,  short working lives in comparison to mineral oils.  On lengthy
exposure to air at room temperature, there is a tendency for the
fatty oils to become sticky and rancid.  They are also relatively
expensive and many are in short supply.  For example, sperm oil
supplies have been drastically affected by the international re-
strictions imposed on the hunting of sperm whales to conserve the
"species.

However, despite these disadvantages, fatty oils have played and
will continue to play an important role in industrial lubricatjon.
This role is not only in the compounding of mineral oil lubri-
cants.  In specific applications,  fatty oils are utilized in their
own rights as lubricants, without admixture with mineral oil.  An
example is the use of palm oil in the steel industry for the roll-
ing of thin gauge strip, a process for which no mineral oil prod-
uct can give the same performance.

Emulsified Oils—Approximately fifty percent of metalworking oils
are used as emulsified oils f24].   Emulsified oil concentrates.are
derived from high viscosity petroleum feedstocks.  These oils con-
tain additives such as emulsifiers and biocides so that they may
be diluted with water 10:1-20:1 for metalworking service, the degree
of dilution depending on the severity and type of operation  [24].

The soluble oils are used as emulsions of oil in water and are
the most widely used cutting fluids.  Emulsions of soluble oil,
when prepared in water, are of a milky or clear appearance.  This
will depend upon the degree of dispersion, or the size of the oil
particles, present in the continuous phase of the emulsion.  In
general terms, the greater the amount of emulsifying agent present
in the soluble oil, the more clear and transparent will be the
er.,ulsion prepared from it.  Emulsion stabi" ity is of great impor-
tance in service and the selection of the optiirum emulsifier
system for the particular oil used is a prime consideration.
Also,  the oil must be able to produce stable emulsions in the
waters of various degrees of hardr.cjr met in industry [17].

Soluble oil emulsions, because of theii cooling power, are .ideal-
ly suited for use in rapid and light machining operations, such
as turning, drilling, and grinding.  However, it is possible to
include extreme pressure additives in soluble oils to increase
their range of application.  The presence of the dispersed oil in
the emulsion has seme lubricating power but the primary charac-
teristic of the soluble oil emulsion is its cooling ability.  The


                                68

-------
 concentration of the soluble oil dispersed in vhe water will depend
. upon the individual application.  It may range from 1 part of oil
 to 10 parts of water for turning,  to 1 part of oil to 50 parts of
 water for grinding.  For operations, such as grinding, it is  .1-
 portant that the machinist can have a clear view of his work as it
 progresses.  It is therefore common practice to use transparent
 soluble oil emulsions for this application.

 Water-based fluids are subject to bacteriological attack.  The
 presence of hydrocarbons, water, and often nitrogen,  sulfur, and
 phosphorus compounds, makes an excellent diet for bacterial growth.
 Initially, bacterial infection of the aqueous cutting fluid is
 usually caused by airborne dust, or the water used to prepare the
 emulsion.  Once established, bacterial growth rates can be very
 rapid.  Sometimes the machine tool may not have been cleaned
 effectively before the introduction of the cutting fluid.  Stag-
 nant pockets of a previously infected emulsion m=iy be left behind.
 The bacterial attack may be of the aerobic type when air is pres-
 ent, or the anaerobic type in the absence of air.  Aerobic bac-
 teria frequently produce acidic components which can cause corro-
 sion of the machine tool and workpiece.  The anaerobic type can
 attack the emulsifying agent used in the soluble oil, with the
 result that emulr  n breakdown can take place [17].

 Synthetic Fluids--Many synthetically produced hydrocarbons find
 specialized applications in metalworking.  Unlike the conventional
 mineral oil products which contain a multitude of mixed hydorcar-
 bons, the synthetic hydrocarbons are relatively pure and possess
 relatively narrow boiling ranges.  They may be paraffinic or aro-
 matic in nature.  The aromatic synthetic-type oils find outlets in
 such applications as high temperature heat transfer.   The rynthetic
 paraffinic types may prove useful in the metal rolling field, or in
 other applications where narrow boiling liquids of good oxidation
 stability are advantageous  [17].

 The synthetic lubricants are classified as silicone polymers,
 polyoxyalkanes, polyesters, fluorocarbons, chlcrocarbons, and
 phosphorus derivatives.  These products are first manufactured
 chemically and then refined and compounded for use as lubricants.

 Because of their poor -solvent properties, silicones have proved
 Difficult to use as lubricants for steel, and additives are needed
 to increase their lubricity.  They have found their pumary lub-
 rication application in the form of greases [24].

 Liquid polyoxyalkanes are generally polymers of polyethylene gly-
 cols or polypropylene glycolc or copolymers of ethylene or propy-
 lene oxide.  They have bepn successfully used as metal forming
 lubr: cants.  They can be tailored to various degrees of oil so?u-
 bility.  Lubricants made from these products have hic,h enouoh
 viscosity indexes and low enough pour points to be used as all-
 weather engine oils.


                                 69

-------
Polyester-type lubricants have been synthesized with trimethyl-
olpropane reacted with various fractions of mi.'.ed fatty acids,
adipic acid reacted with various  fi actions of mixed branched  alco-
hols; esters of adipic acid and branched nonyl alcohols; and
esters of methyl adipic acid and  mixtures of branched alcohols.
There also are many commercially  available esters suitable  for
lubricating oils which are prepared from oxo process branched
chain alcohols reacted with adipic, azelaic, and sebacic acids or
'other polycarboxylic  acids.  These ester lubricants are widely
used in military and  commercial aircraft as engine oils and as
instrument oils and greases.

The phosphate ester oils are probably the most commonly used  syn-
thetic oils in the United States  today.  Most turbine powered
aircraft utilize diester lubricants.  These ester oils show
excellent response to many types  of lubricant additives such  as
antioxidants, rust inhibitors, viscosity irdex improvers, deter-
gents, and antiwear agents.  They are available in a variety  of
viscosity grades.  Further, they  have the advantage that their
hydrolysis or oxidation products  are mild wear additives and  rust
inhibitors.  Because  of the good  solvent properties, the esters
behave like good detergent oils  [24].
 For  iT'Ore  general  lubrication  applications,  outside  the  field  of
 fire-resistant  lubricants,  the  synthetic  esters  are sometimes
 utilized  in  certain  circumstances,  such as  in  compressors  and gear
 boxes,  when  the operating  conditions- are  severe  enough  to  warrant
 them.   The synthetic organic  esters can be  manufactured with
 higher  stabilities than mineral oil based products.   The use  'of
 special additives allows the  esters to be utilized  at much higher
 temperatures .

 The  synthetic esters were  originally developed for  the  lubrication
 of high speed aircraft and aviation gas turbines.   The  diesters,
 utilized  as  base  oils for  these applications,  are based on prod-
 ucts derived from such materials as sebacates, azelates, and
 adipates.  The  diester lubricants were originally designed for
 aviation  purposes.   In the high temperature region,  it  is  essen-
 tial that the synthetic lubricants be able  to  lubricate not only
 under high speed  conditions,  but also under high bearing loads.
 The  ester fluids  have excellent thermal stabilities but special
 high temperature  anti-oxidants  are utilized to increase, the oxida-
 tion stabilities, and also additives are  incorporated for  the
 improvement  of  the load carrying properties [17].

 These synthetic base stocks,  though each  possess special prop-
 erties, must be formulated in much the same manner  as the  hydro-
 carbon  base  stocks;  that is,  with antioxidants,  rust inhibitors,
 wear additives  and other materials to improve  the lubricating
 properties 01 the oils. All  of the synthetics are  inherently more
 costly  than  hydrocarbon-based oils because  they  must first be
 synthesized  in  a  complex chemical operation.


                                 70

-------
Additj.ves--In many industrial metalworking applications,  the selec-
tion of a certain hydrocarbon-type oil may not be enough tc cope
with the working conditions imposed upon it.  Additives are then
incorporated into the oil to enhance its properties [17].

Table 15 summarizes the types of lubricant additives most frequent-
ly used in metalworking fluids [28].  The following paragraphs
describe the purposes and types of additives used in metalworking
oils.

Oxidation Inhibitors—The rate at which the oxidative process pro-
ceeds depends predominantly upon the quality of the'oil.   When
severe oxidation conditions are present in an industrial applica-
tion, it is common to use oxidation inhibitors to reinforce the
inherent stability of the oil.  These oxidation inhibitor addi-
tives normally function by prolonging the induction period which
precedes the main oxidation reaction.  The additives may be of the
oxidation chain breaker type that interrupt the initial stage of
the rtrct.ion before it can proceed catastrophically.  Alternative-
ly, tfrey may be of the metal deactivator type which minimize the
cataly.ic effect of the metals present in the system by adsorption
onto their surfaces, thereby passifying them.  In certain appli-
cations, it may be necessary to employ both types of oxidation
inhibitor in the oil [17].

Rust Prevfcntatives—Oils prevent rusting by wetting the metal sur-
faces/ thereby preventing air and water coming into contact with
them.  The nse of rust inhibitors as additives can assist the oil
in this rertect, by making the oil film become more strongly ad-
sorbed onto the metal surface.

In certain application, it is necessary to incorporate vapor phase
corrosion inhibitors into oils to prevent corrosive attack occur-
ring in spaces above the o:' level in the system.  These types of
inhibitors function by possessing relatively high vapor pressures,
which allows them to migrate from the oil solution into the air
spaces where they are adsorbed onto the metal surfaces to be
protected [17].

Anti-Foamants—Oils dissolve air, the amount depending predomi-
nantly on the air pressure and also to a lesser extent on the tem-
perature.  When the air remains in solution, there is no problem.
However, if the air pressure above the oil is suddenly reduced,
then the air will tend to come out of solution and form small bub-
bles which may become trapped in the oil.  It is possible to break
such foams by the incorporation of anti-foam agents into the oil.
However, care must be taken that the use of such agents does not
 [28] Weinstein, J. J.  Waste oil recycling  and disposal.  Cincin-
     nati, OH; U.S. Environmental Protection Agency; 1974 August.
     327 p.  EPA-670/2-74-052.  PB  236  148.


                                71

-------
                                   TABLE 15.   LUBRICANT ADDITIVES  | 28|
i-o
Tvoe
Oxidation
Inhibitor
Rust
Preventive,
(Liquid Phase)
(Vapor Phase)
Anti-fouunts
Viscosity
Index
Iiaprovers

Reason for u»e

formatico of var-
nish, sludge and
corrosive coapounds.
Limit viscosity
Inciease.
Vrtvent formation of
rust in areas under
the oil especially
during equipment
shutdovn.
Prevent rust fo mat ion
in areas above the
oil level.
Ensure rapid collapse
of large air bub-
bles, prevent e»-
tion.
Reduce the ratt of
viscotity change
with temperature
How they work

formation, and pas*
sivate metal sur-
faces
Polar type compound*
react with or are
adsorbed on metal
surfaces.
Volatile basic com-
pounds are vaporised
condensatc basic.
Attracted to oil/air
inl.-'-face-. they
lower the surface
bles, causing the
formation if quick-
breaking lirge
bubbles
Thes>* polymets art
tightly coiled (and
relatively insoluble)
in oil at low tem-
col led (and qtutt
soluble) in oil at
high tempei aturea.
VI i op rovers con-
tribute to oil vis-
cosity at htqhet
temper atur es prt *
venting "thinnii g "


promote (in the case
of zinc organic*}
heavy oil sludging
and darkrning (in
come nitrogen coa-
pounds)
Reduce oil oxidation
resistance and pro-
mote formation of
cauls ions
Reduce oil oxidation
resistance and pro*
enulsions
Silicone types tend
to promote air en-
trainmen t (the for-
long-lastirg bub-
bles). Other types
may ptoavote emulsion
formation
Polymers shear in
ing the compounded
oil to suffer both

ity lots when high
VI finished oils are
desired, the base
oils must have low
viscosities, hence,
low flash points
I init* of act ivity
Host aJditives have an
r«ncje ar»d are not
uniformly effective
form* of catalytic
Ok id* I ion
Only effective in the
oil-wetted parts of
the system.
Re-inhi*>it ion required
in systems volatil-
ising large volumes
of water.
Some lubricant addi-
tives or contami-
nants may render
ant i-foaaants in-
effective
Hany polymers exhibit
"VI humps" (t g .
concentration ranges
beyond which further
additive addition

Other
Typical roapounds po**ib)e con^ouna»
Hindered phenols, bis- B*riux dtalkyl dithio-
phenols, metal phosphates, phos-
(especially sine) phites, amines.
dialkyl dithiophos-
ph a t e s . c oapou/id* o f
nitrogen and sulfur.
Sulfonates. soaps. Alkyl amines, aminc
fatty acids, phos* phosphates, acid
di functional organic
Low -molecular -weight
amines having a wide
boiling range.
Silicone polymers. Waxes.
methacrylate
polymers
Polyisobutylene (such Succinimidt-acrylic
as STP), m*lhacryl* acid reaction prod-
ate polymers, soot ucls. ethylenc-
copolymers propylen* polymer
der ivat ives
                                                                                               (contlnu*d|

-------
                                                                      TABLE  15  (continued)
TYP*
Puur
Depreseants
f

(or "freeting
pOlAt*) Of f-afaf-
finic oil* no«t
pourpotnt depres-
40°f (say fro* 20 to
20°f) and art
achieved with less
- than 2\ additive.
How they work Adverse effect*

growth or oil ad-
sc-rpt toe, at lov
tevperatui*).
l.iauts of act ivity
The pour-point depres-
sion effect of any
l it*} If p&lyntt i*
liaitted and often
specific, to combi-
nation* of pour de-
U&rd
Typical compound*
Hethacrylate pol;*er»,
alkyUt*d n'-phth*-
lr-*r cr .-^.rftelt
Other
possible compounds
Polyacrylaaide*
           (••tree**
           Pressure  (BP)
           Oiliness  and
           Antxvcar
U)
Hodlfy friction prop-
  trtiea.  reduce wear,
  prevent  Calling and
  seizing
For* physical  or  che»-
  ical bonds with rub-
  bing surface*  that
  provide supplemental
  "wearing surface* "
  The key is friction
  and wear control.
  rather  than  elimina-
  tion
Proatott oil oxidation,
  foaming.  e»u1aif i-
agent* require heat  Oiln«aa-fatty acid*
                                                                           tendencies   Thermal
                                                                           •lability is weak-
                                                                           ened
                          (generated by atetal-
                          to-a>etal contact) to
                          be effective.  Not
                          all desired oiliness
                          properties are con-
                          tributed by one set
                          of additives.
                      and soaps   Anti-
                      wear -iapure tri-
                      cresyl phosphate*
                      CP-organic phos-
                      phates, lead and
                      chlorine compounds.
Organic compounds with
  bar lusi,  ant iatony.
  bisamth.  silicon.
  •olybdenu*.  sulfur,
  phosphorus,  nitro-
  gen,  halogens,  car-
  bony! or  carboxyl-
  ate salts,  sllicone*,
  polyphenyls.
           Laujlsifier*
                          Hold oil and wster
                            together in evul-
                            sion-type cutting
                            fluids, coolants
                            and hydrauli-
                            fluids.
                       Polar-type (both ionic  Reduces oil oxidation   Different ewulsifiero    Metal sulfonates.       fatty acid soaps.
                                                                                               glycols, ethojiylated
                                                                                               phenols, alcohols or
                                                                                               acid*, ntphthonic
                                                                                               acid*.
or non ionic) cosi-
pounJs line up at
oil/water interfaces.
*nd thu* they provide
solubility bridges
between the oil and
water.
resistance Fights
activity of anti-
wear, EP. oiliiiess.
antirust, and anti-
foaa agents May
cause seal swelling.
•u*t be used for
every oil. every
concentration of
water and. often
ever/ service
lenperature
           Other
           Additives
 trfuMm  and for»«16chyd* co«f>ound> «• *ntlodorants with EP additivee; alcohols, phenol*,  chlorine compounds a* antiaeptlct for tmulftion
  lubricanta, aain* ccvnpoundj aa color itabilltera. poIyacrylateR and polybulenea a* tackineaa agenta  (or gear oil*

-------
aggravate the trapped air problem by retarding t'ne rate of escape
of the small air bubbles from the body of the oil.

Certain silicone polymers are added as anti-foam agents to many
industrial mineral oils in concentrations of a few parts per mil-
lion.  The presence of such '.races of silicone has a dramatic
effect in accelerating the rate of collapse of a mineral oil foam.
The action is possibly caused by the silicone polymer altering the
interfacial tension force existing between the gas and liquid in-
terfaces of the foam [17].

Extreme Pressure (EP)--Extreme pressure (load carrying) additives
are included in oils when the load, temperature, or velocity be-
tween two surfaces does not allow a hydrodynamic oil film to build
up.  There is then nothing to prevent metal surfaces from coming
into contact, with resulting wear, unless a load-carrying additive
is present in the oil.

This type of additive functions by chemical reaction with the
metallic surfaces but only when the conditions of temperature or
pressure prevailing in the contact zone are severe enough.  This
means that at lower temperatures and pressures the additives re-
main inert.  The main chemical elements used for extreme pres-
sure conditions are sulfur, chlorine, phosphorus, and lead.  They
are normally present in the form of oil-soluble organic compounds,
but sometimes -ulfur may also be present in its elemental form..
The additives are controlled chemical release agents which, on
reaction, yield metallic films such as chlorides and sulfides.
These films prevent welding and metallic pick-up between the sur-
faces under heavy duty conditions. .                           , ,,

Selected fatty oils such as rape seed, lard, tallow, arachis,
sperm, olive, palm and castor have been utilized  for the manufac-
ture of fatty additives which have extreme pressure agents such
as sulfur and chlorine incorporated in them.

Fatty acids function by forming a strongly adsorbed polar film on
the metallic surface, which reduces the frictional value.  The
polar type films formed have relatively low melting points com-
pared, for example, to sulphide films.  The polar films break
down under extreme pressure conditions and are used as  friction
reduction agents and not as anti-weld agents  [17].

Viscosity Index Improvers—In the majority of applications, the
most important characteristic of a lubricating oil is its dynamic
viscosity value; i.e., the stress required to shear unit thickness
of the oil at unit velocity.  This is because under hydrodynamic
lubrication conditions, when two moving surfaces  are completely
separated by an oil film, the only friction source is the oil vis-
cosity.  The values of viscosity vary with temperature.  However,
determinations at various temperatures allow a calculation to be
made of the viscosity index.  This index can be used to compare


                                74

-------
different oils, since the higher its value, the lower the change
in oil viscosity with temperature.  The types of hydrocarbons
present in the crude oil and the refining process given to it de-
termine the viscosity index level.  For example, paraffinic oils
have generally higher index values than naphthenic oils and
solvent-refined oil [17].

Pour Point Depressants—Certain applications for industrial oils
demand that they remain fluid at low temperatures.  In general,
naphthenic oils have lower pour points than the paraffinic oils.
The pour point gives an indication of Tow temperature fluidity.
However, pour point depressant additives can be incorporated into
paraffinic oils in order to increase their fluidity at low temper-
atures.  The additives are thought to function by inhibiting the
honeycombing of the wax separating out from the oil at low
temperatures [17].

Emulsifiers—Outside the main field of additive-treated industrial
oils which are used in the neat oil form, it will be found that in
several specialized applications, industrial oils are employed in
admixture with water to form stable emulsions.  Typical examples
are soluble cutting fluids.  Mineral oils and water are not mutu-
ally soluble.  A very large quantity of energy has to be expended
to shear a mineral oil down to colloidal dimensions so that it
can be dispersed in water to form a stable emulsion.  On an indus-
trial scale, this mechanical method is not usually practicable
so additives are dissolved in the oil to facilitate the -task.

The additives ur.ed are called erculsifiers, or surface active
agents, and they work chiefly by lowering the interfacial tension
between the oil and the water.  This allows an emulsion to be  ,
readily formed.  Afterwards, the surface active agent has the  ad-
ditional task of making the emulsion stable and preventing coal-
escence back into separate oil and water layers.  There are two
main types of emulsion, the oil in water and the water in oil.  In
the former type, the water forms the continuous phase and the  oil
the dispersed phase.  In the latter type,  the reverse is true, and
the oil forms the continuous phase and the water the dispersed
phase.  Primarily, the type of emulsifier  selected will determine
the type of emulsion formed.  Emulsifiers normally contain com-
ponents, or groups, which are solub?.e in both water and oil to
varying extents.  The ratio and relative influences of these com-
ponents, or the so-called hydrophilic and  lipophilic balance,  will
normally determine the type of emulsion formed when an emulsifier
is present in an oil and water mixture.

The two main types of emulsifier used for.  the preparation of in-
dustrial oil emulsions are petroleum sulfonates and' nonionic sur-
face active agents.  The former type are very commonly utilized
for the preparation of soluble cutting fluids, which are always
used in the form of oil-in-water emulsions.  The petroleum sul-
fonates are ionic materials, which means they form electrically


                                75

-------
charged ions  in solution.  This  phenomenon is  advantageous when
it becomes  necessary to dispose  of an emulsion after service,
tecause it  allows the emulsion to be split readily into separate
oil and water phases by the'addition of a salt solution or acid.
Sue!: materials upset the electric charge stabilization"of the
emulsion.   This process cannot be done with  an emulsion based on
a so-called nonionic emulsifier,  and the disposal  problem after
st rvice is  therefore not quite so easy [17].

Fi eservatives—Water-based  fluids, emulsified  oils,  and synthetic
fluids are  subject to bacteriological attack and require bacteri-
cide additives to extend operating life.  Selected commercially
    LTable cutting fluid preservatives are listed in Table 16  [29]

             TABLE 16.  CHEMICAL CATEGORIES OF  CUTTING
                        FLUID PRESERVATIVES  [29]
aval!
Chemical Compound
o-Phenylphenol
Sodiuir salt of o-phenyl
Category
Phenolic
Phenolic
Trade name
Dowicide 1
Dowicide A
Company
Dow Chemical
Dow chemical
 phenol
2.3.4.6-Tetrachlorophcnol

o-Benzyl-p_-chlorophenol
Sodium salt of o-phenyl-
 phenol and sodium
 mercurio. saiicylate
                      Phenolic

                      Phenolic

                      Phenolic/saiicylate
                        combination
Dowicide 6

Santophen-1

Elicide 75
Dow Chemical
Honsanto

Eli Lilly  '
2-Hydroxymethyl-2-nitro-l ,
3-propanediol
Hexahydro-1 ,3,S-r.ns-2-
h>droxyethyl-(s)-tnazine
Hexahydro-1 . 3. 5-tri-etl,yl-
(s)-triazine
l-(3-chloro ally>-3.5.7-
Triaza-1-azonia-adamantane
3.4' . 5-Tribromosalicyl
anilide (76-88\) and 3.5-
dibi . .lOsalicylanilide
(12-24%)
3.4. 5-Tnbromosalicyl-
anilide (98-100%)
Formaldehyde "donor"
Formaldehyde "donor" (?)
Formaldehyde "donor" (?)
"C/uat" Formaldehyde "donor"
Salicylanilide
Salicylanilide
Tris Nitro
Cimcool Wafers
Cretan
Vancide TH
Dovicil 100
Tuasal 85
Tuasol 100
TBS 95
Commercial solvents
Cincinnati Hilling
Hallemite
(Sterling Drug)
Vanderbilt
Dow Chemical
Dow Chemical
Fine Organics
Dew Chemical
Maunee Chemical
      Smith,  T. H.  Toxicological and microbiological aspects of
      cutting fluid preservatives.  Lubrication Engineerina.
      25:313-319, 1969 August.
                                  76

-------
5.1.3  Waste Description

Metalworking operations produce wastes in either liquid/ solid, or
sludge form.  These wastes are primarily composed of the materials
being processed and the materials used to achieve a desired finish.
The types of waste generated by various operations are primarily
classified into the following three categories:  straight oils,
emulsified oils, and synthetic fluids.  Table 17 lists the types
of waste generated by various metalworking operations.

   TABLE 17.  WASTE TYPES GENERATED BY METALWORKING OPERATIONS


                 ~~~~~~~~   Straight     Emulsified     Synthetic
 	Operation	oil	oil	fluid

 Metal forming

 Rolling                        XXX
 Drawing                        XXX
 Stamping and extrusion         X             X
 Casting and molding            X                            X

 Metal removal

 Cutting                        X .            X              X
 Grinding                       XXX
 Machining                   .X             X              X
 Polishing and buffing          X             X
 Barrel tumbling and
   abrasive machining           X                            X

 Heat treating

 Tempering and quenching        XXX

 Rust prevention

 Oil coating                    X             X
The  following  subsections describe  the three waste types.  For  each
type of waste  potential contaminants, their sources, and  factors
affecting  their concentrations  are  described.

5.1.3.1  Straight Oils—
The  contaminants of neat or  straight oils  are of various  kinds,
depending  on initial  composition, the type of usage, and  the  sur-
rounding atmosphere.  So, waste oil characteristics will  vary from
plant  to plant within a company,  and also  from  company  to company.
Waste  neat oils m
-------
initial composition of neat oil, its application,  and surrounding
atmosphere.  "                            •

Waste neat oils often have a high water content due to water leak-
ages from other parts of 'machinery, mixing with water soluble oil
from other parts of machinery, or because of water held in suspen-
sion by detergent/dispersant additives [24].  The chlorine content
of waste neat oils may be high.  The chlorine is derived from the
additive package added to the oils to improve their performance.
To improve their performance under pressure, straight oils are
mixed with pressure additives which may contain as much as 18%
chlorine [30].  Waste oils may contain phenolic compounds as they
are added as preservatives or for odor control [30].  PCBs can
enter metalworking oil through PCB-contaminated tramp oil accumu-
lations.  Tramp oil is oil (usually hydraulic oil) from other parts
of the machine that leaks or drips into metalworking oil.  Hydrau-
lic oil is likely to be contaminated with PCBs, and it can accumu-
late in metalworking oil.  Until 1972, PCB-based hydraulic fluids
were commonly used.  When manufacture of these fluids was discon-
tinued, it was not recommended that hydraulic systems be drained,
flushed, or refilled.  Rather the public was advised to merely
replace these fluids (without PCBs)-as leaks and spills occurred.
Also the extreme complexity of hydraulic systems makes it very
difficult to eradicate all PCB contamination from these systems.
As a result, PCB levels in hydraulic systems range from 60 to
500,OOC mg/L  [30].

Atmospheric dust and metal chips and fines also become incorpor-
ated into waste ueat oils [31].  There ere three basic variables
which determine the metallic particulate characteristics.  They
are as follows [32]:

      1.  The first variable is the metal being worked.  Obviously,
          if cast iron is the metal being worked, cast iron partic-
        -  ulate will be generated.

      2.  The type of operation is the seconj variable.  The oper-
          ation may be grinding, machining, broaching, gun drilling,
          honing, boring, nobbing, lapping, or whatever, and each
          will produce characteristic metallic particulate.  Because
          of variations in feed rates, speeds, size of work-piece,
          etc., no two specific operations will produce identically
          sized particulate.
  [30] Listing waste oil as a hazardous waste.  Washington, DC;
      U.S. Environmental Protection Agency; 1981.  SW-909.

  [31] Sargent, L. B., Jr.  Lubricant conservation .in industry.
      Alcoa Center, A; Aluminum Company of America.
  [32] Nehls, B. L.  Particulate contamination in metalworking fluids,
      Lubrication Engineering.  33(4):179-183, 1977 Apxil.


                                78

-------
     3.  The type of metalworking fluid is the third variable.
          Field studies and laboratory research indicate that
/         different types of  fluids will cause generation of
          different sized metallic particulate under identical
          operational parameters.

Waste neat oils may also contain zinc, sulfur, phosphates,  lead,
nitrogen, amine compounds, suifates, barium, calcium, maqnesium,
and  fluorides  from various additives added tc tne metalworking
oils.

Depending on the ambient conditions, 'lubricants and additives may
undergo oxidation and other types of chemical changes.  Petroleum
oils are a cor.plex mixture oi three primary types of hydrocarbons,
all  of which will react with  oxygen (oxid?.tion) at high operating
temperature<$.  The reaction of mineral oils causes several  unsatis-
factory results.  Paraffin-based oils tend to form corrosive acids,
aromatic oils  form sludges and varnish, and naphthenic oils gen-
erally yield a co-nbination of both acids and sludges.  These mate-
rials may be further oxidized or they may react with each other
to form high molecular weight polymers.  Some of these are  oil
soluble and result in an increase in oil viscosity, while the in-
soluble polyMers create sludge and eventually hard deposits.  In
nearly all jises, the oil begins to thicken during oxidation, and
may  eventually become too thick for proper equipment functionings,
and  may' sffec- product quality  [33].

Tallow ^il,  lard oil, palm oil, 50/50 mixtures of tallow oil and
miner.iix ril, and straight nuneral oils are used in the metal form-
ing  captations of rolling and stamping.'  Rolling oils from  tire
stoaj/ _ndx;atry are usually recovered  from the mill's wastewater
tveatnent plant.  This results in a number of oils oeing mixnd
together, along with the animal fats, greases, etc., which
accumulate en  top of the skimming tanks.

.Tempering and  quenching of metals generate waste quench oils.
They are often very black in  appearance.  They have a low adriitive
content, and are usually made /.rom paraffinic base stocks.  These
oils are found at heat treating and metalworking shops.  While
these shops do not generate large volumes of oil, when a bath is
changed  (typically every six  to nine months), several drums of
waste are generated,  while some oil  is lost to evaporation and
by clinging to the dripped parts, a higher percentage (approxi-
mately 50 percent of total quench oil purchased) is collected rel-
ative to other metalworking oils  [24].

Rust preventive oil coating operations normally do, not generate
any  waste  [2^].  Oil that drips after coating is usually collected
and  reused'.
 [33]  Increase  fluid life  with oxidation/corrosion  inhibitors.
      Fluid and Lubricant  Ideas.   24-25,  1979  Spring.
                                 79

-------
Raw waste straight oil couposition data obtained from the-state
environmental regulatory agencies are presented in Appendix A by
the type of the metal finishing operation.  Examination of data
indicates that waste oils have-water, heavy metals, phenols, or-
ganic solvents, sulfur, and chlorine as ma}or contaminants present
separately or in various coniDinations.  Because of increasingly
restrictive regulations concerning disposal of waste oils into
environment, the djsposal,problem is becoming serious, and it is
affecting economics of metalworking oils use.  It may be possible
to economically refine the waste oils for reuse or to use the
waste oil in other applications.  These aspects ars discussed in
detail in Section 6.

5.1.3.2  Emulsified Oils—
Characteristics of waste emulsified oil tend to be plant specific
and depend on the uses to which the oil ha  been put.  Waste emul-
sified oils often contain contaminants such as metal particles,
biodegradation products, tramp oil, nitrosamines, and residues
from oil additives, including  sulfur, phosphorus, chlorine, zinc,
lead, copper, and phenolic compounds.

Emulsified oil systems are affected by accumulation of tramp oil.
If an emulsified oil starts at a 1:20 oil-to-water ratio, or about
5 percent oil, accumulation of tramp oil may raise the oil content
to 10 percent by the time the  oil is changed.  This accumulation of
tramp oil reduces the effectiveness of the emulsified oil to the
point it must be changed.

Waste emulsified oils may contain'residues from oi] additives and
metal fines and chips similar  to those described for straight oils
in Section 5.1.3.1.  Also, recent studies indicate that emulsified
oils may contain nitrosamines, either as contaminants in amines,
or as products from reactions  between amines and nitrites.  The
nitrosamine content of emulsified oils is attributed to the addi-
tive package, specifically to  the antiwear/extreme pressure,
corrosion and rust inhibitors; friction modifiers; antioxidants;
.and r.-.etal deactivator additives  [30],  According to NIOSH, a
recent study showed concentrations of 1,000 mg/L of diethanol
nitrosamine in cutting oil before use and 384 mg/L after use  [34].
This means 616 mg/L of nitrosamine was emitted into the surround-
ing atmosphere.

Bacteria growth is the most common cause of emulsified oil spoil-
age.  Once the emulsified oil  is placed in operation, bacteria and
fungi can enter the oil from five sources:  air in the plant,
water used to prepare the emulsified oil, the iretal or other mate-
rial being processed, a contaminated holding tank, or the operator
himself.  Once the microorganisms enter the emulsified oil, they
 [34]  Concentrates  -  industry/business..  Chemical  and Engineering
      News.   p.  12,   1976 October  18.,                •
                                 80

-------
encounter excellent conditions for growth:   moisture,  warmth,  and
food in the form of the emulsified oil.  Bacteria growth can occur
to the extent that organisms'may plug nozzles,  pipes,  and filters,
thus restricting emulsified oil flow and decreasing-tool, life.
Most problems, however, relate to emulsified oil life expectancy
and stability.  The microorganisms will attack the emuisifiers,
corrosion inhibitors, and other additives in the emulsified oil
and reduce their effectiveness.  Since the emuisifiers are criti-
cal to the stability of the oil/water emulsion, this can lead to
complete destruction of the emulsified oil.  Lower pH will cause
increased corrosion of cutting tools, machinery and work pieces,
leading to poor workmanship and reduced equipment life.  Perhaps
the most widely known effect is the creation of a foul, rotten-egg
smell known as "Monday morning odor."  This is caused by attack
of sulfur-reducing microorganisms on sulfur-containing additives,
and is particularly noticeable after a weekend shut-down during
which time these microorganisms have an opportunity to come to
the surface.  Circulating the fluid over the weekend will elimi-
nate the smell, b1 t will do nothing to get rid of the organisms.
Most manufacturers reconur.end keeping the pH between 8.5 and 9.2,
but the rapid growth of some bacteria can lower the pH below 7.0,
and cause metal corrosion.  Use of a buffering agent rather than a
biocide can reduce the corrosion effects but will not reduce the
level of growth [35].  The oil-water ratio has a significant effect
upon the magnitude of microbial growth in emulsified oil.  Table 18
shows tl.at a 1:5 ratio is inhibitory, and normally there is very
little growth.  The 1:10 ratio is partially inhibitory, but in
several days the organisms begin to proliferate.  The 1:25 tc 1:50
ratios are almost invariably ideal for maximum growth.  In ratios
greater than 1:50, the inhibitory components are diluted out, and

        TABLE 18.  EFFECT OF OIL-WATER RATIO ON GROWTH OF
                   BACTERIA IN AN'OIL EMULSION  [36]
       (Results are expressed as number of cells x 106/mL)

Oil-water
ratio
1
1
1
1
1
:5
:10
:15
:50
:100
Davs
0
0
0
0
0
0
.0
.0
.1
.1
.2
2
0.0
0.0
5.6
6.3
2.9
6
0.
0.
20.
20.
8.

0
003
5
5 >
5
12
0.
8.
24.
24.
12.
16
0
0
0
0
8
0
19
36
42
10
.0
.0
.0
.0
.0
' 20
0.0
8.5
25.0
33.5
7.0


 [35] How to improve metalworkirg operations by organizing a
     biocide treatment program.  Fluid and Lubricant Ideas.
     22-25, 1980 September-October.

 [36] Bennett, E. O.  Biology of me'talworking fluids.  Journal of
     American Society of Lubrication Engineers.  28(6):237-247,
     1972 July.


                                81

-------
 the concentration of oxidizable materials,seems to be the major
 limiting  factor  (36].

 Table  19  presents data on pollutant concentrations found in waste
 emulsified oils  from metai  finishing plants.  'This table was com-
 piled  by  EPA by  actual sampling and analysis  of waste emulsified
 oils from various metal  finishing plants  during preparation.of the
^development document for effluent limitations guidelines and
 standards for  the metal  finishing industry  [2].  Raw waste emul-
 sified oil composition data obtained from the state environmental
 regulatory agencies are  presented in Appendix A by the  type of
 metal  finishing  operation.  Examination of  state and U.S. EPA data
 indicates that waste emulsified oils have heavy metals, sulfur,
 chlorine, various organic compounds, and  solvents as major contam-
 inants present separately or  in various coab-inations.'   They have
 high BOD5, COD,  and oil  levels.  Generally, environmental regula-
 tions  do  not allow discharge  of untreated emulsified oil into
 surface waters because of its contaminants.   Various treatment,
 recycle,  reuse alternatives and ecomonic  aspects of waste emulsi-
 fied oil  are discussed in detail in Section 6.

 5.1.3.3   Synthetic Fluids—
 Characteristics  of waste synthetic fluid  tend *io be plant specific
 and depend on  the uses to which the fluid has b:-en put.  Waste
 synthetic fluids may contain  contaminants sucn as metal fines and
 chips, biodegradation products, trarcp  oil,  nitrosamines, and resi-
 dues from.,additives similar to those described for waste emulsified
 oils in Section  5.1.3.2.

 Since  synthetic  fluid formulations are generally proprietary,
 very lit-tle  information  is  available about  their composition.  A
 study  was conducted at the  University  of  Houston to develop data
 pertaining to  the COD and BOD5 values  of  synthetic  fluids.  The
 data are  presented in Table 20 [37].   These data show that waste
 synthetic fluids have very  high BOD5 and  COD  values.

 Waste  synthetic  fluid composition data obtained  from state environ-
 mental regulatory agencies  are presented  in Appendix A.  Owing to
 limited usage  and formulation confidentiality, only limited data
 were available at state  offices.  Nevertheless,  examination of
 data presented in Table  20  and Appendix A indicates that waste  /
 synthetic .fluids have high  BOD5, COD,  and metal  contaminants.
 Generally, untreated waste  synthetic fluids may  not be  allowed to
 discharge into surface waters, since they are organic or inorganic
 compounds with contaminants.   Waste syntnetic fluids treatment,
 [37]  Adams,  M.  C.;  et al.   BOD and COD studies of synthetic and
      semisynthetic  cutting fluids.  Water,  Air,  and Soil Pollut-
      ant.   11:105-113,  1979.
                                 82

-------
             TABLE  19.
                                            POLLUTANT CONCENTRATIONS  FOUND  IN EMULSIFIED
                                            OILS FROM MKTAL  FINISHING PLANTS  |2|
CD
U)
 I .
 1
 3
 4,
 *>
 6.
 7.
 8.
 9.

10.
11.
12.
13.
14.
IS.
16.
17.
18.

19
20.
21.
22.
23.
24.
26.
27.
28:
29.
30.
31
32.
33.
34.
35.
36.
37.
38.
35>.
40.
41
                                               Minimum
                                                            Maximum
                    \\f\\..f\\O
          ii lot I 
      hloiot-rngritc
      . i-Oicliloi oet hano
      . 1 . t-Tl icl\luiorlluiits
      , ) -Dichloioolhdiie
      . 1,2-Ti ichloroethane
     1, 1.2, 2-Tcti jchloro-
       ethane
     Bio-chlotomrthyl  ether
     BiB(2-chloiocthyl )  ether
     2-Chloioh.iphthalene
     2,4.5-Trichlorophenol
     p-Chloro-a-cresol
     Chlorofoira
     2-Chlorophcnol
     1, 1-Dichloroethylene
     1,2-Trans-dichloro-
       nthy lene
     2,4-Olchloiophenol
     2. 4-DiMQvhylplienol
     1 , 2-Dipht-riylhydraiine
     Ethylbenzene
     F'uotdnthene
     Bi u( 2-i:Mor>~>t 3opropl )  -
       ether
                     Methylcne chloride
                     Methyl  Chloride
                     Btomofotm
                     Oichloi otjiomomrt hane
                     Trtchlorof loiomet hane
                     CM orodibioraome thane
                     Naphthalene
                     Nitrobenzene
                     2-Nltrophcnol
                     4-Nltrophenol
                     2, 3-D>nit:ophenol
                     4 , 6-Dinitro-o-cresol
                     N-iutroscd:phenyluunne
                     Pe'ntachlotophenol
                     Phenol
O.OS7
0.001
0 001
O.Oll
0 OO4
l> 001
O 002
0.006
0 006
0 009
0.004
0 130
0.010
0.004
0.002
0.076
0.002
0 008
0.010
C 001
0.005
0.00)
0.001
s
a
10
"0
i
\ . 100
t
I
0
0
0
0
1
8OO
0
0
10
1
0
31
1 0
5
55
. IQ
lit)
.0
MO
10

. 10
.30
.570
009
.010
.130
.80

.691
.620

.70
.008

.012 •
50

2 .an
0.01.'
3 .t>0
0 JIO
1.12
M.H
456
0 331
C.2B8
0.009
0 007
0.130
0.613
104
0.058
0 348
1.51
0.507
O.OJ9
5 21
0.008
0 380
8.26
                                  0,004

                                  0 003
                                  0.005
                                  0 001
                                  0.010
                                  0 001
                                260
                                  0.001
                                  O Oi 1
                                  0.001
                                  0.010
                                  0.010
                                  0.010
                                  0.010
                                    004
                                    OlO
•J
0
0.003
                                                  b  ooj
  0.004

  0 003
  / 60
  4 70
  0.010
  0.010
290
  0.01.0
260
  0 010
  0 320
  0.010
 10
  5 70
  0 '100

  6 '.I.

 •'•» 10
 U 004

 0.003
 0 604
 1.18
 0.010
 0 005
>5
 0 004
36.3
 0.005
 0 122
 0.010
 3.34
 2 US
 0.48R
18.4
 I I?

 O.ttlH
                                                                                         Median
                                           2. Hit
                                           0 inlil-
                                           0 09 I
                                           0 110
                                           1 IS
                                           0 265
                                           0 603
                                           0.010
  0.288
  0 009
  0 007
  0. 130
  0.030
  2 33
  0.010
  0.348
  0. 195

  008
  0 039
  0 OlO
  0.008
  0.012
  0. 108

  0.004

  0 00)
  0.092
  '0.009
  0,010
  0.005
275
  0.002
  0. 104
  0.005
  0 03b
  0.010
  0.013
  2.H5
  0.750
  5.20
  <).44Q

  0 U'M
N'imliei
of
A1" "'to 	
7
IB
1
6
18
It
4
2
1
Z
1
3
8
19
t
12
9
2
6
2
16
8
1
1
29
4
1
2
2
3
10
2
1
1
. 3
2
5
3
1
Ntintef
of
zetos
1S
19
is
31
1 9
26
33
35
)6
35
36
34
29
18
35
25
34
35
31
35
21
29
36
36
8
T;
jr.
35
35
34
27
35
24
J6
34
35
32
14
24
                                                                                                       20
                                                                                                                1 1
                                                                                                         11.1 ,\\ i
                                                                                                                 1>t >

-------
                                                     TABLE  19  (continued)
oo
42.  Butyl benzyl phthalate
43.  Di-n-butyl phthalate
44.  Di-n-octyl phthalate
4b.  Diethyl phthalate
46.  Dimethyl phthalate
47   1,2-Benzanthracene
48.  Benzo(a)pyrene
49.  Chrysene
50.  Acenaphthylene
51.  Anthracene
52.  Flr.orene
53.  Phenanthrene
54.  Pyrene
55.  Tetrachloroethylene
56.  Tcluene
57.  Tnchloroethylene
58.  Aldrin
59.  Dieldrin
60.  Ciilordane
61.  4,4'-DDT
62.  4,4'-DDE(P,P-DDX)
63.  4,4'-DDD(P,P-Tl)E)
64.  o-Endor.ul fan
t>b.  (l-KntloMul 1 i
1
0
0
0
0
0
0
0
0
0
0
0
0
8
1
23
0
0
0
0
0
0
0
0
0
0
0
<0
<0
0
0
0
J
0
46
3,240
117,000
40,700
2
1,960
27,600
2,720
112
?!3/i:

.63
.269
.06?
.415
.401
.047
.010
.025
.406
.360
.176
.393
.079
.91
.77
.2
.007
.003
.007
.006
.014
.005
.018
.003
.010
.000
.012
.001
.001
.012
.006
.007
.588
.9CO
.6



.50




- 	 	

Median
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
<0
<0
0
0
0
0
0
7
1,440
11,600
6,060
0
1,640
1,640
680
4
.130
.016
.062
.048
.001
.007
.010
.002
.140
.034
.075
.028
.075
.010
.033
.110
.007
.003
.007
.006
.002
.004
.018
.003
.011
.008
.012
.001
.001
.013
.007
.007
.588
.980
.93



.238



.37
Number
of
points
9
15
2
9
3
4
1
3
3
7
7
8
5
18
25
11
2
1
2
2
4
3
2
2
4
2
2
1
1
3
3
2
2
2
10
21
16
37
34
9
37
35
37
Number
of
zeros
28
2;
35
28
34
23
36
34
34
°.6
30
29
32
19
12
26
35
36
35
35
33
34
35
V>
33
35
35
36
36
34
34
35
35
35
27
16
21
0
3
28
0
2
0

-------
                TABLE  20.   BOD AND  COD VALUES  FOR
                           SYNTHETIC  CUTTING FLUIDS

Fluid
A
B
C
D
E
F
G
H
I
J
K
L
M
N
0
P
BOD5
mq/L x 10s
2.00
2.37
1.18
1.55
0.97
1.88
2.05
0.49
1.97
1.02
0.87
0.20
1.15
0.17
0.52
0.00
COD
mg/L x 10s
6.46
10.40
6.28
8.38
5.95 .
11.60
15.80
4.10
18.30
11.90
11.30
2.88
17.50
5.45
18.50
20.90

recycle, reuse alternatives along with economic aspects are dis-
cussed in detail in Section 6.

5.1.3.4  Geographic Distribution—
It is reported that approximately 1,890 million liters per year
(500 million gallons per year)  of used oils are generated by metal-
working operations [31].  Also, approximately 878 million liters
per year (232 million gallons per year) of new metalworking oils
are sold [31].  Since metalworking operations do not consume any
oil except for evaporation and drag-out losses, it is estimated
that of the 1,890 million liters per year (500 million gallons per
year) generated, 1,012 million liters per year (268 million gal-
lons per year) are recycled, and 878 million liters per year (232
million gallons per year) are disposed of.

Since sufficient data are not available to determine accurately
the waste volume produced by each state, the total estimated waste
volume generated was proportionately distribute^ airong states
based on the total number of metal finishing plants (with more
than twenty employees) in each state.  The estimated geographic
distribution of waste generation is presented in Table 21, and
Figure 18.  Seven industrial states (California, Illinois, Texas,
Michigan, New York, Ohio, and Pennsylvania) generate approximately
53 percent of the total industry waste.
                                85

-------
The total waste will consist of approximately 50 percent straight
oils,  45 percent emulsified oils,  ana 5 percent synthetic fluids.

        TABLE 21.  GEOGRAPHIC DISTRIBUTION OF WASTE OILS
                   GENERATED BY METAL FINISHING INDUSTRY


1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.

State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
District of Columbia
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island

Million
liters/year
11.3
0
5.5
6.2
110.9
7.4
24.7
0.9
0.2
19.4
12.2
0.6
1.2
66.5
31.0
9.4
8.2
9.2
6.6
2.3
7.9
32.6
61.3
17.3
6.4
16.4
0.7
3.9
1.0
4.4
39.3
1.3
65.4
19.1
0.7
64.5
9.5
8.1
53.4
10.2
(continued)
                                86

-------
                    TABLE  21  (continued)


41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
State
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Million
liters/year
6.4
0.9
15.5
43.2
3.6
1.7
9.6
9.6
3.6
26.3
0.2

  MILLIONS LITERS PER YEAR
       D
       D 10 - 50

       D >»
Figure 18.  Geographic distribution of waste  oi]s generated
            by metal  finishing plants in the  United States.
                              87

-------
5.2  SOLVENT CLEANING

This section describes solvent cleaning operations,  including sol-
vents used and waste solvents generated.

5.2.1  Process Description

5.2.1.1  Cold Cleaning [38] —
Cold cleaning is the simplest, least expensive, and most common
type of degreasing.  It is most often used for the removal of oil-
base impurities from fabricated metal parts in a batch-load pro-
cedure.  The cleaning solvent is generally at room temperature,
although it may be heated slightly -co well below its boiling
point.

The solvent dissolves the greasy dirt on the part to be cleaned
as it is immersed.  The part is usually lowered into the solvent
bath in a metal basket.  The cleaning action is often enhanced by
spraying solvent on the part and by agitation of the solvent by
pumps, compressed air, mechanical motion, or sound.  After clean-
ing, the part is dried by allowing evaporation and drainaye of the
solvent en (frying racks which are located inside the cleaner or on
external racks which route the drainage back into the cleaner.

Figure 19 illustrates the simple design of a typical cold
cleaner [39].

5.2.1.2  Emulsion Cleaning [38]—
According to current estimates, approximately 15 percent of the
metal cleaning processes used in this country use emulsion clean-
ing.  Generally, emulsion cleaning is a process for removing soils
from meta] surfaces by the use of common organic solvents dis-
persed in an aqueous medium with the aid of an emulsifying agent.
The stability of the emulsion may be accentuated by such additives
as  surface-active agents,  finely-divided solids, etc.  Depending
on  the solvent used, cleaning is done at temperatures from room
temperature to 60°C to 80°C.  Dilution  of solvent with water is
generally over 95 percent.

A vast increase in interfacial surface  results from en.ulsification.
Because of the large solvent  surface provided  in the emulsion,
 [38]  Peter, R.; Tanton, T.; and Leung, S.; et al.  Alternatives
      to  organic solvent degreasing.  Sacramento, CA; California
      Air Resources  Board;  1978 May.  232 p.  ARB-A6-2-6-30.
      PB  282 466.

 [39]  Suprenant, X.  S;  and  Richards,  E. W.  Study to  support new
      source performance standards  for  solvent metal  cleaning  -
      operations.  U.S. Environmental Protection Agency.   1976
      April.   EPA  Contract  66-02-1329.


                                88

-------
         BASKET-*
        SOLVENT —•
                                             --CLEANEK
                                            —   PUMP
                 Figure 19.  Cold cleaner [59].

less solvent is required to achieve the same cleaning efficiency.
Surface-active materials added to ,the solution are attracted ,to
the surface of the droplet, and they provide a mechanical barrier
between the solvent droplets to keep them dispersed in water rather
than to permit them to coalesce.

Emulsifiable solvent mixtures can be applied without prior dis-
persion in water.  In this way, the advantage of solvent cleaning
(greater soil removal) is coupled with the ability to rinse with
water.  This results in less solvent usage than with straight
solvent usage.

Factors affecting the degree of cleaning include agitation,
operating temperature, contact time, concentration of cleaner,
and degree of rinsing.

The size and configuration of the part and the nature of the soil
are the main considerations that influence the selection of type
of cleaning method.

Two types of cleaning methods are commonly used in emulsion metal
cleaning.  Immersion cleaning is preferred for small parts that
must be placed in baskets.  Spray cleaning is often used to clean
large parts with surfaces exposed for impinging.  Hard-to-remove
soils are generally removed with this method.  In this type of
application the cleaner in a concentrated form is sprayed on the
                                89

-------
work surface and then rinsed with a pressure spray.  Combination
cycles of immersion, spray washing, and pressure-spray rinsing
are often used to clean intricate parts.  A9itation is Ubually
provided to help in removing soil.

Compared to conventional solvent degreasing, emulsion cleaning
has the following advantages [38]:

     Emulsion cleaning is an effective means of removing a wide
     variety of soils froT metal surfaces, especially when rapid
     superficial cleaning is required.  This is mainly because a
     mixture of solvent and wat-?.r is used.

     It is usually less costly than solvent cleaning because a
     large amount of water is added to a relatively small amount
     of solvent.

     Since it can be operated at room or slightly elevated
     temperatures, hazards from fire and toxic fumes are not
     great.  Much less hydrocarbon is emitted to the ambient air.

     Emulsion cleaning leaves a thin film of oil on tlie work;
     this thin film provides some protection against rusting.

5.2.1.3  Ultrasonic Degreasing—
Ultrasonic cleaning is a special application of solvent metal
cleaning, employed most frequently in the manufacture of electric
and electronic equipment and aircraft parts [38].

Ultrasonic degreasing combines a precleaning cycle, such as vapor
degreasing or immersion cleaning, with subsequent treatment by
immersion in a ultrasonically agitated lic.uid bath of the degreas-
ing solvent.  Transducers which convert electrical energy to
mechanical energy are placed in the bath either at the bottom or
on the sides to supply the power for agj tation.  Solvent filtra-
tion for particle size down to 2 pra, 5 ^m, or 10 um, depending
on the type of soil, is provided.  The frequency and intensity of
the ultrasonic energy are selected on the basis of tests.  An
application example is the removal of residual oil from roller
bearing cones.  The cones are ultrasonically cleaned in tri-
chloroethylene at 60°C, with the immersed transducers operating
at a frequency of 400 kHz (400 kilocycles).  The average power
intensity at the transducer is 2.5 x 104 W/m2 [7].

Capacity of ultrasonic cleaning tanks may be as little as 0.6
liter and generally are designed to be appropriate to the size of
the parts to be cleaned  [38].

5.2.1.4  Vapor Degreasing—
Vapor degreasing provider an efficient and economical method for
preparing clean, dry articles for  subsequent finishing or fabri-
cating.  Vapor degreasing makes use of a convenient difference


                                90

-------
between the soils removed in solvent metal cleaning and the sol-
vents used to remove them.  The solvents boil at a much lower
temperature than the oils.  Consequently,  a mixture of solvent
and metalworking oils can be boiled, and the vapors produced will
be essentially pure solvent.  These pure solvent v'apors will con-
dense on metal parts until the temperature of the parts approaches
the boiling point of the pure solvent.   The condensed solvent
dissolves the oils present on the parts and drains from them as
new solvent condenses [39].   Vapor degreasers are satisfactory
for removing oils and greases that are partially or completely
soluble in the degreasing solvent.

The two types of vapor degreasers used for industrial solvent
metal cleaning are:  (1) open top vapor degreasers, and (2) con-
veyorized vapor degreasers.

The open top vapor degreaser cleans by condensing vaporized sol-
vent on the surface of the metal parts.  The condensing solvent
dissolves oil and grease, washing the parts as it drips down into
the tank.  To condense rinsing vapors and prevent solvent loss,
the air layer or freeboard above the vapor zone is cooled by a
series of condensing coils which ring,the internal wall of the unit.
Most vapor degreasers also have an external water jacket which cools
the freeboard to prevent convection up hot degreaser walls [38].
The freeboard is usually 50 to 60 percent of one width of the de-
greaser [39].  Steam, electricity, or gas is used to boil tha
solvent.  Nonflammable solvents are usually used.

Figure 20 illustrates a basic open top vapor degreaser.
            FREE-
            BOARD
VAPOR LEVEL
     I
                         VAPOR ZONE
                 HEATER
WATER JACKET
                 CONDENSATE
                 COLLECTING
                   TROUGH
            VAPOR GENERATING
                 SUMP
        Figure 20.  Basic open top vapor degreaser [7]

-------
Open top degreasers represent a compromise between the extreme low
capital investment of cold cleaning and the more capital intensive
conveyorized systems discussed next.  As such,  they are often
located in one or more convenient sites in the plant.  Open-top
degre-asers process parts manually and are frequently used for only
a small portion of the workday or shift.  In contrast,, conveyor-
ized vapor degreasers tend to be central cleaning stations where
the parts to be cleaned are transported to the machine [39].

Conveyor-operated solvent degreasers provide an efficient and
economical method for preparing clean, dry articles for subsequent
finishing of fabricating [40].  There are several types of convey-
orized degreasers and each can operate with either cold or vapor-
ized solvents.  The basic steps found in the typical conveyorized
vapor degreaser include a vapor rinse upon entry to the degreaser
vapor space section, liquid immersion, liquid spray, vapor rinse,
and finally, a slow withdrawal through a cold air space drying area.
Conveyorized vapor degreasers employ the same process techniques
as do open-top degreasers; the only significant difference is mate-
rial handling.

There are several basic designs which are termed conveyorized de-
greasers:  gyro, vibra, monorail, cross-rod, mesh belt, and strip
cleaners.  Figures 21 through 25 present sketches of the ferris
wheel, vibra, monorail, cross-rod, and mesh belt degreasers [7].
Conveyorized degreasers are generally large, automatic units
designed to handle a high volume of work in either a straight-
through 'process or a return type process in which the work pieces
enter and leave the degreaser unit from the same end.  Their use
minimizes the.human element and produces consistently high quality
cleaning with minimum solvent losses.

5.2.2  Raw Materials

5.2.2.1  Requirements

Ten characteristics are required of solvents used in degreasing
processes [7].  Solvents must:

     Either dissolve or attack oils, greases, and other
     contaminants.

     Have a low latent heat of vaporization and a low specific
     heat so that a maximum amount of solvent will condense on a
     given weight of metal and keep heat requirements to a minimum.
 [40] Allen, R. D.  Inspection source test manual for solvent metal
     cleaning (degreasers).  V/ashington, DC; U.S. Environmental
     Protection Agency; 1979 June.  150 p.  EPA-430/1-79-008.
     PB 80-125743.
                                92

-------
Figure 21.  Ferris wheel degreaser [7].
   Figure 22.  Vibra degreaser [7]
                   93

-------
Figure 23.  Monorail degreaser [7).
Figure 24.  Cross-rod  degreaser  17]
                  94

-------
       Figure 25.   Mesh belt coiweyorized degreaser [7].

     Have a high vapar density relative to air and a low rate of
     diffusion into the air to minimize solvent losses.

     Be chemically stable under conditions of use.

     Be essentially noncorrosive to common materials of
     construction.

     Have a boiling point low enough to permit the solvent to be
     easily separated from oil, grease, and other contaminants by
     simple distillation.

     Not form azeotropes with liquid contaminants or with other
     solvents.

     Have a boiling point high enough so that sufficient solvent
     vapors will be condensed on the work to ensure adequate
     cleaning.

     Be available at reasonable cost.

     Remain nonexplosive under the operating conditions of vapor
     degreasing.

Table 22 [41] lists typical applications for vapor degreasing sol-
vents.  Table 23  [7] lists the physical properties of commercially
available solvents.  Table 24  [7] gives the estimated consumption
of solvents used in degreasing operations.

5.2.2.2  Solvent Description [38]—
Four main types of organic solvents are used in industries with
solvent-degreasing operations:  alcohols, ha3ogenated solvents,
[41] Metal finishing guidebook and directory, 1974 Edition.
     Hackensack, NJ; Metals and Plastics Publishing, Inc.
                                95

-------
             TABLE 22.   TYPICAL APPLICATIONS  FOR VAPOR-DECREASING  SOLVENTS  (41)
      	    jVDjy I icat ion	
      Solvent
Approximate
   vapot
temperatur e,
     °C
Removal of soils from parts
Remocal of slightly soluble  (high
  melting) soils

Removal of water films  from  metals
Cleaning coils and components  for
  electric motors
Cleaning temper-ture-sensitive materials
Cleaning compoiiPiils  for  rockets
  or missiles
limning will) ultrasonics
It ichloroPthylene
Perchloiocthylane
                                            Herchloroethylene
Methyl chloroform
Trichlorotrifluoro-
  ethylene
Kethylene chloride
Trirli] orotrifluoro-
  etliylenf
Trichloroe thy lent1
Trirlilorcrthylene
t-ei chloi oe I hylene
Hethylene chlotide
rluot mated hydio-
  cat bun
     87


    121


    121


     74

     48




     40

     48



     87
                                                                         87
                                                                        121
                                                                         40

                                                                         48
 Factors affecting selection

Host commonly used degreasing
  solvent.

Used where  higher operating
  tempprature is desirable.

Rapid and complete drying in
  one operation.

Solvent must not damage  wire
  coating or sealing agents.
  Requires  special equipment
  design.  Selection should
  be based  on preliminary
  tr
-------
1— 1
l_l
rt Ed
C (D
H JU
H- ft
3
ic n>
X
0 O
O JU*
• (U
3
M (O
cn
-J rt
' g.
fD
-J3
|— " fl)
3
T) £
• »
10
-J

^
tu
rt
0)
tr
c

"r
§5
1
f j ^Cj
o o>
*"
H-
MCC
fD •
**!
fc> •
cn
0 O
TABLE 23.
Solvent
Honhalogenated
Toluene
Methyl ethyl ketonr
Acetone
n-Butanol
sec-Butano]
a H Naphtha, coal tar
(ft irt
, ^jj Naphtha, safety (Stoddard)
3 Mineral spirits
!3 O Ethers (petroleum
o
. f) Benzene
g o-Xylene
M ft Cyclohrxane
CT> JJ Hexane
MlQ
* Halogenatfd.
rt
fp Trichlorotrifluoroethane
2 Q. Methylene chloride
• 5
O
. . .

H1 t-> Trichloroethylene
O O
|-i uO 1 ,1,1-Trichloroethane
1 ^ Carbon tetrachloride
PROPERTIES OF COMMERCIALLY AVAILABLE
tloi 1 ing Lat« t>l lu*dl i
point vnpol i/al i 01
T )/y

110 6
79 6
56 7
117 2
107.2
150 to 200
150 to 200
m to 17S
40 to 70
80.1
143.9
80.7
66.7



74 1
40 0
171 1
87 2
74 1
76.7

361 4
443 8
5? I 3
591 6
578 2
326
301 5
326 6
2BB 9
394
347
158.4
337 0



146 i
310 4
2(19 4
239 5
221 1
218.1
-• O a
to 
p»
O
 I
 Lntent heats of vapotization were estimated from Reference 43

 Specific heali. were estimated flow Reference 41 for the temperature range of 0 to 250°C, where applicable.

 API gravities were assuwed for the various petroleum fractions tespective to the list above, to be 25°C,  13°C,  31°C.  and 100°AP1

 Carbon tetrachloride is the basis tot  evaporation rate comparisons.  Its evaporation rate is given a value  of 100.

 Estimated value

d24°C

e25°C.

-------
TABLE 24.   DISTRIBUTION OF U.S.  DECREASING SOLVENT, CONSUMPTION [7]
       Chemical
1974 Apparent
    U.S.
 consumption,
103 metric tons
  1974 Apparent
solvent/degreasing
   consumption,
 103 metric tons
   Cold    Vapor
          Percent of
            total
          consumption
           for metal
           cleaning
            and
          decreasing
 Halogenated hydrocarbons:
   Fluorocarbons
   Methylene chloride
   Perchloroethylene
   Trichlorocthylene
   1,1,i-Tncyloroe thane

 Hydrocarbons:
   Hexane
   Toluene
   Xylene
   Cyclohexane
   Ethers
   Mineral spirits
   Naphthas

 Ketones:
   Acetone
   Methyl ethyl ketone

 Alcohols^

   Butyl alcohol
     428.6
     235.4
     330.2
     173.7
     236.3
     135
    3,085
    2,635
    1,066.7
      56.3
     210
    4,450
     882.5
     237.2
      159.6
    6
   46.2
   11.4
   43.8
   78
    7
   14
   12
    1
    6
   30
  188
   10
    7.5
    3.3
 11.
 10
 43
112.
 90
 4
24
16
90
71
             5
             0.5
             0.5
             0.1
             11
             14
             4.2
             1.1
             3.1
             2.1
hydrocarbons, and  ketones.  The maintenance type of  cold degreas-
ing and wiping uses  mainly hydrocarbons,  such as mineral spirits.
Manufacturing cold degreasing and  conveyorized cold  degreasing
use a wide variety of solvents.  Open-top vapor degreasers and
conveyorized vapor degreasers use  halogenated solvents exclusively.

Alcohols and ketones are selected  for cold degreasing mainly be-
cause they evaporate faster than petroleum products  and leave
cleaner surfaces;  they are preferred to halogenated  solvents '
mainly because of  their solvency and cost.

The five major halogenated solvents  listed in Table  24 are manu-
factured and sold  under a variety  of trade names.  While they are
all certainly suitable to general  vapor degreasing processes,
each has limitations associated with it.
                                   98

-------
Trichloroethylcne has been the historical favorite for vapor
degreasing usage.  It is felt that the development of the vapor
degreasing process and associated industry was largely based on
the particular properties, availabilities, and low cost of this
versatile solvent.  The boiling point (87°C) allows adequate
vapors to condense on the work being cleaned,  yet the work is
not too hot to handle upon removal from the degreaser.  Utility
requirements also are easily met with 15 psig steam (or less) and
nominal cooling.  The other properties of trichloroethylene have
created such wivlespread general usage that many vapor degreasers
must be retooled or otherwise modified to allow alternate solvent
usage.  However, regulations restrict the use of trichloroethylene
for vapor degreasing because of its photochemical reactivity and
resultant production of atmospheric oxidants.

Another halogenated solvent, 1,1,1-trichloroethane, is second
only to trichloroethylene in nationwide usage for vapor degreasing.
General behavior is similar -co trichloroethylene primarily due to
a similar boiling point.  However, the chemical stability of 1,1,1-
trichloroethane can cause significant problems associated with
water contamination and use with "reactive" metals (i.e., alum-
inum or zinc).  The primary advantages to the user of choosing
1,1,1-trichloroethane over trichloroethylene are that parts are
lower in temperature on removal from the degreaser (~14°C lower)
and are thus easier to handle..  An important consideration for
air quality is the substantially lower photochemical reactivity
of 1,1,1-trichloroethane compared to that of trichlcroethylene.

Perchloroethylene is used in about 15 percent of the vapor de-
greasers nationwide.  Perchloroethylene has inherent stability to
reactive metals and thus requires less stabilization.  Beca'use of
its higher boiling point  (121°C), significantly more vapor con-
denses on the work than with either of the other two solvents.
Because of the combined effects of higher temperature and in-
creased vapor flushing, better cleaning efficiency is generally
obtained with Perchloroethylene.  Further, because of its signifi-
cantly higher boiJing point, perchloroethylene drives off trans-
ient water from the workload more quickly.  As with most advan-
tages, the higher boiling point also creates some disadvantages.
A minimum of 60 psig steam is required for vapor degreasers using
perchloroethylene, usually requiring a larger steam coil (and prob-
ably a licensed engineer's presence).  If electric or gas heaters
are used, significant additional utility costs result.  Safety and
comfort of employees also suffer as the vapor degreas-jr is oper-
ated at 121°C rather than at 87°C.

Methylene chloride may be used to remove polymer residue because
of its high solvency.  It is especially useful for cleaning heat-
sensitive parts because of its low boiling point.  Less heat is
required for degreasers using methylene chloride as solvent;
however, methylene chloride diffuses more readily because of its
low vapor density.  Extensive modification of a vapor degreaser


                                99

-------
is required to convert from trichloroethylene to methylene chlo-
ride.  The low boiling point and the low volume of condensate
generated may cause low cleaning efficiency.

Fluorocarbon-type solvents,, such as Freon-113,  have the same
advantages as methylene chloride and are suitable to remove poly-
mer residue and heat-sensitive parts, but since the vapor density
of Freon-113 is much higher than that of methylene chloride less
Freon will diffuse out of the degreaser.  A slightly higher boil-
ing point and a larger volume of condensate have made Freon a
better solvent thar methylene chloride to clean small,  delicate
parts.  The cost of Freon is, however, much higher than that of
any other halogenated solvents.

Carbon tetrachloride is not often used for degreasing except in
special applications because of problems with toxicity to
operators.

Brief descriptions and selected analyses of degreasing solvents
and stabilizers are provided in Appendix B.

5.2.3  Waste So.vent Description

The degreasing equipment, sump, and stills contain spent solvents
along with removed oils, greases, waxes, and metallic particles.
These spent solvents are also commonly known as degreasing sludges.
The following subsections describe waste solvent characteristics
and their geographic distribution.

5.2.3.1  Waste Characteristics—
Waste solvent composition will depend on the solvents used for
degreasiny and type of soils (oils, greases, waxes, buffing con-
pounds, metallic particles, etc.) to be removed from the material
being processed.  It is independent of the nature of the plant.

The volume of waste solvent from a vapor degrea~er per load is
less than that from cold cleaners because the solvent in a vapor
degreaser may be used for  * longer time.  Vapor degreasing wastes
can contain from 15 percent to 30 percent oil contamination, where-
as cold cleaning waste solvent can only contain about 10 percent
oil contamination before it must be replaced [7].  Table 25 pre-
sents data for the fraction of solvent consumed that becomes waste
solvent by type of degreasing operation  [7].

Some criteria have been established to determine when a vapor
degreaser should be cleaned.  Most commonly, the need for clean-
ing the degreaser is established when the boiling point of the
contaminanved solvent is from 5 to 10 degrees above the boiling
point of the pure solvent  [21].  In most shops, experience, shows
that this will take place at nearly consistent intervals.  Gener-
ally, this corresponds to a contaminated solvent with contaminant
                                100

-------
           TABLE 25.  WASTE  SOLVENT  GENERATION  BY  TYPE
                     OF,DECREASING  OPERATION  [7]


                                     Total  solvent consumption,
                                    that  becomes  waste  solvent,  %
      Degreasing operation	      Range	Average	
Cold cleaners
Manufacturing (44%)
Maintenance (56%)
Open top vapor degreasers
Conveyorized vapor degreasers
40 to 60
50 to 75
20 to 25
10 to 20
50.0
62.5
22.5
15.0

level approaching 30 percent [7].   Table 26 presents boiling
points of clean and contaminated chlorinated solvents [44].

TABLE 26.  BOILING POINTS OF CLEAN AND CONTAMINATED SOLVENTS [44]


                                     Boiling point,  °C
                                                 30%
                Solvent            Clean     Contaminated
Trichloroethylene
Perchloroethylene
1,1, 1-Trichloroe thane
Methylene chloride
87.2
121.1
74.1
40.0
90.5
126.7
85.0
43.9

Raw waste solvent composition data obtained from the state envi-
ronmental regulatory agencies are presented in Appendix B, by
type of degreasing operation wherever it is known.   Examination
of data indicates that waste solvents are contaminated with oils,
greases,  and heavy metals.   Since the Resource Conservation and
Recovery Act (RCRA) lists waste degreasing solvents >s hazardous
wastes, they should be disposed of in accordance with the regula-
tions.  Waste solvents can be reclaimed and reused.  Various waste
solvent reclamation technologies along with economic aspects are
discussed in Section 6.

5.2.3.2  Geographic Distribution—
It is reported that in 1980 approximately 1.8 million kg/day (4
million Ib/day) of waste solvents are generated by the metal
finishing industry [2].  This corresponds to 468 million kg/yr
[44] Vapor degreasers.  Clarke,  NJ; Branson Equipment Co.


                                101

-------
(1,040 million Ib/day) for a five-day work week.   This estimate
is based on a random survey conducted by EPA of 900- manufacturers
having Standard Industrial Classification (SIC) Codes between
3400 and 3999.  Since the manufacturers were selected at random,
the survey data are considered representative of the entire popu-
lation of manufacturers within those SIC Codes.

Since sufficient data are not available to determine accurately
the waste volume produced by each state, the total estimated
waste volume generated was proportionately distributed between
states based on the total number of metal finishing plants (with
more than twenty employees) in each state.  The estimated geo-
graphic distribution of waste generation is presented in Table 27
and in Figure 26.  Seven industrial states (California, Illinois,
Texas, Michigan, New York, Ohio, and Pennsylvania) generate
approximately 53 percent of the total industry waste.

 TABLE 27.  GEOGRAPHIC DISTRIBUTION OF WASTE DECREASING SOLVENTS
            GENERATED BY METAL FINISHING INDUSTRY
                       State
Million
kg/year
              1.  Alabama
              2.  Alaska
              3.  Arizona
              4.  Arkansas
              5.  California
              6.  Colorado
              7.  Connecticut
              8.  Delaware
              9.  District of Columbia
             10.  Florida
             11.  Geoi -jia
             12.  Hawaii
             13.  Idaho
             14.  Illinois
             15.  Indiana
             16.  Iowa
             17.  Kansas
             18.  Kentucky
             19.  Louisiana
             20.  Maine
             21.  Maryland
             22.  Massachusetts
             23.  Michigan
             24.  Minnesota
             25.  Mississippi
             26.  Missouri
     .5
     .1
     .3
     .5
 6.0
 0
 2.9
 3.3
59.1
 3.9
13.2
 0.
 0.
10.
 6,
 0.3
 0.7
35.4
16.5
 5.0
 4.4
 4.9
 3
 1
 4.2
17.4
32.7
 9.2
 3.4
 8.8
     .5
     .2
                                            (continued)
                                102

-------
                      TABLE 27  (continued)


27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
'.>7.
38.
39.
40.
41.
42.
^3 .
44.
45.
sr .
48!
49.
50.
51.
State
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Caroline
North Dakota
Ohio
Oklahoma
Cregr •
P'jr-Ti-yivi.nia
Rhode T
-------
              MILLIONS KGS. PER YEAR

                     0 <5
                     D 5  - 25
                     a >25
                       Figure 26.   Geographic distribution of waste  degreasing solvents
                                   generated by metal finishing plants  in the United States.
v

-------
5.3.1.1  Spray Painting [45]—
The principle of spray painting is to break up the liquid paint
composition into tiny droplets and propel them through the air
onto the surface of the merchandise to be coated.   'Owing to the
airborne solid and semisolid wastes generated by spray painting
operations, they must be performed in a confined area.  A paint
spray booth may simply be an area enclosed on three sides with
an exhaust fan and filter in an overhead hood, or it may be a
much more elaborate arrangement.  There are several methods for
atomizing the paint composition, and-a variety of spray painting
equipment is currently in use.

Air Atomization—In this method, a jet of compressed air impinges
on a stream of liquid paint which emerges from an orifice in the
tip of the spray gun.  The air jet atomizes the paint and propels
(transfers) the droplets onto the surface of the merchandise
(Figure 27).
           COMPRESSED
             AIR 	
                                               OVERSPRAY
              Figure 27.  Air atomized spray [45].

Pressure Atomization—In this method, the liquid paint is forced
through a small diverging orifice at a relatively high pressure of
about 600 psi.  The paint emerges from the orifice as a fine spray
with sufficiently high kinetic energy to propel (transfer) it
through the intervening air onto the surface of the merchandise
(Figure 28).

Electrostatic Field Assisted Spray Painting—In this method, the
atomized paint is given a polarized h:.gh-voltage electrical charge
(usually about 100,000 volts) at or r.«ar the point where it emerges
from the paint gun and the merchandise is electrically grounded to
 [45] Brewer, G. E. F.  Calculations of painting wasteloads asso-
     ciated with metal 'finishing.  Cincinnati, OH; U.S. Environ-
     mental Protection Agency; 1980 June.  85 p.  EPA-600/280-144.
     PB 80-226731.
                                105

-------
             VENT
                                           OVERSPRAY
                             PRESSURE
                             PUMP

            Figure 28.  Pressure atomized spray

the opposite polarity of the power source.  Thus,  the charged paint
particles are electrically attracted to the surface of the merchan-
dise (Figure 29).
        HIGH
       VOLTAGE
         DC
Figure 29.  Electrostatic field assisted spraying painting [45],

Centrifugal Atomization—In the most commonly used centrifugal
atomization method, liquid paint is gradually coated onto the
center inside surface of a rapidly rotating bell.  The centrifu-
gal force of the rotating bell moves the paint to the open 3nd
where it passes through an electrostatic field and emerges as a
charged, atomized spray.  As the spray emerges, the electrostatic
field directs (transfers) it to the surface of the merchandise
(Figure 30).

A common variation of the centrifugal atomization method uses a
horizontally rotating disk instead of the bell described above.
This variation has about the same transfer efficiency and provides
a wider coverage area.  In this method, the merchandise is usually
carried by a conveyor in a horseshoe-shaped loop around the disk.
                                106

-------
          Figure 30.  Centrifugal atomized spray [45].

5.3.1.2  Dip Coating [45]—
In the dip coating method,  the merchandise is actually  submerged
in a container of liquid paint and then lifted back out.   The
excess paint drips off the merchandise either directly  back into
the paint container or into a drip recovery tray.   Dip  coating of
rigid, profiled merchandise requires that each piece be submerged
individually (Figure 31).
    Figure 31.  Dip coating rigid,  profiled merchandise [45].

The drip-off process is sometimes aided by the use of a high volt-
age electrostatic field which is effective in eliminating drops of
paint that might otherwise form on the botton of the merchandise.

5.3.1.3  Flow Coating [45] —
In the flow coating method,  liquid paint is poured over the top of
the merchandise and allowed to drip off the bottom.   The merchan-
dise is positioned over a container of paint,  part of the paint is
pumped to a dispensing head over the merchandise,  the paint flows
                                107

-------
over the merchandise forming a coating,  and the excess drips back
into the container (Figure 32).
                  CONVEYOR     #
                 ^
           O
yELECTROCOATlNC
1     BATH
               ULTRAFJLTER
            X
                Figure 32.  Flow coating [45].

Drip off is sometimes aided by use of. a high voltage electro-
static field.  The expected transfer efficiency for the flov; coat-
ing method is about the same as for the dip coating method (75
percent to 90 percent).

5."3.1.4  Roll Coating  [451 —
In this method, liquid paint is applied by a transfer roll direct-
ly to the surface of the merchandise.  This method can be used to
paint any flat meterial, rigid or flexible, individual pieces or
continuous sheets, to one side or to both sides simultaneously.
The principle of roll coating is to cover the surface of the
transfer roll with liquid paint, control the amount of paint on
the surface of the transfer roll by means of a metering roll, and
then to transfer the paint from the transfer roll directly to the
surface of the merchandise by direct contact (Figure 33).

Figure 33 illustrates a typical arrangement for roll coating both
sides of a continuous sheet of material simultaneously.  In a
typical arrangement for coating only one side, the transfer and.
metering rolls on the opposite side would be replaced by a single
roll for the purpose of maintaining pressure between the transfer
roll and the material.

There are a number of variations to the typical merhM of roll
coating shown in Figure 33.  For example, a better application of
the paint to the surface of the merchandise is sometimes achieved
by reverse roll coating.  In other words, at the point of contact
between the transfer roll and the material, the transfer roll is
rotating  in the opposite direction.from the direction of travel
of the material.  This causes a wiping action at the point of
transfer-.
                                108

-------
                           CROTCH FED PAINT
                   METERING I    TRANSFER
                     ROLL   /      ROLL
                                             MERCHANDISE
                            PAN FED PAINT

                 Figure 33.  Roll coating [45].

13.3.1.5  Electrodeposition [45] —
In this method, the merchandise is submerged into a dilute,.(low
viscosity) dispersion of specially formulated nonvolatile paint
solids mixed with water.  A low-voltage (50 to 500 volts), direct
current electrostatic field is applied, which attracts the non-
volatile paint particles to the surface of the merchandise,  where
they form a highly viscous deposit.  The merchandise is then
lifted out of the electrocoating bath and subjected to several
ultrafiltrate rinse stages.  Any droplets of paint lifted out
of the bath on the newly painted surface are rinsed back into
the dip tank (Figure 34).

5.3.1.6  Powder Coating [45]--
The principle of the powder coating method is to apply a layer of
fusible powdered plastics (powder paint) to the surface of the
merchandise where it is melted and heat cured into a nonvolatile
solid film coating.  There are three principal techniques for
applying the powder paint composition to the manufactured product.

Fluidized-Bed Technique—A "fluidized bed" is achieved by instal-
ling a false bottom made from a porous material inside the paint
tank.  A thin layer of powder paint is placed on the top of the
porous material.  A controlled flow of air or an inert gas such as
.nitrogen is pumped into the tank chamber below the porous material.
The turbulence caused as the air or gas passes through the porous
material and out the top of the tank causes the particles of paint
                                109

-------
                  CONVEYOR
                       o
            ,  ELECTROCOATING
            1      BATH
               ULTRAFIITER
            t
                Figure 34.  Electrocoating [45].

powder to rise and remain suspended like dust particles in the air.
The flow rate is controlled at a point where none of the particles
is raised as high as the top of the tank.  The merchandise is pre-
heated to a temperature about the melting point of the paint pow-
der and then is dipped into the fluidized bed.  The paint powder
particles that contact the hot surface melt and form a film
coating.

Fluidized Bed Plus Electrostatic Field Technique—A shallow
"fluidized bed" is formed as described above, then the paint pow-
der particles are charged by a high voltage electrostatic field
(Figure 35)

ATR

GAS


-m_L-^m^
—
' . ', "FLUIDIZED"
• • ,' \ » , POWDER
,' - ' • ' • PAINf
_f. COMPRESSED AIR
1 OR INERT GAS

^^•™



HIGH
V/OITAPF
VULInut
r\(*
DC
          Figure 35.  Electrostatic fluidized bed [45]
                                110

-------
In this technique, the merchandise is not preheated but is elec-
trically grounded to the power source that supplies the electro-
static field.  The merchandise does not actually enter t'>e
fluidized bed, but when it passes above the surfac.e the  'larged
paint powder particles are attracted to it and form a co, ting of
powder.  The particles are retained on the surface of th.- mer-
chandise by the residual electrostatic charge.  The merchandise
is then processed into a heating chamber where the paint powder
particles melt and form a film coating.

Fluidized Spray Technique—The powder paint is fluidized by mix-
ture with air or an irert gas such as nitrogen and sprayed from a
paint gun under a very small pressure.  The paint particles are
charged by an electrostatic field at or near the point at which
they leave the spray gun and the merchandise is grounded electric-
ally to the power source that provides the field.  The paint pow-
der particles are attracted to the surface of the merchandise
where they form a powder coating (Figure 36).
       P:W:E=  PAINT
ELECTROSTATIC
 ATTRACTION
                                               HIGH
                                              VOLTAGE
                                                DC
ELECTROSTATIC
 REPELLENCY
    Figure 36.  Fluidized electrostatic powder spraying  [45].

The thickness of the powder coating on the merchandise can be pre-
determined and controlled by the strength of the electrostatic
field.  Due to the weight of the paint particles and the low pres-
sure of the operation, without the electrostatic charge they would.
settle as they emerged from the paint gun.  Even if they contacted
the surface of the merchandise they would not be retained.  When
the powder coating has reached the desired thickness, the attrac-
tion is counteracted by the residual charge in the particles
already attached and no more par icles will be retained.  This
residual charge in the particles attached to the merchandise will
also cause them to be retained on the surface while the merchan-
dise is processed to a heat chamber where they melt and form a
film coating.
                                Ill

-------
Unlike liquid paint spraying,  all the "overspray" in powder spray-
ing operations is collected in a filter chamber and reused.

5.3.1.7  Paint Curing Methods [45]—
The process by which the fresh paint composition is transformed
into a solid, wear-resistant nonvolatile film coating on the mer-
chandise is known as curing.  Most paint compositions are formu-
lated to function best when a specific curing method is used.
However, some compositions may be used under several curing
methods, or even with a combination of methods.  Curing methods
fall into the three general types described below.

Ambient Temperature Curing—The simplest method of curing is pro-
vided by those paint compositions that "dry" in an atmosphere at
or near the ambient temperature of the work area.  There are three
general classes of paint compositions that are normally cured at
ambient temperature:  (1) solvent and/or water-borne paints that'
cure through evaporation of the liquid components; (2) paints
which cure through the absorption of moisture from the atmosphere;
and (3) two component paint compositions which, when mixed, form
a polymerized film and solidify within a few minutes.  Since only
a limited time is available to apply the paint after the two com-
ponents are mixed, they are usually used in spray operations where
they are mixed in the spray gun chamber.

Bake Curing—The application of heat to accelerate the evaporation
process is the curing method most widely used by industry.  There
are a number of ways to achieve bake curing, but they all function
«-r> the principle of subjecting the painted merchandise to tempera-
ture in the range of 120°C to 175°C  (250°F to 350°F) for a period
usually about 8 to 30 minutes.  Continuous air circulation through
the baking chamber is essential to remove the organic volatile
waste and to dilute the vapors to below the explosive l°vel.

Radiation Curing—There are several  classes of liquid paint compo-
sitions that will solidify quite raptdly when exposed to radiant
energy.  Electronic beam radiation-curable paint compositions may
be applied by a variety of method? such as spray, roll, flow, dip,
etc.  After  the paint is applied, the merchandise is placed in a
chamber containing a relatively oxygen-free atmosphere (usually
less than 500 ppm) and exposed to high energy electron beams
(p-rays).  When the (J-rays impinge on the liquid paint components,
a chemical reaction is initiated which causes them to solidify
into a  solid  tilm coating.  Paints in this class are used where a
comparatively -chick film coating is  required on a flat surface.

Ultraviolet  ray-curable paint compositions are used where  a com-
paratively thin film coating is required on virtually flat sar-
faces,  therefore, they are generally applied to the merchandise
by the  roll  coating aethod.  The  freshly-coated merchandise is
then passed  within a few .\nches of one or more ultraviolet lamps
(usually mercury vapcr tubes) which  emit 315 to 400 nanometer
waves.

                                112

-------
5.3.2  Raw Materials

5.3.2.1  Composition--
Surface coatings consume  more than 600 chemicals and chemical in-
termediates, a greater number and variety than in ar.y other seg-
ment of the chemical  industry.   Figure 37 presents typical lists
of the various chemical raw materials used in surface coatings
[8].  In I960, surface coatings consumed an estimated 4.3 billion
kilograms of raw materials,  excluding water [9].  Over 2.3 billion
kilograms were resins and pigments,  the part of the coating that
ends up on the coated product [9].

Paint is a dispersion of  pigment in a liquid "vehicle."  The
vehicle consists of  a volatile solvent and a nonvolatile portion
called the binder.   Organic solvents or water may be used as the
former and resins  or oils function as a binder.

Surface coatings consist  of four basic components:  film formers,
pigments, solvents,  and additives.  These components are discussed
below.
                                                        U«iJ-12.:2	U
                                                        .  >."	ft i
                                                 - "  I   p-...-.I .^-••..   ,1
                                                 C5.-«t: "I  I*"** of'"'"«    H~
                                                ••.ji»:i  I  r--i'<*c • i* -  »»•
                                                    Reproduced from     ,
                                                    best available copv. \*^
       Figure 37.   Raw materials flow diagram  for  the  paint
                   and allied products industry  [8].
                                 113

-------
Film Formers—Film formers consist of synthetic resins (alkyd,
vinyl,  acrylic, epoxy,  urethane,  cellulosic,  etc.).  drying oils
(linseed oil,  tall oil, tung oil,  castor oil, etc.),  and natural
resins (resin, shellac, etc.).  These materials form the protec-
tive film of the surface coating and, hence,  they are the backbone
of the protective coating.

The surface coating industry classifies the surface coatings by
the chemical type of the film former (alkyd paint, acrylic
lacquer., etc.) [8].

     Resins are the usual binders which contribute to the dur-
     ability,  adhesion, flexibility, and gloss of coatings.
     They may be purchased either as solutions or as solids and
     fall into three general classes:  (1) those used in lac-
     quers which dry purely by the evaporation of solvent
     (cellulose derivatives, acrylic, vinyl,  and bituminous
     resins);   (2) those which dry by a chemical reaction with
     air (alkyds) or moisture (urethanes); and (3) those which
     dry (or set) at high temperature (phenolics and others)
     [46].  Many coatings involve blends of more than one type
     of resin, and the division between classes is not always
     sharp.  Table 28 shows resins used by the United States
     paint industry [46].

     Plasticizers - Many of the resins used by the coating in-
     dustry, such as cellulose nitrate, many phenolics, vinyls, •
     and others, are,  by themselves, too brittle to have ade-
     quate adhesion or exterior durability.  For that reason,
     they are usually mixed with plasticizers, a procedure
     which will yield flexible films.  The plasticizers are
     relatively soft materials which resist oxidation on ex-
     posure and provide continuing compatibility with the
     resin so  it will remain plasticized.  One must be selected
     which will not come off the film at high temperatures.
     Some of the common plasticizers, are esters, such as cas-
     tor oil,   or polymerized oils.  Alkyds made with nondrying
     oils are often used to plasticize urea resins [46].

     Oils - Traditionally, before the present resins were devel-
     oped, drying oils—primarily linseed with lesser amounts of
     soybean,   tung, oiticica, perilla, and dehydrated castor—
 [46] Scofield, F.; Levin, J.; Beeland, G.; and Larid, T.  Assess-
     ment of industrial hazardous waste practices, paint and
     allied products industry, contract solvent reclaiming opera-
     tions and factory application of coatings.  Washington, DC;
     U.S. Environmental Protection Agency; 1975 September.  304 p.
     EPA 1530/SW-119C.  PB 251 669.


                                114

-------
          TABLE 28.   RESINS USED BY PAINT  INDUSTRY [46]
 Resins for solvent-thinned v^hirles

 Acrylic, lacquer type
 Acrylic, thermo-setting type
 Alkyds
 Cellulose acetate
 Cellulose butyrate
 Cellulose nitrate
 Epoxy resins
 Epoxy ester resins
 Ethyl cellulose
 Hydrocarbon resins
 Maleic resins
 Phenolic resins, pure
 Polyurethane resins
 Silicone resins
 Urea and melamine formaldehyde  resins
 Vinyl (formal and butyral) *cetal resins
 Vinyl acetate solution-type copolymers
Water emulsions

Acrylic emulsions
Casein
Polyvinyl acetate emulsions
Polyvinyl chloride emulsions
Styrene-butadiene emulsions
Other emulsions

Water-soluble  resins

Water-soluble  oil and alkyd types
Other water-soluble types

Miscellaneous

Asphalt and coal-tar pitch
Chlorinated paraffins
Natural resins (Manila,  Dammar,
  Copal, etc.)
Shellac
Waxes
Other miscellaneous resins and
  polymers
     were  used as paint vehicles, either by themselves  or
     cooked with natural  resins as varnishes.   The newer
     resins,  some of which (particularly alkyds) incorporate
     some  of these oils,  have largely replaced the straight
     oils  due to cost advantages.  A few nondrying oils,
     such  as coconut and  cottonseed, are used in small  amounts,
     usually in alkyds.   Various oils used in paints are  given
     in Table 29 [46].

Pic/rents—Pigments are, in general, finely divided, insoluble,
organic (phthalocyanine,  azo, and nonazo pigments, etc.)  and in-
organic (titanium dioxide,  zinc-oxide,  carbon black, etc.)  powders
which contribute color, opacity, consistency,  and durability to
paint  [40].  They may be  described as white,  transparrent,  colored,
and metallic.  However, they are also used for fillers, reinforcers,
corrosion  inhibitors, and mildew control.   The pigment  section of
the NPCA Raw Materials Index lists several thousand different mate-
rials, but many of these  differ only slightly in color, particle
size, or surface treatment.   There are  probably five hundred dif-
ferent pigments available to the paint  industry, many of  which are
used in only very small amounts for specialty products.   The amount
                                  115

-------
                  TABLE 29.  .OILS  USED BY PAINT
                             INDUSTRY [46]
                     Oils

                     Castor oil,  raw
                     Castor oil,  dehydrated
                     Tung oil
                     Coconut oil
                     Linseed oil
                     Safflower oil
                     Soybean
                     Fish oil
                     Cottonseed oil

                     Fatty acids

                     Coconut
                     Linseed
                     Soybean
                     Tall oil
                     Other fatty acids
of pure pigments required can be reduced by the use of cheaper
matetials which are classified as extenders.  These include cal-
cium carbonate and talc.  Table 30 lists the major pigments used
in paints and coatings [46].

Solvents--Solvents are used to reduce the viscosity of the sur-
face coating for easier handling and application.  They influence
setting rate, drying time, flow properties, and flammability.  The
solvents used are either petroleum derivatives (hydrocarbons, oxy-
genated hydrocarbons, chlorinated hydrocarbons, etc.) or water [8].

The primary function of solvents used in coatings is to adjust
the viscosity for easy application.  Since the solvent does not
form a part of the final film and contributes little to the prop-
erties of that film, the cheapest material which will dissolve
the resin and will evaporate at the desired rate is usually
chosen.  A major consideration in the choice of solvents is air
pollution control regulations.  If a mixture of solvents is used,
they should be chosen so that any change of solvency due to the
lower boiling solvent coming off first will not have an adverse
effect on the performance of the coating.  Other things being
equal, a petroleum fraction of suitable boiling range—mineral
spirits, VM&P naphtha, textile spirits, etc.,—is used.  When
these will not dissolve the resin, aromatic solvents, such as
toluene or xylene, esters (ethyl acetate, etc.) or ketones
(methyl ethyl ketone, etc.) are employed.  A few alcohol-soluble
resins, such as shellac, are dissolved in ethanol or isopropancl.


                                116

-------
   TABLE 30.  PIGMENTS  USED BY  THE PAINT INDUSTRY  [46]
Greens
  Chrome green3
  Chromium oxide and hydrated
    chromiiua oxide
  Phthalocyanine green
  Pigment green B

Reds and Maroons-inorganic

Reds and Maroons-organic
  B. O. N. maroon
  Chlorinated para reds
  Lithol red and rubine
  Other organic reds and maroons

Flushed Colors

Aqueous Dispersions
  Hans a yellow
  Iron oxides
  Phthalocyanine blue3
  Phthalocyanine green3
  Toiuidine red
  Other aqueous dispersions
  Other pigment dispersions

Metallic
  Alominum pastes
  Aijminun> powaer
  Bron2e powders
  Copper powders3
  Other metalx!'? flakes
Iron oxides
  Synthetic iron oxides (reds)
  Synthetic iron oxides (yellows)
  Synthetic iron oxides (other)  -
  Natural iron oxides
  Ochres, siennas,  and umbers

Extenders
  Calcium carbonate - precipitated
  Calcium carbonate - natural
  Magnesium silicate (talcs)
  Barytes - natural
  Diatomaceous earths
  Kaolin (calcined  and other
    clays)
  Mica,  dry ana water-ground
  Silicas, ground
  Other extender pigments
Whites
  Antimony oxide
  Lithopone
  Titanium dioxide, pure
     (usually 50% Ti02)
Zinc oxide, leaded
Zinc oxide (pure)
Other white pigments

Blacks
  Carbon black
  Lamp black
  Other black pigments
     (except black iron
    oxide)

Yellows & Oranges-inorganic
  C.P. cadmium oranges
    and reds
  Cadmium lithogone
  Chrcme yellow
  Molybdate orange
  Strontium chromate"
  Zinc chromate
  Other inorganic yellow
    and organge pigments
  Organic yellows and
    oranges

Blues and Violets
  Iron blue (Milon-Chinese-
    Prussian
  Ultramarine blue
  Other inorganic blues and
    violets
  Pht'ialocyanine blue0
  Other organic blues and
    violets

Miscellaneous
  Cuprous oxide
  Fluorescent pigments
  Zinc dust
  Other miscellaneous
    pigments

Lead
  Basic lead  carbonate
  Basic white lead silicate
  Red leada
  Other lead  pigments
a.
 Indicates hazardous  materials.
^Except iron oxide -
                               117

-------
Water is increasingly used for water-soluble  resins and to thin
emulsions.   Small  amounts of other'solvents  are used in paint and
varnish removers,  spirit stains, and other miscellaneous materi-
als.  Solvent  usage in the paint industry  is  summarized in Table 31
[46].

         TABLE 31.   SOLVENTS USED BY PAINT INDUSTRY [46]
    Aliphatic hydrocarbons
     Mineral spirits, regular and
       low odor
     Mineral spirits, odorless
     Kerosene
     Mineral spirits, heavy
     Other aliphatic hydrocarbons

    Aromatic and naphthcnic hydrocarbons
     Benzene
     Toluene
     Xylene
     Naphtha, high flash
     Other aromatic hydrocarbons
Terpenic hydrocarbons
  (Pine oil and turpentine)

Ketones3
  Acetone
  Methyl ethyl ketone (MEK)
  Methyl isobutyl ketone (MIBK)
  Other ketones

Esters
  Ethyl acetate
  Isopropyl acetate
  Normal butyl acetate
  Other ester
     Indicates hazardous material.

Additives—Additives are used to  facilitate production and  to im-
prove  the  application and performance properties of the coating
system.  Additives consist of surface agents, driers, thickeners,
flow modifiers,  anti-skinning agents,  fungicides, flame retardants,
etc.  [8].

A wide variety of materials  is  added to many paint formulations
in  small amounts for specific purposes.  Driers are used  to ac-
celerate the  oxidation (or drying)  of drying oils and alkyd
resins.  They are organic soaps of  cobalt, lead, manganese,  or
other  metals.   The organic portion  confers solubility in  the
organic solvents used but otherwise does not appear to affect
the catalyst  properties, which  are  determined by the metal.   A
few nonmetallic materials are also  used as driers [46].

Anti-skinning agents are the reverse of driers in that they delay
the drying of oils or alkyds in the can with the formation  of a
"skin."  They are usually volatile, so that they evaporate  rapid-
ly  after the  coating is applied [46].

Various mercury compounds have  historically been used as  preserva-
tives  and  fungicides.  Water-thinned paints are, for various rea-
sons,  excellent food for many bacteria.  Without a preservative,
                                  118

-------
many of those paints will decay in the can.  Both water-  and
solvent-thinned paints are susceptible, after  application,  to an
assortment of fungi,  ?hich are czten called,mildew  although there
is some doubt about this nomenclature.  Mercury  is  effective both
as a bactericide and a fungi^ic'e.  For that reason  it is  preferred
by paint manufacture!j.  ..1 though a wi-"*- variety of nonmercurial
bactericides an • fungiciue? are  *vaila.ble, they  rarely perform
both functions, and their durability or -.svosure hiis been found
to be poor compared to that of mercury compounds [4>'l.

A wide variety of mecerlals, genially classified as surface-
active agents, ere ased to adjust tha nixing an,? dispersiryj of
pigments, consistency of the paint, Rcr.f "•.ing pronert: 2-2.
application, and flow and leveling of the  J.r..3iied coating.
are often proprietary compounds whose composi£.?.-". i-~. uo*.  ot
The proper use of these materials is more  an ar\. \j:«u r «c:..-r;-".
c.nd often small amounts of several may be  t-sed in the "at^ form
lation [46].
                    \
Miscellaneous materials used as additives  in paints dnd surface
coatings are listed in Table 32

            TABLE 32.  MISCELLANEOUS MATERIALS ADDED
                       TO SURFACE COATINGS [*6]
              Anti-skinning  agents

              Metallic  soaps

                Aluminum  stearate
                Zinc  stearate
                Calcium stearate
                Other metallic  soaps

              Bodying agents, solvent systems
                (other  than  above)

              Bodying agents, water systems

                Carboxymethyl cellulose (C.M.C.)
                Hydroxethyl  cellulose
                Methyl  cellulose
                Others

              Dispersing  and mixing aids
                                           (continued)
               alndicates  potentially hazardous
               materials.


                                 119

-------
                       TABLE 32 (continued)
              Driers

                Calcium soaps
                Cobalt soaps
                Lead soaps
                Manganese soaps
                Zirconium soaps
                Other driers

              Fungicides, Germicides,  and Mildewcides

                Phenols,  halogenated phenols,  and
                  their salts
                Phenyl mercuric acetate
                Phenyl mercuric oleate
                Others


              alndicates potentially hazardous
               materials.

5.3.2.2  Classification—
Product coatings are classified as one of three basic types:
(1) solvent-borne, (2) water-borne,  or (3) powder coatings.

Solvent-Borne--Solvent-borne coatings may be subdivided into con-
ventional solvent-based coatings (composition <70 percent solids)
and high solids coatings (>70 percent solids) [9].  The three
types of solvent-based coatings used in industry are paints, en-
amels, and lacquers.  Paints are highly pigmented drying oils
diluted with a low-solvency-power solvent known as thinner.  Ap-
plied paints dry and cure in the oven by evaporation of the thin-
ner and by oxidation during which the drying oil polymerizes to
form a resinous film.  Enamels are similar to paints in that they
cure by polymerization.  Many coatings contain no drying oils but
cure by chemical reaction when exposed to heat.  Applied lacquers
are dried by evaporation of the solvent to form the coating film.

The amounts and types of solvents and thinners used in surface
coating composition varies.  The solvents used in enamels,  lac-
quers, and varnishes are aromatic hydrocarbons, alcohols,  ketones,
ethers, and esters.  The thinners ustfQ in points, enamels,  and
varnishes are aliphatic hydrocarbons,  mineral spirits, naphtha,
and turpentine [10].

High solids coatings contain a solid composition up to 70-80 per-
cent by volume.  The remaining organic solvent portion is neces-
sary for proper application and curing.
                                120

-------
Use of conventional solvent-based coatings for metal product
coatings is declining because high solids coating formulations
can more readily comply with current air pollution regulations
limiting solvent emissions [9].

Water-Borne [47]~-The term water-borne refers to any coating
which uses water as the primary carrier combined with organic
solvent and is differentiated from pure organic solvent-borne
paints.  There are basically three types of water-borne coatings:
latex or emulsion paints, partially solubilized dispersions, and
water-soluble coatings.  Table 33 lists the properties of these
three types of paints.  Most current interest in centered around
the partially solubilized dispersions and emulsions.  Emulsions
are of particular interest because they can build relatively
thick filrnr without blistering and they contain no noxious amine
solubilizers.

       TABLE 33.  PROPERTIES OF WATER-BORNE COATINGS [47]

Properties
Molecular weight
Viscosity


Viscosity control


Solids content
Gloss
Chemical resistance

Exterior durability
Impact resistance
Strain resistance
Color retention on
oven bake
Reducer

Wash-up

Latex or
emulsion paints
Up to 1 million
Low - not depend-
ent on molecular
weight
Require thickness


High
Low
Excellent

Excellent
Excellent
Excellent
Excellent

Water

Difficult

Partially
solubilized
dispersions
50,000 to 200,000
Somewhat depend-
ent on molecu-
lar weight
Thickened by
addition of
co-solvent
Medium
Medium
Good to
excellent
Excellent
Excellent
Good
Good to
excellent
Water

Moderately
difficult
Water-soluble
coatings
20,000 to 50,000
Very dependent on
molecular weight
,
Governed by molec-
ular weight and
solvent control
Low
High
Fair to good

Very good
Good to excellent
Fair to good
Fair to good

Water or solvent/
water mix
Easy


 [47] Surface coating of metal furniture - background information
     for proposed standards.  Research Triangle Park, NC; U.S.
     Environmental Protection Agency; 1980 September.  406 p.
     EPA-450/3-80-007a.  PB 82-113938.
                                121

-------
Most of the solubilized water-born paints are based on alkyd or
polyester resins.  Table 34 shows the solids and water content of
several types of water-borne paints.


TABLF 34.  SOLIDS AND SOLVENT CONTENT OF WATER-BORNE PAINTS  [47]


                                 Solids contentWater to
      Waterborne paint system    volume percent  solvent ratio
High solids polyester
Coil-coating polyester
High solids alkyd
Short oil alkyd
Water reducible polyester
Water reducible alkyd
High solids water reducible
conversion varnish
80
51
80
34
48
29

80
80/20
51/49
80/20
34/66
82/18
67/33

90/10
 A common  method  of  solubilizing  is to incorporate carboxyl-
 containing  materials  siich  as maleic  anhydride and acrylic acid
 into  the  polymer.   The  acids are then "solubilized" with low
 molecular weight amines such as  triethylamine.  After app]ication,
 the coatings  are baked  and the water, solvent, and amine evaporate
 leaving a pigment film  on  the object.

 The use of  water-borne  coatings  can "reduce  the explosion problem
 associated  with  organic solvent-based paints.  Some organic sol-
 vents are used,  but the amount used  is  greatly reduced.  Water-
 borne coatings have the additional value  of reducing the amount
 of air flow needed  from the application areas and curing ovens
 and can reduce energy consumption.

 In organic  solvent-based paints, relatively few monomers can be
 used  because  of  solubility and viscosity.   Molecular weights are
 especially  restricted.   In water-borne  coatings, the selection
'of usable monomers  is much wider.  In addition, water-borne
 paints can  contain  a  higher solids content  than organic solvent-
 based coatings without  an  increase in viscosity.  An additional
 advantage of  water-borne paint systems  can  usually be cleaned
 with  water  whereas  organic solvent-based  systems require solvents
 for cleaning.  Organic  solvent may be needed for cleanup of water-
 borne systems if the  paint has dried.        *

 Summaries of  the advantages and  disadvantages of water-borne
 paints are  present  .in Tables 35  and  36.   The use of these coatings
 in the metal  finishing  industries is limited at present; however,
 it is expected to increase.
                                 122

-------
       TABLE 35.   ADVANTAGES  OF WATER-BORNE COATINGS  [47]



    1.   Reduction of fire or  explosion potential  and  toxicity
        in both the storage and application areas.

    2.   Greater van..  " •: ~. "'"liable monomers.

    3.   Higher solids  ci       -ossible at same  viscosity.

    4.   Lower raw material   ^.z (e.g.,  water vs.  solvent).

    5.   Ease of clean-up.

    6.   Good selection of colors.

    7.   Good quality finish.

    8.   Can be formulated for metallics.

    9.   Rapid color changes possible.
      TABLE 36.   DISADVANTAGES OF WATER-BORNE COATINGS [47]



    1.  Protection of equipment against rust needed.

    2.  More pretreatment may be required than for organic
       ..solvent-based paint.

    3.  Longer flash-off may be required.

    4.  Humidity control equipment may be necessary.

    5.  Possible emission of amines to the atmosphere.

    6.  "Faraday effect" is a problem for certain shapes.

    7.  Metallic finishes from organic solvent-based costings
        have not been matched with other waterborne coatings.
Powder Coatings—Powder paint compositions have characteristic
differences from liquid paint compositions.  A bulk volume of
liquid paint composition contains a specific volume percentage of
nonvolatile solids,  with the balance being volatile liquids.  A
bulk volume of powder paint composition contains only about 50
volume percent of nonvolatile solids,  with the balance being air.
Powder paint compositions "as bought"  have a bulk volume density
weight in the range of 0.6 to 0184 kg/L (5 to 7 Ib/gal); however,
when the powder is melted into a nonvolatile solid, the solid
density is in the range of 1.2 to 1.8  kg/L (10 to 15 Ib/gal) [45].

Before powder can be applied as a coating, part size, part ma^s,
part shape, paint thickness, color changing and matching,  and
"Faraday Effect" are the most important evaluations to be made.


                                123

-------
Chemical compositions of powder coatings used in surface coating
industries consist of synthetic resins,  pigments,  solid-additives,
and from 0 to 10 percent entrapped volatiles. .The film -formers
are the synthetic resins (alkyd, vinyl,  acrylic, epoxy. urethane,
etc.)-  The surface coating industry classifies surface coatings
by the resin type (e.g., alkyd paint, vinyl paint, etc.).  Pig-
ments consist of both inorganic and organic compounds which are
used for color and opacity.  Additives are used to aid in produc-
tion and improve application and performance properties of the
film former (47].

There are two general synthetic resin types of pow'der coatings:
thermoset and thermoplastic types.  Thermosetting powders harden
during heating inside a bar.e oven as a result of cross-linking or
polymerizing of the resin.  Thermoplastic powders soften with the
application of heat and r< solidify during cooling.  Table 37 lists
the powder coatings groups.' by synthetic resins.  Thermosetting
and thermoplastic coatings are usually applied by electrostatic
spray and fluidized bed, respectively.  Most thermoplastic coat-
ings require a solvent or powder primer before the coating can be
applied.  The most widely applied thermosets in the metal finish-
ing industry are epoxies and polyesters.  There materials provide
a tough, chemical and abrasive resistant coating which achieves
excellent adhesion to almost any metallic substrate.  Several of
the thermoplastics listed in Table 37 are being applied succeas-
fully to metal products.  Most of the thermoplastics are applied
to thick films for wear resistance [47].

           TABLE 37.  POWDER COATING RESIN GROUPS [47]


       Thermosetting	Thermopl as tics	

       Epoxy            Polyvinyl chloride or "vinyl"
       Polyester        Polyethylene
       Acrylic          Cellulose acetate butyrate (CAB)
                        Nylon
                        Polyester
                        Acrylic
                        Cellulose acetate propionate (CAP)
                        Fluoroplastics
Both powder coating types offer several advantages and disadvan-
tages  (Table 38) when compared to solvent-based coatings.

5.3.3  Waste Coaiinq Description

Fac'..
-------
                   TABLE  38.    COMPARISON  OF POWDER  COATINGS  TO SOLVENT-BASED COATINGS  (47]
to
ui
                                	  _ Advantages
 1.   Provides  toughei more abrasive resistant finish

 2.   Fewer rejects  and sags

 3.   Lower energy consumption.

 4.   Production rates can sometimes be increased.

 5.   Less metal products are damaged during packing and shipping
     because coating is more abrasive resistant.

 6.   Eliminates OSHA requirements foi solvents.

 7.   Usually no final refinishing required.

 8.   Less metallic  preparation for parts to be coated.

 0.   Preferred for  wire-type parts.

10.   Superior  for tubular parts.

11.   No additional  solvents for controlling viscosity or cleaning
     equipment required to be purchased or stored at facility.

12.   Less powder required to co^er same surface area at same coating
     thickness.

13.   Good coatings  for electrical insulation and ambient temperature
     variations.

14.   Significant reduction of VOC emissions

15.   No primer required for thermosets and some thermoplastics.

16.   Problems  associated with watei uungc .>rr rrilucfd 01 i;l Imin.ttcd.

17.   In many opplic.itions powder ran be rerlaimod and reused, provulinq
     higher powder  utilization efficiency than transfer effiri
     achieved  with  conventional solvent-based coatings
                                                                                      	  Disadvantages
 I.   Coloi  changes  require  that appii-
     c.it ion area  and powdei  r'-covery
     system be  thotoughly cleaned.

 2.   T.ipped holes in parts  require
     masking.

 3.   Almobl all thermoplastics pres-
     ently  tequire  an organic or powder
     piimer.

 4.   Certain shapes cannot  be electro-^
     statically.coated because of the
     "Faraday Effect."

 5.   Difficult  to coat small numbers of
     parts.

 6.   Powders are  explosive,  but minimum
     ignition temperature of powders is
     higher than  for organic solvents.

 7.   High capital costs  for  manufac-
     turing and application  equipment
     for  powder coatings.

 8.   Electrostatic  gun hoses may plug
     frequently.

 9.   Difficult  to touch-up  complex
     surfaces

10.   Metallic and some other types of
     finishes available  from otgnnic
     tiolvrnl-bauctl  conlliicju  have not
     been duplicated commercially in
     available  powder coatings.

-------
sludge.  Factors affecting quantity and composition of wastes are
described in the following subsections along with an estimation
"of the quantity of waste generated by the industry and its geo-
graphic distribution.

5.3.3.1  Waste As a Function of Application Method--         ^ ..
Generally some paint loss is expected during transfer of a pa'int
composition from Lts- container to the surface of the merchandise
[48].  Losses will generally occur regardless of the degree of
sophistication of the methods of application and equipment used.
These  are so-called  "unavoidable losses" since they are inherent
to the method of application and equipment used for the painting
operation.  The method of application may be dictated by the size
and shape of the article ,-ieing coated, the type of coating and
the curing conditions required [46].

The total amount of  "unavoidable losses" represents the differ-
ence of the volume of nonvolatile solids in the paint used in the
operation and the volume of nonvolatile solids in the film coating
on the finished merchandise.  For planning and calculation pur-
poses, this is usually expressed as "percent expected transfer
efficiency" (% exp.t.e.).

However, a single distinct % exp.t.e. cannot be established for
each painting method.  "Unavoidable losses" for each method will
vary with the peculiarities of the specific operation.  For exr
ample, there are more overspray losses when painting small irreg-
ular pieces of merchandise than when painting large flat surfaces;
there  are more clean-up losses if the operation requires frequent
changeover or shutdown; etc.  The range of % exp.t.e. is presented
in Table 39, followed by brief description of waste volume gener-
ated by various application methods.

The loss from spray  application will run from 10 to 70 percent
of the total coating applied, depending on shape and size of the
article being coated and equipment used, with the majority of
such wastes falling  in the range of 40 to 60 percent [46],

Other  application methods generate considerably smaller amounts
of wastes since nearly no paint is wasted, and all excess paint
is captured and suitable for reuse.  Most wastes result from equip-
ment cleanup following a change of color or coatings.  Thus, the
losses from these applications are a function of the frequency
with which such changes are made and are not related to the amount
of coating used.  In general, each cleanup of roll and powder
equipment results in very little waste, but changes may be made
fairly frequently [46],  The amount of total wastes from roll
 [48]  Calculations  of painting wasteloads associated with metal
      finishing.  Cincinnati, OH; U.S. Environmental Protection
      Agency;  1980.  EPA-600/2-80-144.
                                 126

-------
          TABLE 39.   EXPECTED TRANSFER EFFICIENCY  [48]
  	Painting Method	Percent expected transfer efficiency
  Air atomized, conventional                   43.a 50,  ,  30-60C
  Air atomized, electrostatic                  87,a 68-87
  Pressure atomized, conventional              65-706
  Pressure atomized, electrostatic             85-90f
  Centrifugally atomized, electrostatic         93,a 85-95
  Dip, flow, and curtain coating               75-90.
  Roll coating                               90-98,f 96-989
  Electrocoating                              90-96,  99,
  Powder coatings                             50-80,  98,  90-991

  aE. P. Miller, Ransburg Co., SHE Paper, FC73-553.
   J. A. Antonelli, du Pont Co., SHE Paper, FC74-654.
   J. A. Antonelli, du Pont Co., "depending upon requirement and  shape of
   merchandise"  (direct communication).
  ^. P. Miller, Ransburg Co., "depending upon object being coated" (direct
   communication).
   W. H. Cobbs,  Jr., Nordson  Corp., (direct communication).
   F. Scofield,  Wapora, Inc., EPA Contract 68-01-2656.
  %. Wismer,  PPC  Industries, (direct communication).
   S. B. Levinson,  D. Litter  L'-\b.. Journal of Painting Technology, pp. 35-56.
   July 1972.
  XT. W. Seitz,  Sherwin-Williams Co.. "newer reuse  methods" (direct
   communication).
coating  varies  from two percent to 10 percent of the weight of
purchased coating  material  [46).  However,  this  waste includes
cleaning solvents  and other contaminants in addition to paint
wastes.
In dip coating,  any paint which drains  from articles which have
been coated flows  back to the dip tank  for reuse.   However,  this
process  and electrocoating  will generate much larger amounts of
cleaning wastes  at the end  of a run than roll and powder equip-
ment, but the runs are usually much longer [46].
In many  plants,  the coating material  in the dye  tanks is drummed
at the end of a production  run and stored for reuse when that type
and color of coating is  rtquired again.   This means wastes are
generated only  from the  cleaning of tanks  and hangers  [46].

                                   127

-------
5.3.3.2  Waste as Function of Materials Coated [4tQ—
Waste quantities are principally a function of application method
and the physical shape of the object being coated.' A range of
"application methods are used for most substrates, the nature of
which is only one of a number of factors considered when the
application method and coating are chosen.  No correlation is
evident between the quantity of waste generated and materials
coated.

5.3.3.3  Waste Composition—
Waste composition is largely a function of the type of coating
used.  As discussed in Section 5.3.2, surface coatings consist of
four basic components:  film formers (recins or oils), pigments,
solvents (organic or water), and additives.  Wastes consist prim-
arily of these four basic components since there are no chemical
changes occurring in surface coating operations.

Raw waste coatings composition data obtained from the state envi-
ronmental regulatory agencies are presented in Appendix C.  Also
waste source is identified wherever it is known.  Each composition
listed is that of a specific waste stream generated by a specific
firm, and is provided to serve as an example of wastes generated
by the surface coating industry.  Waste composition will vary from
company to company.  Examination of Jata indicates a waste paint
sludge *nay have high concentrations of organic solvents, resins,
and heavy metals.  Waste paint sludge may or may not be a hazard-
ous waste depending on its composition.  Disposal practice will
depend on whether waste is hazardous or noahazardous.  Resource
Conservation and Recovery Act (RCRA) testing will be required to
classify a waste paint sludge as hazardous or nonhazardous.  Also
it might be economical to recover organic solvents from solvent
based waste paint depending on solvent concentrations.  Various
paint reclamation techniques and recycle/reuse/disposal alterna-
tives along with economic aspects are discussed  in Section 6.

5.3.3.4  Geographic Distribution—
Insufficient information was found in the literature, state envi-
ronmental regulatory agencies offices, and industry to provide
accurate clata on the quantities of waste generated by the  appli-
cation of coatings in the metal finishing industry.  Approximately
60 percent of the coatings are spray applied.  The waste from this
process constitutes approximately 90 percent of  the total  industry
waste.  Other methods of application account for the remaining  10
percent of waste generated  [48].

On the average, an estimated 20 percent of the total coating ap-
plied become waste due to overspray, drip-off, and spillage  [45].
As reported in Section 5.3.2, in 1980 an estimated 101 million
dry gallons of coatings were used by the metal finishing industry.
Based on this, in 1980 total coating wastes from all  factory-
applied coating operations in the metal finishing  industry are
estimated to be 20 million dry gallons annually.


                                128

-------
Since insufficient data are available to accurately determine
waste volume produced by each state, the total estimated industry
waste volume is proportionately distributed between states ac-
cording to the total nurber of metal finishing plants (with roc'/re
.than twenty employees) in each state.  The geographic distriba-
tion of wastes is presented in Table 40, and Figure 38.  Seve.-n
industrial states (California, Illinois, Texas, Michigan, Ne«
York, Ohio, and Pennsylvania) generate approximately 53 percent
of the total industry waste.

      TABLE 40.  GEOGRAPHIC DISTRIBUTION OF COSTING WASTES
                 GENERATED BY METAL FINISHING INDUSTRY


1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.

State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
District of Columbia
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico

Million
dry liters/
year
0.973
0
0.477
0.534
9.576
C.636
2.127
0.070
0.019
1 . 673
1.C48
O.J49
0.106
' * 5.730
2.672
0.814
0.712
0.795
0.568
0.201
0.681
2.812
5.261
1.495
0.549
1.416
0.057
0.333
0.037
0.382
3.384
0.117
(continued)
                                 129

-------
          TABLE 40 (continued)
                                Million
                              dry liters/
	State	year, '

33.  New York                    5.640'
34.  North Carolina              1.646
35.  North Dakota                0.061
36.  Ohio                        5.564
37.  Oklahoma                    0.825
38.  Oregon                      0.704
39.  Pennsylvania                4.603
40.  Rhode Island                0.874
41.  South Carolina              0.556
42.  South Dakota                0.080
43.  Tennessee                   1.340
44.  Texas                       3.728
45.  Utah                        0.310
46.  Vermont                     0.144
47.  Virginia                    0.825
48.  Washington                  0.825
49.  West Virginia               0.307
50.  Wisconsin                   2.271
51.  Wyoming                     0.019
                   130

-------
MILLIONS DRY LITERS PER YEAR
       G  <2.0
       D  2.0  - 5.0
       n  >5.o
                                              I
         Figure 38.  Geographical distribution of coating wastes generated
                     by metal finishing plants in the United States.

-------
                            SECTION 6

        IDENTIFICATION OF BYPRODUCT UTILIZATION SCHEMES


6.1  DISPOSAL AND RECLAMATION OF EMULSIFIED OILS

The disposal, recycling, or reclamation of emulsified oils used
in metalworking operations are heavily influenced by environmen-
tal regulations and economic considerations.  Oil and other con-
taminants are usually separated from water to meet regulations
governing the discharge of water into the environment.  Wastewater
discharge regulations limit the concentration of oil discharged to
a surface stream to 5-15 mg/L, provided the oil is not floating or
visible.

Since most emulsified oils used in metalworking typically contain
less than 10 percent of oil, separation of oil for reuse is not
economical, and many machining operations tend to extend the life
of the metalworking fluids for as long as possible.

The most common technologies employed in recycling include grav-
ity separation and skimming, centrifuging, filtration, and water
coalescing [49].  Recycling equipment can be associated either
with individual machines or through central systems.  Since water
and solids are the two most common contaminants, these physical
recycling technologies offer low cost methods for recycling large
quantities of low or medium quality oils.

Handling spent metalworking fluids is an expense for the owners
of machining operations.  When the fluid becomes spent and is no
longer usable, owners must pay a contractor t^> have the spent
fluid hauled away.  In some cases, where the volume of spent
fluids generated is small, the cost to have a contractor haul
away metalworking fluid as it becomes spent is exorbitant.  In
these cases, typical of small machining operations, the spent
fluids are temporarily stored in tanks or lagoons.  The spent
fluids are then hauled away on an intermittent basis, with stor-
age costs adding to disposal costs.  Less scrupulous firms may
simply dump the spent fluids down the drain.
 [49] Making recycling work for you through proper process selec-
     tion.  Fluid and Lubricant Ideas.  10-13, 1979 Summer.
                                132

-------
In many operations,  the spent emulsified oil becomes incorporated
into oily wastewater,  either intentionally or unintentionally.
When the volume  of oily wastewater generated exceeds about
200 gallons per  day,  it becomes economical for 'the machining
operation to  maintain its own wastewater treatment plant rather
than pay a contractor to haul away the  oily wastev/ater. ^

Figure 39 is  a-diagram of the steps  involved in fluid reclaiming.
Reclaimers and refiners charge on a  sliding scale for oil waste
pick-up.  The scale depends upon:  (1)  percent oil, (2) percent
bottom sediment  and waste, (3) the distance the waste must be
hauled,  (4) the  size of the generator,  (5) how the generator has
been doing business with a reclaimer or rerefiner, (6) how wf»ll
the personalities involved get along,  (7) how much the generator
wants to get  rid of the waste (most  reclaimers will not handle
over the legal limit for PCBs), and  (8) how much the reclaimer
or rerefiner  wants that particular batch of oil.  Many large cases
are handled on a bid basis only  [50].
                            Fluid Reclaiming


                               Spent Fluid
            Dunped               SJtinasad         Sold to Reclaimer

      I          i            |              i                  i
   Dviiped   Sisplo emulsion   Fortified   <   Concentrated       Sold to Reclaimer
            brolcon        enulsion     •     using
                         broken        Ultrafiltratiou
                     Heclaixsar

                   Buy* and breaks to 95% oil - soils ox further processes
                         I
                   Concentrate! to 99.9% oil - sells or reprocesses


                   Distills to 99.99% oil - selXs

               Figure 39.   Fluid reclaiming [50].  ,

Reclaimers'  feedstocks are generally  fairly constant  from source
to  source over time; however, the everyday input of feedstock
waste  oils varies from 2 percent to 98 percent oil.   Reclaimers
 [50]  Gabris,  T.  Emulsified  industrial oils recycling.   Bartles-
      ville,  OK; U.S. Department of Energy; 1982 April.   155 p.
      DOE/BC/10183-1.
                                  133

-------
find most of their feedstocks falling between 25 percent and 70
percent oil.  It is preferred that the waste oils be pretreated
and concentrated first by the generator.  This is to the genera-
tor's benefit also as they can then get paid for their waste and
profit rather than pay to have it hauled away.  This pretreatment
varies from use of a simple gravity settling tank,-to sophisticated
in-plant waste treatment facilities installed for water clean-up.
Getting money for the oil or reprocessing it themselves is a by-
product of complying with Federal and State clean water standards
in the latter case.

A categorical description of the sources of the emulsified waste
oil heis been adopted by some reclaimers as follows:

Small users -  produce 50,000 gallons/year
Medium users - produce between 50,000 and 2 million gallons/year
Large users -  produce over 2. million gallons/year

In a wastewater treatment plant the following technologies may be
employed [50]:

     Skimming
     Coalescing
     Emulsion breeiking
     Flotation
     Centrifugation
     Ultrafiltration
-  •  -Reverse osmosis
     Carbon adsorption
     Aerobic decomposition

In-plant recycling can be either .batch or continuous.  In a
typical batch system spent fluid is transferred into the dirty
oil tank and pre-filtered.  The pre-filter removes large dirt
particles before the fluid is centrifuged and heated.  The final
clean up is accomplished by Ultrafiltration and the fluid is re-
cycled back to the clean oil tank.  A continuous system accom-
plishes the same degree of clean up in an operation which contin-
uously processes small amounts of spent fluid.  No containment of
spent fluid is needed; however, maintaining an acceptable level of
contaminant removal is required at .all times.  The use of one or
the other system normally depends upon factory logistics.

6.1.1  Description of Technologies and Equipment Used for In-Plant
       Processing

This section discusses nine generic types of technologies commonly
used by the metal finishing industry to clean up and recover metal
working flu. ds.

To assess relative applicability, comparison of advantages and
disadvantages for the nine oil removal technologies is presented


                                134

-------
in Table 41 [2, 51] with a more detailed discussion of each tech-
nology to follow.

6.1.-1.1  Gravity Separation and Skimming—
Gravity separation and oil skimming are used in the metal finish-
ing industry to remove oily wastes from many different process
wasx;ewater streams.  They are applicable to any waste stream
containing pollutants which float to the surface.  They are used
in conjunction with emulsion breaking, dissolved air flotation,
clarifiers, and other sedimentation devices.

Gravity separation used in metalworking operations are simply
large circular or rectangular vessels which allow the oil co
float to the top and solids and water to settle to the bottom.
Time required for separation may be in days or weeks, so the
tank is normally large enough to handle thousands of gallons at a
time.  Gravity separation often includes provisions for heating
(to lower the viscosity) and extended baffle surfaces (to decrease
the effective height that must be traversed by a rising oil glob-
ule).  Still, reasonable capital and manpower costs make this a
relatively low cost-per-gallon process.  More elaborate units
contain baffles to facilitate oil/water separation and drag con-
veyors for swarf removal.

Gravity separators equipped with skimmers are the most widely
used [52].  The most common skimming designs include the blade,
which skims the floating oil from the surface and directs it into
a trough, and the rotor, which continuously removes oil from the
surface as it turns.  More elaborate units contain belts or drums
which attract, the oil and are scraped of the oil in a skimming
chamber.  Some units incorporate pipes that contain slotted suc-
tion openings for oil removal.  Another version includes a tele-
scoping pipe that lowers and allows oil to enter by gravity
flow [53].  In addition, chain an^ flight, rotating pipe and
helical model skimmers are available  [54].

A decanter is used if the skimmed oil is frothy.  This allows the
oil to separate from the water because of the difference in spe-
cific gravity.  An oil skimmer is employed to remove leaking lub-
ricant and hydraulic oils from rolling mills to prevent damage to
 [51] Ford, D.; and Elton, R.  Removal of oil and grease  from
     industrial wastewater.  Chemical Engineering.  49-56, 1977
     October  17.

 [52'J Evans, R. A.  Solving the oil pollution problem.  Lubrica-
     tion Engineering.  521-524, 1968 November.

 [53] Paulson, E.  Keeping pollutants out of troubled water.
     Lubrication Engineering.  508-513, 1968 November.

 [54] FMC Corporation, Product Literature.


                                135

-------
           TABLE  41.   OIL-REMOVAL PROCESS SUMMARY  [2,51]
            Process
 Advantaces
   Disadvantaces
Gravity separation
  (API, CPI,  PPI separators)
Centrifuging
Filtration
Coalescing filter
Emulsion breaking
Air flotation
  (DAF and IAF)
Membrane processes
Economical
Simple operation
Economical
Simple operation
Requires less
  space

Handle high
  solids
High potential
  efficiency
High reliability
Low capital and
  operating
  costs
High percentage
  of oil removal

Handles high
  solids
Reliable process
  (handles shock
  load)

Soluble oil re-
  moval indicat-
  ed in labora-
  tory tests
Limited efficiency
Susceptible to weather
  conditions
Removes little or no
  soluble oils
Limited removal of
  emulsified oil

Higher power cost
Noise
Disposal of concen-
  trate

Requires backvashing
Backwashing stream a
  subsequent problem
Disposal of sludge and
  filter media

Cannot handle high
  solids due to foul-
  ing, but vertical
  type can handle
  higher loadings
Potential biological
  fouling
Not generally effec-
  tive in removing. -
  soluble or cnemicai
  stabilized emulsi-
  fied

High chemical and
  energy costs

Chemical sludge dispo-
  sal when coagulants
  are used (DAF only)
Requires chemicals
Low flux rates
Membrane fouling and
  questionable mem-
  brane life

           (continued)
                                     136

-------
                        TABLE 41  (continued)
           Process
 Membrane processes (continued)
 Carbon adsorption
 Biological
            Advantages
            Removes soluble
             oil
            High potential
             efficiency
            Removes soluble
             oil
            Relatively high
             tolerance for
             oil and grease
   Disadvantages
 Narrow temperature
   range
 Not demonstrated as a
   practical process
   for oil and grease
   removal
Pretreatment required

 Expensive
 Regeneration required
 Requires extensive
   pretreatment
 Full-scale operation
   not proven in
   refinery

 Solid carryover
 Prone to upset
 Pretreatment pre-
   requisite
pumps and pipes.
re-refining.
Skim oil is usually hauled away for  disposal or
Common gravity separator designs  include API (American  Petroleum
Institute),  CPI (corrugated plate interceptor) and PPI  (parallel
plate interceptor) separators  [55].  . The API gravity  separator
is most  frequently used.  It contains a basin from which free oil
droplets  rise  due to buoyance  forces (see Figure 40).

The corrugated plate interceptor  is  composed of groups  of plates
parallel  to  one another.  Oil  floats into the corrugations and
coalesces on the plates.  The  advantage of CPI and PPI  system? is
that 20  percent less installation area is needed.  Disadvantages
of the API include construction cost, fire haz »'d, evaporation
losses,  and  high steam consumption [56].
[55] Tabakin,  R.  B.; Trattner, R.;  and Cheremisinoff,  P.  N.v
     Oil/water separation technology:   The options available,
     Part  1.   Waste and Sewage Works.   74-77, 1978 July.
[56] Stone,  R.;  and Smallwood, H.   Aerospace industrial waste
     pretreatment.   29th Industrial Waste Conference  1976 May 7-9.
     West  Lafayette, IL; Purdue University, 1976.  pp. 51-59.
                                  137

-------
                                           clean water outlet
                                           chamber.
                                  Wimg lugs .
             surge
             pipe
lifting.  , .
lugs nalcn covers
                                                                    weir
                                                                  sheen barf
                                                              clean water
                                                              flow
                                                          oil retention battle
                                                       sludge battle


                                                 support members
 inlluer.t
 llow conlrol
 baffle
                                          vertical slot
                                          drrfuser baffle
                                     flow control
                                     baffle
       setlieable
       solids
       catch
       basin
                                1 outer shell
                        msulstion
                  Figure 40.  API  separator  [55].

The PPI  reduces the  path that the oil must travel,  as oil coagu-
lates  on the undersurface of the  plates and moves* upward.   Solid
particles,  on the other hand, collect on top of  the plate and
slide  down to the bottom.

To determine utilization of gravity separators in the machining
operation,  the following points are considered:   (1) type of
swarf;  (2)  type of coolant/oil; (3) type of installation; (4) type
of operation; (5) availability and cost of  floor space;  (6)  fin-
ish and  accuracy requirements; (7) initial  and continuing cost of
cleaning equipment;  and (8) production downtime  [57].

Table  42 illustrates examples of  the performance of a skimmer
system [2].
 [57]  Patterson, M.  M.   Why separation filtration for abrasive
      machining.   Lubrication Engineer, 458-461,  1979 December.
                                   138

-------
            TABLE 42.  SKIMMER SYSTEM PERFORMANCE FOR
                       OIL AND GREASE REMOVAL [2]

Sample
number
1
2
3
4
Influent
mg/L
149,779
19.4
232
61
Effluent
ncr/L
17.9
8.3
63.7
14
Removal ,
%
>99.9
57.2
72.5
77.0

6.1.1.2  Centrifugino--
Centrifuginc is primary iy used in rcet.a.1 finishing operations to
remove metallic pcrticlis and/or to separate water from the oil
that has been gravity e;>paratcd or skimmed from the waste emul-
c-ified oil.  It will not. brsak emuls:ons and therefore cannot be
used for removing oil froir. emulsified oil.

Centrif-t^rlnc uses the same principle as giavity separation, but
the higntr gravitational force in centrifu^ing permits separation
to take place more quickly and efficiently ar.-~ within a smaller
space.  Forces several thousand times liigher thaii Vra force of
giavity may be developed in centrifuges to achieve separation of
solids and suspended water from mineral-based fluids and lubri-
cants or to separate tramp oils from water-based coolants  [49].
In the metalworking industry, by removing metal fines and tramp
oils, the coclant and cutting tool life can be greatly extended
[58-61].

Centrifuging may be accomplished either w^rh a batch or a contin-
uous process.  Batch centrifuging is normally employed when there
is a low rate of impurities accumulation or when a considerable
amount of accumulation may be tolerated.  Otherwise, continuous
centrifuging is used.  Typically, the centrifuged fluid is
emptied from the machine sump into the transfer tank and the
surcp is cleaned.  The cleaned oil is returned to the sump after
the addition of additives [50],
[58] Sluhan, C. A.  Grinding with water miscible grinding fluids,
     Lubrication Engineering.  352-354, 1970 October.

[59] Improving coolant life.  Fluid and Lubricant Ideas,  p. 28,
     1979 Winter.

[60] Centrifugal oil purification at an aluminum can plant.
     Fluid and Lubricant Ideas.  19-20, 1980 May/June.
[61] Recycling metalworking coolants through cantral systems.
     Fluid and Lubricant Ideas.  24-25, 1981 January/February.
                                139

-------
There are three common types of centrifuges:   the  disc,  basket,
and conveyor "types.  The fundamental  difference  between  the three
types is the method by which solids are  collected  and discharged
[50].

In the disc centrifuge (see Figure 41),  suspended  particles are
collected and discharged continuously through small  orifices in
the bowl wall.  The oil-water mixture spreads out  across a
series of conical discs which allow the  light oil  fraction to
separate and flow across the topside  of  the disc to  a discharge
pipe.  The heavier water flows across the bottom of  the  discs to
a separate discharge pipe.

                                         INLET PIPE
                                         OUTLET PIPE
                                         PASING DISC

                                         DISTRIBUTOR
                                         BOW. HOOD

                                         LOCK RING

                                         BOWL BODY
                                         DISC STACK
                                         BOWL SPINDLE
                Figure  41.   Disc-type centrifuge.

In the basket  centrifuge,  dirty oil is introduced at the bottom
of the basket,  and solids  collect at the bowl wall while clari-
fied effluent  overflows  the lip ring at the top.   Since the bas-
ket centrifuge does not  have provision for continuous discharge
of collected cake,  operation requires interruption of the feed
for cake  discharge for a minute or two in a 10- to 30-minute
overall cycle.

In the conveyor type or  decanter centrifuge (see Figure 42), an
electric  motor drives  the  decanter bowl via a V-belt drive.  The
bowl drives the conveyor through a gearbox.  Waste oil enters the
revolving bowl through an  inlet pipe in the center of the screw
conveyor.  Aided by strong centrifugal force, the solids "settle"
out of the liquid and  are  transported by the screw conveyor to
the narrow end of the  bowl, where they are discharged by centrifu-
gal force.  Both solids  and purified oil collect in compartments
in the center  cover of the machine before falling by gravity into
receivers.

Decanter  centrifuges can reduce the amount of solids reaching a
disc-type centrifuge.  Thus, for many oils, a two-stage operation
consisting of  a decanter followed by a disc-type unit is used.
                                 140

-------
  CONVEYOR DMIVK
  CYCUOCEAft
SLUOGt
DISCHARGE
                           CONVEYOR
                                       •OWL
NEOULATING
MING
                                                         IMPtULKM
              Figure 42.  Decanter centrifuge [2].

In one test, a decanter reduced solids in the disc-type units feed
by 50 percent [62].

Centrifuges have minimal space requirements and achieve a high
degree of effluent clarification.  The operation is simple, clean,
and relatively inexpensive.  The area required for a centrifuge
system installation is less than that required for a filter system
of equal capacity, and the initial cost is lower.

The major difficulty encountered in the operation of centrifuges
has been the disposal of the concentrate, which is relatively high
in suspended, nonsettling solids.

Table 43 illustrates centrifuge performance in removing oil and
grease from oily wastewater [2].

          TABLE 43.  OIL AND GREASE REMOVAL PERFORMANCE
                     DATA FOR CENTRIFUGE [2]
Sample
number
1
2
Influent
mg/L
373,280
14,639
Effluent
mg/L
3,402
1,102
Removal ,
98.9
&2.5

 [62] Centrifuges for re-refining and reprocessing waste oils.
     ALFA-LAVAL Inc., Prodact Literature.
                                141

-------
6.1.1.3  Filtration—
Filtration is widely used in.metal finishing plants,to remove
metallic particles from the raetalworking fluids during daily
operations, and the filtered fluids are recycled.  Filtration
increases the life expectancy of the fluids.  At the same time,
with use of filtered fluids, better products are attained along
with increased metalworking tool life.  Also, filtration is used
as a treatment step in a total waste emulsified oil treatment
scheme.

Although centrifugation and 'gravity separation have been dis-
cvssed as suitable methods of solid particle removal, filtration
appears to be the most common means of removing solid particles.
The selection of filtration methods depends on cost, the type of
contaminants present, and personal preference.

Several different types of filtering devices are used to reclaim
oil coolants.  Some of these have permanent media such as screens
which permit their regeneration within the system, others utilize
a moving filter media; and some utilize a diatomaceous earth as a
precoat to assist in the filtration [63].

Smaller size chips, which arise from grinding or surface finish-
ing operations are usually handled by filters.  The: driving force
of filtration can be either vacuu" or pressure [2].  Vacuum fil-
ters operate by employing a vacuum/under the media which draws the
particles to the media.  The pressu're filters require a pump,
which  feeds fluid to the media.  The diagrams of these two fil-
ters are shown in Figures 43 and 44, respectively.  The advan-
tages  and disadvantages of these two filters are summarized in
Table 44.  Generally, pressure and vacuum equipment can remove
particles as small as 3 micrometers, though 25 micrometers is the
most common filter size [49].

Cartridge type filters are available for smaller loads of particles.
Cartridge is a broad term for a self-containing device, v.hich has
a filtering medium that may be replaced or regenerated.

These  filters may contain paper, cloth, or nonwoven media  [64].
When filtering waste oils it is best to use several different
 [63] Fochtman, E. G.; and Tripathi, K. C.  Research needs in
     coolant  filtration.  Proceedings  in Lubrication Challenges
     in Metalworking and Processing;   1970 June 7-9; Chicago.
     ITT Research Institute, First  International Conference,
     117-121.

 [64] Brooks,  K. A.,  Jr.  A review of disposable nonwoven filtra-
     tion media for  cutting coolant and process fluids.  Lubrica-
     tion Engineering.  542-548, 1974  November.
                                 142

-------
    PERFORATED
    BACKING PLATE


   FA1RIC
   FILTER MEDIUM
                                          FADRIC
                                          FILTER MEDIUM
  SOU Id
  RECTANGULAR
  END PLATE
                                          6NTRAP»CO SOLIDS
                                           PLATES AND FRAMES ARE PRESSED
                                           TOGETHER DURING FILTRATION
                                           Crete
                                         \
          FILTERED LIQUID OUTLET
                                          1KCTANGULAR
                                          METAL PLATE
                                     RECTANGULAR PRAM*
              Figure  43.   Pressure filtration

size cartridges  in  series,  rather than one fin** f?l"'rsi.   A 25-mi-
croraeter filter  can be used to remove most of  ...    irye  particles,
followed by a 10-micrometer filter to remove most of  the remaining
contamination.   Stepwise  filtration v/ill require  che  least number
of filter changes,  particularly the finer filtPLS,  which are often
more expensive.

Another type of  filter, wedge wire, allows the metal  chips to
perform the actual  filtering.  The wedge wir   filter  is  a screen
of wires with triangular  cross sections wh •   support the col-
lected chips.

Paper filters are used for soluble oils and are considered accept-
able for filtering  steel,  aluminum, and brass  fines frv.,m soluble
oils.  However,  paper is  viewed by some as being  too  expensive.
                                 143

-------
                  FABRIC Or* WIRE
                  FILTER HCDIA
                  STRETCHED OVER
                  REVOLVING DRUM
                                            DIRECTION OF ROTATION
              ROLLER
  SOLIDS SCRAPED
  OFF FILTER MEDIA
                tt
              vi
   SOLIDS COLLECTION
   HOPFER
                               TftOUOH
                                     \
                               FILTERED LIQUID
                                                                 INLET LIQUID
                                                                 TO BE
                                                                 FILTERED
                  Figure  44.   Vacuum filtration [2].
       TABLE 44.   COMPARISONS OF  VACUUM AND  PRESSURE FILTERS
Filters
           Advantages
                                            Disadvantages
Pressure   1.  Simple
Vacuum
2.  Indexes automatically

3.  Cleanable medium
4.  Moderate investment
5.  Dry sludge cake

1.  Removes fine particles
                                  1.  Initial pressure forces
                                        particles into filter me-
                                        dium.  Impending pennea
                                        bility.
                                  2.  Possible high cost for fil-
                                        ter paper
                                  3.  Disposal of filter media
                                  1.  May require additional fil-
                                        tration
2.  Efficient with low viscosity   2.  Disposal of sludge and fil-
      fluids                            ter media
3.  Indexes automatically          3.  Blinds off because of tramp
                                        oils
                                      144

-------
Very fine material  arises from honing or superfinishing opera-
tions.  Filtering very fine material requires the use  of a pre-
coat filter, which  is  a pressure filter using diatomaceous earth.
A pre-coat  filter or a centrifuge is necessary  for.removing sub-
micron particles.   Pre-coating is the application of material such
as do^tomaceous  earth,  fuller's earth, etc., on the media prior to
filtration.  The pre-coat application will prevent media from
being clogged  and provides greater filtrate clarity.

Other types of filtration/separation equipment  include hydrocy-
clones and  magnetic separators.  The hydrocyclone is  for smaller
chips.  It  has been estimated that hydrocyclones are  capable of
reclaiming  particles  larger than 20 microns in  size with a flow
rate ranging from 100-600 gpm.  Hydrocyclones and cartridges are
often used  together, with the hydrocyclone used for larger par-
ticles and  the cartridge for separation of fines.

Magnetic  separation uses a magnetic drum rotating in  a pool of
oil coolant.   The magnetic.systems attract the  particles of swarf
which are in turn scraped from the drum  [57].   In metalworking,
large ferrous  particles may 'be removed with the use of a magnetic
separator which captures the particles by means of dense magentic
field.  These  particles, in turn, form a filter medium for remov-
ing other solid particles.  The magnetic filter may be employed
as a primary device for grinding, rolling, polishing  and honing
operations  and as a secondary apparatus  in drilling,  hobbing,
milling and broaching operations.'  The advantages  and disadvan-
tages of  hydrocyclone and magnetic separators  are  summarized in
Table 45.

  TABLE 45.  COMPARISONS OF HYDROCYCLONE AND MAGNETIC SEPARATOR
  Filters
  Advantages
      Disadvantages
 Hydrocyclone
 Magnetic separator
1.  Automatic discharge of  1
     solids minimizes
     service requirements
2.  Inexpensive
3.  Small size

4.  Nonmechanical

1.  Does not remove
     coolant additives
2.  Very compact


3.  Removes ferrous
     particles
   Will not clean oil
     based coolants

2.  May become clogged with
     large particles
3.  Will not remove tramp
     oil
1.  Does not remove tramp
     oil
2.  Does not remove parti-
     cles smaller than 35
     micrometers
3.  Doe's not remove non-
     ferrous particles
                                  145

-------
In many cases it is more economical to install a central filtra-
tion equipment and return the recovered oil coolant to each
machining operation.  Filtering is difficult to perform on indi-
vidual machines but the removal of swarf and chips in order to
prevent their recirculation with the cutting fluid is necessary
[65].

Several hundred percent increases in tool life and in oil life due
to good coolant filtration have been reported [63].  Great improve-
ments in the quality of metal surface finish are also reported.

6.1.1.4  Coalescing—
Coalesers are primarily used to remove tramp oil (free floating
oil) from waste enulsified oil from metal finishing plants in the
cases where oil may become suspended in the waste emulsified oil
and cannot be removed by gravity separation.  This suspended oil
can be efficiently removed with a coalescing filter.  The basic
principle of coalescing involves the preferential wetting of a
coalescing medium by oil droplets which accumulate on the medium
and then rise to the surface of the effluent.  The same principle
is applied to removal of water from oil effluent [2,49].  The
most important requirements for coalescing media are wettability
for oil and large surface area.

Coalescing stages may be integrated with a wide variety of grav-
ity oil separation devices (see Figure 45).  In this design, coa-
lescing plates generate a flowpath of modified sinusoidal shape
in order to create velocity changes in the flow stream.  This
produces a high incidence of particle collision which results in
the coalescing of small particles -of oils into particles of 20 mi-
crometers or larger in size.  These then move upwards, due to
their lower specific gravity, and are collected above the plates.
The design of the coalescing plate section makes use of laminar
flow, oleophilic plate material, and reduced plate spacing.  All
these factors, together with the pulsation of flow achieved by
changes of cross-section, enable removal of oil droplets down to
7 micrometers.  The collected oil will generally contain less than
5 percent water [66].

The separator can be supplied with plates arranged horizontally,
vertically or in a combination of both horizontal and vertical.
 [65] Coursey, W. M.  The application, control, and disposal of
     cutting  fluids.  Lubrication Engineering.  200-204, 1969 May.

 [66] Fraa  Industrial Filtration and Separation.  Product
     Publications. •
                                146

-------
  INFLUENT   OIL SKIMMER
  OIL-VBATER
  MIXTURE
  OIL OUTLET— g
           OIL
SEP&RATF.O OIL SKIMMER  OIL DAM
                                                           CUTLET
                                                           WEIR
                    iMsag^vgffiEa^a^^Eas^^^^g
                                                             CLEAN
                                                             WATER
                                                             EFFLUENT
                                                            DRAIN
   DRAIN
                  INLET WEIR
           \
         COALESCING
         PLATE ASSEMBLY
         Figure 45.  Coalescing gravity  separator [2].

For influent oil concentrations less  than  10  percent by volume
and solids concentrations less than 500  ppm,  the  horizontal con-
figuration of plates is usually suitable.   This configuration is
also particularly efficient in reducing  the oil content of the
effluent to the lowest possible amount.

The vertical plate configuration  is especially suitable for high
oil and/or solids loadings.  The  solids  separate  out under gi'^v-
ity and are collected below the plates.  The  oil,  meanwhile,  v
rises along the plates to the surface.   Maintenance is  exception-
ally easy since the plates can be hosed  down  in place.

For many applications a combination of both types of plates will
achieve the most effective separation.   In this case, vertical
plates are used for the first stage and  horizontal plates for the
second.

Some systems may be incorporated  with several coalescing stages.
In general, the provision of preliminary oil  skimming treatment
is desirable to avoid overloading the coalescer.

Coalescing allows removal of oil  droplets  too finely dispersed
for conventional gravity separation/skimming  technology.  It can
also significantly reduce the residence  times (and therefore sep-
arator volumes) required to achieve separation of oil from some
wastes.  Because of its simplicity, coalescing oil separators
provide generally high reliability and low capital and  operating
costs.

The units have no moving parts, require  no filters or electri-
city, and can operate with influent temperatures'to 212°F (100°C)
and a pH range of 2-12.  They require no chemicals or absorbents
and are virtually maintenance free.   They  can nandle flow rates
up to 10,000 gallons per minute (360,000 barrels/day) and surges
                                 147

-------
of up to 100 percent oil with effluent quantities down to 5 ppm
of oil.  They can capture solids and oil drops as small as 5
micrometers.

Coalescing is not generally effective in removing soluble or
chemical-stabilized emulsified oils.  To avoid plugging,  coales-
cers must be protected by pretreatment from very high concentra-
tions of free oil, grease, and suspended solids.  Frequent
replacement of prefilters may be necessary when raw waste oil
concentrations are high.

Coalescer oil and grease removal efficiency is illustrated in
Table 46 [2].

   TABLE 46.  COALESCER OIL AND GREASE REMOVAL EFFICIENCY  [2]


Sample
1
2
Raw waste
mg/L
8,320
4,240
Effluent
mg/L
490
619
Removal,
V
fa
94
85

6.1.1.5  Emulsion Breaking--
Emulsion breaking technology can be applied to the treatment of
emulsified oil from the metal finishing operations wherever it is
necessary to separate oils, .fats; etc., from wastewater.

Breaking of oil-in-water emulsions is a major waste-handling
problem for automotive and other manufacturing plants involved
with the cutting, machining, and grinding of metals because the
maximum allowable concentration of oil that can be discarded in
wastewater is no more than 50 ppn.

The individual plant wastes—including "soluble oil" emulsions,
cutting fluids, and cleaners—are typically combined and treated
with chemicals to separata oil and water.  Other available meth-
ods of emulsion breaking include thermal processes and combina-
tions of the chemical and thermal processes [2].

Chemical emulsion breaking can be accomplished either as a batch
process or as a continuous process.  A typical system (with skim-
ming incorporated) is illustrated in Figure 46.  The mixture of
emulsified oils and water is initially treated by the addition of
chemicals to the wastewater.  A means of agitation, either mechan-
ical agitation or by increasing the turbulence of the wastewater
stream, is provided to ensure that the chemical added and the
emulsified oils are adequately mixed to break the oil/water emul-
sion bond.  Finally, the oily residue (commonly called scum) that
results rises to the surface and is separated from the remaining
                                148

-------
              Owical Addition
 Bwlsified OU*
                                      Skimtr
                  Using Tar*
                                                  Oil*
                                   Combination Flotation
                                         And
                                      Settling Tank
                                                        Trrated Mastewater
                                        Sludge

             Figure 46.  Typical emulsion breaking/
                         skimming  system  [2],

wastewater by a skimming or decanting process.   The skimming proc-
ess can be accomplished by any of  the many  types of mechanical
surface skimmers that are presently  in use.  Decanting methods
include removal of the oily surface  residue via  a technique such
as controlled tank overflow or by  removal of the demulgated
wastewater from the bottom of the  tank.  Decanting can be accom-
plished with a series of tap-off lines at various levels which
allow the separated oils to be drawn off the top or the waste-
water to be drawn off the bottom until oil  appears in the waste-
water line.  With any of these arrangements, the oil is usually
diverted to storage tanks for further processing or hauling by -a
licensed contractor.

Chemical emulsion breaking can be  accomplished by a large variety
of chemicals which include acids,  salts, or polymers.   These
chemicals are sometimes used separately, but often are required
in combination to break the various  emulsions that are common in
the wastewater.  Acids are used to lower the pH  to 3 or 4 and can
claave the ion bond between the oil  and water, but they can be
very expensive.  Acids are more commonly employed in oil recovery
systems than in oily waste removal systems.  Iron or aluminum
sulfate are more commonly used because they are  less expensive.
These salts combine with the wastewater to  form  acids,  which in
turn, lower the pH and break the oil/water  bond  (and have the
additional benefit that these salts  aid in  agglomeration of the
oil droplets), but the use of these  salts produces more sludge
because of the addition of iron or aluminum.  Polymers, such as
polyamines or polyacrylates and their copolymers, have been
demonstrated to be effective emulsion breakers and generate less
smdge than do metal salts [2, 67].
[67] Montens, I. A.  Treatment  of wastes  originating from me'_al
     industries.  West Lafayette, IN;  Purdue University,  ^82-791.
                                 149

-------
           A less freq-iently+ernplo^ed method involves tjjie addition of a
           cation such as Fe 2,  Fe 3,  Al 3,  Cu :,  or Cu 2,  in a volume of at
           least 1 ppm tj the oil in water emulsion.  The pH is adjusted to
           the range of 6 to '0.  The emulsion is  then treated-with a dissolv-
           able iron electrode.   An electric current is transmitted to dis-
           solve the electrode,  resulting in a ferrous ion/oil weight ratio of
           at least 0.02.  The optimum efficiency  of the process is obtained
           when 3 to 5 ppm of the cation is added  to the emulsion at a pH range
           of 6 to 8.  The addition of the cation  reduces the time required to
           break the emulsion from 24 hours to forty minutes or less [68].

           After chemical addition, the mixture is agitated to ensure com-
           plete contact of the emulsified oils with the demulsifying agent.
           With the addition of the proper amount of chemical and thorough
           agitation, emulsions containing 5 percent to 10 percent oil can be
           reduced to approximately 0.01 percent remaining emulsified oil.
           The third step in the emulsion-breaking process is to allow suffi-
           cient time for the oil/water mixture to separ-ite.  Differences in
           specific gravity will permit the oil to rise zo the surface in
           approximately 2 hours.  Heat can be added to decrease the separa-
           tion time.  After separation, the normal procedure involves skim-
           ming or decanting the oil from the tank.

           The main advantage of the chemical emulsion breaking process is
           the high percentage of oil removal possible with this system.
           For proper and economical application of this process, the oily
           wastes (oil/water mixture) should be segregated from other waste-
          .waters either.by storage in a holding tank prior to treatment or
           by feeding directly into the oily waste removal system from major
           collection points.  Further, if-a significant quantity of free
           oils are present, it is economically advantageous to precede the
           emulsion breaking with a gravity separator.  Chemical and energy
           costs can be high, especially if heat is used to accelerate the
           process [2].

           In addition to the chemical treatment of emulsion breaking, a con-
           tinuous electrolytic treatment is being developed to remove emulsi-
           fied oil from dilute oily wastewater streams, such as is generated
           in metalworking operations.  In this work, electrophoretic transport
           of charged oil droplets was exploited as a concentrating mechanism,
           using the cell shown schematically in Figure 47.  A porous diaphragm
           is placed between the two electrodes which inhibits convective mix-
           ing of the treated and concentrate streams, while permitting the
           emulsified oil droplets to pass through unhindered.  Separate
           emulsion streams containing the negatively charged oil droplets
           are passed through both the cathode and anode compartments.  The
           oil droplets migrate through the diaphragm under the influence of
           [68] Golovoy, A.  Method of breaking an oil-in-water emulsion.
                U.S. patent 4,087,338.
                                           150
L /

-------
EMULSION BROKEN
AND
on SEPmno




±-





e - e
e -- e
ec e
e e
e e
e e
6 e e
e e
ees
© €
e - €

OK DROPLETS
REMOVtO
e
e ..

	 6
6 e
6 e
6
e
e
e e
0
                                       WOOtMC
                         »»STI' SOLUBLE OH' EMULSIONS
     Figure 47.  Electrochemical oil removal/recovery cell:
                 negatively charged oil droplets [69].

an electrical field to the analyte, where the emulsion is broken
by electrochemical action to yield a separate oil layer [69-71] .
In a pilot plant test run,  wastewater with initial oil concentra-
tions Ir the range of 300 to 7,000 ppm of solvent extractables
has been reduced to less than 50 ppm in 90 percent OA." the test runs
and to less than 25 ppm in 83 percent [71].

The recovered oil from emulsion breaking can be burned, reused for
another purpose, sold, or disposed of by any acceptable method.

The water constituent obtained from the split emulsion must then
receive further treatment before the water may be discharged into
the plant wastewater system. ' The degree of treatment required on
the water phase of emulsion will be governed by local pollution
regulations.

The performance attainable by a chemical emulsion breaking proc-
ess is dependent on addition of the proper amount of de-emulsifying
agent, good agitation end sufficient retention time for complete
emulsion breaking.  Since there are several types of emulsified
oils, a detailed study should be conducted to determine the most
[69j Snyder, D. D.; and Willihinganz, P. A.  A new electrochemical
     process for treating spent emulsion.  31st Industrial W?ste
     Conference; 1976 May 4-6.  West Lafayette, IN; Purdue Univer-
     sity.  782-791.

[70] Kramer, G.; Buyers, A.; and Brownlee, B.  Electrolytic
     treatment of oily wastewater.  34th Industrial Waste Confer-
     ence; 1979.  West Lafayette, IN; Purdue University.  673-680.

[71] Gealer, R. L.; Golovoy, A.; and Weintraub, M. H.  Electro-
     lytic treatment of oily wastewater from manufacturing and
     machining plants.  Cincinnati,  OH; U.S. Environmental Pro-
     tection Agency; 1980 June.  48 p.  EPA-600/2-80-143.
     PB 80-225113.
                                151

-------
effective treatment techniques and chemicals for a particular
application.  Table 47 illustrates emulsion breaking process
performance data [2].

            TABLE 47.  EMULSION BREAKING PROCESS OIL
                       AND GREASE REMOVAL DATA [2].

Sample
1
2
3
4
5
6
7
Influent
mg/L
3,320
210
12,500
2,300
13,800
192.8
6,060
Effluent
mg/L
42
24
27
52
18
10.6
98
Removal ,
%
98.7
38.6
>99.9
97.7
>99.9
94.5
98. 4

6.1.1.6  Flotation—
Flotation un^t? are commonly used in metal finishing operations
to remove free and emulsified oils and grease.  Flotation is the
process of causing particles such a^ oil or metal hydroxides to
float tc -che surface of a tank where they can be concantrated and
removed.  This is brought about by releasing gas bubbles which
attach themselves to the particles, increasing their buoyancy;
and causing them to rise to the surface and float [2].

Dissolved air flotation (DAF) utilizes the emulsion-breaking
techniques that were previously discussed and in addition uses
bubbles of dissolved air to assist in tne agglomeration of the
oily droplets and to provide increased buoyancy for raising the
oily droplets to the surface.  Coagulants, i.e., lime, alum fer-
ric salts or polyelectroiytes are added to enhance floe forma-
tion.  In addition, air will oxidize sulfides, which will release
adsorbed oil [50,2].  Equipment required for the process includes
the flotation tank, recycle pumps, dissolved tank, and the air sup-
ply and controls (see Figure 48)  [72].

A dissolved air flotation unit may be incorporated in a treatment
systeai utilizing an oil-water separator.  Wastewater passes
through an API oil-water separator and following the skimming off
of free oil is passed to a dissolved air flotation unit.  Oil is
again skimmed off and the water is processed through the clari-
fiers in a biological oxidation system.  This system may not
 [72] Hoover, W.; Sitjnan, W.; and Stack, V.  Treatment of wastes
     containing emulsified  oils and greases.  Lubrication Engi-
     neering.   1964 May.
                                152

-------
                      Oil
                    To Disposal  Sludg-. Line (If Req'd)

                       1	t
                                       FLOTATION
                                         TANK
                                                           SCfiuent
                                                          Optional source
                           Ar Supply
    Figure 48.   Typical dissolved  air  flotation system  [2].

effectively  separate the oil and water if the volume of oil  is
too great:.   Ths  concentration of oil in the effluent from  the dis-
solved air flotation unit may be 1CO-150 ppm, which exceeds  the
capability of  the bio-oxidation process [2].  When low molecular
weight organic polymers are added  to the inlet of the dissolved
air flotation  unit,  the concentration  of oil in the effluent was
reduced to 15-30 ppm [73].  Generally,  with dissolved air  flota-
tion., the effluent will.contain less than 50 ppm.of oil.   It will
contain, less than 100 ppm if the•influent does not contain more
than 1 000 ppm of oil.

Results of emulsion breaker application in the API-DAF system is
presented in Taole 48 [2].

    TABLE 48.  RESULTS OF EMULSION BREAKER APPLICATION  IN  THE
               API-DAF SYSTEM - OIL AND GREASE [2]


                       API       API      Removal,    DAF     Removal,
    	influent   effluent	%	effluent	%

    Ko treatment       1,500     200-300     83     100-150      50

    Er.ulsion  breaker
      treatment        1,500     100-125     93     15-30        79


    Determination  by Freon extraction,- values expressed in parts  per mil-
    lion (volume basis).
 73] Gruette,  J.   Primary wastewater treatment and oil  recovery
     in  the refining industry.   National Petroleum Refiners Asso-
     ciation Meeting; 1978 March 19-21.
                                  153

-------
The use of dissolved air for oily waste flotation subsequent to
emulsion breaking can provide better performance in shorter reten-
tion times (and therefore smaller flotation tanks) than with emul-
sion breaking without flotation.  A small reduction in the quantity
of chemical needed for emulsion breaking is also possible.  Dis-
solved air flotation units have been used successfully, in con^unc-
tion with subsequent processes, to reclaim oils for direct reuse
and/or use as power plant fuels.

However, flotation requires higher operating costs and yields a
thicker sludge.

Induced air flotation (IAF) is an available means of removing oil
and suspended solids from waste waters.  Induced air flotation
would not be selected in instances where turbulence would be un-
desirable since it would disturb flocculation.  It is considered
by some to be a simpler and less expensive method than dissolved
air flotation, although its present usage is about 1/5 that of DAF.
Dispersed air flotation requires less floor space (100 square feet
or greater, depending on the machine), and a shorter retention time
(4 minul.es) [74].  The method of producing air and introducing it
into the liquid differs from the dissolved air flotation system.

The apparatus has been identified as the dispersed air flotation
machine because it contains air dispersing mechanisms that pro-
duce dispersed air in the form of finely divided bubbles.  The
bubbles rit>e to the top carrying oil droplets and are removed by
a revolving froth skimmer.  The individual dispersed air flotation
mechanism is composed of a vertical shaft with an attached impeller
surrounded by a diffuser and .circulation hood attached to a vertical
pipe.  The impeller displaces liquid which results in the flow of
air down the standpipe.  Liquid mixes with the air flowing from the
standpipe resulting in the formation of air bubbles.  The amount
of aeration is produced by adjusting the speed of the impeller and
the rare of fluid circulation through the impeller [74],

An electrolyte flotation method requires electrocoagulation cells,
flotation basins, and a chemical treatment and sludge system.  The
advantages of the system lie mainly in the need for less chemicals
and the creation of less turbulence in removing of suspended and
emulsified materials.  The electrocoagulation cell functions by
destabilizing suspensions and promoting flocculation.  This unit
operates by passing electrical current through water between a
series of electrodes.  The electroflotation basin concentrates
the floe and separates it from other floatables.  Material is
floated to the top by means of bubbles created by an electrical
current [2].
 [74] Tylor, R. W.  Dispersed air flotation.  Pollution Engineering.
     1973 January.


                                154

-------
The performance of a flotation system depends upon having suffi-
cient air bubbles present to float essentially all of the sus-
pended solids.  An insufficient quantity of air will result in
only partial flotation of the solids, and excessive air will
yield no improvement.  The performance of a flotation unit in
terms of effluent quality and solids concentration -in the float
can be related to an air/solids ratio.  The shape of the curve
obtained will vary with the nature of the solids in the" feed.
Table 49 illustrates dissolved air flotation system performance
data [2].

          TABLE 49.  DISSOLVED AIR FLOTATION SYSTEM OIL
                     AND GREASE REMOVAL DATA [2]

Sample-
1
2
Influent
mg/L
412
65.8
Effluent
mg/L
108
28.9
Removal,
%
73.8
56.1
6.1.1.7  Ultrafiltration  (UF) —
Ultrafiltration is employed in metalworking plants for the sepa-
ration of oils, toxic organics, and residual solids from waste
emulsified oils,  in an Ultrafiltration system, a wastewater feed
is introduced into a membrane module (see Figure 49).  Water and
low-molecular weight solutes (for example, salts and some sur-
factants) pass through the membrane at a pressure of 0.767 kg/cm2
and are removed as permeate (filtered effluent), which may con-
tain less than 100 mg/L of oil and 10 mg/L suspended solids.  If
this effluent discharge level does not attain effluent limitation
guidelines, the permeate  may be treated by a filtration process
such as biological degradation, carbon adsorption or reverse
osmosis.  Emulsified oil  and suspended solids are retained by the
membrane, concentrated to about 60 percent oil and solids content,
and removed as concentrate [75,76].  At present, an ultrafilter
is capable of removing materials with molecular weights in the
 [75] Wahl, J. R.; Hayes, T. C.; Kleper, M. H.; and Pinto, S. D.
     Ultrafiltraticn for today's oily wastewaters:  A survey of
     current Ultrafiltration systems.  34th  Industrial Waste Con-
     ference; 1979 May 8-10; West Lafayette.  Ann Arbor, MI, Ann
     Arbor Science Publications, Inc., 1980,  719-733.

 [76] Pinto, S. D.  Ultrafiltration for dewatering of waste emul-
     sified oils.  First international conference on lubrication
     challenges  j.n metalworking and proc3ssing; 1978 June 7-9;
     Chicago.  IIT Research Institute, 1978,  129-134.
                                155

-------
                                PERMEATE        FIBERGWSS -REINFORCED
                                             EPOXY SUPPORT TUBE
      1WSTCWATER
                                          MEMBRANE
                                 •O
                              PERMEATE

     Figure 49.  Simplified ultrafiltration membrane module.

range of 1,000 to 100,000.  A survey of plants utilizing ultrafil-
tration revealed the mean removal efficiency for oil and grease
removal to be 92 percent and for total toxic organics to be 88
percent [50].  The liquid oil concentrate can be disposed of by
hauling or incineration.  Solid waste is practically nonexistent
because there is no addition of the chemicals required for
demulsification.

The semipermeable membrane is a thin film of a proprietary non-
cellulosic polymer t:hat will withstand high operating tempera-
tures and extremes in pH and solvent exposure.  The thin "skin"
(<0.5 pm) of the membrane covers =1 highly porous substance.
Since the pores of the ultrafiltration membranes are much smaller
than the particles rejected, the particles cannot enter the mem-
brane structure and plug the pores.  The pore structure and small
size (less than 0.005 micrometers) of the membrane are quite dif-
ferent from those of ordinary filters.  With an ordinary filter,
pore plugging results in drastically reduced filtration rates and
requires frequent backflushing, which may produce extra solid or
liquid wastes.

The performance of ultrafiltration systems is typically character-
ized by two parameters:  membrane flux and membrane rejections
(for a specific species).  The flux is defined as the rate of per-
meate production per unit membrane area and is usually expressed
as gallons per square foot per day  (gal/ft2/day).  The design
flux for oily waste treatment is typically 30 gal/ft2/day  [75].

The rejection measures the degree to which the membrane prevents
permeation of a given constituent from the feed into the permeate.
Rejection for oil and grease is normally greater than 99 percent
[75].

A typical ultrafiltration system for treating oily water is shown
in Figure 50.  The .process begins with oily wastewater collection
in an equalization tank, with 1-2 days retention time, from which
free-floating oil and settleable solids are removed.  The remaining
oily wastewater is transferred to a process tank.


                                 156

-------
         OIL EMULSION
         WASTE FEED
                           FREE OIL REMOVAL
             SETTADLE
             SOLIDS
LEVEL  i_ _
COLTROLLfR
                                                  ULTRAFILTRATION
                                                  MODULES
                           FINAL CONCENTRATE             OIL-FRE
                           DISPOSAL                   PERMEATE
                                                    DISCHARGE
       Figure 50.   Semi-batch ultrafiltration system  [75].

The process tank  is sized for 0.5-1 day capacity depending  upon
feed concentration.  Wastewater is pumped through the membrane
module's from the  process  tank at about 50 psig.

Usually, a semi-batch  concentration cycle is employed.   In  this
cycle, the permeate is discharged continuously, while the oily
wastewater is retained in the system and gradually concentrated
with time.  Oily  makeup water is added to the process tank  to
maintain a constant process  level.

On the final day  -   t-.he semi-batch concentration cycle,  flow to
the process tank  . s stopped  and a batch concentration on the
process tank contents  is  performed.  This final step reduces the
concentrated wastewater to the- minimum residual volume.  The
final concentrate is removed from the system for further proces-
sing or disposal.   The system is then cleaned in preparation for
the next concentration cycle.

In large oil-water  systems,  cleaning of the membranes normally
will be required  once  a week to remove foulants that build  up on
the membrane surface.   These cleaning methods are  [75]:

     (1) Mechanical cleaning,
     (2) Dispersing, and
     (3) Solubilizing.
                                 157

-------
Mechanical cleaning is only applicable in practice to large diam-
eter ultrafiltration membranes and is very effective in removing
chemically precipitated species that adhere tenaciously to the
membranes and are difficult to remove by any other method.  This
method works best when the adhesion between the fouling layer and
the membrane ir, weak.

Dispersing methods of cleaning function by breaking up deposits
in the membrane and dispersing them into colloidal sized par-
ticles.  The most commonly used dispersants are detergents.

Cleaning by solubilizing consists of dissolving, by physical or
chemical means, fouling deposit.  This is the most effective of
the three cleaning methods.  It is most oftam used to clean the
membranes of metal hydroxide or other chemical deposits.  Solu-
tions of acids and chelating agents are usually used for this
purpose.  The filtering membrane used for emulsified industrial
oils should therefore be resistant to acidic, alkaline, and caus-
tic cleaners.

Ultrafiltration is recommended by metalworking fluid manufac-
turers as a disposal method for oily wastewater for the following
reasons:

     (1) Reduces sludge disposal problem
     (2) Less expensive than incineration
     (3) Less expensive than contract hauling
     (4) Costs less per gallon for treatment
     (5) Requires less skill for operation

A limitation of ultrafiltration for treatment: of process effl.u-
snts is its narrow temperature range (18°C to 30°C) for satis-
factory operation.  Therefore, surface area requirements are a
function of temperature and become a trade-off between initial
costs and replacement costs for the membrane [2].  Table 50
illustrates ultrafiltration performance data for oil and grease
removal  [2].

6.1.1.8  Reverse Osmosis  (RO)—
Reverse osmosis is the process of applying a pressure to a concen-
trated solution and forcing a permeate through a semi-permeable
membrane into a dilute solution.  With respect to oily wastewater,
reverse osmosis is used primarily as a polisMng mechanism to
remove oils and metals that still remain after treatments such
as emulsion breaking or ultrafiltration  [2].

Feed water is pumped under pressure of either 400 or 600 psi
through the reverse osmosis permeators, where 50 or 75 percent
of the water permeates .through the minute pore spaces of the m«ra-
brane and is delivered as purified product water.  Impurities in
                                 158

-------
           TABLE 50.   ULTRAFILTRATION PERFORMANCE DATA
                      FOR OIL AND GREASE REMOVAL [2]
                      Influent   Effluent   Removal,
             Sample	mg/L	mg/L	%

               1          95.0     22.0      76.8
               2       1,540       52.0      96.6
               3      38,180      267        99.3
               4      31,000       21.4      99.9
               5      .1,380       39.0      97.2
               6       3,702      167        95.2
               7       1,102      195        82.3
               8       7,500      640        91.5
               9         360       18.0      95.0
              10          70.0     10.0      B5.7

                  Mean removal efficiency    92.0
the water are concentrated in the reject stream [77].  Small dry-
ing bed lagoons are proposed for disposal of the small amount of
RO concentrate.  However, if appreciable amomat of oil is to be
collected from the gravity oil skimmer, the small amount of the
RO concentrate can probably be incinerated [78].  Reverse osmo-
sis is capable of removing 90-98 percent of total dissolved solids
and 99 percent of organics, and it is an effective shield against
pyrogens, bacteria, and other microorganisms.
            •
While a new technology, membrane systems appear more attractive
than a chemical treatment process with its attendant sludge
disposal problems.  The improved effluent coiaid be more easily
incorporated into existing water reclamation systems, thereby
eliminating direct discharge of treated water.  Although the
UF/RO system requires a higher capital investment than would a  .
UF system, utilizing RO permeate as a substitute for deionized
water in the reversing mills might eliminate the need for an
additional deionizer at the plant.  Table 51 lists the estimated
capital and operating costs for chemical, membrane, and evapora-
tion processes on pilot-scale equipment.  All costs were based on
treating 100,000 gal/day and indexed to 1978.  Credits were given
to all processes for potential oil recovery and, in the cass of
[7'] Product literature.  Continental Water Systems Corporation,
     El Paso, Texas.
[78] Chian, E. S. K.; and Gupta, A.  Recycle of wastewater frcn
     vehicle washracks.  29th industrial waste conference; 1974
     May 7-9.  West Lafayette, IN, Purdue University, 9-20.
                                159

-------
             TABLE 51.  ESTIMATED COST ANALYSIS [79]

System
Chemical
Evaporation
UF
UF/RO
Capital
cost
$1,730,000
2,650,000
1,450,000
1,550,000
Total unit
operating cost
(S/1000 qal)
$11.33
8.75
7.73
8.81
Net unit
operating cost
($/1000 qal)
$5.36
2.90
1.77
1.12

UF/RO, for production of a high purity water that could be used
as a substitute for mill water and/or deionized water.  Recovery
and utilization of waste heat to generate steam is planned for
the evaporation process.

Examples of reverse osmosis performance are presented in
Table 52 [2].

            TABLE 52.  REVERSE OSMOSIS OIL AND GREASE
                       REMOVAL PERFORMANCE DATA [2]

Sample
1
2
3
Influent
mg/L
117
10.6
129
Effluent
mg/L
8.5
4.1
41
Removal ,
%
92.7
61.3
68.2

6.1.1.9  Carbon Adsorption—
Alternatively, a carbon adsorption process may be employed to
remove oils and toxic organics  [80] that have not Lctu removed by
emulsion braking and ultrafiltration.  Activated carbon is an
efficient means of removing organics with an adsorption capacity
of 500-1,500 square meters/gram.  It is limited to treatment of
less than 5,000 gal/day, due to column saturation [76].  Pretreat-
ment is desirable to maintain an influent of less than 50 ppm
suspended solids and less than 10 ppm for oil and  grease [2].
 r ••» ^N •»
 i / - •
  3]  Sonksen,  M.  K.;  Sittig,  F.  M.;  and Maziarz,  E.  F.   Treatment
     of oily wastes by ultrafiltration/reverse osmosis;  a case his-
     tory.   33rd  industrial waste conference;  1978 May.   West La-
     fayette,  IN,  Purdue University,  p.  696.
[80]  Skovronek, H.  S.; Dick,  M.;  and Des Rosiers,--P.  E.   Selected
     uses of activated carbon for industrial wastewater  pollution
     control.   Second annual  conference on new advances  in separa-
     tion technology;  1976 September 23-24; Cherry Hill,  NJ.


                                160

-------
In addition to a filtration unit, a granular activated carbon ad-
sorption treatment system requires two or three activated-carbon-
containing adsorption columns, a holding tank,  liquid transfer
pumps, and equipment for reactivation; i.e., a furnace, quench
tank, spent carbon tank, and reactivated carbon tank [2].

The necessary equipment for a two-stage powdered carbon unit is
as follows:  four flash mixers, two sedimentation units, two
surge tanks, one polyelectrolyte feed tank, one dual media fil-
ter, one filter for dewatering spent carbon, one carbon wetting
tank, and a furnace for regeneration of spent carbon.

Powdered carbon is less expensive per unit weight than granular
carbon and may have slightly higher adsorption capacity, but it
does have some drawbacks.  For example, it is more difficult to
regenerate; it is more difficult to handle (settling characteris-
tics may be poor); and larger amounts may be required than for
granular systems in order to obtain good contact.

Thermal regeneration, which destroys adsorbates, is economical if
carbon usage is above roughly 454 kg/day (1,000 Ib/day).  Reacti-
vation is carried out in a multiple hearth furnace or a rotary
kiln at temperatures from 870°C to 988°C.  Required residence
times are of the order of 30 minutes.  V.'ith proper control, the
carbon may be returned to its original activity; carbon losses
will be in the range of 4-9 percent and must be made up with fresh
carbon.  Chemical regeneration may be used if only one solute is
present which can be dissolved off the carbon.  This allows mate-
rial recovery.  Disposal of the-carbon may be required if use is
less than approximately 454 kg/day (1,000 Ib/day) and/or a hazard-
ous component makes regeneration dangerous.  Wet oxidation for
regeneration has been introduced for powdered carbon systems [2].
The resins, generally raicroporous styrene-divinylbenzenes, acrylic
esters, or phenol-formaldehydes, can be used to substitute carbon
in  ..he adsorption system [2].

Table 53 illustrates performance data for - i.1 and grease removal
by carbon adsorption [2].

          TABLE 53.  CARBON ADSORPTION PERFORMANCE DATA
                     FOR OIL AND GREASE REMOVAL  [2]
                      Influent   Effluent  Removal,
             Sample	mg/L	mg/L	%

               1         4.1       3.3       19.5
               2        41.0       2.0       95.1
                                161

-------
6.1.1.10  Aerobic Decomposition--
Aerobic decomposition is the biochemically actuated decomposition
or digestion of organic materials in the presence of oxygen.   The
chemical agents effecting the decomposition are microorganism
secretions termed enzymes.  The principal products in a properly
controlled aerobic decomposition are carbon dioxide and water.
Aerobic decomposition is used mainly in the treatment of organic
chemicals and lubricants used in the industries that u^e organic
lubricants [2].

As a waste treatment aid, aerobic decomposition plays an impor-
tant role in the following organic waste treatment processes:

      1.  Activated sludge proces.s
      2.  Trickling filler process
      3.  Aerated lagoon

Advantages of aerobic decomposition include:  (1) low BOD concen-
trations in supernatant liquor, (2) production of an odorless,
humus-like, biologically stable end product with excellent de-
watering characteristics that can be easily disposed of, (3)  re-
covery of more of the basic fertilizer values in the sludge,  and
(4) few operational problems and low initial cost.  The major
disadvantages of the aerobic decomposition process are (1) high
operational cost associated with supplying the required oxygen,
and (2) sensitivity of the bacterial population to small changes
in the characteristics of their environment

6.1.1.11  Evaporation [50]—
Evaporation is used in West Germany to dewater emulsified oils.
The emulsified oil is heated in an unit as shown in Figure 51.
The oil concentrate is taken off by a pump and further dewatered
in an evaporator.  A typical example of this process is the Faudi
process.  The Faudi process involves the evaporation of water by
an evaporator with several (different level) platforms.  This pro-
vides best utilization of the energy since the oil phase furnishes
the calories needed by the process.  A preliminary filtration is
applied to catch the oils which escaped.  An active carbon bed is
connected to the equipment, which eliminates the odor of the water
phase.

In the process a water phase of less than 20 mg of oil per liter
is produced.  Completely automatic and continuous type installa-
tions exist with capacities of 250 to 3,000 liters per hour.

6.1.2  Economic Evaluations

The literature indicates that metal finishers perform emulsion
treatment only to fulfill environmental regulations and local
sanitary sewer ordinances.  Also, reclaimers are willing to
handle only emulsions of high oil concentrations.  Such circum-
stances may suggest that no or weak economic incentives exist for


                                162

-------
J
                                           •ItfflOl
                                     Hf	
                                         circulating cis
      Figure 51.  Evaporation unit for emulsified oil [50].

handling emulsions for the purposes of oil recovery.  However,
this generally speaking, is not the case.

For those end users/reclaimers/re-refiners who are highly cost
conscious and technically capable, there are economic benefits to
be gained from emulsion treatment.  Technically capable end-users
can save significant amount of money from treating emulsions and
knowledgeable reclaimers/re-refiners have lucrative businesses
treating these materials.  The following sections present a
compilation of information available in the open literature
concerning costs of emulsion treatment.

6.1.2.1  In-plant Processes and Costs—
No two companies process the same fluid compositions, or have the
same equipment and the sanie overhead; hence, there are no "typi-
cal" cost examples.  Equipment costs vary considerably depending
upon type, size, and supplier.  Table 54 gives approximate equip-
ment costs at different processing volumes for continuous gravity
settxing tanks, oil separators and skimmers, pressure and vacuum
filters, dissolved air flotation, and centrifuges.  Table 55 gives
approximate equipment costs at 1,000 gal/day for ultrafiltration
systems and coalescing filters.

Table 56 shows the estimates of capital and oper; -ing costs for
electrolytic treatment for a plant size of about 76 m3/day
(^O^OO gallon/day"   Economic projections are presented for a
process with air bubblers—without automation, with dissolved
air  "• otation—without automation, and with dissolved air
flotav. on—with automation.

Purchase costs can vary considerably by the volume to be processed.

Costs of operating a waste oil recycling plant include variable
costs (chemicals, utilities), fixed costs (labor, overhead), and
if processed and sold by the company, corporation expenses and tax
                                163

-------
TABLE 54.   LOME EQUIPMENT CHOICES AND ESTIMATED COSTS
             AT DIFFERENT  PROCESSING  LEVELS  FOR 1981  |50]

Continuous flow
gravity settling
tanks
Oil separator
and skimmer
Pressure
filter
Vacuum
filter DAF
Centrifuge
Purchase cost

50,000 gallons           $ 7,000
500,000 gallons            8,000
1,000,000 gallons         14,000
5,000,000 gallons         18,000

Installation cost

50,000 gallons            $4,000
500,000 gallons            6,000
1,000,000 gallons          9,000
5,000,000 gallons          9,000

Yearly maintenance
  cost	

50,000 gallons              $500
500,000 gallons              500
1,000,000 gallons            500
5,000,000 gallons            700
                        $ 3,000
                         10,000
                         13,000
                         15,000
                         $3,000
                          3,000
                          3,000
                          3,000
                         $J ,500
                           J ,500
                           1,500
                           2,000
$ 1,500
2,000
3,000
15,000
$1.500
2,000
3,000
5,000
$ 1,000
2,000
5,000
20,000
$40,000
40,000
40,000
50,000
$5,000
5,000
5,000
5,000
$1,000
2,000
4,000
8,000
$8,000
8,000
8,000
8,000
$16.000
16.000
16,000
16.000
$ 600
600
600
3,000
$27,000
27,000
35,000
55,000
$ 54,000
54,000
70,000
110,000
$1,000
1,100
1,300
1,500
                                                                 (continued)

-------
                                            TABLE 54  (continued)
                              Continuous flow
                              gravity settling
                                   tanks
                 Oil  separator
                  and skimmer
                Pressure
                 filter
          Vacuum
          filter
DAF
Centrifuge
         Depreciation cost
           (Average total
           costs over 10
           year equipment
           life)
in
50,000 gallons
500,000 gallons
1,000,000 gallons
5,000,000 gallons
$1,600
1.9CO
2,800
3,400
$2,100
2,800
3,100
3,800
$ 1,300
24,000
4,600
13,000
$ 5,500
6,600
8,500
13,500
$2,000
2,700
2,700
5,400
$ 9,100
9,200
11,800
18,000
                 Gallons    Gallons/hour   Gallons/minute
                   50,000
                  500,000
                1,000,000
                5,000,000
125
250
500
800
 2
 4
 8
13
(operates  one  shift,  20% at  time)
(one shift)
(one shift)
(three daily shifts)

-------
         TABLE 55.  ESTIMATED COSTS FOR ULTRAFILTRATION
                    SYSTEM AND COALESCING FILTER,  1961


                                                  Coalescing,
 	Ultrafiltration3	(vertical)	

 Purchase cost,  S             56.490              26,500 (with separator
                                                29,500)
 Operating cost, $
    (250 days per year,
    2 shift per day)           28,938              Low

 Depreciation (over 8
    years, 50% after tax), $     3,630/year          10%

 Maintenance, $                                 Low
 Membrane replacement,  $      2,550/2 ye-' rs        No


 aDerived from Table 18 of Reference [35].

   Manufacturer contact.
            TABLE  56.   CAPITAL AND OPERATING COSTS OF
                        ELECTROLYTIC TREATMENT [71]     .     -  -

                                             CapitalOperating
  	    Process	cost,  $   cost,  $/m3

  With air bubblers  -  without automation    50,000       0.09

  With dissolved air flotation - with
    automation                               80,000       0.08

  With dissolved air flotation - without
    automation                               85,000       0.08


  aManpower would  be decreased.

expenses.  These are broken down in Table  57 for a company  annually
recovering 200,000 gallons of oil from  one million gallons  of waste
fluid.  According  to figures in Table 57,  the cost of  reclaimed
oil is $0.88/gallon.  Virgin oil costs  range from $0.80-1.90/gallon
depending upon  the oil grade and additive  content.  So oil  reclam-
ation is economical.

The potential for  reuse depends on the  original application and  on
how clean the recycled oil is.  If not  suitable for the original
                                 166

-------
    TABLE 57.   WASTE OIL RECYCLING PLANT OPERATION COSTS  [50]
             Cost itera
             Cents/gallon of
              recovered oil
$/Million gallons
 of waste fluid
CnemJcals
Electricity
Total variable costs
Direct labor
Supervision and indirect labor
Building maintenance
Equipment maintenance
Insurance and property taxes
Depreciation
Capital interest
Total fixed costs
Total process costs
25.000
6.000
31.000
16.000
16.000
0.187
1.460
1.470
9.9550
11.595
56.662
87.662
50,000
12,000
62,000
32,000
32,000
375
2,920
2.940
19,900
23,191
113,386
$175,386

application, a new application with less stringent quality  speci-
fications must be found.  Typically, because of price variations.
the soluble oils are more likely to be recycled than the cutting
oils (Table 58).                 '                    -       ..
    TABLE 58.  METALWORKING FLUID TYPES AND PRICES, 1981  [50]
       Fluid
                 $/gallon
   Cutting oil
   Lube start
   Hydraulic oil
   Soluble oil
0.55
1.30
1.60
1.85 (may cost $7-10/gallon with additives)
The water phase from emulsion breaking can be discharged  in  the
local sewer system after appropriate clarification or  recycled
back into the plant for nonpotable uses.

The sludges produced in the process can be either hauled  away or
further processed to a 95 percent oil concentrate at a cost  of
about 5-35C/gallon.  Selling the oil concentrate may bring 20-
70C/gallon in revenues while substantially reducing disposal
costs.

The solids which are separated during concentration steps are
mostly metal fines suitable for landfill or can be sold as scrap.
                                167

-------
6.1.2.2  Reclaimer Costs [50]—
Reclaimers work wath oil emulsions varying in concentrations from
5 to 95 percent oil and available from the metal finishing industry
at a cost of 10-2(K/gallon plus up to 20C/gallon freight charges.
Heat, acid, and polymer may be added to break the emulsion and form
a 95 percent oil concentrate.

The concentrate from in-house processing and the 95 percent oil
concentrate purchased from outside sources are treated with earth
and clay followed by solids filtration (refer to Section 6.2.2).
This costs about 54C/gallon and produces a 99.9 percent oil con-
centrate.  This concentrate is worth $0.70-$1.50/gallon (average
$1.10/gallon) and it may be sold as fuel or gear cutting fluid,
or be further processed.

The oil concentrate can be vacuum stripped (medium temperature
re-refining at 550°F) producing a 99.99 percent oil at a cost of
about, 30C/gallon.  The value of the oil ranges from $1.50 to
$2.20/gallon (average $1.80/gallon) and may be sold as base stock
for new lubricants or fluids or as fuel.

Some relcaimers/re-refiners may replace lost additives before the
oil is sold back to the user.  This may cost: 10-650/gallon for
hydraulic oils and even more for the expensive additives for roll-
ing fluids.  Rejuvenated fluids are generally sold back to the
user at anywhere between $0.70-1.00/gallon for hydraulic fluids
and from $1.00-3.00/gallon for rolling oils.

6.1.3  Alternative Disposal Technologies

Waste' oils can be disposed of by incineration, landfilling,' "land
application, or road oiling.  The following discussion addresses
these disposal technologies.

6.1.3.1  Incineration—
Waste oil  from metalworking operations may i>e thermally decom-
posed by incineration.  Usually the incinerators are privately
owned and centrally located.  A few plants may have sufficient
waste to economically justify installation of an incirarator on
site.  It is possible to recover the heat generated via incin-
eration and use it to heat the plant, produce hot water, etc.
This results in a reduction in the quantity of fuel needed for
these heating and process requirements.

The types of incinerators available for combustion of waste oils
include:   liquid waste  incinerators, rotary kilns, multiple
hearth furnaces, and fluidized beds [81-83].  Waste oils are
 [81] Wachter, R. A.; Black-wood, T. R.;  and Chalekode, P. K.  Study
     to determine need  for standards of performance  for new sources
                                                       (continued)


                                168

-------
also sometimes combined with refuse and disposed of by incin-
erators designed primarily for solid waste.  Table 59,shows
waste oils and other liquid wastes from metalworking operations
which can be burned by incineration.

         TABLE 59.  LIQUID WASTES BURNED BY INCINERATION
                 Separator sludges
                 Skimmer refuse
                 Oily waste
                 Cutting oils
                 Coolants
                 Phenols
                 Vegetable oils
                 Still and reactor bottoms
                 Animal oils and rendering fats
                 Lube oils
                 Soluble oils
                 Polyester paint
                 PVC paint
                 Latex paint
                 Thinners
                 Solvents
                 Resins
Liquid injection incinerators can be used to dispose of most com-
bustible liquid waste with a viscosity less than 10,000 SSU. -
Fluidized bed and rotary kiln incinerators can be used to dispose
of solid, liquid, and gaseous combustible wastes.  The multiple
hearth incinerator has been utilized to dispose of sewage, sludges,
tars, solids, gases, and liquid combustible wastes.
 (continued)

     of waste solvents and solvent reclaiming.  Washington, DC;
     U.S. Environmental Protection Agency; 1977 February.  106 p.
     Contract 68-02-1411.

 [82] Sxttig, M.  incineration of industrial hazardous wastes and
     sludges.  Pollution Technology Review No. 63.  Noyes Data
     Corporation, 1979.

 [83] Ottinger, R. s.; Blumenthal, J. L.; Dal Proto, D. G.;
     Gruber, G.  I.; santy, M. J.; and Shih, C. C.  Recommended
     methods of  reduction, neutralization, recovery, or disposal
     of hazardous waste; Volume III, disposal process descrip-
     tions - ultimate disposal, incineration, and pyrolysis proc-
     esses.  Cincinnati, OH; U.£. Evironmental Protection Agency;
     1973 August.  251 p.  EPA-670/2-73-053C.  PB 224 582.
                                169

-------
In order to determine the proper type of incinerator system for
use in a particular waste disposal situation, certain basic fac-
tors must be considered.  These include waste toxicity, disposal
rate, corrosiveness, operating temperature and material selection,
secondary abatement requirements (air, water or solid pollution
control), steam plume generation, waste heat recovery and costs.

The exhaust gases resulting from incineration may contain mater-
ials such as trace metals from waste oils that should be removed
from the gas before expulsion.  Not all the metals leave the
incinerator in the flue gases.  Some form of organic-metallic
compounds are left in the ash, so consideration should be given
to the environmental impact of disposing of ash with a high
metallic content.

Although incineration can be extremely effective in destroying
certain types of wastes, it is important to recognize that the
cost of incineration for wastes can vary widely.  The cost de-
pends especially on the type of facility required to handle the
waste, which determines the capital investment, the costs of
energy (e.g., as auxiliary fuel), and the cost for air and water
emission control equipment required [82-84].

The cost of incineration of high-Btu-value waste with no acute
hazard is in the range of $50-300/metric ton ($0.19-1.14/gallon).
.For highly toxic heavy .metals liquid wastes, the cost of incin-
eration can be as high as $300-1,000/metric ton ($1.14-3.78/gal-
lon)  [85],

Generally speaking, incineration is technically viable and envi-
ronmentally desirable, although the high unit costs will cause
industry to prefer to utilize other less costly alternatives if
they are acceptable to regulatory agencies.

6.1.3.2  Landfill Disposal—
Landfill disposal of waste oils in an environmentally safe method
when properly regulated.  This method of disposal is also econom-
ically attractive since it is relatively cheap.

The RCRA does not list waste metalworking oils as hazardous waste,
so it is necessary to conduct RCRA testing  to determine whether
waste oil is hazardous or nonhazardous.  Di~oosal practice and
 [84]  Ackerman,  D.;  Clausen,  J.;  Grant,  A.;  Johnson,  R-;  Shih,  C.;
      Tobias,  R.;  Zee,  C.;  Adams,  J.;  Cunningham,  N.;  Dohnert,  E.;
      and Harris,  J.  Destroying  chemical  wastes  in  commercial
      scale  incinerators;  Final Report - Phase  II.  "Washington,  DC;
      U.S. Environmental Protection Agency;  1978.  130 p.   EPA-630/
      SW/55C.  PB  278 816.

 [85]  Industry Week, p. 56,  1971  June  15.


                                 170

-------
costs will depend on whether waste oil is hazardous or nonhazard-
ous.  If waste oil is hazardous, its disposal mus\: meet RCRA
requirements, and must be disposed of in a hazardous waste land-
fill. ' Nonhazardous waste oil can be disposed of cheaply in a
sanitary landfill.  Waste oil is often mixed with refuse cr soil
or other oil absorbent materials to solidify it prior to landfill
disposal.  This practice will minimize leachate problems.  Poten-
tial contamination of the grcundwater through leachate is a major
concern in disposing of waste oil by landfiiling; nevertheless,
landfilling is safe if properly managed and regulated.

6.1.3.3  Land Application—
.Waste oil can be disposed of by breaking it down into harmless
products.  This is accomplished by soil microorganisms.  The used
oil is spread atop the land where it can be biodegraded.  The soil
microorganisms oxidize the oils or convert oiJy waste into cell
protoplasm, producing byproducts of gases and humus  (partially
reacted organics) along with organic acids (an intermediate prod-
uct).  The b?.cteria and fungi which grow the fastest are those
using hydrocarbons for food.  Some mineral nutrients important for
microbial growth are carbon, hydrogen, oxygen, potassium, sodium,
calcium, and especially nitrogen and phosphorus.  Microbial growth,
and therefore oil decomposition, is increased by the use of fertil-
izers.  Soil microorganisms favor neutral soil; therefore, soil
which is acidic may require the addition of agricultural-grade
limestone as a neutralizing agent.

Temperature also plays a role in the oil decomposition rate.  Oil
decomposes much faster in warm than in cold climates.  The opti-
mum temperature for the incubation of most hydrocarbon-oxidizing
organisms is reported to be 86°F.  To provide oxygen for soil
Microorganisms, the soil is- aerated by disking.  This disking or
stirring of the soil also disperses the hydrocarbon molecules,
making them more readily available to microbial attack.  Soil
saturated with oil or water has its air spaces filled, reducing
the oxygen available to soil microorganisms.  Without sufficient
oxygen the number of microorganisms are few, resulting in a very
slow oil decomposition rate.  Some hydrocarbons, such as waxes
and heavy oils, are more resistant to decomposition, because less
surface area is exposed to microbial attacks.

Oil, when discharged without adequate treatment or proper dis-
posal, is a  serious pollutant of water and land.  In 1969, the
Marathon Oil Company in Robinson,  Illinois, used land spreading
to dispose of oily sludge stored in two lagoons over a period of
five years.  The sludge, consisting of 35 percent oil, was spread
on the ground to a depth of about 4 inches.  When the sludge was
dry it was mixec* with the soil by disking to a depth of about
18 inches.  A rainstorm occurred before cultivation of the sludge
                                 171

-------
and resulted in erosion of the oily sludge and its deposition in
a small lake, killing some fish [86].

Plants may also be affected by such oil.  Large applications of
oil to land are often toxic to plants due to the narcotic effect
that volatile fractions have on plants and the reduction of
manganese to the toxic manganous form.  Plants growing on the
land-spread area may acquire high levels of metal ions.  Trace
metals may be found in many used oils.  If oils containing trace
metals are deposited on the ground, vegetation may be contami-
nated and eventually animals may eat this vegetation.

The British attempted to use municipal sewage sludge as a soil
conditioner until they discovered that the metal content of the
sludge constituted a hazard to agriculture.  Twelve years after
the project was discontinued, vegetables grown on'the soil still
contained abnormally high levels of chromates, copper, nickel,
lead, and zinc.  Land saturated with oil eventually returns to a
productive state, however,  Humble Oil Company near Houston, Texas,
land-spread oily sludge 4 to 5 inches thick; 3 to 4 months later
grass was growing.  More oil may be added to the soil of a land-
spreading site when the soil returns to a brown friable condition
[85].

Other used oil components, such as aromatic hydrocarbons, may-pre-
sent problems because of their lengthy degradation process.  In
addition, many of the additives that are combined with industrial .
oils may cause adverse environmental effects if not properly  -
treated before disposal.  Additive compounds containing phos-
phates or phenols can adversely affect water quality.  M\nute
quantities of phenols cause objectionable taste and odor in  •
drinking water and induce cancer in lower animals [86].

Favorable locations for land-spreading sites are those with deep,
fine-textured soils which readily absorb oil, thereby reducing
the chances of a contaminated water table.  Clay subsoils also
help prevent contaminated water tables.  To reduce surface water
contamination, the site should be flat with poor drainage.
Indiscriminate dumping on porous, coarse, or shallow soils is
likely to cause runoff water pollution.

Soil farming can be a viable disposal method for oily waste under
diverse and sometimes adverse conditions of topography, soil type
and climate.  One aluminum manufacturer has successfully disposed
of over 55 million gallons of waste oil emulsion coolant from their
rolling mills by means of soil farming.  The waste oil emulsion,
 [86] Yates, J. J.; Groke, K. G.; Klazura, A. G.; Spaite, A. R.;
     Chiu, H. H.; Mousa, Z.; and Budach, K.  Used oil recycling
     in  Illinois:  data book.   ETA Engineering,  Inc., 1978 October.
     135 p.


                                172

-------
containing approximately 0.5 to 1.0 percent mixed hydrocarbons, is
being applied at a rate of 0.5 inch per week in a 14.6-acre field
situated on the flood plain of the Ohio River with minimal cost.
Continuous monitoring of the disposal area has indicated no obvious
deterioration of the physical, chemical, or biological conditions
of the soil, other than the accumulation of approximately 40 mg of
hexane-extractable residue per 100 grams of soil in the surface
horizon [87,88].

6.1.3.4  Road Oiling/Dust Control  [86]—
Road oiling and dust control are indirect methods for the dis-
posal of used oil.  Although virgin petroleum products are used
for road oiling, a large fraction  is used oil, which is generally
cheaper than a specially compounded oil and thus more economical-
ly attractive in the short run.  In 1974, it was estimated that
200 million gallons of used crankcase oils plus unknown amounts
of other used oils were used annually in the United States for
road oiling and dust control.

The oil is usually applied to rural dirt roads through drilled
pipe spray headers mounted on tank trucks.  The application rate
is left to the discretion of the applier and ranges from 0.025 to
0.05 gallon per square foot of road, depending on road composi-
tion and dust conditions.  Very little of the oil applied to the
road actually remains there, necessitating periodic reapplications.
A road may be oiled from one to four times a year.  In a study
dealing with used oil applied to rural roads, it was observed
that "one percent of the total oil' applied to the roads remained
in the top inch.  The rest was lost in a number of ways, includ-
ing being washed from the road by  rain, leached through the road,
carried away by the wind on dust particles, picked up by passing
vehicles and carried elsewhere, biodegraded, and volatilized.  The
extent and rate of oil loss depends on road composition, weather
conditions, the time of the first  rain after oiling, the type  and
quantity of oil applied, road traffic conditions, and the ability
of the road surface to biodegrade  the oil.  Around 25 to 30 per-
cent of the oil applied to the road is lost by biodegradation,
adherence to vehicles, and volatization.  The remaining 70 to
75 percent  leaves the road with water runoff and dust transport,
contaminating surface waters.

Oil which makes its way into  a water  system becomes a nuisance
and, in sufficient quantities, a health and ecological hazard.
Used oil enters water systems in many ways:  direct discharge
 [87]  Kincannon,  C.  B.   Oily waste  disposal  by  soil  cultivation
      process.  Washington, DC;  U.'s.  Environmental Protection
      Agency;  1973.   EPA R2-72-110.

 [88]  Liu,  D.  L.;  and Townsley,  P.  M.   Lignosulfonates  in  petroleum
      fermentation.   Journal of  the Water  Pollution  Control  Feder-
      ation.   531-537,  1970 April.


                                 173

-------
 into waterways,  dumping  into  storm  sewers, washing  off -roadways
 into water ways  (rainwater may  scavenge  oil  from  road surfaces
 and then percolate  into  the groundwater), or direct deposition on
 or in.the ground.

 Along with the oil  that  leaves  the  road  surface and is' deposited
 into the surrounding ecosystem  are  heavy metals and other  addi-
 tives -which  are  taken up by plants  and consumed by'animals,  either
 by drinking  contaminated water  or by eating  plants  that  have tak/tn
 up metals.   In Alberta,  Canada,  in  1971, cattle were poisoned by
 drinking water containing lubricating oil  from a  road treated with
'an oil  that  contained triaryl phosphate  as an additive.

 Because of the negative  environmental effects resulting  from the
 runoff  of used oils from roads,  most states  prohibit the use of
 any used oil fcr road oiling  or dust control. Because this  regu-
 lation  is difficult to enforce,  used oil may still  be widely used
 for road oiling  and dust control.

 6.1.4   Sludges Generated by Oily Waste Treatment,

 Sludges are  produced from in-plant  processing equipment  such as
 oil/water separators, centrifuges,  filters,  coalescers,  ultrafil-
 tration and/or reverse osmosis  systems,  dissolved air  flotation,
 and still bottoms from vacuum distillation.   Composition data for
 these  sludges are difficult to  find in published  literature  except
 for sludges  from oil/water separators.  Table 60  gives character-
 ization data for sludges obtained from various sources  (as indi-
 cated  at the footnote of the  table).  Table  61 shows the organic
 components  in sludges designated in Column 3 of Table  60.  The
 concentrations and even  presence of various  hazardous materials
 varies  due  to differences in  the characteristics  and origins of the
 various sludges  collected during any given time period.  Sludges
 from  in-plant processing usually contain a large  amount  of heavy
 metals  and  are considered to  be potentially  hazardous.

 Sludges can  be disposed  of by using compatible techniques  men-
 tioned  in Section 6.1.3. However,  incineration is  the most  popular
 method  for  disposal.  The disposal  methods are used both on-site
 and off-site, using either plant facilities  or contractor  p.lcint.

 6.2  DISPOSAL AND RECLAMATION OF STRAIGHT  MINERAL OILS

 6.2.1   In-Plant  Reclamation Technologies

 In-plant  reclamation technologies are usually employed to  remove
 the two most common contaminants, solids and water, in used min-
 eral  oils  and offer a low-cost  method for  recycling large  quanti-
 ties  of used oils.   These include gravity  separation of  solids
 and water,  centrifuging, filtration, and water removal by  coal-
 escing. Descriptions of processes  and equipment  have been dis-
 cussed in  Sections 6.1.1.1  through  6.1.1.4.


                                 174

-------
       TABLE 60.  ANALYTICAL CHARACTERIZATION  OF SLUDGES
                   COLLECTED FROM  IN-PLANT PROCESSING
                   EQUIPMENT FOR EMULSIFIED OILS  ,

Sample desionation
Sample collected at
Inorganic metals, mg/kg
Ag
Be
Cd
Co
. Cr
Cu
Fe
Hg
Li
Ni
Pb
Zn
Inorganic nonmetals, mg/kg
Br
Cl
P
s -
As
Noncombustible ash, %
Solids, %
Compounds contained, mg/kg



Major components


Flash point, °F
PH
1
oil separator

h
ND
ND

48
Trace

ND

ND
ND
510

ND
ND
650
ND
ND
ND
24
Phosphates, 1988



Oil, 40%
Water, 60%



2
oil separator

0.6

7.4
2.6
15.0
436
317
0.2
0.5
15.6
402
4,905



1,550


8.02
9.1




Oil, 41.1%
Water, 49.8%
Dirt, 8.1%
Over 200
B.Z
3
API separator


0.84
13

370
970

0.6

200
1.700
8,400

5.7
1,300
• 730
"'6,300
4.6

. 05
Cyanides, 0.94
organic com-
pounds, see
Table 61



206
6.2

Designation No.  1 to 3 are  from generator waste  analysis form to landfill ob-
tained from State EPA offices.
Not detected,  detection limit = 0.2 mg/kg.
                                  175

-------
 TABLE 61.  ORGANIC COMPONENTS IN SLUDGES DESIGNATED
            IN COLUMN 3 OF TABLE 60.
             ,'arameter
Results, ppm
Base/neutral fraction

Combined anthracene and phenanthrene
Bis (2-ethylh zxyl )phthalate
Chrysene
1,3-Dichlorobenzene
Fluoranthane
Fluorene
Naphthalene

Acid fraction

Phenol
Pentachlorophenol

Volatile fraction

Benzene
1,1-Dichloroethane
1,1-Dichloroethene
Ethylbenzene
Methylene chloride
Tetrachloroethene
1,1,1-Tr:' chloroethane
Trichlorofluoromethane
Toluene
Xylene
    24.0
     8
     2.3
     8.9
     1.8
     8.6
    58
     2.6
     0.11
     0.23
     5.2
     0.91
    10
     1.6
     0.52
     6.0
     0.034
    21
    17.2

  (continued)
                          176

-------
               TABLE 61 (continued)
	Parameter	Results, ppm

3,5-Dim thylheptane                         4.4
Octane                                      4.8
Propan •>!                   .                 0.7
2,3-E-j nethylcyclobutanone     ,              1.6
Benze; =>  (T-1 methylethyl)                  0.33

Miscellaneous base/neutral

Various saturated hydrocarbons
  Cn-Cas                               4,000

Miscellaneous acid fraction

Thallic acid           ...                2.5
Hexadecanoic acid                          22.0
Octadecanoic acid                          16.0

Miscellaneous volatile

2-Methyl-l-pentene                          0.46
2,2-Dimethyl propanol                       2.26
1, l-.Uimethylcyclopentane                    0.23
4-Methyl-l-hexene                           0.82
Methylcyclohexane                           5.9
Ethylcyclopentane                           0.1
4-Methyl-2-pentanone                        1.46
3,4-Dimethylheptane                         2.96
2,3,3-Trimethylhexane                       0.94
l,2,3-Trimethylcyc3opentane                 0.46
Ethylcyclohexane                            4.6
1,3-Dimethylcyclohexane                     3.65
                           177

-------
For highly refined mineral oils, which are generally formulated
without polar additives,and usually are removed from service
after only slight contamination, more sophisticated equipment is
used to return the used oil to a like-new condition.  The two
most common processes are flash distillation and chemical
adsorption [49].

The flash distillation step.is usually carried out around 200°F
and with a partial vacuum.  This temperature ensures rapid and-
complete removal of water and low-boiling-point materials such as
solvents, yet is not high enough to thermally degrade the oil it-
self.  Chemical adsorption uses polar absorbent materials to re-
move the usually polar acid degradation products.  Chemical •
adsorption is most effective with waste oils that have,an acid
number of 2.0 mg KOH/g or less and that have been treated to
remove particles and water.  High acidity oils require larger
volumes of adsorbent, which makes the adsorption uneconomical.
The most common filter material is fullers earth, though other
clays are available.

Reclamation systems are available for either fixed or portable,
batch or continuous operation.  Reclamation services are also
available from independent companies.

Used straight mineral oils can also be used on site as fuel.  How-
ever, special furnace design considerations are necessary.  Low
flash point, introducing the risk -of explosions, and presence of
sulfur and chlorine compounds used as additives, may cause damage
to furnace linings and other equipment and also form gaseous pol- •
lutants which require control. '

6.2.2  Re-refining Technology

Most straight mineral oils can be re-refined by indepandent ;re-
refiners.  The waste oil is pre-filtered to remove most of the
solids, solvents, and water, leaving essentially the base oil and
additive package.  The additives and degradation porducts are
then removed so that a high quality basestock is produced.  This
basestock is reformulated with a conventional additive package to
produce a product which can be used in the same applications as
an oil using a virgin basestock.  The prevalent re-refining "tech-
nologies are discussed in the following section.

6.2.2.1  Re-Refining Technologies—
6.2.2.1.1  Acid/Clay Treatment  [89-92]—This is the most commonly
used re-refining process for waste mineral oils, (see Figure 52).
 [89] Hess, L. Y.  Reprocessing and disposal of waste petroleum
     oils.  Park Ridge,- NJ,-Noyes Data Company, 1979.

                                                      (continued)


                                178
                    . t>

-------
                                                                  CONOtNStR
       FLASH
       OCHtORATOflS
             <*»
                     OIL
-O
VD
                                   Figure  52.  Acid/clay treatment  (92].

-------
Waste oil is dehydrated by ".ash distillation at 300°F and atmos-
pheric pressure.  Light oij.s are also removed in this step.  When
the product oil has cooled to 100°F, it is transferred to an acid
treating unit where 4-6 volume-percent of 93 percent sulfuric acid
are"added.  The mixture is then agitated for 24-48 hours.  The
oxidized products and ash thus produced separate from the oil and
are removed as acid sludge from the reactor bottom.

The acid-treated oil is transferred to a stripping tower and heat-
ed to 550-600°F by steam to remove the remaining light oils and
odorous compounds.  The heating is discontinued after 12-15 hours
and the oil is transferred to a clay slurry tank where'it is al-
lowed to cool to *00°F.  About 0.4 Ib of clay, consisting of mate-
rials such as fullers earth, bentonite, attapulgite and diatomaceous
earth, per gallon of oil is then added while the mixture is ac-
tively stirred.  The cleaned oil is separated by filtration, and
the necessary additives are replaced before the oil is reused.

The acid/clay process is quite effective in removing the addi-
tives and degradation products, but unfortunately it generates
considerable amounts of acid sludge and contaminated clay.  Some
of this clay and sludge is used as fuel, but most has-to be dis-
posed of at waste disposal sites, (see Section 6.2.2.3).  The
increased cost of waste disposal and limited availability of
disposal sites has prompted a number of companies to develop
alternative clay and sludge disposal approaches.  Some of the
processes have reduced the amount of acid and clay necessary to
treat 'a gallon of re-refined oil, while others have completely
eliminated the use of acid and/or clay.

6.2.2.1.2  The IFF (Institut Francais du Petrole) Process  [89,
93-96]—OriginaTly, the IFF process was based on propane extrac-
tion of the dehydrated waste oil followed by conventional acid/
clay treatment.  It has since incorporated distillation to replace
the acid treatment and hydrofinishing as a final treatment,
(see Figure 53).
 [90] Whisman, M. L.; Goetzinger, J. W.; and Cotton, F. 0.  Waste
     lubricating oil research.  An investigation of several re-
     refining methods.  U.S. Department of the Interior, Bureau
     of Mines; 1974.  25 p.  RI-7884.

 [91] Blatz, F, J.;  and Pedall, R. F.   Re-refined locomotive engine
     oils and resource conservation.   Lubrication Engineering.
     618-624, 1979  November.
 [92] Waste oil recycling.  U.S. Department of the Interior, Bur-
     eau of Mines;  1975.   Issue Report Papsr.
 [93] Quang, D. V.;  et al.  Spent oil reclaimed without acid.
     Hydrocarbon Processing.  130-131, 1976 December.

                                                      (continued)


                                180

-------
      EXTPVUON SECTION
                                PfWAJff Sf PAIWTIfW SECTION
 fs'.'T Ci'.
 «"V OEH^CR'TION
                                 PROFANE
                                                        pnor>v:t ntcnvw SECTION
                                                       ...  	f-	.
                                                                 PROPANE
                                                                 MAKE UP
                 Figure  53.   IFF Process [95].

Dehydrated and preheated spent oil is mixed with liquid propane
in a reactor.  Propane addition is from 6 to 13 times the volume
of used-oil feed  [96].   Propane containing the dissolved oil is
removed from the reactor top whiTe insoluble residues are drawn
off at the reactor bottom.   Bottoms are mixed with a small amount
of fuel-oil and are  flashed  to recover the propane.  The remain-
ing residues with fuel oil are burned in a rotary furnace.

Propane is separated from oil in a double-stage flash distilla-
tion and is reliquefied  and  recycled.  The product oil is either
subjected to acid/clay treatment or distilled, clarified with
clay, and hydrofinished.

The IFP process does not totally replace acid/clay treatment, but
it uses a smaller quantity of treatment materials which results in
less waste.  The process also produces a high ash fuel oil which,
(continued)

[94] Audibert, M. M.;  et al.   The regeneration of the  spent
     oils.  Chemical Age of India.  26(12):1015-1019,  1975.
[95] Quant, D. V.;  Carriero,  G.;  Schieppati, R.; Comte, Al;  and
     Andrews, J.  w.  Re-refining uses propane treat.   Hydrocarbon
     Processing.  129-131,  1974 April.

[96] Deutsch, D.  F.  Bright prospects loom for used-oil re-
     refiners.   Chemical Engineering.  86(16):28-32, 1979.
                                 181

-------
if burned in ordinary combustion equipment,  causes tube fouling
problems.

Although the reported process yield is 82 percent of high quality
lube stock, the plant at Lodi, according to a DOE source, shows a
much lower yield of about 70 percent.

6.2.2.1.3  The PVH (Propane-Vacuum-Hydrogen) Process [89,97j—The
PVH process, developed by Pilot Research & Development Company,
consists of filtration and dehydration, followed by treatment
with propane at 180-190°F.  The propane is then stripped, the oil
is vacuum-fractionated at 650°F, and all but 10-15 percent is
distilled.  The condensed oil is hydrotreated and finished with
filtration.

The PVH process has a reported yield of 73 percent of high-quality
lube stock.  It is knov/n to require considerably less chemicals
and energy than many other commercial processes, and hence is more
economical.

PVH's dehydration and propane treatment steps are claimed to work
without heat-treating the used oil to excessive temperature.  Pro-
pane requirements are only four times the used oil feed rate,
which is two to three times less than other conventional propane-
based processes.

6.2.2.1.4  Snamprogetti Process [89,98]—This process, (see
Figure 54) was developed by Snamprogetti for Clipper Oil Italiana
S.p.A.  The process consists of water and light hydrocarbon elim-
ination by flash distillation, followed by selective extraction of
metals and polymers with propane.  This is followed by fractional
distillation and hydrogenation to produce virgin quality base oil.
The peculiarity of the process is in the second extracf.cn phase
and in the recycle of the residue from this phase to tl Q first
extraction stage.  It is known that the previous heatii>c; of a
charge prior to extraction (thermal treatment) allows ,v.-lymer
peptization and makes separation easier.

Construction costs are said to be twice those for a comparable
acid/clay plant, but operating costs are lower because of no need
for the  acid/sludge control system.
 [97] Cutler, E. T.  Re-refining:  selecting the best process.
     Third  international conference on waste oil recovery and
     reuse; 1978; Houston.  Pilot Research and Development
     Center, Merlon Station, PA, 163-168.

 [98] Antonelli, S.  Spent oil re-refining.  Third international
     conference on waste oil recovery and reus*; 1978 October 16-
     18; Houston.  121-125.
                                182

-------
           3. 4  f light hydrocarbons
           7. 1  I water
                     85.4
I	» gasoil
                                                   23.4
                                               ir   40,8
                                                        light oil
                                                        medium-oil
                                                  J_8-I_» bright STOCK
                                         «— propane
             Figure 54.  Snamprog&tti process  [98].

6.2.2.1.5  The Krupp Process  [95]—An application of propane at
supercritical conditions has been successiully tested at Fried-
rich Krupp, West Germany.  The process uses  countercurrent pro-
pane extraction to extract usable oil products from  a dehydrated
waste-oil feed.

Yields are said to be 90 percent (of drier oil,  after atmospheric
distillation removes water and gas oil)  and  costs are comparable
to those for conventional acid/clay technology.   Propane require-
ments are only one volume of propane per volumee of  water-oil
flow.  A patent has been filed but not yet granted for the
process,

6.2.2.1.6  The BERC Process  [89,91,99-105]—The BERC process,
developed at the Bartlesville Energy Technology Center of the
U.S. Department of Energy (DOE), (Figure 55) consists of dehydra-
tion, solvent precipitation of polymers  and  additives,  vacuum -
distillation, and clay treating or hydrofinishing.
 [99] Whisman, M. L.; et el.
      U.S. patent 4,073,719.
[100] Whisman, M. L.; et al,
      U.S. patent 4,073,720.
 U.S. Department of Energy,  assignee.
 1978 February 14.
 U.S. Department of Energy,  assignee.
 1978 February 14.
                                                       (continued)
                                 183

-------
               J
              Dohydraton/
              Stripping
Centrrfugitjon
Solvent
Stripping
                              Mytirohnifhing
                                           n
                                             OiStilUtwn

       Figure 55.   BERT re-refining process outlite  [105].
(continued) .

[101] Cotton,  F. 0.; et al.  Pilot-scale used  oil  re-refining
      using a solvent treatment/distillation process.   U.S.
      Department of Energy; Bartlesville Energy  Technology Center;
      1980.  BETC/RI-79/14.

[102] Brinkman,  D. W.; et al.  Environmental,  resource conserva-
      tion, and economic aspects of used oil recycling.   U.S.
      Department of Energy; Bartlesville Energy  Technology Center;
      1981 April.  DOE/BETC/RI-80/11.

[103] Brinkman,  D. W.; et al.  Solvent treatment of used lubri-
      cating oil to remove coking and .-fouling  precursors.  U.S.
      Department of Energy; Bartlesvii:.e Energy  Technology Center;
      1978 December.  BETC/RI-78/20.

[104] Engineering design of a solvent treatment/distillation used
      lubricating oil re-refining.  Houston, TX;. Stubbs Overbeck
      and Associates, Inc; 1980 June.  Final report to U.S.  Depart-
      ment of Energy, Division of Industrial Energy Conservation.

[105] Brinkman,  D. W.; and Whisman, M. L.  Waste oil recovery and
      reuse research at'the Bartlesville Energy  Technology Center.
      Third international conference on waste  oil  recovery and
      reuse; 1978 October 16-18; Houston.  1C9-175.
                                184

-------
The BERC process uses a solvent mixture of 1-butanol,  2-propanol,
and methylethyl ketone in a 1:2:1 ratio by volume.  This mixture
is used in a 3:1 solvent-to-oil ratio.  The solvent is continu-
ously recycled, with sludge the only waste.  The sludge can be
burned as fuel in the process with proper stack emission control
or used as an asphalt extender.  Clay-contacting or hydrofinishing
are usually incorporated into the BERC process for color and odor
improvement.

It appears that operating costs are almost identical for clay
treatment and hydrofinishing.  Capital costs are higher for the
hydrofinishing facility but this initial cost is offset somewhat
by higher product yields, better color and odor, and elimination
of oily-clay disposal costs.

6.2.2.1.7  Aliphatic Alcohol-Acid Treatment [S9,106]—This re-
refining prc ;ess was patented by Brownwel? and Renard and assigned
to ESSO Research and Engineering Company.  It involves treating
predistilled oils with 1-butanol.  The oil-alcohol solution is
then filtered to remove sludge and the alcohol is removed by dis-
tillation.  Fuming sulfaric acid is then added to strip the oil.

6.2.2.1.8  Gulick Process  [89,107]—This method is intended for
breaking the films absorbed on colloid-sr.zed contaminants that
are held in suspension by detergent additives.  The used oil is
treated with sodium hydroxide and hydroc,«n peroxide.  After set-
tling, the oil is removed from the sludge and centrifuged.  The
oil is then either distilled or treated with aluminum chloride',
which is effective for colloidal lion and organometallic iron
removal.

6.2.2.1.9  Caustic Treatment [89,108]—This process uses caustic
instead of acid to treat the oil.  Treatment with caustic mini-
mizes the formation of waste products which must be disposed of.
The process was patented by Chambers and Hadley to re-refine
used lubricating oil.  It involves flash dehydration to remove
water, mixing with oil with a boiling range of 150-250°F, treat-
ment with 1 weight percent of a 50 percent sodium hydroxide solu-
tion, centrifuging, and distillation.

The process eliminates acid sludge, but spent clay disposal
remains a problem.  In addition, a sludge is produced daring
 [106] Brownawell, D. W.; and Renard, R. H.  Esso Research and
      Engineering Company, assignee.  U.S. patent 3,639,229.
      1972 Feburary 1.
 [107] Gulick, G. L.  Quove Chenrcal Industries, Ltd., assignee.
      U.S. patent 3,620,967.  1W1 November 16.
 [108] Chambers, J. M.; and Hadley, H. A.  Berks Associates, Inc.,
      assignee.  U.S. patent 3,625,881.  1971 December 7.
                                185

-------
pre-treatment, and a high ash bottoms product  results  from the
distillation step.

6.2.1.1.10  The Philips PROP .Process  [39, 91, 96,109-113]—The'
Philips PROP process, Figure 56,  is an  oil  re-refining technology
developed by Philips Petroleum Company.   Waste oil  is  first blend-
ed with aqueous diammonium phosphate  (DAP),  which results in
formation of essentially insoluble metallic phosphates.   No pre-
drying of the feedstock, use of  solvents  or acids,  or  settling
are required.  Following removal of water ard  other.diluents,
temperature cycling of the oil agglomerates the solids,  which are
removed by filtration.  The resulting demetalized and  dehydrated

              DIESEL FUEL USE
                     BATTEO" LIMITS PLANT
                     PL*«JT o^'ONS
                     BurEB ALTERNATIVES
           Figure  56.   The  Philips PROP process [110]
 [109] Berry, R.   Re-refining waste oil.   Chemical Engineering.
      104-106,  1979  April  23.

 [110] Linnard,  R.  E.   Philips re-refining oil program.  Third
      international  conference en waste  oil recovery and reuse;
      1978; Houston.   Bartlesville,  OK,  Philips Petroleum Co.,
      127-135.

 [Ill] Re-refining.   Fluid  and Lubricant  Ideas,  p. 27, 1980 May/
      June.

 [112] Packaging re-refining technology:   the PROP process.
      Fluid and Lubricant  Ideas.   1979 Fall.

 [113] Linnard,  R.  E.;  and  Henton,  L. M.   Re-refine waste oil
      with PROP.   Hydrocarbon Processing.  1979 September.
                                 186

-------
oil is hydrotreated to remove unwanted sulfur, nitrogen, oxygen,
and chloro compounds and improve color.  This is followed by  fur-
ther stripping and fractionation.  Pre-fabricated skid-mounted
plants are available in 2, 5 and 10 million gallon-per-year ca-
pacities, and require only conventional utilities, services,  and
process materials.  The process is claimed to provide  90 percent
of recovery from waste oil.

6.2.2.1.11  The Recyclon Process [89,96,114-116]—This method of
re-refining spent oil is being marketed world-wide by  Leybold-
Heraeus of West Germany.  The most significant stages  of this
method, Figure 57, are treatment of waste oil after  it has been
filtered, dehydrated and freed from low-boiling components with
dispersed metallic sodium at elevated temperatures.  The sodium
serves to polymerize unsaturated olefins into components with
high boiling points.  When the reaction is completed,  the mixture

ft,
1
r^
-1
^
m»

T
I
mm

I

                    I Fihti
                    2 OrttytfrtiKwt |uofcm turani
                     Tout cvtpnati
                     Fraction* |. i.1
               Figure 57.  Recyclon process  [115]
 [114] Erdweg, K. J.  Recyclon  -  a  new  process  to revert spent
      oils into lubricants.  Third international conference on
      waste oil recovery  and reuse;  1978  October 16-18; Houston.
      93-97.
 [115] Fauser, F.  Recyclon  - a new method of re-refining spent
      lubrication oils without detriment  to the environment.
      Conservation and Recycling.   3:135-141,  1979.
 [116] Recyclon - a new process for the re-refining.of waste oil.
      Leybold-Heraeus, Vacuum  Process  Engineering Division.
      Trade Literature.
                                 187

-------
is stripped of its components in a conventional vacuum column.
The bottoms of the stripping column are subjected to total evap-
oration in short-path evaporators, leaving the impurities and
reaction products as residue.  The distillate is subsequently
split into the required fractions.  Process yield is'over 70 per-
cent re-refir.ed o"11: the remaining byproducts are used as fuel.

6.2.2.1.12  The Haberland KTI (Kinetics Technology International)
Process; 196,109,117]—This process, developed by Kinetics Tech-
nology International, B.V. (Zoetermeer, The Netherlands) in close
cooperation with Gulf Science and Technology Company, Figure 58,
involves a dewatering and gas/oil stripping step, an efficient
high vacuum distillation step, and a hydrofinishing step.  Frac-
tionation of base oils can be included if desired.  A 97 percent
effective yield compares favorably with typical acid/clay re-
refining yields of about 83 percent.  The process also eliminates
the problems of disposal of large quantities of contaminated clay
and sludge.
                 Figure  58.   KTI  process  [117].
 [117]  Havemann,  R.   Haberland and company and the KTI  waste oil
       re-refining process.   Third international  conference  on
       waste oil  recovery and reuse;  1978  October 16-18;  Houston.
       83-92.
                                 188

-------
6.2.2.1.13  The Matthys/Garap Process  [118]—This process  includes
settling and atmospheric distillation  at  180°C  to eliminate resid-
ual water and solvents.  Vacuum distillation is used'to  obtain the
different cuts, and hot centrifuging of the bottoms  is used to
extract heavy metals and carbonaceous  products.  Continuous acid-
ification of the cuts and bottoms  followed by centrifuging is used
to extract the acid tars.  Then, neutralization and  hot  bleaching
in a furnace are conducted,  followed by continuous cooling and
filtration.

6.2.2.1.14  Ultrafiltration  Process  [119,120]—The ultrafiltra-
tion process, Figure 59, involves  use  of  a solvent to provide
molecular-scale filtration of used oils.  Hexane is  used to re-
duce the viscosity of the oil.  The mix is then passed through a
semipermeable membrane, usually made of acrylonitrile co-polymers,
which allows only the light  hydrocarbons  to pass through and
                         Solv*M Rocowry
            Drying     Uttritiltrition
                         UltrvfilMrod So*** Rocowy from Uluatittrata
                           oil
 Figure 59.  Reclaiming  of spent oils by Ultrafiltration [119]
 [118] Dumortier, J.  Matthys/garap techniques.   Third internation-
      al conference  on waste oil recovery and reuse; 1973 October
      16-18; Houston.  99-107.

 [119] Audibert, F.;  et al.   Reclaiming of spent lubricating oils
      by Ultrafiltration.   Third international  conference on
      waste oil recovery  and reuse;  1978 October 16-18; Houston
      109-120.

 [120] Pare, G.; et al.  Institut Francais du Petrole, France,
      assignee.  U.S. patent 3,919,075.  1975 November 11.
                                 189

-------
retains heavier  hydrocarbons and metals.  Once  the  bulk of the
contaminants have  been removed,  the filtrate  is treated with an
acid/clay process  to remove the final level of  contamination.
Hydrofinishing is  used to bring the base oil  bacx to virgin qual-
ity.  The process  greatly reduces the amount  of acid and clay
necessary to achieve high product quality.  When an ultrafiltra-
tion process is  added to an existing conventional plant, the oil
yield increases  by about 7 percent and the sludge volume is dras-
tically reduced.   The ultrafiltration investment is paid off with-
in 3 to 5 years  for a plant with 20,000 ton-per-year capacity [120]

6.2.2.1.15  The  Pfaudler Test Center Proces?  [1211—The Pfaudler
test center process,  Figure 60, includes  a  filtration and dehy-
dration steps  that also remove galoline and other low boiling
contaminants.   A solvent extraction process is  then used to
remove sludge,  with evaporation cf the solvent  in a wiped film
evaporator.  The solvent stripped oil is  then degassed to remove
                                     2 Add solvent mulur* to O«ftv0ratad Oil
                                      Decam a'.*f mtttwre t«r>*t
                                     3 ReT*ov« wvriv wt*ng **'
                                     t D*gat o>i :o 'move runtinatt rmdual
                                      toiv*nt ano icm boufs
                                     5 Dniiii wi >n •" •« «*£ to l*M'«l«
                                                  WO mic>ont
                                                      '620°F
                                                             Oil
                                                             75\
                                                            fl«o»«r>
                                                 Onraludg*
       Figure  60.   The Pfaudler test  center process f!21].
 [121]  Bishop,  J.;  and Arlidge, D.  Recent technology development
       in evaporative re-refining of  waste oil.  Third internation-
       al conference on waste oil recovery and reuse; 1978 October
       16-18;  Houston.  Rochester, The  Pfaudler Company, 137-150.
                                 190

-------
any residual solvent and vacuum distilled.  This is followed by
clay treatment and filtration to recover 75 percent  of the start-
ing material as high quality base oil.

6.2.1.1.16  Luwa Process [122]—The Luwa process uses a thin film
evaporator of the "fixed blade clearance" type instead of conven-
tional distillatio:-. column.  The advantages of Luwa's thin-film
evaporator include:

      Short-residence time-allowing heat-sensitxve products to be
      exposed to less severe conditions.

      Minimum fouling of distilling surfaces.

      Lower "real" vacuum because of large evaporation surfaces
      and the short distance vapor has to travel to escape the
      liquid (film thickness).

      Internal, self-cleaning mechanical separator.

      External condenser which allows more time for entrained
      liquid to separate from the vapor.

      High tip speed - consequently, higher heat transferability
      with lower fouling characteristics.

Figure 61 provides an example of re-refining process using Luwa's
thin film evaporator.
                    ea
I
                                     |V— »
                   ForKvt Sl>g«
        Figure 61.  Oil is distilled in two  stages using
                    Luwa's thin  film evaporator  (122].
 [122] Pauley, J. F., Jr.  Thin-film distillation  as  a tool  in  the
      re-refining of used oil.  Third  international  conference on
      waste oil recovery and  reuse; 1978 October  16-18; Houston.
      Charlotte, Luwa Corporation, 151-161.
                                 191

-------
6.2.1.1.17  The MZF Process  [123]--This process, developed  by
M. Z. Fainman Associates, involves diluting the feedstock with
selected hydrocarbons (naphtha) and nixing of the combined  hydro-
carbon stream with a 50/50 solution of isopropyl alcohol and
water plus 1 percent sodium  carbonate.  The overall mixture is
then centrifuged.  Three fractions result.  The alcohol fracton
is stripped to recover the isopropyl alcohol.  The crude oj.1
fraction is vacuum distilled.

The extraction step removes  metals, clearing the way  for success-
ful distillation and downstream catalytic hydrogenation for
upgrading the crude product.

6.2.2.1.18  Resource Technology Process  [124j—Resource Technol-
ogy, Inc., (Kansas City, Kansas) has developed a new  process for
re-refining used oils, Figure 62.  According to the firm, this
method does not require acids, solvents, or additional chemicals
and does not produce hazardous wastes as do traditional acid/clay
re-refining methods.  In contrast, the new technology uses  a
series of vacuum distillation equipment of unique design that
minimizes coking.  The method will recover 97 percent of a  gal-
lon of dehydrated used oil as marketable products.
                                                      tuc* dm> ifltt
      • X r.. J 31 * <>•• e>'0««ii*i«N
      KB — • 100- * OM M OBI i.«u
      *ri :.» 3t—>-. '<>• Wt tt,
                      11%
                      n
         Figure 62.  Resource Technology process  [124]
[123] Davis, J. C.  New technology revitalizes waste-lube-oil
      re-refining.  Chemical Engineergin.   63-65,  1974 July 22

[124] Oil refining route is set  for two plants.   Chemical Engi-
      neering.  92-93, 1981 October 5.
                                192

-------
The process costs are less than $0.30/gallon.  Resource Tech-
nology projects that, given an oil feedstock cost of $0.32/gallon,
a 5-million-gallon facility will produce a before-tax earning of
$2.5 million/year; a 10-raillion-gallon plant should produce an
estimated $5.3 million.

It is also possible to retrofit the technology to an existing
plant.  The retrofitting involves the addition of a cyclonic
vacuum distillation tower, which would replace the acid-treatment
in an acid/clay process.  Cost of skid-mounted equipment with a
capacity of 3 million gallons/year is $525,000.  The firm esti-
mates that retrofitting can result in a net process saving of
nearly $0.34/ga.llon, and at the same time eliminates the problems
of hazardous waste generation and disposal.

6.2.2.1.19  Motor Oils Refining Process [96]—M^tor Oils Refin-
ing Company is already using its own technique at plants in
hcCook, Illinois, and Flint, Michigan.  The process involves an
undisclosed pretreatment technique to remove low-boiling materials,
followed by vacuum distillation of the lube-base cut, and final
treatment using clay filtration.  The oily clay waste generated
is a  fairly dry product disposed of at a controlled landfill.
The new technology is claimed to yield higher-quality products,
to improve process yields, and to eliminate problems with
acid-sludge.

6.2.2.1.20  WORLD (Waste Oil Reclamation through Lube Distilla-
tior ) Process  [96]—This process consists of a two-stat-e tr_: -
film  vacuum distillation column followed by conventxoii£l -lay
contacting.  The nonrotary design of the key unit differs from
that  of other  thin-film distillation equipment available.  In the
first stage, used lube oil is stripped to remove water and light
hydrocarbons.  The dehydrated oil is then fed to the high-vacuum
second stage distillation column.  The distillate oil produced is
a light neutral lube which is comparable in quality to virgin oil.
Residue from the vacuum distillation is asphalt flux which is
marketed as an additive for asphalt and roofing tar.

6.2.2.2  Re-Refining Costs—
The cost of re-refining the oil depends on how badly the oil is
contaminated.  The cost of restoring it with additives depends on
how well the spent oil responds to the re-refining treatment.  The
overall cost depends on collection problems  and many other factors,
including type and amount of virgin blending stock required  for
viscosity adjustment due to dilution in use  and handling of the
used  oil before it is received at the re-refinery.  Another cost
variable is additive addition required to meet quality
specifications.
                                193

-------
The costs for the various re-refining processes are summarized in
Table 62 [28].  Costs for the acid/clay process are about 3C to"
SC/gallon of lube product higher than those for the other re-
refining processes.

The distillation/hydrotreating alternative has the advantage of
producing no waste products, but the process has not yet been
demonstrated on a commercial scale.

The economics presented here are for comparison only.  An assump-
tion inherent in the economic comparison of the lube producing
processes is that product quality is the same for each process.
Insufficient data are available to properly examine the validity
of this assumption.

Alternative techniques of waste oil disposal, such an uncon-
trolled combustion, road oiling, and dust control, may return
anywhere from 1
-------
                              TABLE 62.   SUMMARY OF WASTE OIL  PROCESSES  [28]
ID
01
Process
Acid/clay
Primary product
Lube blending
stock
Primary wastes
and byproducts
Acid sludge,
spent clay
Grass roots econcray
5 milHon gallons/year
Operating
Investment cost
$1,153.000 21.9C/gallon
lube
Comments
Widely used in
U.S.
      Extraction/acid/clay
        (IFF process)
      Distillation/clay
        (caustic treatment)
      Distillation/H2
        treating
        (KTI process)
Lube blending
  sotck
Lube blending
  stock
Lube blending
  stock
Acid sludge,
  spent clay;
  high ash fuel
  byproduct

Spent clay;
  high ash fuel
  byproduct

High ash fuel
  byproduct
$1,363,000   18.4C/gallon   One  operating
               lube           plant  in
                             Italy.
$1,173,000   17.3
-------
                       TABLE  (>:i.     RE-KI:KININC;  i  uoct:sr;   WATKK  ANALYSES  \\'J*>\
 On Stt» Te»%»

 Tenpersturs *C
 Ph
 Dissolved Oxfte
 Sulflte, ES/L (As SO.)
 Oxidation Raductloo potential
Total Nitrogen. ng/I. (As N>
/kmcnia Nitrogen (NH_) «g/I-
Nitrate (As H). mg/X
Nitrite (Ac H). ras/L
Cyanldo, ng/L
Phenol «, mg/L
Total S»l/ur (As 6'..  tng/L
Sulfate (As SO.), ns/L
Sulfirlo (At S>7 na/L
Organic Olirld«. ng/L
loo- m.r Chloride, ng/I.
T<"     ,;phates, sgl*
r . / Cream. ns/L
Cwmlcal Obcygcn Demand, ng/L
Blolozicil Oxygen Demand, itg/L
Total Orffmnic Carbon, nff/L
CArtonatc-Blc&rbonato,
TotU Acidity/Alkalinity,
Tct&l Suspended Solids
Total DlK»lv«] Solids
Total Itirdnoas (As CaO3.)
Hvtals,  Kg/L
   Nickel
   Copper
   Chrcmiul
   Iroo
   Silver
   Cac&nitn
   Calclta
r» «C
   Zinc
   Sodlui
   ttetasslua
   Lead
   Tin
   Silicon
   Vanadlus
   Arienic
   Uercury
   Selemio
Dohyd.
9H-039
22.8
2.3
7.0
3
+300322.8
220
223
33
0.09
4.6
0.24
1890
37O
1440
<1
14
<0 1
2.0
7610
N.A.
2GOOO
*3000
8
2200
SB
2.4
4.0
0.77
16.6
0.14
<0.05
2.0
O.SO
13.5
• 1.3
<0.2
0.33
49

-------
                                                                     TABI.F-:  03


                     Gas Chro«totT»t*ilc/Vas« Spoctrowter RamilU                    ,._..,_.

                     ffi^SV£2£-ni~ «=«* « noted        91U&   S^  .fffli 'iHSlr  Mfie    -gigg"     «-g

                        1,2 Dlchlorobenaeno                                            *>                              180
                        1,4 Dlchlorobenzeoe                                                               290                                  13
                        Nitrobenuca                                                             1100
                        Bl!i(2 ChloimtUMJllfathan*                                                1600
                        laupteronv                                                   ,„,                              230      640
                        Raprrthal«na                                                  '!°                 700          470                    180
                        2-CMorocaplilbalefM                                  •••      "°
                        Floorers
                                                                            7.2
                        Dlethy  Pbthalata                                    7.6                    8.9    29                     72          49
                        H-NltrusodlphenylaniM                              64                             270                    jj
                        Anthraceas                                                                                     31
                        Dl-o-Dutyl Phthalato                                18         »                               14                     %.
                        Bla(2 EthylhexrDPbtbalat*                                      7-e                280            4.7
                        Dl-o-Octyl Fhthalat*                                                                                      1.0
                        2 Cblorophsnol                                      38       2200                  160          140       60            }•
                        2 Nitrophenol                                                                                  390                     32
                        Phenol                                           6000      46000       89000    19000        48000     19000          9100
                        2,4 Dlmethylplienol                                2100        900                                      33OO          2600
                        2,4 Dlchlorophenol                                            130                                                      12
                                                                                                1600      170                                  39
                        Pcntacbloropfaeool                                              1?                                                      __
                                                                                      !!                              MO      110            "
%                      tethylano Chloride                                   4.1-68          K       38          52        2.9         »"
rj                      TrlcbloronuomtbaM                                                       ....           2-8                  «,«
^                      1.1 Dlchlorortban.                                                          7.8     24                                82O
                        1.2-t-mchloroothyl«n«                                                               _                                 j?
                        Cblorofora                                          11          13                    »         100        3.9          "
                        1.2 Dlcbloroeth»o»                                  80                             f«J         290
                        1 1,1 TrichlOTOthaiw                              250          42         990     1800        1900       39           *»

                        ItK'SSSSSS!^                                           "        «      g        "       "           »
                        5=1^^                                "5          I-      J      g        iS      1?           S
                        Toluene                                           840         1»        2900      930        MOO      640           830
                        CblorobenBH*                                                    7.9                            900       22             «
                        Etbylb«tt«»,                                       K                    530      960         «00       go           130^

                        AlJhl^BHc'"*                                      <>      <10                    
                        Dleldrin                                          "-10
                        4,4'-m
                        Endrln
4 4'-trn                                          *'u        <10         <10
«,« -HB                                     -                             ,„

-------
                                                                TAIU.n  63   (cent i nued)
                    .
                   Alpha-Butaculfin
                   4.4'-arr
                   DxJasulfw Sulfate
                   Er.drlB tltietyde
                   PCS-1212
                   PC&-12M
                   PCB-1221
                   PCS-1232
                   PC8-1248
                   PCS-1260
                   PC8-1016

                C1-C8 BC ppn/vol.
                Surtactuts, ag/L
                                                                               00
00
                                                                                                *3
                                                                                                                                        *LL
                                                                     D.hyd.   Caifcincl      D.hyd.   Finlihina      DetmJ   T,.,^..        ,	...
                                                                    911-039  911-290      912-120    912-121      a^\:n  **?**?»*      Co*insd
           A2H2S    212^121'    9ii.;;8   •££%?
                                                                                                                                       912-127
4500       4700
   0.39      0.04
          6000 '
             3.6
                      00
1SOO
  0.03
6300
   1.9
6800
   0.31
3000
  0.94
oo

-------
This table shows that the process wastewaters contain high concen-
trations of phenols and other water-soluble compound.';.  Table 64
shows analytical data on four acid sludges from different sources
[126,127],  Variances indicate the difference in additives used
in each type of oil.  Table 65 shows analytical data on one re-
refining caustic/silicate sludge.  Table 66 shows analytical data
on re-refining process hydrocarbon/sludge/clay from five re-refin-
eries as defined in Table 63.  The high metals content, such as
aluminum, magnesium, iron, and sodium, among others, reflects high
concentrations of these elements in naturally occurring clay.  The
lead content includes that usually found in the sludge and the clay
from processes using pretreatment.

It should be noticed that the analytical data reported here are
mostly  for lubricating oils  and  crankcase oils.  No data pertain-
ing specifically to metalworking oils were found.

6.2.2.3.2  Ultimate Disposal of  Wastes—Re-refining sludges,
clays,  and untreated wastewaters, particularly that produced by
steam stripping during distillation,  are considered to be poten-
tially  hazardous wastes  due  to the acid, metals, and  hydrocarbon
constituents contained in the wastes.

Acid sludge and spent clay can be disposed of by secure  landfill.
The cost of sludge  disposal  is at present only a minor contribu-
tion to the total cost of re-refining.  About 0.1  gallon of  sludge
is  produced per gallon of re-refined  oil.  Most re-refiners  pay
less than 0.5C  per  gallon of finished product  for  sludge disposal.
Clay disposal costs are  much lower, less  than  0.25C per  gallon of
product on the  average.  Generally, re-refiners depend on local
refuse  -companies  for removal of  acid  sludge  and spent clay.   In
some  areas of  the  country Class  I dumps are  available for sludge
dispos?!.   In other areas,  local ordinances  prohibiting  the  dis-
posal  of untreated hazardous wastes may force  some re-refiners
 out of business.   Acid sludge can be  neutralized,  but at greatly
 increased cost,   one re-refiner  quoted  a cost of  about 3.5 cents
 per gallon of  product for treatment with calcium  carbonate [127].
 [126] Swain, J. w.  Assessment of industrial hazardous waste man-
       agement - petroleum re-refining industry.  Washington, DC;
       U.S. Environmental Protection Agency; 1977 June.  162 p.
       PB 272 267.
 [127] Cukor, P. M.; Keaton, M. J.; and Wilcox, G.  A technical
       and economic study of waste oil recovery.  Part III:  eco-
       nomic, technical, and institutional barriers to waste oil
       recovery.  Washington, DC; U.S. Environmental Protection
       Agency; 1973 October.  136 p.  EPA-530/SW-90C3.  PB 237 620.


                                 199

-------
       TABLE 64.  ACID  SLUDGE ANALYSES COMPOSITE  [126,127]

Acid. \
Aih lulfate. %
Sulfur, %
Sulfur calculated from
percent acid »»ii»ing
H,S04. \
Diesel
47.5
4.45
14.9


15.5
Stock
40.6
17.26
14.1


13.3
Stock
MA
HA
NA


HA
Lubricating
oil


" '



          Elemental analyiit, opa
CU
Al
re
Si
Pb
Ag
Zii
Ba
Cr
Ca
Ha
P
B
Mi
So
Mg
Cd
Ho
Kn
A*
Be
Co
sr
V
40
40
soo
800
1.000
14
200
400
190
12.600
200
1,000
40
10
35
70
9
18
63
45
0.1
0.8
2.7
18
40
140
1.100
1.400
20,000
0
2.100
1,300
SO
6,400
4,000
4.300
50
30
30
1.000
KA
NA
KA
NA
NA
HA
NA
HA
190
560
2,200
NA
10,000
0.8
2.100
740
28
KA
NA
1,700
18
8
KA
KA
KA
NA
KA
KA
KA
KA
KA
HA

13
796

1,431

1,128
KA

3,898
9,257
1.500
KA


1,162








TABLE 65.  ANALYSIS OF REREFINING CAUSTIC/SILICATE SLUDGE  [126]
                      Element	ppm_
Fe
Pb
Cu
Cr
Al
Ni
Ag
Sn
Si
B
Na
P
Zn
Ca
Be
S
350
27,500
48
18
24
I
1
70
6,250
10
1,000
1,100
1,500
1,000
3,000
0.















14%
                                200

-------
              TABLE  66.    RE-REFINING  PROCESS HYDROCARBON/
                             SLUDGE/CLAY  ANALYSES  [125]

                             (1653)
                             Debyd
                             Light
                             Ends
                             911-038
 API Gravity  9 60 *?           34.0
 Specific Gravity 9 60 *T       0.8550
 Viscosity 8  100 cst   ;         2.51
 Viscosity 8  210 cs:   '         1.13
 Viscosity, Index
 Acid Ease No. ,mgKTl/ga         0.96
 Saponification Nusber.mgKCH/gm  9.55
 Pentaae  Insol., fft.X           0.122
 Benzene  Insol., Wt.X           0.328
 Aniltoe  Point, T            133.2
 Carton,  tft.X                  84.14
 Rydrwgea, Wt.X                15.00
 Nitrogen, Wt.X'                0.070
 Oxygen,  Wt.X                   0.10
 Sulfur,  Wt. J                  0.136
 Hydrogen Sulfide,  ppn wt.      <1
 Mercaptao Sulfur,  ppa wt.      <1
 Total Chloride, Wt.J           0.287
 Organic  Chloride,  Wt.X         0.260
 Total Hydrocarbons,  Vol.I
 Water, Wt.J                    0.24
 Con Carbon, Wt.X               0.242
 Ash, Wt.X                      0.023
 Hash Point,  (PHX)  T      +80
 Color, ASIM    .               3.5
 Copper Strip Corrosion         2C
 Pour Point, °F              -45
 Peating Value,  BTD/lb.(gross) 19091
Paraffins, L.V.X
S'aphthenes, L.V. *
Arcmatics, L.V.  X
Olefins, L.V.  X
Non Volatile Residue, Wt.X
Distillation:
(GC)
(ATTW 2887)
IBP/10
 30/50
 70/90
  FBP
        ppn wt.
   Bariua
   Nickel
   Copper
   Iron
   Silver
   Zinc
   Uagnesiua
   Calciun
   Sodlxn
                34.79
                25.45
                32.06
                7.70
160/289
375/455
640/721
  825
                6
                1
               <1
               11
               <1
                2
                1
                5
               U
               SI

(1661)
Solvent
Sludge
911-301





8.74

16.43
1.94

70.11
10.93
2.69
0.41
0.881


1.82



19.15




14492

(1674)
Distillation
Btius
911-240
18.4
0.9440
• 2750
87.4
93
10.98
36.93
0.393
0.101
144.0
82.04
12.58
0.127
0.81
0.850
<1
226
0.123
0.080
<0.05
5.56
3.14
+330

U
+30
18362 •
(1675)
Distillation
LN 2 Trap
Liquid
911-241
34.1
0.8545
1.62
N.A.

25.46
90.95
0.093
0.093

83.35
11.27
0.299
4.72
1.27
10.2
318
1.11
1.11
4.90
0.800
0.132
<-20
5.5
4C
<-80
12496
                                91.43
                 155
                 243
                  32
                  70
                  62
                 703
                   2
                  18
                 120
                 163
                 8?8
                 202
  33
  25
  15
  36
   7
 117
  <1
  20
 126
 535
1715
                  50/150
                 160/215
                 230/241
                  465
 4
 1
57
50
                                          201

-------
                             TABLE  66  (continued)
                              (1653)
        ppa wt.
   Potassiua
   lianganesa   •
   Lead
   Tia
   Silicon
   Vanadiun
   Arsenic
   Selecixza
   Mercury
   Boron
   Phosphorus

Benzene, Wt.J

Total Polychlorinated
Biphecyls,  ppa wt.
(As Arochlor 1242)

Polynuclear Araoatic, tft.S
   Acenaphtheae
   Flucraathene
   Naphthalene
   Bei57o (a) Anthracene
   Benzo (a) Pyrene
   34 Benzofluorantbeae
   Benao (k) Fluoranthene
   Chrysene
   Acer.apbthvleae
   Anthracene
   Bcnzo (ghi) Perylene
   Fluorene
   Phenanthrene
   Dibe^zo  (ah) Anthracene
   Indeno (123cd) Pyrene
   Pyrene

Pesticides, ppa wt.
   Aldria
   Dieldrln
   CUlorodaoe
   44'-H7T
   44 '-ECE
                              Ligtot
                              Ends
                             911-038
    2
    5
    3
    1.0
    2.1
   <0.01
   11
  211   '

    0.06
(Max)
    0.13
   <0.02
    0.19
    0.02
   <0.02
   <0.02
   <0.02
   <0.02
    0.08
    0.03
   <0.02
    0.26
    0.15
   <0.02
   <0.02
    0.04
                  (1661)
                  Solvent
                  Sludge
                  911-301
 195
 233
87600
 176
   2.1
   2.1
   0.10
   2.5
 148
                 (1674)
              Distillation
                 BUI&
                 911-240
  12
 106
1090
  25
  <1
   4
   0.01
  <0.01
  <0.01
  <0.01
3703
                 (1675)
              Distillation
                LS 2 Trap
                 Liquid
                 Sll-241
 <0.01
  C.9
  0.06
 62
273

 <0.02
                                                    H.A.
                                   <0.10
                                   <0.10
                                   <0.10
                                   <0.10
                                   <0.10
                                   <0.10
                                   <0.10
                                   <0  10
                                   <0.10
                                   <0.10
                                   <0.10
                                   <0.10
                                   '0.10
                                   <0.10
                                   <0.10
                                   <0.10
   HeptAchlor Ijpooclda
   Alpha-Bar
   Beta-BBC
   Garasa-BHS
                                           202

-------
                            TABLE  66  (continued)
API Gravity 8 60 T
Specific Gravity 9 60
Viscosity 8 100 cst
Viscosity 9 210 cst
Viscosity, Index
Acid Base No. .
                0.26
rttiU 00**= "*" l*"p"	 "—
Saporufication Nu=ber,=2CCH/ga 4.KJ
        _   »   v*^_ «           n m
Pentace Insol., Wt.S
Benzene Insol., Wt.S
Aniline Point, °F
CarboJ, Wt.S
Hydrogen, Wt.S
Nitrogen, Wt.S'
Oxygen, Wt.S
Sulfur, Wt. %
Hydrogen Sulfide, ppn wt.
Merc?.ptan Sulfur, ppo wt.
TotrJ Chloride, Tt.J
Orr.arjic Chloride, Vt.5
Total Hydrocarbons, Vol.J
ffater, Wt.X
Con Carbon, Wt.S
Asa, Wt.S
Flash Point, (PVCC) T
Color, ASTH
Copper Strip Corrosico
Pour Point, *F
                  .017
                0.010
               180.3
                83.57
                14.58
                0.017
                0.12
                0.259
                <1
               181
                0.205
                0.200

                1.10
                0.058
                0.150
               +56
                •s-8
                 IB
               -10
 Heating Valus, BTD/11>.(gross) 19330
 Pa^-alfins,  L.V.i
 Kapht><»r.£3, L.V. S
 Aronatics,  L.V.  "i
 Olefins,  L.V. $
 Hon Volatile Residue, Vt.S
 Distillation:
 (X)
 (ASIU 2887)
IBP/10
 30/50
 70/90
  7B>
                4X.30
                37.15
                15.45
                 6.10
135/320
446/612
709/789
  920
 Uetals,  ppa «t.
    Barium
    Nickel
    Copper
    ChrcmiuB
    Iron
    Silver
    Cadniuto
    ZlflC
    Magaesivxa
    Calcium
    Sodium
                 5
                38
               Finishing
                 Light
                 Ends
                911-295

                  35.3
                   0.8438
                   4.61
                   1.60

                   0.45
                   5.41
                   0.067
                   0.003
                 192.3
                  82.36
                  14.31
                   0.016
                   0.18
                   0.248
                  <1
                 283
                   0.200
                   0.180

                   2.60
                   0.208
                   0.088
                 +52
                  +8.
                   1A
                   0
                 15U08
                  37.86
                  35.80
                  15.04
                  11.30
125/306
430/600
705/824
  985
                                  3
                                  3
                                 <1
                                 14
                    3
                    3
                    9
                   77
                                                                               Acid
                                                                              Sludge
                                                                              911-238
                   3.90

                  68.01
                  77.39

                  22.68
                   3.56
                   0.029

                   0.131
                   0.264
                   0.004
                  87.69
                                                             .-3807
                                                 99.74
                14400
                  124
                   42
                   15
                   10
                  942
                    4
                   11
                   76
                 1838
                  516
                 1898
140

 60.93
 n.63

 83.04
 13.83
  0.190

  5.23
                                    0.107
                                    4.29
                                                                                11228
                                                    81. C3
  71
 467
   4
  20
  <1
  16
   2
   7
  45
  18
  23
  12
                                            203

-------
                           TABLE  66  (continued)
 Metals.  ppa wt.
    Potass ivxo
    Lead
    Tin
    Silicao
    Arsenic
    Mercury
    Bo ran
    Pbosptjorus

Benseae,  wi.X

Tbtal PolyeMorinated
Biphesyls, ppn wt.
(As Aroeilor 1242)

Polynuclear Arcmatic, Vt.Z
    Acenaphtbece
    Flucractheae
    Kapbthalena
    Benao  (a) Anthracene
    Benzo  (») Pyrene
    34 Seczcnuorantheae
    Beozo  (k) riuorantheae
   Acer.aphtbylene
   Ant.^ncese
   Banzo (g*ii)
   Flucrene
   Phenasthrene
   Dlberjo (y^i) Anthracene
   Indeoo (123cd) Fyrete
   Pyreas

Pesticides, ppn wt.
   Aldria
   Dieldrin
   Chlorociaae.
   44--CCD
   Endrln
   BeptacMor
   HeptacMor Ejxixlda
   Alpha-B=C
                              Debyd
                              Li girt
                              Eods
                             911-291
    3
   <1
    3
   <0.01
   <0.01
   v'D.Ol
    2
   45

    o.os
    1.7

(MM)
    0.11
    0.05
    0.11
    0.04
  <0.02
    0.07
    0.07
   0.07
   0.07
   0.05
  <0.02
   0.09
   0.05
  <0.02
  <0.02
   0.04
                 Finishing
                  Light
                  Ends
                  911-295
   2
  <1
   4
 <0.01
 <0.01
 <0.01
  6
 73

  0.04
  1.7
  0.09
  0.06
  0.03
  0.06
  0.06
  0.06
 <0.02
  0.09
  0.13
  0.11
'<0.02
  0.09
  0.09
 <0.02
 <0.02
  0.02
2048
  35
  11
  12
  24
  <0.01
   O.C2
 113
 189
                                  Acid
                                 Sludge
                                 911-298
                                                   9960
   4.7
  <0.01
   0.06
  63
1668
   Canai-SC
   Deltft-BcC
                                         204

-------
                            TABLE 66  (continued)
API Gravity 9 60  *7
Specific Gravity  8 60  T
Viscosity 8 100 cst
Viscosity 0 210 cst   :
Viscosity, ladsx
Acid Base No. .ragMH/pa
S-iponification "
Ptjntaae Insol.. *t.»
Biir-zene Insol., Wt.X
Aniline Point, °T
Ciirboa, Wt.X
Hydrogen, Wt.X
Knrogeo, Ht.J-
OJO'gen, nt.X
Sulfur, »t. X
Hydrogen Sullide, ppn  wt.
Uercap.ftn Sul'ur, ppa  wt.
Total Cilorids, »t.X
Crganic Chloride, fft.X
Tota.1 Hydrocarbons. Vol.X
Vfjiter, Wt.X
Con Carbon, fft.X
     wt.:
      Point,  (PMX) T
Color, ASTV
topper Strip Corrosion
Pour Point, T-
                               1.96
   0.003
   0.004
 102.7
  72.17
  13.01
   0.029
   0.35
   0.156
  42
  80
  13.67
  10.60

   0.05
   0.159
   0.56
<-20
  L2
   3B
<-80
r^i** *-w*—»,  •              -
Ht-ating Valu«, BTO/lb.( gross) 17228
           L-V.J
KsLphtheaea, L.V. 5
Arcwulcs, L.V. X
Olefins, L.V. X
Non Volatile Residue, Wt.X

Distillation: IBPAO
(CO           30/50
(ASTO 28S7)    70/90
                              51.54
                              30.84
                              17.62
                              <0.10
                             55/185
                            270/314
                            345/385
                                                                               Acid
                                                                              Sludge
                                                                              912-125
   35.4
   0.8478
   1.69
   0.81

   0.25
   26.06
   0.026
   0.017
  133.3
   80.37
   14.41
   0.011
   0.10
   0.130
   <1
   1.2
   4.93
   0.25

   0.05
   0.007
   0.002
 +78
  L3
   2C
<-BO    -
18454
  42.83
  34.97
  14.54
   7.60
161/297
346/415
535/636
  865
                                                                5.89

                                                               33.15
                                                               37.61

                                                               59.93
                                                                9.82
                                                                0.032

                                                                0.199
                                                                 0.105
                                                                 0.060
                                                                44.32
                                                              11230
                                                                83.03
                 282

                  60.12
                  40.61

                  41.93
                   6.99
                   0.142
                  33.56
                   3.52
                                                                                 0.209
                                                                                 8.64
                 9275
                                    58.97
   Alunicua
   Bariua
   Copper
   Qxraaiua
   Iroo
   Silvar
   Ziztc
   M&gsesita
   Calcixa
   Sodixn
                               2
                              <1
                               3
                              <1
                               r.
                               3
                                              19
   3
  11
12700
  <1
  25
  IS
  18
 467
   1
  12
  66
 891
  30
 273
                                                                               1349
                                                                                544
                                                                                23
                                                                                170
                                                                                14
                                                                                381
                                                                                 •>
                                                                                 8
                                                                                64
                                                                               1320
                                                                               1149
                                                                                41
                                           20!

-------
                        TABLE  66  (continued)
                                        Finishing
                                          Light
                                          Ends
                                         912-123
Metals, ppa wt.
   Potassium
   Manganese
   Lead
   Tin
   Silicon
   Vanadium
   Arsenic
   Selenium
   Mercury
   Boron
   Phosphorus

Becaene, Wt.J

Tbtal Polychlorinated
Bipheayls, pps wt.
(As Arochlor 1242)

Polynuclear Aromatic, Bt.t
   Acaiipbtbene
   Fluoranthene
   Naphthalene
   IWnTD (a) Anthracene
   Benzn (a) Pyreae
   34 Benzofluorantheao
   Banzo (k)
   Chrysene
   Acenaphthylene
   Anthracene
   Eonso (ghi)
   Fluorene
   Phenanthrene
   Dibenza (ah) Anthraceoe
   Indeno (123cd) Pyreae
   Pyrene

Pesticides, ppa wt.
   >ldrin
   Oieldrin
   Cnlorodane
44 '-UE
44'-ICD
Endrin
Hcpuchlor
Heptacnlor 5pcod.de
                           13
                           <0.01
                            0.12
                            2
                            2

                            0.29
                            N.A.
                            0.12
                           <0.03
                            0.21
                           
-------
                             TABLE  66  (continued)
 API Gravity 9 60 *F           42.4
 Specific Gravity 8 60 T       0.8137
 Viscosity 8 100 cst .  ,         1.05
 Viscosity 9 210 cst   :         0.58
 Viscosity, Index
 Acid Ba.se No. ,rcsKCH/ea         0.09
 Saponific.cioa Nurber.mgKCH/SP 12.54
 Pentane Insol., Wt.J           0.039
 Benzene Inscl., Wt.Z           0.003
 Aniline Pos-nt,  'F            127.6
 Carbon, fft.I            *      82.66
 Hydrogen,  Wt.J                 15.06  -
 Nitrogen,  Wt.S'                0.018
 Oxygen, n.J                   0.10
 Sulfur, Wt.  5                  0.107
 Hydrogen Suifide, ppra wt.    • <1
 Uercaptan  Sulfur, ppa wt.     <1
 Total  Chloride:  wt.S            1.97
 Organic Chloride, fft.?          1.85
 Total  Hydrocarbons, Vol.5
 Water,  Wt.J                    0.05
 Con Carbon, fft.Z              0.045
 Ash, fft.J                      0.035
 Flash Point,  (PSCC) "T       +54
 Color,  AZIH                   12
 Copper  Strip Corrosion         1A
 Pour Point, *?   ••          <-80
 Heating Value, BTO/lb.Cgross) 190S9
 Paraffins, L.V.J              37.94
Naphthenes, L.V. J            35.20
 Anr-atlcs, L.V. J             19.95
Olefins, L.V. J                6.90
Non Volat-le Residue, tft.X
Distillation:
(ASIH 2£
-------
                             TABLE  66  (continued)
 Metals,  ppn wt.
    Manganese
    Lead
    Tin
    Silicon
    Vanadiun
    Arsenic
    Seleniun
    Mercury
    Boron
    Phosphorus

Benzene, Wt.J

TbtJd  Polychloriaated
Biphenyls,  ppm wt.
(As Arodalor 1242)

Polynuclear Aromatic, Wt.X
    Acenaphthene
    Fluoranthene
    Naphthalene
    Banao (a) Anthracene
    BenzD (a) Pyrene
    34 Benzofluoranthene
    Benzo (k) Fluorantbeae
   Chrysane
   Acenaphthylene
   Anthracene
   Bc-nzo (ghi) Peiylene
   Fluor en e
   Phenanthrene
   Dibeazo  (ah) Anthraceoe
    Indeno (123cd) Pyrene
   Pyreue

Pesticides,  ppm wt.
   Aldrio
   Dieldrio
   Chlcroaana
   44'-DOT
   44
   Reptachlor
   Heptachlor Epoxide
   Alpha-BIC
   Beu-BSC
                              Dehyd
                              Ugnt
                              Ends
                             911-149
    3
   <1
  107
   <0.01
    0.90
    0.04
   39
   16

    0.20
(Max)
   0.01
  <0.01
   0.16
  <0.01
  <0.01
  <0.01
  <0.01
  <0.01
  <0.01
  <0.01
  <0.01
   0.03
  <0.01
  <0.01
  <0.01
  <0.01
                Finishing
                  Light
                  Ends
                 911-146
 <0.01
  1.0
  0.04
  8
149

 <0.02
                    1.8
  0.21
 <0.02
  0.05
 <0.02
 <0.02
 <0.02
 <0.02
 <0.02
  0.13
  0.06
 <0.02
  0.24
  0.09
 <0.02
 <0.02
  0.03
                  Spent
                  Clay
                 911-147
                  671
                   14
14
 7
 3.7
<0,01
 0.06
16
67
            Distillation
                Bttns
               911-150
 113
  11
4235
  <1
   1
   6
   1.0
   0.90
  <0.01
  38
1346
   DeltA-BlE
                                          208

-------
                            TABLE  66  (continued)
API Gravity  S 60  T
Specific Gravity  8 60 *P
Viscosity 8  100 cst
Viscosity 9  210 cst
Viscosity, Index
Acid Base No. .mgXCH/pa
Saponif3 cation Nuaber.mgKQH/en
Pentane Insol., Wt.X
Benzene Insol., Wt.X
Aniline Point, T
Carbon, Wt.X
Hydrogen, Wt • X
Nitrogen, Wt.X '
Oxygen, Wt.X
Sulfur, Wt.  X
Hydrogen Sulfide, ppn wt.
Mercaptan Sulfur, ppz wt.
Total Chloride, Wt.X
Organic Chloride, Wt.X
Total Hydrocarbons, Vol.*
Water, Wt.X
Con Carbon, Wt.X
Ash, Wt.X
Flash Point, (PMX) TF
Color, ASU4
Copper Strip Corrosion
Pour Point,  °F
Heating Value,  BTD/lb.(gross)
Paraffins, L.V.X
Naphthenes, L.V. X
Aromatics, L.V. X
Olefins, L.V. X
Non Volatile Residue,  Wt.X
Distillation:
(OC)
(ASW 2887)
IBP/10
 30/50
 70/90
  FBP
Metals, ppm wt.
   Aluninxn
   Bariua
   Nickel
   Copper
   Iron
   Silver
   Cadmiua
   Zinc
   C&lciva
   SodiUD
                      Ccefttined
                        Light
                        Ends
                        912-126

                         30.9
                          0.8713
                          9.26
                          2.38

                          2.38
                         10.48
                          0.014
                          0.133
                        183,0
                         82.68
                        * 14.20
                          0.035
                          0.24
                          0.29S
                         15
                         30
                          0.413
                          0.180

                          2.10
                          0.015
                          0.034
                        +78
                         +6
                          U
                          0
                       18851
                         34.20
                         35.52
                         19.78
                         10.50
178/385
573/680
762/855
 1012
                          1
                         <1
                          4
                        15
                        28
                         4
                                                          Spent
                                                          Clay
                                                         912-128
                      11.95

                      69.87
                      65.43

                      35.78
                       5.44
                       0.032

                       0.266
                       0.222
                       0.005
                      59.41
                    8357
                                            95.95
                  27800
                     <1
                     36
                      6
                     17
                    750
                      3
                     13
                     60
                   2698
                    113
                     64
Distillation
    Btms
   912-129

      9.1
      1.0064
  11768
   1099
    123
      8.17
     69.22
      6.92
      1.86
    227.7
     77.17
     11.26
      0.348

      1.17
     <1
    105
      0.304
      0.18

      0.05
      6.91
      8.19
   +310

      4B
    +75
  17050
   378
   940
    45
   262
    63
   780
     6
    29
   133
   174
   879
   432
                                           209

-------
                            TABLE 66  (continued)
 Metals,  ppm wt.
    Potassiua
    Manganese
    Lend
    Tin
    Silicon
    Vanadium
    Arsenic
    Selenium
    Mercury
    Boron
    Phosphorus

 Benzene, Wt.J

 Total  Polychlorinated
 Bipbenyls,  ppm wt.
 (As Arochlor 1242)

 Polynuclear Arccatic, fft.X  (Max)
    Acenapbtbene
    nuorantbeiw
    Naphthalene
    Rpnan (a) Anthracene
    Benzo (a) Pyrene
    34 Benzof luorantbene
    Beazo (k) Fluorantnene
    Chrysene
    Acanaphthylene
    Anthracene
   Ecnzo (ghi) Per>-lene
    Fluor ene
   Phenanthrene
   Dibenzo (ah) Anthracene
    Indeno (?i3cd) Pyrene
   Pyrene

Pesticides, ppn wt.
   Aldrin
   Dieldrin
   Cblorodane
   44'-EDT
   44--DCE
   Endria'
   Eept=--,hlor
   Hsptacblor Epoxida
 <0.01
 <0.01
  0.01
.  4
373

 <0.02
  9.7
  0.10
  0.10
  0.02
 <0.02
 <0.02
  0.19
  0.14
 <0.02
  0.05
  0.10
  0.04
  0.07
  0.10
  0.10
 <0.02
  0.04
                                                         Spent
                                                         Clay
                                                        912-128
                    809
                     71
   7
  17
  15
  <0.01
   0.02
  51
485
                                    Distillation
                                        Btrtw
                                       912-129
  439
  169
10300
   28
   <1
    6
   15
   <0.01
   <0.01
  109
 3390
   Beta-BBC
   Ganna-HC
   Delta-BBC
                                         210

-------
Acid sludge can be burned by use of equipment and methods, such
as incinerators, reverberatory furnaces, fluidized bed furnaces,
and pyrolysis.  The major problem in burning acid sludge is
achieving a homogeneous mixture with a viscosity reducer such as
re-refinery-produced distillate.  Heater or boiler materials of
construction must also be considered because of the potential
corrosion and erosion possibilities.  Since metallic and chemical
impurities remain in the acid sludge, it can also result in the
release of toxic air pollutants unless adequate control measures
are implemented [126].

Resource recovery of acid sludge is a feasible goal.  The proc-
essed sludge is used as ar asphalt product extender and plasticiz-
ar [126].  The Peak Oil Company of Tampa, Florida, in cooperation
with the United States Department of Energy, has completed a study
for the incorporation of acid sludge, derived from the re-refining
of used lubricating oil into a useful and salable building material.
Both bricks and paving materials have been produced using a formu-
lation developed by Peak [128].

Clay presents a less difficult disposal problem.  First, the
hazardous constituents are present in greatly reduced quantities.
Second, a large part of the hazardous constituents can be removed
by washing with solvents and even a water/detergent mixture.  A
final burning in a -kiln to remove occluded materials provides a
reclaimed and reusable material [126].

Steam stripping water, after oil (hexane solubles) removal can bs
'•reated by well established wastewater treatment methods, such as
coagulation, flocculation, air flotation, and filtration.  Such
water can be reused in boilers or discharged.  Minimal treatment
of the water from steam stripping allows the water to be reused
for cooling if not as boiler feed water  [126].

It is not ..o-ipossible, difficult, or even too expensive to achieve
zero dische.:je with comp? te recycling.  Sludge and solids from
adequate wat>ir treatment are of small quantity compared to pre-
treatment sludge and spent clay.

6.3  DISPOSAL AND RECLAMATION OF FATTY OILS

Fatty oils have three major applications in metalworkinq:  (1) as
emulsified rolling lubricant, particularly for rolling of thin
strips of steels; (2) compounded as straight oils, mixtures of fat-
ty oils, ad mineral oils; and (3) as raw materials for the manu-
facture of fatty additives.
 [128] Suarez, M.; Morris, D.A.; and Morris, R. C.  Acid sludge
      utilization.  Bartlesville, OK; U.S. Department of Energy;
      1980 September.  31 p.  Contract No. DE-AC-19-79BC/0089.


                                211

-------
Emulsified rolling oils from the steel industry are usually re-
covered from the steel mill wastewater treatment plant.   A number
of types of mineral oils are mixed together with animal  and vege-
table fats and greases, and these oils accumulate on top of the
skimming tanks.  These mixed fatty oils and mineral oils have been
used as fuels, but future use will be limited by EPA regulation
on burning of waste oils.  The large percentage of fatty oils
used in rolling oils makes more difficult the separation and re-
fining of the petroleum-based oil.

Some fatty oils recovered from wastewater may be purified for use
in soepmaking.  Recovery requires process steps similar to those
discussed in the -ection on emulsified oils [28].  Since fatty
oils are prone to oxidation and rapid deterioration, some fatty
oils are not recoverable and must be disposed of.

Effective techniques for recovery or disposal of fatty oils are
chemical coagulation, air flotation, and biological treatment  [28].
This is demonstrated at Swift and Company's high-volume edible fat
and oil refining plant at Bradley, Illinois [129].  The plant
uses skimming, chemical treatment, and centrifugal separation to
upgrade the quality of the removed fatty materials.  A simplified
process flow diagram for both the wastewater clarification and the
oil recovery systems is shown in Figure 63.  An overall economic
evaluation indicated the 7,000 pounds of oil recovered (99 percent
ether-soluble), valued at 4-1/4 to 4-5/8 cents per pound, would
offset 60 percent of the total daily direct operating costs for
the waste treatment systems, including the oil reclaiming system.

In compounded oils, the fatty oils act as emulsifying agents in
high-moisture environments, incorporating accumulated water into
the body of the oil in the form of a water-in-oil emulsion.
Recovery of compounded oils necessitates removal of any water
emulsified in the oil.  Then the saiae techniques applicable to
the mixed fatty and mineral oils separated from plant wastewater
are suitable  for compounded oils  .

The fatty oil additives in metalworking fluids add to the com-
plexity of the problem of re-refining and reuse.  The re-refining
process may be adversely affected by the additives in the waste
oil, or fatty oil.  If the additives are successfully separated
from the waste oil in the refining process, they present a dis-
posal problem.  Instead of recovery of the additives from waste
oils, the current practice is reconditioning, that is, addition
of a new additive package to bring the refined oil properties up
to specifications.
 [129]  Seng, C.  Recovery of  fatty materials from edible oil re-
       finery effluents.  U.S. Environmental Protection Agency;
       1973 December.  148 p.  EPA-600/2-73-015.  PB 231 268.
                                212

-------
to
          pH_PROBE_
                                                  TURa,TEM?.,D.O. PROBES	
                                                      • '" r  ~"  ~- ~~-*    —— ——  •
                        \DECAHTED
                          WATER PHASES
                                           66'Bc
                                           H2S04
"on _ JTJ
-i _ en
                    WATER
                    PHASE
                    TAHK
HECOV'O
  OIL

X
                                   50 ny
                                                    STcAti
                              STEA
             tw
                                                            TREATUE«T TANKS
                     Figure  63.   Bradley waste treatment flow diagram [1291.

-------
6.4  RECLAMATION, TREATMENT, AND DISPOSAL OF SYNTHETIC FLUIDS

Only limited information is available about treatment and recla-
mation of waste metalworking synthetic fluids.   Some recyclers
claim that no feasible technology is currently available for waste
synthetic fluid treatment or reclamation.  Others say that it is
possible but only after extensive work with arm-twisting of the
fluid manufacturer.  Many large companies currently will not use
synthetic fluids if the manufacturer does not offer a method of
breakdown and disposal.  Some manufacturers do accept'waste syn-
thetic oils for reprocessing.

Synthetics will commonly last a year but longevity depends upon
how effectively the in-plant recycling system operates.  Some
elaborate systems can minimize microbial spoilage of fluid and
keep the fluids very clean.  Those with less elaborate systems
are often forced to pour the fluids down the drain if the manu-
facturer will not be of assistance or if no method really exists
for destabilizing waste synthetic fluids.

Also, by setting up a periodic synthetic fluid analysis and bio-
cide treatment schedule, synthetic fluid and metalworking tool
life can be extended, and production efficiency greatly improved.
The costs and time involved for such a program are more than
offset by reduced fluid purchases and tool reworking, with the
bonus being greater production efficiency.  Not surprisingly,
this production bonus can have a tremendous impact on bottom line
profits.

Waste synthetic oils should be segregated and recycled where pos-
sible, because of their high'cost and because they may contaminate
otherwise recyclable oils  [28].  Good filtration equipment in
the in-plant fluid recycling system will greatly extend fluid and
metalworking tool life by removing metal fines and chips.  This
will result in better product, and increase productivity by re-
ducing downturns.

It has been reported that flash distillation and chemical adsorp-
tion are the two most common processes used for reclamation of
synthetic fluids formulated without polar additives.  These
processes are described in detail in Section 6.2.1.

Some waste synthetic fluids exhibit susceptibility to biodegrada-
tion and can be disposed of by biological treatment  [130].  A
biodegradable synthetic fluid can undergo destruction by micro-
organisms.  To be biodegradable it must consist of materials which
are nontoxic to life and are not considered to be dangerous pol-
lutants.  In addition to readily passing through conventional
 [130] Bennett, E. O.  The disposal of metal cutting fluids
      Lubrication Engineering.  300-307, 1973 July.
                                214

-------
disposal systems, a degradable product should produce no persistent
intermediate residues, it should have no objectionable effects on
the receiving water or its subsequent reuse, it -hould net taint
•fish flesh, and it should not produce objectionable growths in the
marine environment.

Consideration must always be given to the time required for the
process to take place.  Many materials are biodegradable if de-
tained long enough in a disposal system.  Thus, one biodegradable
fluid may require only a few hours while another may require
several days.  A company purchasing a biodegradable product must
consider this factor and must make sure that the product will be
degraded in the disposal plant during the normal retention period.

In a study conducted by the University of Houston, eight synthetic
fluids were subjected to biodegradation under the most ideal con-
ditions for a period cf,four weeks.  The result of this study is
presented in Table 67 [130].  The results show that some fluids
exhibit greater susceptibility to biodegradation than others.

       TABLE 67.  BIODEGRADATION OF SYNTHETIC FLUIDS  [130]
                 	Synthetic fluids	
                 Fatty acids   Percent degraded
A
B
C
D
E
F
G
H
68
100
100
100
53
100
100
100

Many synthetic fluids contain glycols.  The higher viscosity
(higher molecular weight) polyalkylene glycols are resistant to
rapid bio-oxidation  [37].  Thus, under the customary five-day
test for biodegradability, a very small value of BOD would be  .
obtained.  Nevertheless, under longer-term exposure, such as might
occur in a river, the products would biodegrade slowly.

The rate of biodegradation of polyglycols is influenced by molec-
ular weight with higher viscosity members of the family showing
slower degradation.  Because of the low BOD values, only a portion
of the polyglycol would be removed in a waste treatment plant.  At
low concentrations (high dilutions), the products should not ad-
versely affect the biological oxidation in the waste treatment
plant.  Furthermore, studies to date indicate a low order of tox-
icity with aquatic life.
                                215

-------
Because of their complete water solubility, the polyglycols never
produce an "oil film."  However, despite complete water solubility,
local, state or federal regulations may preclude the discharge of
any major quantity of used polyglycol lubricant to the waste water
stream.  Under these conditions, incineration is an option.

Waste synthetic fluids can be disposed of by incineration or
landfilling.  However, it is sometimes economical to reduce the
bulk volume prior to disposal, using techniques such as reverse
osmosis or ultrafiltration.

Osmosis is the passage of solvent, in this case water, from a
dilute to a more concentrated solution through a semi-permeable
membrane.  The flow of solvent continues until the pressure is
high enough to prevent further transfer.  This equilibrium pres-
sure is known as the osmotic pressure.  If a pressure greater
than the osmotic pressure is applied to the concentrated solu-
tion, solvent will flow as a "pure" solvent.  This principle can
be applied to remove water from used synthetic cutting fluids
(Figure 64).  The permeate stream produced is substantially
purified water, although it contains low concentrations of or-
ganic and inorganic matter.  Colloidal, particulate, and micro-
bial contaminants are retained in the concentrate.
                              \— T -• -"taisfr.
                              1.1—— •__ Ce-'CfMr
                              f • > i > ii i i ii > • t t
                                    '$«•".
        Figure 64.  Reverse osmosis can be used to reduce
                    the water content of syntheticj  [131].

Ultrafiltration, sometimes called molecular filtration, is
another membrane separation process.  The membrane is porous and
the constituents are separated on the basis of molecular size.
The separation efficiency is determined by the pore  size.

There are two features which distinguish between the processes,
operating pressure and the separation.  Reverse osmosis uses
pressures in the order of 500-1,000 psi while the pressures in
ultrafiltration are usually about 10-50 psi.  In ultrafiltration
small dissolved molecular species, such as organic salts are
 [131] Evans, C.  Treatment of used cutting fluids and swarf.
      Tribiology International.  33-37, 1977 February,
                                216

-------
passed through the membrane, while in reverse osmosis only the
solvent is transferred.

There are more exotic synthetic fluids coming into the market.
Reclamation, treatment, and disposal aspects of these expensive
fluids will likely be evaluated pricr to their usage.  Products
that can be discarded with a minimum of difficulty have an eco-
nomic advantage over fluids that must be subjected to complicated
treatment during the disposal process.

6.5   DISPOSAL AND RECLAMATION OF ORGANIC SOLVENTS

Contaminated organic solvents generated in various metal finish-
ing operations such as '-"-:greasing or metal cleaning, coating and
painting are commonly subjected to reclamation and reuse.  They
include a wide range of aliphatic, aromatic, and halogenated
hydrocarbons, alcohols, ketones, and esters.  Tnis section des-
cribes organic solvent reclamation tecnnology as an adjunct of
metal finishing operations as well as by independent operations
contracted to collect and distill waste material.  The economics
of on-site reclamation are compared with those of off-site
processing.  Future trends, developments of such technology, and
alternative d:sposal technology are also discussed.

6.5.1  On-Site Reclamation

Organic solvents used in metal cleaning and metal painting become
contaminated with oils, water, pigments, or other undissolved sol-
ids.  Basically, five types of reclamation technology have been
applied to waste solvents generated from metal finishing opera-
tions [81], namely, (1) adsorption, (2) condensation c.. refrig-
eration, (3) absorption, (4) distillation, and (5) evaporation.
These are discussed in detail in the following subsections.  How-
ever, the discussion does not include undissolved solids and
water which are removed from liquid waste solvent by initial
treatment through mechanical separation such as decanting, fil-
tering, draining, settling, and use of a centrifuge.

6.5.1.1  Adc jrption—
6.5.1.1.1  Description  [7,81,132,133]—Adsorption is the -orocess
by which components of a solvent vapor are retained on the surface
of granular solids.  There  are many types of solid adsorption
 [132] Larson, D. M.  Activated carbon  adsorption for solvent
      recovery  in vapor degreasing.  Metal  Finishing.  42-45,-
      1974 October.
 [133] Control techniques  for volatile  organic emissions  from  sta-
      tionary sources.  Research Triangle Park, NC; U.'S. Environ-
      mental Protection Agency; 1978 May.   57£ p.  EPA-450/2-78-
      022.  PB  284 804.
                                 217

-------
media available;  the most commonly used is activated carbon.
Carbon adsorption systems for solvent vapor recovery can be added
to most vapor degreasers by direct connection downstream of the
adsorption unit.

The two main functions of a carbon adsorption system are that of
collection and cleaning, commonly referred to as adsorption and
desorption [132].  A typical carbon adsorption system consists of
two vessels filled with activated carbon,  a solvent-laden air
inlet and outlet, a blower and filter, a steam inlet and outlet
source, and a condenser and decanter.  Automatic operation is
most common, although manually operated systems are available.
Operational sequence is straightforward.  The solvent-laden air
is passed over the bed of activated carbon.  The carbon collects
the organic solvents and passes the clean air out the exhaust.
Once the carbon has collected its capacity of organic solvents,
it must be cleaned free of the solvents in order to prepare for
the next adsorption cycle.  Some typical working carbon bed
capacities are shown in Table 68.

              TABLE 68.  WORKING BED CAPACITIES [39]
                                         Percent of
                                           carbon
              	Solvent	bed weight

              Acetone         .               8
              Heptane                        6
              Isopropyl alcohol              8
              Methylene chloride            10
              Perchloroethylene             20
              Stoddard solvent             2-7
              1,1,1-Trichloroethane         12
              Trichloroethylene             15
              Trichlorotrifluoroethane       8
              VM&P Naphtha                   7
At the end of the adsorption period the carbon adsorption system
will automatically cycle itself, rotating one bed off adsorption
(in a two-bed system) and into a cleaning cycle.  The cleaning of
the carbon is referred to as desorption or regeneration.  Most
carbon adsorption systems installed on vapor degreasers consist
of dual vessels which permit continuous operation by maintaining
one carbon bed on the adsorption cycle at all times.  The regen-
eration cycle is usually performed automatically by injecting low
pressure steam into the carbon bed.  This input of energy releases
the solvent from the carbon.  The resulting steam-solvent mixture
is then fed into a condenser where the solvent and steam are con-
densed, and then into a decanter, where the solvent and water are
then separated by simple mechanical decantation.  Because degreasing


                                218

-------
         solvents are not water soluble, no further equipment is required.
         Figure 65 is a typical flow diagram  for a carbon adsorption system.
         In the case of a water-miscible solvent the decanter is not used.
         The condensate flows directly  (via intermediate storage) to a strip-
         per where water is separated from the solvent.  In many cases,
         solvents are recovered as a mixture.  The separation of these sol-
         vents and dehydration of the water-soluble components usually in-
         volves several separation techniques depending on the physical and
         chemical characteristics of the solvents  [134].  An alternative  to
         recovery is the addition of an incinerator for combustion ol the
         clesorbed effluent during stripping (adsorption-incineration system),

         A properly sized carbon adsorption system installed on the vapor
         degreaser will remove 95 to 100 percent of the solvent vapors.
         Flowever, total solvent emissions are only reduced 40 to 65 percent.
         This  is because the ventilation apparatus of  the control system
         cannot capture all solvent vapors and deliver them to the adsorp-
         tion  bed [133].  The major loss areas are dragout en parts, leiks,
         spills, and disposal of waste  solvent.  Carbon adsorption systems
         aire available in a series of sizes which handle ventilation rates
         between 600 and 10,000 cfm.

         The total amount of solvent recovery is dependent on the types of
         p>arts being cleaned, proper design of the degreaser, and the
         aictual operation of the degreaser.   The most  important factor is
         the actual operation of the degreaser.  If the degreasers are
         properly operated, solvent savings consistently above 85 percent
         can be expected [132].

         Activated carbon adsorption systems, operated on stabilized
         chlorinated solvents for vapot degreasing, do not substantially
         deplete the stabilizer level in the  solvent,  with the exception
         of 1,1,1-trichloroethane.  This solvent has water-soluble stabi-
         lizers which are completely removed  when the  solvents are stream-
         stripped from the carbon bed.  When  these stabilizers are removed,
         highly corrosive conditions, greater than with the other degreas-
         ing solvents, can be present  [132].  Thus, special metals are
         required to handle this solvent in the recovery system.  Systems
         a.re currently available as complete  packages  to handle adsorp-
         tion, desorption, drying, neutralization, and restabilization of
         1,1,1-trichloroethane  [132].

         In steam stripping of other chlorinated solvents, such as per-
         chloroethylene, trichloroethylene, and rrethylene chloride, quan-
         tities of hydrochloric acid are ge: erated in  the carbon bed.
         [134]  Davis,  W.  L.;  and Kovack,  J.  L.   Solvent recovery  by carbon
               adsorption for the coating industry.   Technical  Association
               of the  Pulp and Paper  Industry;  1980  Paper  Synthetic Con-
|               ference,  1980.
                                         219

-------
                   Here is  the  adsorption phase
                   of a recovery  tank  in  a sol-
                   vent recovery  system.
T.n  the  desorption phase,  the
same tank  reverses its  func-
tion to initiate  solvent recovery.
t\>
K)
O
                                          •f Solvent-laden air dueled
                                            in from emission point
                                          Activate.' carbon bed
                                          adsorbs solvent vapor
                                           Fully refreshed air vented
                                         I  to atmosphere or returned
                                         V  to plant environment
       2
       Sleam/aolvenl
       disliMata liquifies
       in water-cooled
       condenser
       For solvents
       msoliibta in water,
       separator unit
       removes waste
       water, and solvent
       is piped away
M
 Slenm strips vapor from
 saturated cft'bon bed
                         Figure 65.   Carbon adsorption principle of operation[-21].

-------
Therefore, materials of construction for the system must be
designed to provide suitable corrosion resistance.  Baked phe-
nolics, acid-resistant coatings, and certain alloy materials are
the most suitable [132].

6.5.1.1.2  Cost Analysis [133-135]—Costs for adsorption systems
vary with:  (1) the nature of contaminants in the waste vapor,
(2) the concentrations of organics in the vapor, (3) the adsorb-
ent, (4) the regeneration technique, (5) the type of adsorber,
and (6) the vapor volume flow rate.

Adsorption capital costs include costs of the basic equipment,
auxiliary equipment, equipment installation, and interest charges
on investment during construction.  The capital costs for a
fixed-bed adsorber system with recovery of desorbed vapors are
shown in Figure 66.  All costs are indexed to June 1976.  Costs
for moving and fluidized bed adsorbers are slightly lower than
those for fixed-bed systems.  Capital costs for adsorption incin-
eration systems with no heat recovery are approximately 20 to 30
percent higher than adsorption recovery systems handling compar-
able flows.

Annualized costs include labor and maintenance costs, utilities
and materials costs, capital-related charges, and credit for
solvent recovery.  Table 69 shows typical components of such costs
for carbon adsorption systems with assumptions in the footnotes.
When recovered organics are credited at their market values, the
adsorption operation shows a capital return.  Most installations
attain complete return on capital within one to three years rela-
tive to an operating life of at least 15 years for the system.
Reuse of the recovered solvents, however, i? not usually practical
when more than one solvent is involved.  Product separation is
normally too costly to warrant recovery for reuse in the process.
Annualized costs for the adsorption-incineration system are com-
parable to those for the adsorption-recovery system except that no
credit is allowed for solvent recovery.

6.5.1.1.3  Applicability and Feasibility  [133, 135]—Metal fin-
ishing operations that can be controlled by adsorption include
degreasing or metal cleaning, paint spraying, tank dipping, and
metal foil coating.

Adsorption is not normally practiced at organic concentrations of
greater than 25 percent of  the lower explosive limit because the
heat released by adsorption cycle may raise the temperature of
 [135] GrandJacques, B.  Carbon adsorption can provide air pollution
      control with savings.  Pollution Engineering.  28-31, 1977
      August.


                                221

-------
ts>
             toaooo
              •00.000
           m*

           9 «eo.
-------
      TABLE 69.  TYPICAL COMPONENTS OF ANNUALIZED COSTS FOR
                 CARBON ADSORPTION SYSTEMS [7]

Configuration

      1.  Dual fixed-bed adsorber operating at 100°F "(38°C)
      2. ..Solvent recovery with condenser and decanter

Gas stream characteristics

     Flow                      20,000 scfm (9.4 m3/s)
     Concentration             25% LEL
     Process gas temperature   170°F (77°C)


       	Component	Annual cost

       Direct operating costs

         Utilities                             $ 48,700*
         Direct labor                             3,000
         Maintenance                             15,400):
         Carbon replacement                      11,500

       Capital charges                           80,850e

       Recovery (credits)        "   ,           (297,000)f

       Total net annualized costs (credits)   $(137,500)9


       aCooling water at $0.045/1,000 gallon ($0.012/m3),
        steam at $2/1,000 Ib ($0.53/m3), electricity at
        $0.033/kWh ($9.17/GJ).
       bLabor at $8.25/hr.
       Q
        Maintenance as 4% of the capital cost.

       dCarbon at $0.72/lb ($1.58/kg) with 20% of carbon
        replenished each year.
       Q
        Capital charges include as percent of capital
        cost:  depreciation, 12%; taxes, insurance, and
        overhead, 4%; interest, 5%.

        Benzene credited at $0.75/gallon, hexane at
        $0.47/gallon.

        Net costs calculated as capital charges + direct
        operating costs - recovery credits.
                                223

-------
the carbon bed high enough to cause carbon combustion.   For safe
and efficient operation, the inlet gas temperature is limited to
less than 100°F (40°C) and the solvent concentration to less than
25 percent of the lower explosive limit.   For high organics
concentration, (larger than 25 percent),  using incineration tech-
nology becomes attraccive.

6.5.1.1.4  Environmental Impacts [133]—Air and water pollution
may occur in the adsorption system.  If a steam desorption cycle
is employed in the system and the recoverable solvents are solu-
ble in water, then some form of water treatment or separation
process is required to minimize the organic concentration in the
wastewater.

If an incinerator is used to destroy the exit stream from the ad-
sorber, the type and amount of air emission are also of concerned.

The disposal of spent adsorbent is another environmental concern,
but this may be necessary only once in three to five years.

6.5.1.2  Refrigeration or Condensation—
6.5.1.2.1  Description  [7,39,133]—A simple refrigeration device
called a "refrigerated chiller" or "cold-trap1' system is used on
vapor degreasers [7,39].  The vapors created within a vapor de-
greaser are prevented from overflowing out of equipment by means
of condenser coils and a freeboard water jacket to produce a cold
blanket across the surface of the vapor.  The cold blanket con-
denses the rising fumes to the saturation level where they become
droplets and fall back into the tank below.

Refrigerated freeboard chillers are a more dedicated system.  In
appearance, they seem to be a second set of condenser coils lo-
cated slightly above the primary condenser coils of the degreaser
(Figure 67)  [136].  Functionally, they achieve a different purpose.
Primary condenser coils control the upper limit of the vapor zone,
while refrigerated freeboard chilling coils impede diffusion of
solvent vapors from tha vapor zone into the work atmosphere.  This
is  accomplished by chilling the air immediately above the vapor
zone and creating a cold air blanket.  This blanket also reduces
mixing of air and solvent vapors by reducing the air/vapor mixing
zone, which results from a sharper temperature gradient.  In addi-
tion, chilling decreases the upward convection of warm, solvent-
laden air.
 [136]  Chemical  Engineer's Handbook.  Fifth Edition.  J. H. Perry
       and  C. H.  Chilton, eds.  New York, McGraw-Hill Book Com-
       pany,  1973.
                                224

-------
                              COLD TRAP
                                               SLOT EXHAUST
  REFRIGERATION
  COILS

  COOLING WATER
  COILS
  PARTS SCREEN
  BOILING SOLVENT
                   » IN - STEAM — — OUT-/
        Figure 67.  Schematic representation  of degreaser
                    with cold trap  installed  [136].

Patent coverage of the "cold trap"  is  limited to designs that
control the refrigerant temperature at 0°C or colder [137].
Manufacturers operating within  this patent recommend a heat
exchange temperature of -23°C to  -30°C.   Commercial  systems
operating between 1°C to 5°C are  also  available.  Most major
manufacturers of vapor degreasing equipment offer both types of
refrigerated freeboard chillers.

These systems are designed with a timed defrost cycle to remove
ice from the coils and to  restore heat exchange efficiency.  Al-
though liquid water formed during the  defrost cycle  is directed
to the water separator, water contamination of the degreasing
solvent is not uncommon.

Although water contamination of vapor  degreasing solvents has an
adverse effect on the stabilizer  systems, major stabilizer deple-
tions from this source are unusual. Water is a major source of
equipment corrosion and can diminish the working life of the
equipment.
 [137]  Control  of volatile organic emissions from organic solvent
       metal  cleaning.   Research Triangle Park, NC; U.S. Environ-
       mental Protection Agency; 1978 April.  EPA-450/2-77-022.
                                 225

-------
A 'third type of refrigerated chiller is the refrigerated condenser
coil.  Rather than provide an extra set of chilling coils as the
freeboard chillers do, refrigerated condenser coils replace pri-
mary condenser coils.  If coolant in the condenser coils is suf-
ficiently refrigerated, it will create a layer of cold air above
the air/vapor interface.  Refrigerated condenser coils are norm-
ally used only on small, open-top vapor degreasers because energy
consumption may be too great for larger open-top vapor degreasers.
The refrigerated condenser coil offers portability of the open-top
degreaser by excluding the need for plumbing to cool condenser
coils with tap water.

When a rise in the boiling temperature indicates an accumulation
of oils and other soils, the degreaser must be cleaned.  At this
time, the used solvent and oil mixture is removed and taken away
by a reclaiming service or run through the plant's own still for
purification [138].   It is wise to check acid acceptance at this
time and correct it as directed by the solvent manufacturer.

6.5.1.2.2  Cost Analysis [133]—The costs for refrigeration units
depend on the following:  (1) the nature and concentrations of
the vapors in the exhausted gas; (2) the mean temperature differ-
ence between gas and  coolant; (3) the nature of the coolant;
(4) the desired degree of condensate subcooling; (5) the presence
of noncondensible gases in the exhausted gas; and (6) the build-
up of particulate matter on heat exchange surfaces.

Annualized and capital costs for refrigeration vapor recovery
units have been developed by the EPA  [139].  These costs are shown
in Figures 68 and 69  as a function of the hydrocarbon vapor flow
rate.  All costs are  indexed to June 1976.

Capital cost estimates represent the total investment required to
purchase and install  a refrigeration unit.  New installations are
assumed, but retrofitting at existing installations is expected
to be only slightly higher.

An example of annualized cost components for a refrigeration unit
is shown in Table 70.  Utilities costs will vary depending on the
inlet concentration of the solvent vapor.  Solvent credits help
offset about 35 to 75 percent of the annualized expenses.  At
higher flow rates, solvent credits appear to offset operating ex-
penses and capital charges, resulting in a net savings by recover-
ing  the vapors.
 [138] Monahan, R.  Vapor degreasing with chlorinated solvents.
      Metal Finishing.  26-31, 1977 November.

 [139] Control  of hydrocarbons  from tank truck gasoline loading
      terminals.  Research Triangle Park, NC; U.S. Environmental
      Protection Agency; QAQPS;  1977 May.  Draft copy.
                                226

-------
ro
N>
-o
          280,000
          240,000
      2

      £   200.000
      SO
      l/l
      O
      o
          160.000
120.000
           80.000
           40,000
              U0      200      400      600      £00

                        GAS FLOW TO CONDENSER, scfm


       Figure 68.   Capital costs  for refrig-

                     eration vapor  recovery

                     units  (133J.
                                            1000
   24,000

«
"K


1  20,000

 *
<€.


JJ, 16,000





8  12,000


o      !
l*J      !

3   8,000



z

"*   4.000
                                                                                     INLET TEMPERATURE • 60°F
                                                                200    400
                        600   800    1000

                        FLOW, scfm
                                                                                                       1200
                                                   Figure  69.   Annualized costs for refrig-

                                                                  eration vapor  recovery

                                                                  units  [133 |.

-------
         TABLE 70.   COMPONENTS OF ANNUALIZED COSTS  FOR A
                    REFRIGERATION VAPOR RECOVERY UNIT [133]
    Gas stream characteristics

      Flow                       420 scfra (12 m3/min)
      Concentration              20% (by volume)  hydrocarbons
      Inlet temperature          60°F (16°C)

    Direct operating costs

      Utilities                  $  6,000?
      Maintenance                   5,300

    Capital charges                30,000C

    Gasoline recovery (credit)    (21,400)

    Net annualized costs         $ 19,900e


    aElectricity at S0.04/kWh ($11.11/GJ).

     Maintenance as 3% of the capital costs.

    °Calculated at 10% for 15 years plus 4% for taxes,  insur-
     ance, and administration.
    QGasoline valued at $0.40/gallon ($0.10/L) F.O.B.  termi-
     nal before tax.

    eComputed as operating costs +.capital charges - gasoline
     recovery credits.

6.5.1.2.3  Applicability and Feasibility [81,133]—Refrigeration
has been used successfully in controlling organic emissions from
metal cleaning or degreasing operations.  However, it will not
remove all the vapor from the air;  Because of its lower effi-
ciency and other disadvantages,  it is not used widely for solvent
recovery in industry.  The yield from refrigeration is necessar-
ily lower than that from adsorption and absorption systems, but
this may be offset by lower costs.

In general, refrigeration systems are uneconomical as the sole
means of emission control unless the gas contains high concentra-
tions of valuable organic vapors.  The refrigeration operation
can recover o:ily those constituents above the saturating concen-
tration at the condensing temperature.  Therefore, it is only
practical at concentrations well above 10,000 to 20,000 ppm [140].
[140] Harvin, R. L.  Recovery and reuse of organic ink solvents.
      Louisville, KY; C&I Girdler, Inc.; 1975 September.  25 p.
                                228

-------
6.5.1.2.4  Environmental Impact [133]--A condenser seldom creates
secondary environmental problems when the condensation process is
considered by itself.  Problems that do arise include disposal of
noncondensibles in refrigeration systems.  The noncondensible-gas
effluent from the surface condenser is either vented to the atmos-
phere or further processed (e.g.,  via incineration), depending on
the effluent composition.  The coolant never contacts the vapors
or condensate in a condenser; therefore, the recovered organic
solvents are usually reusable.

6.5.1.3  Absorption—
6.5.1.3.1  Description  [81,133]—Absorption is a well known
process in which a liquid medium is used to extract a solutle
vapor from a gas stream.  Absorption recovers vaporized solvents
by close contact with a liquid absorbent at the proper temperature.
In general, absorption ic most efficient under the following con-
ditions [141]:  (1) the organic vapors are quite soluble in the
absorbent; (2) the absorbent is relatively nonvolatile; (3) the
absorbent is noncorrosive; (4) the absorbent is inexpensive and
readily available; (5)  the absorbent has low viscosity; and (6) the
solvent is nontoxic, nonflammable, chemically stable, and has a low
freezing point.

The solvent-laden absorbent stream may be stripped of solvents
and recycled.  Some absorbent will be lost with the stripped
solvent and must be replaced.  The rate of mass transfer between
the gas and the absorbent is largely determined by the amount of
surface area available  for absorption.  Other factors governing
the absorption rate, such as the solubility of the gas in the
absorbent and the degree of chemical reaction, are characteris-
tics of the constituents involved and are independent of the
equipment used.

Absorption equipment must be designed to provide adequate contact
between the gas and the absorbent liquid to permit interphase
diffusion of the organic vapors.  Contact is provided by several
types of equipment such as plate towers, packed towers, spray
towers, and venturi scrubbers.  The fluid is usually pumped to
the top of the tower, distributed and drained by gravity counter-
current to the gas stream being treated.  With proper tower
conditions and fluid choice, removal of the dilute solvent vapors
from air can be effectively accomplished.

6.5.1.3.2  Cost Analysis  [133]—Absorption costs vary widely and
depend upon the following factors:  (1) the type of absorber;
(2) the kind of contacting media; (3) the nature and amounts of
 [141] TreybaD,  R. E.  Mass Transfer Operations.  New York, McGraw-
      Hill Book Company, 1968.  pp. 129, 154, 225-226.


                                229

-------
organic vapors in the gas; (4) the absorbent used;  (5) the value
of recovered solvents or of the absorbent-dissolved organics
solution; (6) the design removal efficiency; and (7) the gas
volume flow rates.

Capital costs for newly installed packed tower absorbers are de-
picted in Figure 70.  These costs include the cost of the basic
equipment, the cost of any auxiliary equipment, and the costs
associated with equipment insta31ation and site preparation.
Retrofits may cost up to two times the illustrated values.  Cor-
rosive properties of certain organic streams require special
construction materials which increase capital costs.  Absorption
systems using absorbents with poor absorption capabilities for
organic vapors would have larger capital costs associated with
the need for larger absorption towers.  Regenerative absorption
systems also have increased capital costs because of additional
equipment needed for absorbent regeneration.

Annualized costs for a cross-flow packed scrubber are presented
in Figure 71.  Utilities include power costs for the recirculat-
ing pump and fan.  Process water costs are ^nsall in this case
since recirculation is assumed.  Treatment costs, although not
included .in Figure 71, should be taken into consideration when
evaluating absorption system costs.  Maintenance costs appear to
average five percent of the capital investment.  Relatively low
capital investments for absorption systems help minimize capital
charges.

6.5.1.3.3  Applicability and Feasibility [133]—Absorption has
been used to control and recover organic vapors in surface coat-
ing and degrea?ing operations.  Commonly used absorbents for
organic vapors are water, mineral oil, and nonvolatile hydro-
carbon oils.  For example, trichloroethyleie vapors in air can be
reduced by absorption in mineral oil.  Hovever, at ambient tem-
perature the air stream leaving the column can wontain about
120 ppm mineral oil.  Thus, this process can result in control-
ling one hydrocarbon but emitting another.  Also, solvent stabi-
lizer is not recovered during the process.  Restabilization of
the recovered solvent will be needed.

It appears that absorption is good for high concentrations of
solvent vapor in air, valuable vapors, or highly toxic chemical
vapors.  The recovery of solvents is not economically achieved by
absorption in dilute gas mixtures (<1%).

The use of absorption may be feasible where chlorinated solvents
are absoroed in metal cutting lubricant oils.  The presence of
the chlorinated solvent in cutting oils increases tool cutting
speed and tool life.  This practice lessens the energy needed for
distillation but results  in slow re-release of solvent vapors to
the atmosphere during use as a metal cutting lubricant.
                                230

-------
          100
(S)

10
        o  00
        2  .0

        ?  "

        •  «o

       *0  00
        o
        O  80
        «t
        O
           19
                                                                   A 	  •
a    4
•  • r

    TO
                                                 to
                                                                   80   49
                                                                                78 COBO
          Figure 70.  Capital costs  for packed tower absorbers  (new  installations) [1331

-------
 '90
  • 0
2
5
• 0
                         fWATBN  •CAUBBINO  IN Cft00S-fLOV
                          PACKKO
o
o
o
  40
O
o
  SO
  to
  10
           SO


             OAI
                       40        00         dO


                        TO »C«UiBB».  tO9  8CPM
    Figure 71.  Annualized costs  for  a cross-flow

                packed scrubber  [133].
                           232

-------
6.5.1.3.4  Environmental Impact--Adverse environmental effects
which can result from the operation of an absorber include im-
proper disposal of the organic-laden liquid effluent,  undesired
emissions from the incineration of the regenerated waste gas,
and loss of absorbent to the atmosphere.

The liquid effluent from an absorber can frequently be used else-
where in the process.  When this is not possible, the nonregener-
ated absorbent effluent should be treated to provide good water
quality.  Such treatment may include a physical separation process
(decanting or distilling) or a chenucal treating operation.

Regeneration consists of heating the liquid effluent stream to
reduce the solubility of the absorbed organics and separate them
from the absorbent.  Thes'. concentrated organics can then be
oxidized in an afterburne    Emissions of SO , NO , and other
incomplete oxidation products may be a result, depending on the
nature of the regenerated gas stream.

6.5.1.4  Distillation—
6.5.1.4.1  Description  [81,142]—Distillation is the process of
partial vaporization of a liquid mixture and condensation of vapor
for the purpose of separating the components,  nsually, in metal
cleaning operations distillation is employed to recover contam-
inated solvents.  Figure 72 schematically illustrates a typical
continuous fractional distillation column [143].  Contaminated
solvents with dissolved materials which cannot be settled or fil-
tered out,•is continuously fed into the distillation column where
it is cycled through the reboiler and heated by steam flowing
through coiled tubes.  Vaporized components return to the distil-
lation columns for separation,»and,the less volatile residual liq-
uids or tars (bottom products) are removed from the system for
reuse or disposal.  In  fractional distillation, the vapors pass
up through the column and are partitioned, according to their
relative volatilities, throughout the sieve and valve tray pack-
ings.  The vapors are drawn off, condensed, and stored in the
accumulator.  From the  accumulator, a portion of the isolated
fraction is returned to the column for refluxing, and the re-
mainder is collected (overhead product) for reuse or disposal.

Distillation is available as atmospheric or vacuum units.  For
atmospheric distillations, the pressure is set at tlie pressure
that the overhead product can be at least partially condensed
 [142] Hengstebeck, R. J.  Distillation.  Principles and Design
      Procedures.  New York, Reinhold Publishing Corporation, 1961.
 [143] Hansen, W. G.; and Rishel, H. L.  Cost comparisons of treat-
      ment and disposal alternatives for hazardous wastes; volume I
      Cincinnati OH; U.S. Environmental Protection Agency; 1980
      December.  272 p.  EPA-600/2-80-188.  PB 81 128514.


                                233

-------
      Feed
Pump
                                              Accumulator
                                          > Overhead. Product
                                           Steam

                                         Condensate
                              Bottoms
                              Product
   Figure 72.  Continuous fractional  distillation column [143].

by heat exchange with a convenient cooling medium,  and liquid
from the bottom stage can be partially vaporized  by exchange with
a convenient heating medium; otherwise-refluxing  and rebelling
would not be readily achievable,  when both  conditions cannot be
met simultaneously, refrigeration may be  used  to  condense the
overhead, or a furnace may be used for rebelling.   When the feed
c> ntains high-boiling materials that  are  too heat-sensitive to be
distilled at atmospheric pressure, distillations  are carried out
under vacuum to reduce column temperatures.  Because temperatures
are highest at the bottom of a column, the properties of the bot-
tom product usually determine whether vacuum must be used [143].
                                 234

-------
The contaminants accumulate in the bottom of the still during the
distillation cycle.  Solvent incinerators are generally used to  -
burn the still bottoms.  The still bottoms can also be disposed
of by landfill and deep well injection.  However, the still bot-
toms which contain less than a few hundred parts, of solvent per
million parts of water can also be drained to a sewer [144].

Distillation column capacity requirements depend on the waste
input rate and volatiles of the constituents to be separated.

Descriptions of the method tor calculating column diameter and
height is available in the literature  [145-147].  If the maximum

diameter and height cannot accommodate the liquid flow, two or
more equal-sized columns are used to treat the waste solvents.
In actual systems there are many possible combinations of reflux
ratio, column pressure, column height, column diameter, and con-
tacting intervals.

6.5.1.4.2  Cost Analysis [143]—The capital costs for distilla-
tion include costs of the basic and auxiliary equipment, equip-
ment installation, and building costs.  Operating costs include
labor and maintenance costs, utilities and materials costs, and
capital related charge.  The breakdown of capital and operating
costs are shown in Tables 71 and 72, respectively.  The change
in the total capital costs  (exclusive of land cost) according to
the scale of separation is shown in Figure 73.  Labor and 'jquip-
ment maintenance costs are shown in Figure 74.  All costs are ad-
justed for inflation to mid-1978 values and are based on charges
as they exist in Chicago, Illinois.  The direct and indirect oper-
ating costs (including debt service and amortization) are used to
calculate the average cost over the 5-year life cycle of the ex-
ample, a 1,000 gpm distillation facility.  The life cycle average
cost is $13.02/1,000 gallons.  This result is shown in Table 73.
 [144]  Reynen,  F.;  and Kuncl,  K.  L.   Solvent recovery systems  nets
       plant approximately $50,000/yr savings.   Chem\cal  Proces-
       sing.   38(9):19,  1975.
 [145]  Robinson,  C.  S.;  and Gilliland,  E.  R.   Elements of frac-
       tional distillation.  New  YorJ:,  McGraw-Hill  Book Company,
       1950.   492 p.
 [146]  Fair,  J.  R.;  and Bolles, W.  L.  Modern design of distilla-
       tion columns.   Chemical Tngineering.   75(8) :156-178,  1968.

 [147]  Colley,  Forster,  and Stafford (eds).   Treatment of indus-
       trial effluents.   New York,  John Wiley and Sons, 1976.
       378 p.


                                 235

-------
                         TABLE  71.   SUMMARY OF  CAPITAL COSTS  FOR  DISTILLATION3  [143]
(s)
W
Capital cost
category nodule
Steam generator
Distillation column
Accumulator
Vaste pump
Piping \
Total
Supplemental capital costs
Subtotal of capital costs
Working capital4
AFDC*
Grand total of capital coats

Site
Preparation
$ 70
120
389
~
675
1,254
--
—
—
—
—

Structures
$ 6,490
4,540
2,130
~
--
13,160
97,323°
—
—
--
--
Cootub
Mechanical
equipment
$414,400
232,730
2,840
2,950
39,300
692,220
—
--
—
—
—
Quantities
Electrical Land,
equipment Land Total ft:
$ -- $ 697 $ ~ 937
11,637 768 — 1,032
321 -- 432
--
._
11,637 1,786 -- 2,401
_.
817,380
179,166
40,869
779,403
Other
steam,
Ib/hr
120,000
--
—
~
«
120,000
—
—
—
--
--
         "Scale = 1,000 gpm; liquid density =  62 Ib/fts; vapor density = 50 Ib/fts.
         bMid-1978 dollars.
         °Building.
          At one month of direct operating costs.
         Allowance for funds during construction at 5% of capital costs.

-------
                  TABLE 72.    SUMMARY  OF FIRST YEAH OPERATING COSTS  FOK DISTILLATION3  (143)
u>
1,
Col 11 Cuoiilitlet
Labor
OSM Cost Type I Type 2
category Operator I Operator 2
module ($7.77/hr) (S9/l9/hr)
Stean generator $ 1.179 $ 209
Distillation column 17,703 10,406
Accumulator
Waste pujp
Piping
Total 18,082 10,615
Supplemental O&M coats
Subtotal of direct O&M costs
Administrative overhead
Debt service and amortization
Real estate taxes and insurance*
Total first year opniat tug coals
Type 3 Energy
laborer electrical Maintenance Chemical kwh/ Natural gas,
(56 76/hr) (S0.035/kWh) costs costs Total yr ft3/yr
$15,586 $956,000 $2.798 1(120,000 5 -- ••• • 2.48 x 109
20.513 -- 1,602
398
1,730 — — -- 49 429 --
179 -- 276
36,278 957,730 5,074 120,000 " 49,429 2.48 H 10*
1,348
1,149,927
229,985
273.668
20,748
l,f>74,328
        Scale = 1,000 gpn.
        bHid-1978 dollars.
        *.t ?0\ of diroct opnrotlng coits.
        At 10\ Internst uvcr J year).
        *At 2% of total capital

-------
   55-
   SO-
        Ttrr/t. CAP ITU.
   «0
   »•
   30'
   29
   SO'
   »9
   10
            1.000      2.000     3.000     ».000     S.OOO
                          9P"
Figure 73.   Distillation:   changes  in total
              capital  costs  with scale [143].
        LABOR
1.000 2.000 3.000 4,000 9.000
       gpn
  I. OPPUT'jii LEVEL 1
  2. CPWA-.a*. LEVCL 2
  3. LABORS*
                                   1.000 2.00-> 3.0OO «.000 9.000
                                          gpn
   Figure 74.   Distillation:   changes in O&M
                 requirements with scale  [143].
                          238

-------
TABLE  73.   COMPUTATION OF  LIFE CYCLE AVERAGE COST FOR IMPLEMENTING
            DISTILLATION  (LIFETIME - 5 YEARS) [143]

Item
Direct
operating
costs3
Indirect
operating
costs
Sum
operating
costs
JPresent
value
annualized
costs
Annual
quantity of
throughput .
(x l.OCO gal)
Year 1
Year 2
Year 3
Year 4
Year 5

Totals
$1,149,927
 1,264,920
 1,391,412
 1,530,553
 1,683,608
$524,401
 547,399
 572,698
 600,526
 631,137
$1,674,328
 1,812,319
 1,964,110
 2,131,079
 2,314,745
$1,674,328
 1,6.47, £79
 1.623,140
 1,601,080
 1,580,971
                          9,896,581    8,,127,098
124,800
124,800
124,800
124,800
124,800

624,000
Simple average (per 1,000 gallon)
Simple average (per cubic meter)
Life cycle average (per 1,000 gallon)
Life cycle average (per cubic meter)
$15.86
$ 4.19
$13.02
$ 3.44

 Assumes 10% annual inflation.
 Inflation increases the administrative overhead only.
C                            "* "
 Assumes- a 10% interest/discount rate to the beginning or" the first year of
 operation.
 1,000 gpm x 60 min x 3 hrs/day x 260 days/yr.
 First year costs in mid-1978 dollars - for Chicago example.

6.5.1.4.3  Applicability and Feasibility [81,1433--SistiIlation
is  a  feasible method of recovering contaminated solvents with
high  boiling points used in metal cleaning operations.  It can
either be a single operation or part of a treatment sequence for
recovering solvents used in metal cleaning,  coating,  ind painting.
Some  private contractors also use distillation in reclamation
services.

6.5.1.4.4  Environmental Impact—In distillation columns,  ejais-
sions can result from  column and  tank  vents amd from  the ste.Mi
ejector of vacuum distillation.  Uncondensed -vapors are release ^
from  these columns.  Most columns, however,  employ some t^pr. oi
vapor recovery system.

Conditions causing excassive carryover of ccsctaminants are the
result of an excessive distillation rate.  Excessive  emissions
can also be caused by  inability of distillation to maintain a
reasonable vacuum.
                                  239

-------
Leaks in the head and side sheets of vertical tubes,  excess water
in t-he condenser tube bundle,  malfunction in float level control,
worn and leaking vacuum pump system, and foaming of still con-
tents causing capacity losses will further create excessive
emission levels.

The final residue from distillation operations is unsuitable for
reclamation and requires proper disposal.  Incineration, landfill,
and deep-well injection are common disposal methods.

6.5.1.5  Evaporation—
6.5.1.5.1  Description [81,142,148]—Evaporation refers to the
removal of a volatile liquid from solvent solutions by vapor-
ization and concentration of nonvolatile dissolved or suspended
solids or liquids.  The process and the equipment are similar to
that of'distillation units, except that in evaporation, no attempt
is made to separate components of the vapor.  As shown in Fig-
ure 75, evaporation technology includes the evaporator unit, the
external separator, and a ccnderser [81].  The waste is introduced
at the product inlet, vaporized, and passed into the separator.
The volatile component is captured in the condenser and may be
incinerated, reclaimed, or disposed.

The concentrated nonvolatile component is removed at the product
discharge and then is disposed of by landfill or incineration.

Single-pass, climbing-film type evaporators are widely used.  They
consist of a long tube bundle combined with a disengaged cheimber.
The solution is evaporated as it passes through the tubes.  The
tubes are heated by contact with steam.  In the external separa-
tor, the liquid is separated and flows to the bottom, while the
vapor goes to a condenser.          -                          • •

Agitated thin-film or wiped-film evaporators utilize a tall
vertical cylinder surrounded by a heating ]acket  [149].  With
this design, solvent is forced into a thin  film along the heated
evaporator walls by rotating blades.  These blades agitate the
solvent while maintaining  a small clearance  from the evaporator
wall to prevent contaminant buildup on heating surfaces.
 [148]  Tierney, D. R.;  and Hughes, T. W.   Source assessment:  re-
       claiming of waste  solvents, state  of  the art.  Cincinnati,
       OH; U.S. Environmental Protection  Agency; 1978 April.
       53 p.   EPA-600/2-78-004f.

 [149]  Reay, W. H.  Recent advances  in  thin-film evaporation.
       London  England,  Luwa  (U.K.) Ltd, 1963 June.  Represented
       from  the Industrial Chemist.   5  p.
                                 240

-------
                           Plon View
        Product Inltt
          Stclion
       Motor Drive
                                             CondtfiMr
Toil Pip*
to Hotimil
                                Product Oixhorg*


                       Elevated View
Figure 75.   Detail  of single evaporator showing
              associated equipment included in the
              evaporator module  [143].
                           241

-------
6.5.1.5.2  Cost Analysis [143]—Capital costs for climbing-film
evaporators are itemized in Table 74.  The most costly elements
are the evaporator (including the external separator), and the
steam generator.  Table 75 summarizes the first year operating
costs.  Ninety percent of these costs are attributable to energy,
water, and chemical requirements for the steam source.  All costs
are indexed to ,T.id-1978.

Figures 76 and 77 show the capital costs (excluding land costs)
and operating costs for five scales of operation, respectively.
The capital and operating cost data indicate economics of scale.
The life cycle average cost for a 1,000-gpm facility is $8.48/
1,000 gallons.

6.5.1.5.3  Applicability and Feasibility—Evaporation is a feasi-
ble method of recovering various contaminated solvents from metal
finishing operations.  Owing to its high cost, it is usually
adopted by private contractors for solvent recovery service.

6.5.1.5.4  Environmental Impact—Evaporation •units often dis-
charge va/ors to a condenser or fractionating tower.  Hydro-
carbons from these units are thus emitted through the vents of
the subsequent control equipment.

The final residue from evaporation is unsuitable for reclamation.
It can be disposed of by landfill, incineration, or deep-well
injection.

6.5.2  Reclamation by Private Contractor [46]

6.5.2.1  Description—
Contract solvent reprocessing operations vary considerably in
size, materials handled, and technology used.  Batch stills, coil
stills, scraped surface stills, or agitated thin-film evaporators
are commonly employed to purify waste solvents.

Two major classes of materials are reprocessed.  One is halogen-
ated hydrocarbons such as methylene chloride, trichloroethylene,
perchloroethylene, and 1,1,1-trichloroethane.  These  spent sol-
vents derive primarily from degreasing and metal cleaning.  The
other category includes a wide range of solvents such as aliphatic
hydrocarbons, aromatic and naphthenic hydrocarbons, alcohols,
ketones, and esters.  These waste solvents are generated by the
chemical process industry, solvent manufacture and distribution,
metal cleaning and coating, industrial paint use, printing oper-
ations, and paint manufacture.

Most of the larger contractors handle both halogenated hydro-
carbons and miscellaneous solvents of the types  listed above
while sc:?.e of the smaller operations process only the more valu-
able halogenated hydrocarbons.
                                242

-------
                          TABLE  74.   SUMMARY  OF CAPITAL  COSTS  FOR  EVAPORATION   |143|
fo
£>
W
Capital cost
category module
Evaporator
Steam generator
Waste pump
Sludge pump
Yard piping
Total
Supplemental capital costs
Subtotal of capital costs
Working capital
AFDCe
Grand total of capital costs

Site
Preparation
$410
38
—
—
225
673
~
—
—
—
—
Costsb
Mechanical Electrical
Structures equipment equipment
$31,100 $216,250 $30,813
1,865 148,500
2,950
798
1,130
32,965 369, 628 10.813
97,324d
—
—
„
_.
Quanti ties
Other
Land, steam,
Land Total ft2 Ib/hr
$1,370 $ — 1,840
353 — 475 40,000
—
—
„
1,723 — 2,315 40,000
—
$513,126
63,615
25,656
602,397
         Scale =  1,000 gpn.
         bMld-1978 dollars.
         GBuilding.
         At one. month of direct operating costs.
         Allowance  for funds during construction at 5% of capital costs.

-------
                     TABLE  75.   SUMMARY  OF  FIRST YEAR  O&M  COSTS  FOR  EVAPORATION3  [143]
to
Costs Quantities
Labor
O&H Cost Type 1 Type 2 Type 3
category Operator 1 Operator 2 laborer
module ($7 77/hr) ($9/19/hr) (S6 76/hr)
Evaporator $17.703 $10.476 $20.513
Stean generator 1.179 209 15.586
Was^a puap
Sludge punp
Tard piping -- -- 103
Total 18,882 10. CBS 16.202
Supplemental 04* coats
Subtotal of direct O&H costs
Administrative overhead0
Debt service and aoortlzatlon
Real estate taxes and insurance*
Tola) firat year operating costs
Energy
electrical Maintenance Chemical kwh/ Natural gas.
(90 035/kWh) coats coats Total yr fl3/yr
9 -- 91.125 $ -- 8
319,000 1.807 372,000 -- -- 44,120
1,730 — " — 49.429
173 — " " 4,943
6
320,903 2,938 372.000 -- 54.372 44.120
1,770
9 763,380
152.676
158.911
12,048
1,087,015
        *Scale • 1,000 gpm
        bHid-1978 dollars.
        CAl 20% of direct operating costs.
         At 10\ Interest over 1 years.
        *At 2\ of total capital.

-------
               1.000    t.OOO    I.000    4.000     (.000
  Figure 76.   Evaporation:  changes  in total
                capital costs with scale [143],
                            „ •
           >.::: < >*.-£ •'•>'• • '•>"• i.ooc     i.oos


             > »T"'3». J«- I
             )
                                    .'-y.) xa ».«c i.soc
                      sx < ooc i »c • ooc l.::c
i Reproduced from
I beil  available copy.
Figure 77.   Evaporation:   changes in  operating
              requirements  with  scale  [143J.
                           245

-------
It is roughly estimated that there were 80 to 100 contract solvent
recovery operations in 1975 distributed throughout the United
States.  They are spread throughout the country's most populated
areas, which also have large numbers of metal finishing operations.
The greatest number of solvent reclaimers are in EPA Region V,
which encompasses Ohio, Indiana, Illinois, Wisconsin, Michigan,
and Minnesota.  Many contractors normally take feedstock from
out-of-state.  In these plants, quantities handled can vary
from 100,000 liters per year to 9,000,000 liters per year.

There are two basic modes of contract operation:

      1.  The contractor recovers the solvent, returns the
          material to its source, and is paid either by the
          quantity of dirty solvent originally taken or by
          the quantity of clean solvent returned.

      2.  The contractor buys the spent solvent (or in some
          cases is paid to haul it away), recovers the sol-
          vent, and sells it on the open market.

One of  these systems is usually the primary mode with the alter-
native  method accounting for a small portion of a contractor's
business.  The one favored depends on the system he finds most
profitable.  Most operations are owned by small individus! com-
panies, and only a few companies own more than one plant.  Most
solvent reclaimers have no substantial financial backing and are
therefore limited in production facilities and expansion potential,

The feedstock is usually transported from its source to the re-
covery  plant by the recovery contractor in his own trucks.  More
than  50 percent is transported in 55-gallon drums, and the re-
mainder is transported in bulk tankers.

U.S. Deparcment of Transportation regulations 
-------
                   TABLE 76.   CHARACTERISTICS OF STILL BOTTOM SAMPLES COLLECTED
                              FROM SOLVENT RECLAIMING OPERATIONS
K>
oVsignat ion
1
2
J
4
S
6
7
a
*
10
it
12
11
14
IS
16
17

Percent
volatile
carried Peicent
off at Percent Cd Cr Cu Nl Pb Zn »*)or fUih point Percent
101 - IOS*C solids »q/L mq/L ny/L mq/l rna/L mi/L components *C °r pH ath
77
79
89
89
99
41
14
14
it
28
9/
97
J9
ja
8)
61


28O 1.700 190 48
60 500 110 44
60 400 130 SI
6\ Irichloroethylene 75
10 1OO 10 40
46
1\ trichloro«thylen« no
S8
SI
90
4S\ trichlocMthylene 04
SOX tricMoroethyleiw 86
160 1.200 100 68
110 1.200 990 8/
10 100 10 74
7>0 J.7CO 410 '9
0 48 20 0 44 60 02) 
-------
                                                                 TABLE  76  (continued)


Simple
designation
vol«tll«
carried
off at
103 - 105°C


Percent
solids


Cd
ng/L


Cr
ng/L


Cu
ng/L


Ni
'mg/L


Pb Zn
og/L ng/L

Percent
na jur
components


FUsh
°C


point
°f pH


Percent
a*h
              IS
                           25
                                       30
                                                                                                                                S    41     7.0
to
it*
00
                                    39       139      346       192   1.898      3,467   25% toluene, mineral                              10.51
                                                                                          spirits, xylene,
                                                                                          trace amounts of  per-
                                                                                          chloroethylene, «eth-
                                                                                          anol, tnchloroethylene

                                                                                       Acetone
                                                                                       Xylene         30 t 10
                                                                                       Toluene        15 ± 10
                                                                                       Naphthas       30 « 10
                                                                                       Paint pigswnts 20 * 10
                                                                                       Oil            1.5  t 0.5
                                                                                       Phenol         <100 ppa

                                                                                       Miscellaneous organic sol-      5    40
                                                                                          vents, 50-70%
                                                                                       Figaents, resin, etc.,
                                                                                          30-50%

                                            <100     <1CO      <100   1,140      1,700   Toluene            0.1%        0    32
                                                                                       Ethyl benzene      0.4%
                                                                                       Xylene             2 9%
                                                                                       Trlsiethyl benzene   4 4%
                                                                                       C. - t,3 aliphatic! 92 2%
                                                                                       Bentene            <0 1%

                                                                                       l,l.l-trlchleio«lhafi*

                                                                                       /aint p*9Mnt* 10-20%

                                                                                       Acetone  77%
                                                                                       Hethanol 12%
                                                                                       Water    11%
                                                                                       J0\ thliuior


'Designation No  I (o 16 are fro* Reference 161.  Designation No. 17-22 are fron generator waste analysis fora  to landfill ing obtained fro* state
 tPA offi.es. Designation No.  23-24  are froa Reference 162.
              20
              21
              22
              21
                                       IS
                                                                                                                                                 2-4
                                                                                                                                                  7.03

-------
characteristics and origins of the various batches of feedstock
received during any given time period.  The findings may be sum-
maried as follows:

     1.   The majority of samples have a high volatile fraction
          indicating a large proportion of solvent and other
          volatile organics.

     2.   Waste streams from the recovery of chlorinated hydro-
          carbons contain considerable quantities of chlorinated
          solvents and therefore must be considered a potentially
          hazardous waste stream.

     3.   Waste streams from the recovery of solvents contain
          considerable quantities of metallic or other constitu-
          ents which are potentially toxic, flajrunable, or both
          and must be considered a potentially hazardous waste
          stream.

6.5.2.2.2 Ultimate Disposal of Sludges [46]—The disposal
method used for most sludges generated is incineration, either
on-site or by an off-site contractor.  Only 14 percent of the
waiite  goes directly to a landfill, and other methods account for
only a fraction of the total waste disposal.  Two plants were
using  still bottoms as asphalt extender and concrete block fil-
lers,  but this type of use represents less than 0.1 percent of
the total waste disposal on a national basis.  The chlorinated
solvent waste still bottoms sometimes are transported to an off-
site contractor for deep well injection disposal.  The ashes
from incineration are landfilled.

6.5.3 . .Economic Evaluation  [46]

The principal factor affecting the economics of a solvent recov-
ery operation is the size of the system used.  Modern equipment
varies in capacity from 2.8 - 6,100 liters  (1/2 - 1,600 gallons)
per hour and the economics improve considerably with size.  This
is because of the relative capital cost per unit of capacity is
less as is overhead and maintenance,  and operating labor costs
are similar for all sizes of evaporators.  Thus, they are con-
siderably less per unit for a larger  system.  However, the eco-
nomics of a large unit are seriously  reduced if it cannot be
efficiently utilized due to lack of raw material.

In general, on-site reclamation utilizes small-capacity systems,
in the range of 75-380 liters (20-100 gallon) per hour due to the
scale  of their operation while private contractors will employ
larger capacity units up to 1,500 liters  (400 gallons) per hour,
especially when located in a highly industrialized area.  Con-
tractors are usually prepared to transport their raw material
from considerable distances since increased quantities of feed-
stock  improve the overall operating efficiency of their plant.


                                249

-------
It appears that in many areas DOT regulations are not enforced
and that old drums are being used to ship solvents to and from
reclaimers.  Strict enforcement of these regulations could add up
to ISC/liter (50C/gallon) to the total cost of hauling solvent to
and from reclaimers in drums [46].

The actual value of recovered solvent varies considerably with
the type of solvent, the size and type of reclaiming process
used, the degree of purity of the product, and the general eco-
nomic climate of the time and place in which it is being sold.
Generally, the value of reclaimed solvent is closely tied to the
value of the virgin material and will sell for from 50 percent to
90 percent of the value of virgin solvent.  Actual prices range
from 5<:/liter (20
-------
6.5.5  Alternative Disposal Technology

Besides reclamation methods mentioned in the previous sections,
solvents can be disposed of by several other routes:   landfill,
deep well injection, incineration and waterways [39,81]-.  Sol-
vents can also be collected and disposed by off-site disposal
service.  Table 77 indicates the percent of plants and the quan-
tity of solvent using various disposal routes [39].  It is shown
in the table that the largest quantity of solvents goes to the
reclaimer.  However, Table 77 only represents 35 percent of the
solvents used in the metal finishing industry.  The major amount
of solvents used seem  to be either lost in the process or just
illegally dumped [39].

     TABLE 77.  QUANTITY OF SOLVENT BY DISPOSAL ROUTES  [39]
Disposal
route
Incineration
Waterways
Landfill
Disposal service
Reclaimer
Solvent disoosed
Percent of
plants
2
13
18
39
21
Gallon/month
(x 103)
8
112
135
547
904
Gallon/year
(x 103)
96
1,344
1,620
6,564
10.848
Average gallon/year
per plant
251
504
441
822
2,509
6.5.5.1  Landfill —
The hazardous v.iste landfill may be used for ultimate disposal of
any hazardous solvent wastes emanating from operation and treat-
ment facilities.  A more detailed description for landfill opera- •
tions is provided in Section 6.1.5.

Major emissions  from landfill operations are sometimes comprised
of fugitive hydrocarbons resulting from vaporization and evapora-
tion of solvent  wastes.  Solvents buried in drums will have a much
slower evaporation rate.  However, it is believed this method is
rarely used due  to the economics.

Methods have been developed to modify landfills to make them ac-
ceptable for receipt of chemical wastes.  These operations provide
for protection ot the surface and subsurface waters by location
to avoid these waters.  Barriers and collection devices may be
employed if there is potential for leaching or percolation to
groundwaters.  Liners are sometimes used to keep leachate from
entering groundwaters.  Landfills should be sited to take advan-
tage of geological factors.  Cover material can also be utilized
to eliminate evaporation and infiltration of water.
                                 251

-------
According to EPA regulations, liquid waste cannot be landfilled
unless it is "solidified."  Solidification of a 55-gallon drum of
100 percent liquid solvent waste by some absorbent results in about
two drums of material.  Commercially, the landfill disposal charge
is in the range of $190 to $230 per drum of liquid waste.   Due to
higher cost, most strict regulations and major environmental threats
of l€;aching/run-off and odor, landfill of most hazardous organic
wastes will not be technically attractive.  The method wilj. norm-
ally be selected only if other methods are not suitable.

6.5.5.2  Incineration—
Incineration is tne control technology most universally applicable
to sources of volatile organics.  Because of its need for supple-
mental fuel [133], incineration is most useful when the heat devel-
oped during combustion can be recovered and used to offset other
plant energy needs.  A description, together with regulations and
costs for incineration are provided in Section 6.2.3.  Although
incineration can be extremely effective in destroying certain types
of wastes, it is important to recognize that the cost of incinera-
tion for wastes can vary widely.  The cost primarily depends on the
type and concentration of organics and the type of facility required
to handle the waste.  Table 78 gives disposal charges for some
organic wastes by incineration.  Transporation costs are not in-
cluded in the table.

Obviously, the disposal charge for halogenated compounds is much
higher than that for other compounds.  Also, wastes which are .hard
to handle or have low heat contents would increase the charge.

Generally speaking, incineration of organic solvents is technic-
ally viable and environmentally desirable, but the high unit costs
will cause industry to prefer to utilize other less costly alter-
natives if they are acceptable to regulatory agencies.

6.5.5.3  Deep-Well Injection—
Deep-well disposal is a mechod for disposing of solvent wastes by
injection into the earth.  The prime consideration is the geology
and hydrology of the area where the deep-well injection plant is
located.  Injection can pollute groundwaters unless site selection,
construction, and operation  are controlled.  If the area is un-
covered, evaporation occurs  and hydrocarbon emission results.

Emissions from deep wells probably occur through the well casing,
through the injection tubing, and out the wellhead facilities.
Corrosion of the casing can  cause leaks through the system where
gases can emanate through the porous strata.  Earthquakes or lat-
eral strata movement to abandoned oil/water drill areas can also
release emissions.  However, emissions  from deep-well disposal
units are considered negligible when the proper type of well is
utilized.
 aPersonal  communication with  Robert  Ross  &  Sons,  Inc.
                                 252

-------
              TABLE 78.   DISPOSAL CHARGES OF ORGANIC WASTE  BY INCINERATION6

Designation
number Wastes
7168
7189
7187
8065
5620
5624
5626
2638
2641
2642
2644
4893
4894
4998
5000
Aprxcot pit oil
Phenol
p-cresol acetate
Thionyl chloride
Motor oil
Acetone
Methanol
Toluene
1 , 2-Dichlorobenzene
Ethylene dichloride
Ethyl benzene
Hexane
Toluene
Toluene
Thionyl chloride
Methylene chloride
Still bovtoms (residual
dimethyl chloride)
Methylene chloride
Still bottoms (residual
dimethyl chloride)
Methanol
Chlorobenzene
Ethylene acetate
Percent
of contents
90 - 100
100
100
100
40
40
11
4
65
80
95 - 100
75 - 90
90 - 100
95 - 100
-0-5
90
10
93
2
85
15
93
Disposal charge,
S55-aallon drum
Regular
25.75

19.10

28.75
111.50
111.50
23.00
23.00
17.25

129.95
135.05
23.60
17.25
Side-door
52.45
63.95
32.45/15
gal drum
276.55
51.75
138.20
138.20
46.00
46.00
40.25
58.10
152.95
158.05
46.00
40.25

a
b








             waste is such that it will not pour  from the drum or when hazard warrants.
             Because "Side-Door" Incineration requires a much longer processing time,
             drums of waste that require "Side-Door" Incineration will be scheduled for
             delivery/pick-up on a limited quantity basis.

           The disposal charge  of deep well injection  for waste solvent is
           in the range of $15  to $40 per metric ton  (6-15C/gal)  assuming it
           is comparable to  the disposal charge for oil  wastewater [85].
                                              253
L

-------
6.5.4  Waterways [151,152]

Dilute wastewaters are sometimes discharged in a receiving lake,
river, estray or ocean after appropriate treatment.   Surface
discharge via a pipe or ditch leading to the shoreline is the
least expensive approach.  Submerged discharge devices include:
open-end pipes, nozzle-end pipes, diffuser systems consisting of
a closed-end pipe with slots on holes along it,  and split dis-
charges through a branched-pipe system.

The location of the discharge point and type of dispersion mechanisn
are of importance in protecting water users and avoiding unsightly
conditions.  A properly designed subsurface dispersion system can
allow the full assimilative capacity of the receiving body to be
utilized.  Treatment requirement can thus be lowered.

Discharge devices are installed to protect against shoreline con-
tamination, oil slicks, and fog formation, and to protect plant
intake water.  The design of a dispersion system is dependent upon
the uses of the receiving water body, location of nearby intakes,
flow and turbulent nature of waterways, and physical/chemical ef-
fluent and stream characteristics.  Although the least expensive
disposal method, waterway disposal is not widely practiced because
of its potential for violating the Clean Water Act and other
regulations.

6.6  DISPOSAL AND RECLAMATION OF PAINTS                 •      ;

6.6.1  Disposal Methods

The paint application method with the biggest impact on the amount
of paint wastes generated by metal' coating processes is spray coat-
ing.  Spray coating, as discussed in Section 5,  is used oy 60 per-
cent of the industry and accounts for 90 percent of the waste paint
generated.  This is estimated to be between 103,500 and 194,400
metric ton/year (112,500 and 216,000 ton/year).  This waste is not
listed specifically as a hazardous waste according to the Resource
Conservation and Recovery Act (RCRA) but it should be tested for
hazard potential according to the RCRA procedures before disposal.
As discussed in Section 5, the variety of materials used in paints
make some paint wastes potentially hazardous while others may not
be hazardous.

The information available indicates that landfilling is the prin-
cipal paint waste disposal method.  One survey  [46] indicates that
13 plants contacted landfilled their paint wastes.  The hazardous

[151] Ross, R. D.  Industrial waste disposal.  New York, Reinhold
      Book Corporation, 1968.  340 p.

[152] Diffusion of effluents into receiving waters.  Manual on
      disposal of refinery wastes, Volume 1.  New York, American
      Petroleum Institute, 1963.


                                 254

-------
or nonhazardous nature of the waste (based on RCRA tests) decides
whether the waste can be disposed of in a sanitary landfill or a
secured landfill, respectively.

It is possible for this waste to be incinerated.  This is. not com-
monly done, however.  This is mostly due to the increased cost of
incineration plus landfilling versus landfilling alone.  One source
[18] provided estimates of typical costs.  A cost of $10/metric
ton (wet) is given  [$13/metric ton (dry)] for sanitary landfilling.
For incineration pJus sanitary landfilling of the ash, the cost
increased to $5l/metric ton (wet) [$67/metric ton (dry)].  The
next best step, which would be incineration plus disposal of the
ash in a secure landfill, increases the cost slightly to $54/metric
ton (wet)  [$71/metric ton (dry)].  Since incineration reduces the
waste to an innocuous ash, this third alternative is not practiced,
according to the literature.  The second method is not commonly
practiced, either.  The survey that indicated that all of the 13
plants landfilled their wastes also indicated that 2 of those
plants sent some (no amount given) of their coating wastes to an
incinerator first.

6.6.2  Reclamation

Reclamation of paint waste is not commonly practiced.  There is,
however, an existing process for converting waste paint to origi-
nal quality product  [153].  Based on the knowledge of this com-
pany, it is the only one in existence today.  It handles wastes
from two automotive assembly plants.  The process has a capacity
of  1,000 gal/day (20, 55-gal drums/day).  This process is specifi-
cally designed to handle overspray paint waste from spray coating
operations.  Because overspray is essentially still the virgin
paint, it  is more amenable to reclaiming (or more correctly re-
cycling).  This process does not handle scrnpings or other dried
waste paint.   It is also sensitive to contamination.  Care must
be  taken to ensure  that the paint is not contaminated by oils,
greases, soaps, silicones, asphaltic sealers, vinyl compounds,
latexes or paint strippers.  For example, excessive quantities of
highly alkaline wash water compounds may dechromatize sensitive
colors such as iron blues, chrome greens, moly-oranges, and some
organic reds.  Acid conditions must also be avoided.  A compound
(such as clay) should be used to keep the solution as close to
neutral as possible.

The overspray  is collected by a vertical wash water curtain.  The
wash water is  chemically treated prior to spraying by adding a
flocculating agent.  The flocculants are of three general classes.
They are sodium or  potassium hydroxides or alkaline salts, suit-
able polyelectrolytes  (such as polyacrylamides, some proteins and
 [153]  Telephone communications with Robert A. Thomas, President,
       Clyde  Paint  and  Supply Company,  Inc., Clyde, Ohio.
                                 255

-------
polysaccharides) and various kaolinites and bentonites.   The over-
spray is flocculated as it hits the wash water and is collected
in a tank under the spray booth.  The paint forms a layer on top
of the water.  This layer is bkirjr.cd off either manually or me-
chanically and put into 55-gallon drums.  The drums are sent tc
the reclaimer [154],

The sludge has a very thick, dough-like consistency.  A prelimi-
nary mixing step using dough-type mixers is performed to make the
sludge easier to work with.  Large particulates are removed through
a rough straining operation.  The particulates are removed because
they will not accept solvent.  The amount of particulates depends
on the waste.  Solvent is then mixed into the sludge to bring it
to a paint viscosity.  The solvent blend used depends on what the
original product, specifications were.  The solvent/sludge mixture
is then dehydrated by vacuum distillation.  Tire solvent-to-water
lost ratio is about 7 gallons solvent/1 g?llonx water.  The solvent
is refluxed back into the kettle.  After dehydration, the mixture
is allowed to cool.  The desired viscosity is achieved by adding
the correct solvents and additives.  These are determined by the
original paint composition.  The mixture is ttoen filtered and
centrifuged to remove any particulate contamiisants.  The final
product should meet the physical standards of the original paint.
The product is filled into drums for shipping or storage.

The most recent (1971) cost figures indicate a cost savings of
SO.50 to SI.50 per gallon delivered to the customer.

6.6.3  Conclusions and Recommendations

The biggest contributor of waste paint is the spray coating oper-
ation.  Almost all of this waste is disposed of directly into
landfills.  Very little is incinerated prior to landfilling.  This
waste paint can be reclaimed and a process for this exists.  How-
ever, there is apparently little interest at tMs time in reclaim-
ing the waste.  This is due to  the apparent ease with which the
waste can be landfilled and the fact that only one small reclaiming
operation exists.

It is quite possible that this  is  not a significant problem.
Since RCRA has mechanisms to determine the hazardous nature of
wastes, this will help to ensure that wastes get proper disposal.
Further study could be done on  determining how much of the paint
waste is actually hazardous.

Since a reclamation process exists, this may deserve further inves-
tigation.  A study of the economic advantages o>£ reclaiming may
also be of im.ei.est.
 [154] Lapointe, A.  J.   Quality  coatings  derived1 from overspray
      solid  wastes.   First  international antiprallution coating
      seminar;  1971 December  14;  Chicago.   Chemical Coaters
      Association.


                                 256

-------
                           REFERENCES
 1.   Richards,  D.  W.;  and Suprenant,  K.  S.   Study  to  support new
     source  performance  standards  for solvent metal cleaning oper-
     ations .   Append:x reports.  U.S.  Environmental Protection
     Agency;  1976  July 30.   Contract  69-02-1329, Task Order No. 9.

 2.   Development document for effluent limitations guidelines and
     standards for the metal finishing point source category.
     Washington, DC;  U.S. Environmental Protection Agency;  1980
     June.   557 p.  EPA-440/l-80-091a.

 3.   19*77 Census of Manufactures,  Geographic Area  Series  MC77-A-1
     through MC77-A-51.   Washington,  DC;  U.S. Department  of Com-
     merce,  Bureau of the Census;  1978.

 4.   Sager,  R.  C.   Comparing lube  demand data.   Hydrocarbon Proc-
     essing.   60(7)-.141-147, 1981  July.

 5.   Helm,  J. L.   Lube-supply problems to crop  up  in  1980s.  Oil  &
     Gas Journal.   89-94, 1979 December 10.

 6.   Sales of lubricating and industrial oils  and  greases.  Cur-
     rent industrial reports series.   Washington,  DC; U.S.  Depart-
     ment of Commerce, Bureau ox the  Census; 1978  November.  16 p.

 7.   Hoogheem,  T.  J.; Hori ,  D. A.; Hughes,  T. W.;  and Marn, P. J.
     Source assessment:   solvent evaporation -  degrear  g opera-
     tions.   Cincinnati, OH; U S.  Environmental Protection Agency;
     1979 August.   133 p.  EPA-600/2-79-019f.   PB  80-128812.

 8.   Hughes,  T. W.; Horn, D. A.; Sandy,  C.  W.;  and Serth, R. W.
     Source assessment:   prioritization of air  pollution  from
     industrial surface  coating operations.  Research Triangle
     Park,  NC; U.S. Environmental  Protection Agency;  1975 Feb-
     ruary.   EPA-650/2-75-109a.

 9.   Dean,  J. C.  The U.S. coatings industry strategy for sur-
     vival in the  '80s.   Chemical  Week.  J981  October 21.

30.   Automobile and light-duty truck  surface coating  operations
     background information document.  Research Triangle  Park,
     NC; U.S. Environmental Protection Agency;  1979 October.
     301 p.   EPA-450/3-79-030.  PB 80-123540.
                                257

-------
11.  Baldwin,  V.  H.   Environmental assessment of iron casting.
     Research Triangle Park,  NC;  U.S.  Environmental Protection
     Agency;  1980 January.   171 p.  EPA-600/2-80-021.   PB 80-
     187545.

12.  Draft development document for the iron and steel manufactur-
     ing point source category.  Vol.  I,  draft document.   Washing-
     ton, DC;  U.S. Environmental Protection Agency; 1979  October.
     EPA-440/1-79-0243.  PB 81-184392.

13.  Hotlen,  B. W.  Bidenate oxygen compounds as boundary lubri-
     cants for aluminum.  Lubrication Engineering.  398-403, 1974
     August.

14.  Proposed development document for effluent limitations guide-
     lines and standards for the iron and steel manufacturing
     point source category.  Volume III - steel making, vacuum
     degassing and continuous casting subcategories.  Washington,
     DC; U.S. Environmental Protection Agency; 1980 December.
     513 p.  EPA-440/l-80-024b.  P3 81-184418.

15.  Parsons, T., ed.   Industry profiles for environmental use
     the iron and steel industry.  Research Triangle Park, NC;
     U.S. Environmental Protection Agency; 1977 February.  209 p.
     EPA-600/2-77-023X.  PB 266 226.

16.  Proposed development document for effluent limitation guide-
     lines and standards for the iron and steel manufacturing
     point source category.  Volume VII - coif forming, alkaline
     cleaning.  Washington, DC; U.S. Environmental Protection
     Agency; 1980 December.  604 p.  EPA-440/l-80-024b.  PB 81-
     184442.

17.  dillett, M.  Industrial lubrication.  New York, Pergamon
     Press, 1979.  136  p.

38.  Levin, J.; Beeland, G.; Greenberg J.; and Peters, G.
     Assessment of industrial hazardous waste practices special
     machinery manufacturing industries.  Washington, DC; U.S.
     Environmental Protection Agency; 1977 March.  328 p.  EPA-
     530/SW-141C.  PB  265 981.

19.  Lahoti, G. D.; Nagpal, V.; and Altan, T.  Selection of lub-
     ricants in hot forging and extrusion.  First  international
     conference on lubrication challenges in metal working and
     processing.  Chicago, ITT Research Institute, 1978.  52-59.

20.  Cook, C. R.  Lubricants for high temperature  extrusion.
     28:199-218,  1971  June.
                                258

-------
21.  Hollowell, J. B.; Valter, L. E.; Gurlis, J. A.; and Layer,
     C. H,  Assessment of industrial hazardouswasta practices -
     electroplating and metal finishing industries - job shops.
     Washington, DC; U.S. Environmental Protection Agency; 1976
     September.  516 p.  PB 264  34°.

22.  Leggett,  R.  The-coated belt:  a production tool.  Metal
     Finishing.  75(12):9-15, 1977 December.

23.  Hignett,  B.  Mass finishing.  Metal Finishing.  76(7):17-21,
     1978 July.

24.  Bigda, R.  J.  Review of all lubricants  used in the U.S. and
     their  re-refining potential.  Bartlesville, OK; U.S. Depart-
     ment of  Energy;  1980 June.   86 p.  DOE/BC/30227-1.

25.  Ackerman,  A. W.  The properties and classification of metal-
     working  fluids.  Lubrication Engineering.  7:285-291, 1969
     July.

26.  Schey, J.  A.  Purposes and  attributes of metalworking
     lubricants.  Lubrication Engineering.   23:193-198, 1967
     May.

27.  Standard classification of  metalworking fluids and related
     materials.   In:   1976 Annual Eook  of ASTM  Standards.  Part  24.
     Philadelphia, PA, American  Society for  Testing and Materials.
     1976.  ANSI/ASTM D  2281-73.

28.  Weinstein,  J. .1   Waste oi3 recycling and  disposal.  Cincin-
     nati,  OH;  U.S.  ': vironmental Protection Agency;  1974 August.
     327  p.   EPA-C,  ?  ,:-74-052.   PB  236  148.

29.  Smith, T.  H.  Toxicological and microbiological  aspects  o'f
     cutting  fluid preservecives.  Lubrication  Engineering.
     25:313-319,  1969 August.

.30.  Listing  waste oil t*s  a hazardous waste. Washington, DC;
     U.S. Environmental  Protection  Agency; 1981.   SW-909.

31.  Sargent, L.  5.,  Jr.   Lubricant conservation  in industry.
     Alcoa  Center, A;  Aluminum  Company  of America.

32.  Nehls, B. L.  Particulate  contamination in metalworking
     fluids.   Lubrication  Engineering.   33(4):179-183,  1977 April.

33.   Increase fluid  life with oxidation/corrosion inhibitors.
     Fluid  and Lubricant Ideas.   24-25, 1979 Spring.

34.  Concentrates -  industry/business.   Chemical  Engineering
     News.  p. 12,  1976  October 18.
                                 259

-------
35.   How to improve metalworking operations by organising a
     biocide treatment program.  Fluid and Lubricant Ideas.
     22-25, 1980 September-October.

36.   Bennett,  E. O.  Biology of metalworking fluids..  Journal of
     American Society of Lubrication Engineers.  28(6):237-247,
     1972 July.

37.   Adams, M. C.; et al.   BOD and COD studies of synthetic and
     semisynthetic cutting fluids.  Water, Air, and Soil Pollut-
     ant.  11:105-113, 1979.

38.   Peter, R.; Tanton, T.; and Leung, S.; et ai.  Alternatives
     to organic: solvent degreasing.  Sacramento, CA; California
     Air Resources Poard;  1978 May.  232 p.  ARB-A6-2-6-30.
     PB 282 465.

39.-  Richards, E. W.; and Suprenant, K. S.  Study to support new
     source performance standards for solvent metal cleaning
     operations.  U.S. Environmental Protection Agency.  1976
     April.  EPA Contract 68-02-1329.

40.   Allen, R. D.  Inspection  source test manual for solvent metal
     cleaning  (degreasers).  Washington, DC; U.S. Environmental
     Protection Agency; 1979 June.  150 p.  EPA-430/1-79-008.
     PB 80-125743.

41.   Me^al finishing guidebook and directory, 1974 Edition.
     Hackensack, NJ; Metals and Plastics Publishing, Inc.

42.   Payne, H. F.  Organic coating technology,  vol. II.  New York,
     John '.Vi]ey & Sons, Inc.,  1961. ' 1019-1020.

43.   Heat exchanger tube manual.  Waterbury, MA; Scoville Manu-
     facturing Co.  1957.  171 p.

44.   Vapor degreasers.  Clarke, NJ; Branson Equipment Co.

45.   Brewer, G. E. F.  Calculations of painting wasteloads asso-
     c1ated with metal finishing   Cincinnati, OH; U.S. Environ-
     mental Protection Agency; 1980 June.  85 p.  EPA-600/280-144.
     PS 80-226731.

46.   Scofield, F.; Levin, J.;  Beel?rrt, G. ; and Land, T.  Assess-
     ment of industrial hazardous  .'afte prac;ices, paint ano
     allied products industry, contract solvent reclaiming opera-
     tions and factory application of coatings.  Washington, DC;
     U.S. Environmental Protection Agency; 1975 September.  304 p.
     EPA-1530/SW-119C.  PB 251 669.
                                260

-------
47.  Surface coating of metal furniture - background information
     for proposed standards.  Research Triangle Park,  NC;  U.S.
     Environmental Protection Agency; 1980 September.   406 p.
     E?A-450/3-80-G07a.  PB 82-113938.

48.  Calculations of painting wasteloads associated with met «.
     finishing.  Cincinnati, OH; U.S. Environmental Protection
     Agency; 1930.  EPA-600/2-80-144.

49.  Making recycling work for you through proper process selec-
     tion.  Fluid and Lubricant Ideas.  10-13, 1979 Summer.

50.  Gabns, T.  Emulsified industrial oils recycling.  Bartles-
     ville, OK; U.S. Department of Energy; 1982 April.  155 p.
     DOE/BC/101S3-1.

51.  Ford, D.; and Elton, R.  Removal of oil and grease from in-
     dustrial wastewater.  Chemical  Engineering.  1977 October 17.

52.  Evans, R. A.  Solving the oil pollution problem.   Lubrica-
     tion Engineering.  521-524, 1068 November.

S3.  Paulson, E.  Keeping pollutants out of troubled water.
     Lubrication Engineering.  1968  November.

54.  FMC Corpora*  >n, Product Literature.

55.  Tabakin, R. B.; Trattner, R.; and Cheremisinoff,  P. N.
     Oil/water separation technology:  the options available,
     Part 1.  Waste and Sewage Works.  74-77, 1978 July.

56.  Stone, R.; and Smallwood, H.  Aerospace industrial waste
     pretreatment.  29th Industrial  waste conference;  1976
     May 7-3.  West Lafayette, IL; Purdue University,  1976.
     pp. 51-59.

57.  Patterson, M. M.  why separation filtration for abrasive
     machining.  Lubrication Engineer.  458-461, 1979 December.

58.  Sluhan, C. A.  Grinding with water miscible grinding fluids.
     Lubrication Engineering.  352-354, 1970 October.

L9.  Improving coolant life.  Fluid  and Lubricant Ideas,  p. 28,
     1979 Winter.

60.  Centrifugal oil purification at an aluminum can plant.
     Fluid and Lubricant Ideas.  19-20, 1980 May/June.

61.  Kecycling metalworking coolants through central systems.
     Fluid and Lubricant Ideas.  24-25, 1981 January/February.
                                251

-------
62.  Centrifuges for re-refining and leprocessing waste oils.
     ALFA-LAVAL Inc.,  Product Literature.

63.  Fochtman, E. G. ;  and Tnpathi, K. C.  Research needs in
     coolant filtration.  Proceedings in Lubrication Challenges
     in Metalworking and Processing; 1978 Jun>; 7-9; Chicago.
     ITT Research Institute, First International Conference,
     117-121.

64.  Brooks, K. A., Jr.  A review of disposable nonwoven filtra-
     tion media for cutting coolant and process fluids.  Lubrica-
     vion Engineering.  542-548, 1974 November.

65.  Coursey, w. >5.  The application, control, and disposal of
     cutting fluids.  Lubrication Engineering.  200-204, 1969 May.

66.  Fram Industrial Filtration and Separation.  Product
     Publications.

67.  Montens, I. A,  Treatment of wastes originating from metal
     industries.  West Lafayette,  IN; Purdue University, 782-791.

68.  Golovov, A.  Xethod of breaking an oil-in-water emultion.
     U.S. patent 4,087,333.

69.  Snyder, D. D.; and Willihinganz, i-. A.  A new electrochemical
     process for treating spent emulsion.  31st Industrial waste
     conference; 1976 May 4-6.  West Lafayette, IN; Purdue Uni-
     versity.  673-680.

70.  Kramer, G.; Buyers, A.; and Brownlee, B.  Electrolytic
     treatment of oily wastewatex.  34tii Industrial waste confer-
     ence;  1979.  Vest Lafayette IN; Purdue University.  673-680.

71.  Gealer, R. L.; Golovoy, A.; and Wointraub, M. H.  Electro-
     lytic  treament of oily wastewater  from manufacturing and
     machining plants.  Cincinnati, OH; U.S. Environmer :al Pro-
     tection Agencv; 1980 June.  48 p.  EPA-600/2-80-132.
     PB 80-225113."

72.  Hoover, w. ; sixjnan, W.; and Stack, V.  Treatment  of wastes
     containing e-ulsified  oils and greast.:.  L ibrication Engi-
     neering.  1964 May.

73.  Gruette, J.  Primary wastswater treatment and oil recovery
     in the refining industry.  National Petroleum Refiners Asso-
     ciation Meeting;  1978  March 19-21.

74.  Tylor, R. W.  Dispersed air flotation.  Pollution Engineer-
     ing.   1973 Jar.uary.
                                262

-------
75.  Wahl,  J. R.; Hayes, T. C.; Kleper, M. H. ;  and Pinto, S. D.
     Ultrafiltratioa for today's oily wastewaters:  A survey of
     current ultrafiltration systems.  34th Industrial waste con-
     ference; 1979 May 8-10; West Lafayette.  Ann Arbor, MI, Ann
     Arbor Science Publications,' Inc., 1980, 719-733.

76.  Pinto, G. D.  Ultrafiltration for devatering of waste emul-
     sified oils.  First international conference on lubrication
     challenges in metalworking and porcessing; 1978 June 7-9;
     Chicago^  ITT Research Institute, 1978, 129-134.

77.  Product Literature.  Continental Water Systems Corporation,
     El Paso, Texas.

78.  Chian, E. S. K.: and Gupta, A.  Recycle of wastewater from
     vehicle washracks.  29th  Industrial waste conference; 1974
     May 7-9.  West Lafayette, IN, Purdue University, 9-20.

7,9.  Sonksen, M. K.; Sittig, F. M.; and Maziarz, E. F.  Treatment
     of oily wastes by ultrafiltration/reverse osmosis; a case
     history.  33rd Industrial waste conference; 1978 May.  West
     Lafayette,  IN, Purdue University, p. 696.

80.  Skovror.ek, H. S.; Dick, M.; and Des Hosiers, P. E.  Selected
     uses of activated carbon  for industrial wastewater pollution
     control.  Second annual conference on new advances in separa-
     tion technology; 1976 September 23-24; Cherry Hill, NJ.

81.  Wach^-ir, R. A.; Blackwood, T. R. ; and Chalekode, P. K.   Study
     to determine need  for standards of performance for new sources
     of wai..e solvents and solvent reclaiming.  Washington, DC;
     J.S. Environmental Protection Agency; 1977 February.  106 p.
     Contract 68-02-1411.

82.  Sittig, M.  Incir.erav.ion  of industrial hazardous wastes  and
     sludges.  Pollution Technology Review No. 63.  Noyes Data
     Corporation, 1979.

83.  Ottinger, R. S.; Blumenthal, J-. L.; Dal Proto, D. G. ;
     Grubar, G.  I.; Santy, M.  J.; and  Shin, C. C.  Recommended
     methods of  reduction, neutralization, recovery, or disposal
     of hazardous waste; Volume III, disposal process descrip-
     tions - ultimate disposal, incineration, and pyrolysis proc-
     esses.  Cincinnati, OH; U.S. Environmental Protection Agency;
     1973 August.  251 p.  EPA-670/2-73-053C.  PB 224 582.

84.  Ackerman, D.; Clausen, J.; Grant, A.; Johnson, R. ;  Shih, C.;
     Tobias, R.; Zee, C.; Adams, J.; Cunningham, N.; Dohnert, E.;
     and Harris, J.  Destroying chemical wastes in commercial
     scale incinerators; Fxnal Report  - Phase  II.  Washington, DC;
     U.S. Environmental Protection Agency; 1978.  130 p.  EPA-630/
     SW/55C.  PB 278 816.


                                263

-------
85.  Industry Week.   p. 56,  1971 June 15.

86.  Yates,  J. J.; Groke,  K. G. ; Kla'zura,  A. G.;  Spaite,  A.  R. ;
     Chiu, H. H.; Mousa,  Z.; and Budach,  K.   Used oil recycling
     in Illinois:  data book.  ETA Engineering,  Inc., 1978 October.
     135 p.

87.  Kincannon, C. B.  Oily waste disposal by soil cultivation
     process.  Washington, DC; U.S. Environmental Protection
     Agency; 1973.  EPA R2-72-110.

88.  Liu, D. L.;  and Townsley, P. M.  Lignosulfonates in potro-
     leum fermentation.  Journal of the Water Pollution Control
     Federation.   531-537, 1970 April.

89.  Hess, L. Y.   Reprocessing and disposal of waste petroleum
     oils.  Park Ridge, NJ,  Noyes Data Company,  1979.

90.  Whisman, M.  L.; Goetzinger, J. W.; and Cotton, F. O.  Waste
     lubricating oil research.  An investigation of several re-
     refining methods.  U.S. Department of the Interior,  Bureau
     of Wines; 1974.  25 p.   RI-7884.

91.  Blatz,  F. J.; and Pedall, R. F.  Re-refined locomotive engine
     oils and resource conservation.  Lubrication Engineering.
     618-624, 1979 November.

92.  Waste oil recycling.  U.S. Department of the Interior, Bureau
     of Mines; 1975.  Issue Report Paper.

93.  Quang,  D. V.; et al.  Spent oil reclaimed without acid.
     Hydrocarbon Processing.  130-131, 1976 December.

94.  Audibert, M. M.; et al.  The regeneration of the spent
     oils.  Chemical Age of India.  26(12 ) :1015-1019, 1975.

95.  Quant,  D. V.; Carriers, G.; Schieppati, R.; Comte, A.; and
     Andrews, J.  W.  Re-refining uses propane treat.  Hydrocarbon
     Processing.   129-131, 1974 April.

96.  Dcutsch, D.  J.  Bright prospects loom  for used-oil re-
     refiners.  Chemical Engineering.  86(16):28-32,  1979.

97.  Cutler,  E. T.  Re-refining:  selecting the best  process.
     Third international conference on waste oil recovery and
     reuse;  1978; Houston.  Pilot Research  and Development
     Center,  Merlon 'jtation, PA, 163-168.

98.  Antonelli, S.  Spent oil re-refining.  Third international
     conference on waste oil recovery and reuse; 1978 October 16-
     18;  Houston.  121-125.
                                264

-------
 99.   Whisman,  M.  L.;  et al.   U.S.  Department of Energy,  assignee.
      U.S.  patent 4,073,719.   1978  February 14.

100.   Whisman,  M.  L;  et al.   U.S. Department of Energy,  assignee.
      U.S.  patent 4,073,720.   1978  February 14.

101.   Cotton,  F.  o.;  et al.   Pilot-scale used oil re-refining
      using a solvent treatment/distillation process.   U.S. Depart-
      ment of Energy;  Bartiesville  Energy Technology Center; 1980.
      BETC/RI-79/14.

102.   Bnnknan, D. w.; et al.  Environmental, resource conserva-
      tion, and economic aspects of used oil recycling.   U.S.
      Department of Energy;  Bartlesville Energy Technology Center;
      ladl April.   DOE/BETC/RI-80/11.

103.   Brinkman, D. w.; et al.  Solvent treatment of used lubri-
      cating oil to remove coking and fouling precursors.  U.S.
      Department of Energy;  Bartlesville Energy Technology Center;
      1978 December.   BETC/RI-78/20.

104.   Engineering design of a solvent treatment/distillation used
      lubricating oil re-refining.   Houston, TX; Stubbs Overbeck
      and Associates,  Ir.c; 1980 June.  Final report to U.S. Depart-
      ment of Energy,  Division of Industrial Energy Conservation.

105.   Brinkman, D. w.; and Whisman, M. L.  Waste oil recovery and
      reuse research at the Bartlesville Energy Technology Center.
      Third international conference on waste oil recovery and
      reuse; 1978 October 16-18; Houston.  169-175.

106.   Brownaweil,  D.  W.; and Renard, R. H.  Esso Research and
      Engineering Company, assignea.  U.S. patent 3,639,229.
      1972 February 1.

107.   Gulick, G. L.  Quove Chemical Industries, Ltd., assignee.
      U.S. patent 3,620,967.  1971 November 16.

108.   Chambers, J. M.; and Hadley,  H. A.  Berks Associates,  Inc.,
      assignee.  U.S. patent 3,625,881.  1971 December 7.

109.   Berry, R.  Re-refining waste oil.  Chemical Engineering.
      104-106, 1979 April 23.

.110.   Linnard, R. E.   Philips re-refining oil program.  Third
      international conference on waste oil recovery and reuse;
      1978; Houston,   bartlesville, OK, Philips Petroleum Co.,
      127-135.

111.   Re-refining.  Fluid and Lubricant Ideas,  p. 27, 1980  May/
      June.
                                265

-------
112.   Packaging re-refining technology:   the PROP process.
      Fluid and Lubricant Ideas.   1979 Fall.

113.   Linnard,  R.  E.;  and Henton,  L.  M.   Re-refine waste oil
      with PROP.  Hydrocarbon Processing.   1979 September.

114.   Erdweg,  K. J.  Recyclcn - a  new process to revert spent
      oils into lubricants..  Third international conference on
      waste oil recovery and reuse; 1978 October 16-18; Houston.
      93-97.

115.   Fauser,  F.  Recyyclon - a new method of re-refining spent
      lubrication oils without detriment to the environment.
      Conservation and Recycling.   3:135-141, 1979.

116.   Recyclon - a new process for the re-refining of waste oil.
      Leybold-Heraeus, Vacuun Process Engineering Division.  Trade
      Literature.

117.   Havemann, R.  Haberland and company and the KTI waste oil
      re-refining process.  Third international conference on
      waste oil recovery and reuse; 1978 October 16-18; Houston.
      83-92.

118.   Dumortier, J.  Matthys/garap techniques.  Third international
      conference on waste oil recovery and reuse; 1978 October
      16-18; Houston.   99-107.

319.   Audibert, F.; et al.  Reclaiming of spent lubricating oils
      by ultrafiltration.  Third international conference on
      waste oil recovery and reuse;. 1978 October 16-18; Houston.
      109-120.

120.   Pare, G.; et al.  Institut Francais du Petrole, France,
      assignee.  U.S.  patent ?,919,075.  1975 November 11.

121.   Bishop,   J.; and Arlidge, D.   Recent technology development
      in evaporative re-refining of waste oil.  Third international
      conference on waste oil recovery and reuse; 1978 October 16-
      18; Houston.  Rochester, The Pfaudler Company, 137-150.

122.   Pauley,   J. F., Jr.  Thin-film distillation as a tool in the
      re-refining used oil.  Third international conference on
      waste oil recovery and reuse; 1978 October 16-18; Houston.
      Charlotte, Luwa Corporation, 151-161.

123.   Davis, J. C.  New technology revitalizes waste-lube-oil
      re-refining.  Chemical Engineering.  63-65, 1974 July 22.

L24.   Oil refining route is set for two plants.  Chemical Engi-
      neeriny.  92-93, 1981 October 5.
                                266

-------
125.   Boos,  Allen and Hamilton,  Inc.   Preliminary analytical data.
      Bartlesville Energy Technology Center;  U.S. Department of
      Energy;  1980 March.

]26.   Swain, J.  W.  Assessment of industrial  hazardous waste man-
      agement -  petroleum re-refining industry.   Washington, DC;
      U.S.  Environmental Protection Agency; 1977 June.  162 p.
      PB 272 267.

127.   Cukor, P.  M.; Keaton,  M. J.; and Wilcox,  G.  A technical  and
      economic study of waste oil recovery.  Part III:  economic,
      technical, and institutional barriers to waste oil recovery.
      Washington, DC; U.S. Environmental Protection Agency; 1973
      October.  136 p.  EPA-530/SW-90C3.  PB 237 620.

128.   Suarez,  M.; Morris, D. A.; and Morris,  R.  C.  Acid sludge
      utilization.  Bartlesville, OK; U.S. Department of Energy;
      1980 September.  31 p.  Contract No. DE-AC-19-79BC/0089.

129.   Seng,  C.  Recovery of fatty materials from edible oil re-
      finery effluents.  U.S. Environmental Protection Agency;
      1973 December.  148 p.  EPA-600/2-73-015.   PB 231 268.

130.   Bennett, E. 0.  The disposal of metal cutting fluids.
      Lubrication Engineering.  300-307, 1973 July.

131.   Evans, C.   Treatment of used cutting fluids and swarf.
      Tribiology International.  33-37, 1977 February.

132.   Larson, D. M.  Activated carbon adsorption for solvent
      recovery in vapor degreasing.  Metal Finishing.  42-45,
      1974 October.

133.   Control techniques for volatile organic emissions from sta-
      tionary sources.  Research Triangle Park,  NC; U.S. Environ-
      mental Protection Agency; 1978 May.  578 p.  EPA-450/2-78-
      022.  PB 284 804.

134.   Davis, W.  L.; and Kovack, J. L.  Solvent recovery by carbon
      adsorption for the coating industry.  Technical Association
      of the Pulp and Paper Industry; 1980 Paper Syntuetic Con-
      ference, 1980.

135.   Grandjacques, B.  Carbon adsorption can provide air pollu-
      tion control with savings.  Pollution Engineering.  28-31,
      1977 August.

136.   Chemical Engineer's Handbook.  Fifth Edition.  J. H. Perry
      and C. H.  Chilton, eds.  New York, McGraw-Hill Book Company,
      1973.
                                267

-------
]37.   Control of volatile organic emissions from organic solvent
      metal cleaning.   Research Triangle Park,  NC;  U.S.  Environ-
      mental Protection Agency; 1978 April.  EPA-45'0/2-77-002.

133.   Monahan,  R.  Vapor degreasing with chlorinated solvents.
      Metal Finishing.   26-31,  1977 November.

139.   Control of hydrocarbons from tank truck gasoline loading
      terminals.  Research Triangle Park, NC; U.S.  Environmental
      Protection Agency; QAQPS; 1977 May.  Draft copy.

140.   Harvin, R. L.  Recovery and reuse of organic ink solvents.
      Louisville, KY;  C&I Girdler, Inc.; 1975 September.  25 p.
                                  \
141.   Treybal,  R. E.  Mass Transfer Operations.  New York, McGraw-
      Hill Book Company, 1968.   pp. 129, 154, 225-226.

142.   Hengstebeck, R.  J.  Distillation.  Principles and Design
      Procedures.  New York, Reinhold Publishing Corporation,
      1961.

143.   Hansen, W. G.; and Rishel, H. L.  Cost comparisons of treat-
      ment and disposal alternatives for hazardous wastes; volume I
      Cincinnati, OH;  U.S. Environmental Protection Agency; 1980
      December.  272 p.  EPA-600/2-80-188.  PB 81 128514.

144.   Reynen, F.; and Kuncl, K. L.  Solvent recovery systems nets
      plant approximately S50,000/yr savings.  Chemical Proces-
      sing.  38(9):19,  1975.

L45.   Robinson, C. S.;  and Gilliland, E. R.  Elements of frac--
      tional distillation.  New York, McGraw-Hill Book Company,
      1950.  492 p.

146.   Fair, J. R.; and Bolles,  W. L.  Modern design of distilla-
      tion columns.  Chemical Engineering.  75(8) :156-178, 1968.

147.   Colley, Forster,  and Stafford (eds).  Treatment of indus-
      trial effluents.   New York, John Wiley and Sons, 1976.
      378 p.

148.   Tierney, D. R.;  and Hughes, T. W.  Source assessment:  re-
      claiming of waste solvents, state of the art.  Cincinnati,
      OH; U.S. Environmental Protection Agency; 1978 April.
      53 p.  EPA-60C/2-78-004f.

149.   Reay, W. H.  Recent advances in thin-film evaporation.
      London ngland, Luwa (U.K.) Ltd, 1963 June.  Represented
      from the Industrial Chemist.  5 p.
                                268

-------
150.  Storm, D. L.  Handbook of industrial waste composition in
      California - 1978.  California Department of Health Service
      Hazardous Material Management Section, 1978 November.

151.  Ross, R. D.  Industrial waste disposal.  New York,  Reinhold
      Book Corporation, 1968.  340 p.

152.  Diffusion of effluents into receiving waters.  Manual on
      disposal of refinery wastes, Volume 1.  New York, American
      Petroleum Institute, 1963.

153.  Telephone communications with Robert A. Thomas, President,
      Clyde Paint and Supply Company, Inc., Clyde, Ohio.

154.  Lapointe, A. J.  Quality coatings derived from overspray
      solid wastes.  First intmational antipollution coating
      seminar; 1971 December 14; Chicago.  Chemical Coaters
      Association.
                                269

-------
                           APPENDIX A

                      OIL COMPOSITION DATA


Composition data for new (raw material) and waste straight oils,
emulsified oils, and synthetic fluids are listed in, this appendix.
Raw material data are listed first (Table A-l)  followed by waste
data (Table A-2).  Data are presented in sequence of straight oils,
emulsified oils, and synthetic fluids for both the raw materials
and wastes.  Also,  raw materials applications and their physical
properties, and the type of metal working operation generating the
waste are identified wherever they  are known.

Data were scrutinized and assigned a data quality rating based
on an A-B-C quality system.  Data with an "A" quality are those
found to have been sampled and analyzed with some QA/QC protocol
attached; e.g., demonstrated comparison with analytical standards,
use of splits, blanks, etc.  "B" quality is assigned to data with
documented sampling and analysis procedures but no evidence of
QA/QC.  "C" quality data are those values for which no documenta-
tion has been provided and/or the accuracy is undeterminable.
                                270

-------
                           TABLE  A-l.   METAL  WORKING OIL COMPOSITION DATA
                                          Material Composition
Process or material  description
                                           Component
                                                                 Weight
                                                                 percent
                                               physical characteristics
                                       Data
                                      quality
Cutting oil,  petroleua base

Cutting oil,  petroleum baoe.
  fatty oil
Cutting oil,  sulfurized
  mineral-lard oil
Cutting oil,  *ulfurized
  mineral-lard oil
Soluble netal working otl,
  petroleua baaed
Soluble oil,  petroleua baoc.d;
  for cachining and grinding
Ruat protective,  cil-based
Rust protective,  asphalt-based
Rust-proofing compound,
  oil-based
Synthetic metal  working  fluid,
  heavy duty for stainless
  steels and hardened  tool
  steels,  grinding,  belt
  grinding and machining
Petroleum hydrocarbons           97

Mineral oils                     64
Ethylene-propylenc copolyraer       2
Laid oil                          8
Di-tertiary-nonyl-polyoulfide      4
Chlorinated paraffin
Odorant (16 ppm)

Mineral oil base
Fatty oil                         6
Sulfur                            1.96

Mineral oil base
Fat.ty oil                         6
Sulfur                            1.99

Petroleum oil
Chlorinated wrx
Enuloi fiers
Odoranti
Dye

Petroleum base oil               SO
Chlorinated paraffin            7-10
Kerosene                         10

Petroleua hydrocarbons
Petroleum aulfonates
Petroleum oxidates

Limestone                        65
Asphalt                          18
Naphtha                          IS
Asbcotoo                          2
Petroleua naphtha               >10
Mineral spirits                 >10
Methylere chloride              >10
Synthetic base fluids
Proprietary grinding aids        20
Chlorine                          8
Sulfur                            2
Specific gravity:   0.912

Specific gravity   0.898
Insoluble in water
Flash point:  182«C (360*F)
Flash point:   177'C (350«F)

Pour point:   -23°C (-10*F)

Flash pointi   171'C <340*F)

Pour point:   -34*C (-30°F)

Specific gravity:   0.99
Water-soluble
Specific gravity:   0.9340  to  0.95J7

Volatilea,  volume  percent:  iO-15

NA
Flammable liquid
Boiling point:   123'C (2S3'F)
Vapor pressure  0 868 ma Hg:  2.0
Vapor Censity (Air • 1):   3.1
Percent volatile by volume, X>  2S
Solubility in water:  0
pH (SX emulsion):   9.0
Weight, Ib/gal:   8.4
Water-soluble
Recooniended dilution:   20:1 to 100:1
                                                                                                             (continued)

-------
                                               TABLE A-J  (coat-ilined)
                                           Material Composition"
 Process or material description
                                            Component
                                WeiqhL
                                pctcent
 Synthetic metal working fluid.
  noderate duty machining and
  grinding fluid for cast iron,
  steel, copper, and aluminun
  alloys

 Coolant, synthetic lubricant
  for machining or grinding
Coolant, synthetic lubricant
   for machining, grinding and
   drilling
Cutting fluid, synthetic
  for grinding, machining, and
  drilling
Forming lubricant for steel,
  tin-plate, and non-ferrouo
  metal cans
Quench oil
Synthetic base fluids
Chlorine/chloride
Sulfur
Synthetic fluid
Alkaline liquid
Water base
Bactericide

Synthetic base fluid
Tertiary am me
Fatty acid
Chelating agent
Bactericide
Oxidizing salt

Synthetic base fluid,
  proprietary-formulation
Mineral oil
Polyglycol
Chlorinated esters
Petroleum sulfonate
Amine soaps
<0.01
 0.32
Fmuloified oil
Horpholine
Sodium nitrite
               rhynlcal  character)oticn
                                        Data
                                       ty
pH, concentrate:  9.9
pH. 1:40 dllutior.:  8.9
Weight, 1'b/gal:  8.35
Water-soluble
Recommended dilution:  20:1 to 50:1

Water-soluble
pU:  10.5-10.9
Biodegradable
Recommended dilution:
         Water-soluble
         Biodegradable
         Recommended dilution:
                                                                                                   6:1  to  25:1
                                10:1  to 40:1
         Water-soluble
         pH:   8.9-9.1
         Biodegradalde
         Recommended dilution:   20:1  to 50:1
         Specific gravity:   1.0428
         Weight,  Ib/gal:   8.69

         Appearance:  clear,  dark oil
         Boiling  point:   600*-680*F
         Flaoh point:  310°F (C.O.C.)
         Fire point:  340*F (C.O.C.)
         Specific gravity:   0.960 i 0.005
         pH of 5-10X dilution:   8.8 t 0.5
         Vapor pressure S >60 mm Hg:   0.005
         Viscotflty at 100°F:  750 sec (S.U.V.)
         Four point:  less than 0*F
         Pounds/gallon at 60*F:   8.25 i 0.05
         Solubility in water
         Recommended dilution:   1:10  to 1:20.

         Specific gravity:   1.07
         Soluble  in water
         Recommended dilution:   1:3 to 1:20
         Appearance:  cloudy yellow fluid

-------
                                   TABLE  A-2.   WASTE OIL  COMPOSITION  DATA
     Process and/or  waste description
                   Waste  composition
               Data
              quality
   One month old cutting oil
ro
-j
w
A.P.I, gravity
Ash content,  %
Carbon residue,  %
Pour point, °F
Flash point,  °F
Fire point, °F
Heat of combustion,  Btu/lb
Viscosity, SUS @ 100°F
Viscosity, SUS & 210°F
Sulfur, %
Silver, mg/L
Sodium, mg/L
Zinc, mg/L
Copper, mg/L
Aluminum, mg/L
Barium, mg/L
Nickel, mg/L
Chromium, mg/L
Calcium, mg/L
Iron, mg/L
Silicon, mg/L
Tin, mg/L
Lead, mg/L
Phosphorus, mg/L
Boron, mg/L
Magnesium, mg/L
Vanadium, mg/L
Molybdenum, mg/L
Manganese, mg/L
Cadmium, mg/L
Titanium, mg/L
  22.0
  0.16
   2.2
   -25
   380
   405
17,800
 106.3
  31.8
   0.3
   0.0
   180
    12
   150
    33
   120
     5
    28
 1,900
   520
    90
    21
    15
   150
   120
    42
     8
     7
    17
     3
     0
                                                              B
                                                                                              (continued)

-------
                                        TABLE A-2 (continued)
  Process and/or waste  description
Machine tool cutting lubricants
  and cooling oil from lathes,
  drill presses,  milling machines,
  grinders,  and screw machines
Waste machine oil and cleaner
Waste cutting oil
Waste composition'
Petroleum oil, %
Watci,  %
Volatile materials at 100°C,  %
Non-volatile materials, %
Non-combustible materials at  650°C,  %

Lead,  mg/L
Zinc,  n\g/L
Nickel, mg/L
Copper, mg/L
Cadmium, mg/L
Chromium, ir.g/L
Perchloroethylene, mg/L

Machine oil, %
Trichloroethylene, %

Ash content, %
Carbon residue, %
Pour point, °F
Flash point, °F
Fire point, "F
Heat of combustion. Btu/lb
Viscosity, SUS e  100°F
Viscosity, SUS @ 210°F
Acid,  mg KOM/g
Sulfur, %
Silver, mg/L
Sodium, mg/L
Zinc,  mg/L
Copper, mg/L
                               eo
                               20
                               33
                               67
                              0.1

                             21.3
                             13.6
                            <0.01
                             12.7
                            <0.01
                            <0.01
                           50-100

                               70
                               30

                             0.05
                              0.1
                               + 5
                              270
                              200
                           20,000
                             27.4
                             10.3
                              0.3
                              0.3
                              0.0
                                1
                              190
                               12
 Data
quality
   B
                                                                                           (continued)

-------
                                           TABLE A-2  (continued)
K>

Process and/or waste description . Waste composition
Waste cutting oil (continued) Aluminum, mg/L
Barium. cng/L
Nickel, mg/L
Chromium, mg/L
Calcium, mg/L
Iron, mg/L
Silicon. tng/L
Tin. mg/L
I. end. BKI/I.
riio;-phoMis, my,'!. „
Do ion. mo/ 1
M.ujnesixim. mu/L
VanAdiiMi, mg/L
Molybdenum, imj/L
Mfiiiy.iKi-uc , m'j/l.

• 3
7
• 0
1
82
IB
2
8
a
15
0 ~
1
0 -
1
0
Data
quality















   Waste cutting oil  and coolant.
      ».  wtj/l.
Titanium, mg/L

Bilayered liquid
  Total  solids.  %
  Dissolved solids,  %
pH
Flash point (organic phase),  CF
  Closed cup (aqueous phase),  °F
Btu per  Ib, organic  phase
Btu per  Ib, aqueous  phase
Ash. %
Kerosene, %
Light lube oils, %
Heavy lube oils. %
Ti ichloioethylcne. %
                                                                                          7.6
                                                                                          102
                                                                                          162
                                                                                        16.550
                                                                                            20
                                                                                            3
                                                                                          0.4
                                                                                            5
                                                                                            30
                                                                                            10
                                                                                                   (rout

-------
TABLE A-2  (continued)

Process and/or waste description Waste composition
Waste cutting oil and coolant Silver, mg/L
(continued) Arsenic, mg/L
Cadmium, mg/L
Chro.p.iura, mg/L
Copper, mg/L
Nickel, mg/L
Lead, mg/L
Zinc, mg/L
Antimony, mg/L
Total cyanide, %
Free cyanide, %
Sulfide, %
Bisulfite, %
N> Sulfite, %
Waste oil from machine lubrication in pH
the manufacturing of cold formed Oil, %
parts Lead, mg/L
Zinc , mg/L
Nickel, mg/L
Copper, mg/L
Beryllium, mg/L
Cadmium, mg/L
Chromium, mg/L
Mercury, mg/L
Arsenic, mg/L
Phosphorus, mg/L
Sulfur, mg/L
Cyanide, mg/L
Phenols, mg/L
PCB, mg/L
Noncombustible ash, %

30
<0.01
4.2
520
96
300
3,500
43
<0.01
0.02
<0.02
3.2
<4.0
4.0
6.8
99
114
324
4.0
41.8
6.5
0.17
2.5
<0.1
<0.1
190
875
0.5
0.96
<0.5
o.aa
Data
quality














B
















                                                  (continued)

-------
TABLE A-2  (continued)

Process and/or waste description

Waste cutting oil from roll presses.
punch presses, etc.




Waste lubricating and cutting oils
from machining operations










Machining fluid waste






Waste composition
High
Water, % 59
Oil. % 66.4
Copper, mg/L 3.5
Zinc, mg/L 5.2
Nickel, mg/L 0.3
Chrome, mg/L 4.3
Oil, %
Water, %
Solids, %
Zinc, mg/L (maximum)
Phosphorus, mg/L (maximum)
Phenolic antioxidant, mg/L (maximum)
Phosphate ester additive, mg/L (maximum)
Sulfur, mg/L (maximum)
Chlorine, mg/L (maximum)
Tricresyl phosphate, mg/L (maximum)
(2,6-di-tert-butylphenol)
4,4'-methylenebis, mg/L (maximum)
Oils, %
Solids, %
Solvent (aliphatic), %
Lead, mg/L
Zinc, mg/L
Nickel, mg/L
Copper, mg/L

Low Average
28.7 33.6
41 66.4
2.4 2.9
10.6 6.4
1.5 0.8
10.6 6.6
70-100
0-30
0-5
75
2,187
10,000
2,600
6,000
21,000
26,000

10,000
97.4
1.6
1.0
r 01
1.2
0.12
0.08
Data
quality

B





C


















                                                  (continued)

-------
                                       TABLE A-2 (continued)
03
Process and/or waste description
Machining fluid waste (continued)









Oil and chlorinated solvent waste
and waste from metal stamping
operation

Waste drawing oil from punch press













Waste composition
Beryllium, mg/L
Cadmium,' mg/L
Chromium, mg/L
Mercury, mg/L
Chlorine, mg/L
Bromine, mg/L
Phosphorus, mg/L
Sulfur, mg/L
PCB, mg/L
Phenols, M9/L
Cutting oil, %
Petroleum oil, %
Perchloroethylene, %
Forsnic acid, %
A.P.I, gravity
Pour point, °F
Heat of combustion, Btu/lb
Viscosity, 3US @ 100°F
Viscosity, SUS S 210°F
Acid, mg KOH/g
Sulfur, %
Silver, mg/L
Sodium, mg/L
Zinc, mg/L
Cooper, mg/L
.' iuni,.'"ini, mg/L
Bai AUTO, mg/L
Nickel, mg/L

0.002
0.22
0.24
0.001
800
8
41.6
3,800
6.9
4.5
25-65
10-15
15-25
5
?5.0
4-20
19 , 500
1546.1
126.4
0.4
0.5
0.0
12
200
3
3
220
0
Data
quality










C



B













                                                                                         (continued)

-------
TABLE A-2  (continued)

Process ancVor waste description
Waste drawing oil from punch press
(continued)












Spent drawing solution from aluminum
wire operation

Quench oil


Sludge from quench oil tank


Waste e-nulsified oil


V/aste composition
Chromium, mg/L
Calcium', mg/L
Iron, mg/L
Silicon, mg/L
Tin, mg/L
Lead, mg/L
Phosphorus , mg/L
Boron, mg/L
Magnesium, mg/L
Vanadium, mg/L
Molybdenum. , rny/L
Manganese, mg/L
Cadmium, mg/L
Titanium, mg/L
Mineral oil, %
Tallow oil, %
Aluminum fines, %
Naphthalene based oil, %
Water, %
Organic solids, %
Paraffinic oil, %
Water, %
Carbon scale, rust, dirt, %
A.P.I, gravity
Viscosity, SUS @ 100°F
Viscosity, SUS @ 210°F

5
38
6
2
7
4
58
0
1
6
1
3
4
0
68
17
15
10-90
10-90
10-30
30-50
10-20
40-60
2.1
229.0
83.9
Data
quality














c


C


C


B


                                                  (continued)

-------
                                           TABLE A-2  (continued)
to
oo
o
Process and/ot waste description Waste composition
Waste emulsified oil (continued) Sulfur, %
Silver, mg/L
Sodium, mg/L
Zinc, mg/L
Copper, mg/L
Aluminum, mg/L
Nickel, mg/L
Chromium, mg/L
Calcium, mg/L
Iron, mg/L
Silicon, mg/L
Tin, mg/L
Lead mg/L
Phosphorus, mg/L
Boron, mg.'L
Magnesium, mg/L
Vanadium, mg/L
Molybdenum, mg/L
Manganese, mg/L
Cadmium, mg/L
Titanium, mg/L
Emulsified oil from a steel mill Oil, %
Water, %
Oil phase analysis
Hydrocarbon oil, %
Polar additives, %

0.1
0.0
400
160
15
39
4
7
0
18
22
140
50
270
2
11
7
16
20
21
21
0.51
99.49

79.56
20.44
Data
quality





















A




                                          Polar additives consist of a mixture  containing petroleum
                                          u/vidates (i.e., oxidized petroleum fraction) and petrole-
                                          um sulfor.ates (i.e., alkyl acrylsulfonate salts)
                                                                                                  (continued)

-------
                                       TABLE  A-2 (continued)
00

Process and/or waste description
Machine coolant

Emulsified oil used as a metal work-
ing fluid in aluminum can manufac-
tui :ng plant












Emulsified oil from machining and
grinding




a
Waste composition
Oil, %
Water, %,
Metals
Cu , ppm
Co, ppm
Ni , ppm
Pb
Sb
Kg
As
Cd
Cr
Solids, %
Volatile organics
Pesticides and PCB's
Base/Neutrals
Acid extractables
Oil, %
Water, %
Oil phase composition
Chlorinated paraffin, %
Kerosene, %
Oil, %

20
80

39
11
100
Not detectable
Not detectable
Not detectable
Not detectable
Not detectable
Not detectable
57
Less than 100 ppb
Less than 100 ppb
Less than 100 ppb
Less than 100 ppb
2
98

7-10
10
50
Data
quality
C

B














B





                                                                                         (continued)

-------
                                           TABLE A-2 (continued)
Process and/or waste description
Emulsified oil from aluminum can
manufacturing plant
Waste composition
Food based oil, %
Water. %
Aluminum fines, %

8
91
1
Data
quality
C
   Spent emulsified oil from cold roll-
     ing of strip and sheet steel from
     a specialty steel plant
oo
to
   Wastewater soluble grinding coolant
     and oil based rust proofing
     materials
pH
BOD5, mg/L
COD, mg/L
Oil and grease, mg/L
TOC, mg/L
Dissolved solids,  mg/L
Suspended solids,  mg/L
Volatile solids, mg/L
Total solids, mg/L
Methylene blue activated
  substances,. mg/L

Water, %
Cimcool Five Star  40, %
No. 2 fuel oil, %
Oakite 117, %
Oakite special protective oil,  %

Cimcool Five Star  40 components
  Cadmium, %
  Chromium, %
  Lead, %
  Nickel, %
  Zinc, %
   6.7
 3,250
18,000
 7,200
 5,200
 1,600
   590
 1,800
 2,190

   180

  88.5
   2.7
   2.2
   3.3
   3.3
                                                                                       <0.0001
                                                                                       <0.0005
                                                                                       <0.0005
                                                                                       <0.0005
                                                                                       <0.0001
                                                                                                   (continued)

-------
                                           TABLE A-2 (continued)
     Process and/or waste description
Waste composition
                                                            Data
                                                           quality
   Wastewater soluble grinding coolant
     and oil-based,  rust-proofing
     materials (continued)
   Wastewater soluble oil
ts>
CD
Oakite 117 components
  Mineral spirits, %
  Petroleum naphtha, %
  Methylene chloride, %

Oakite special protective oil components
  Petroleum hydrocarbons, %
  Petroleum sulfonates, %
  Petroleum oxidates, %

pH
Water, %
Petroleum oil, %
Soap, %
Biocidc, %
Lead, mg/L
Zinc, mg/L
Nickel, mg/L
Copper, mg/L
Mercury, mg/L
Beryllium, mg/i,
Cadmium, mg/L
Trivalent chromium, mg/L
Arsenic, mg/L
Phosphorous, mg/L
Sulfur, mg/L
Cyanide, tng/L
Phenols, ng/L
PCB, mg/L
Noncombustible ash, %
                              8.1
                               78
                               16
                                4
                                1
                             73.9
                            1,110
                              7.5
                               44
                             <0.1
                              7.5
                             <0.1
                               14
                             <0.1
                               25
                               83
                             1.05
                              5.7
                             0.64
                            0.835
                                                                                                   (continued)

-------
\
                                                      TABLE A-2 (continued)
                Process and/or waste description
                   Waste composition
                Data
               quality
              Machining fluid waste (emulsified
                oil)
           CD
              Oily waste generated from the machin-
                ing of metal parts
Water. %
Solids, %
Oil. %
Noncombustible ash, %
Lead, mg/L
Zinc, mg/L
Nickel, mg/L
Copper, mg/L
Beryllium, mg/L
Cadmium, mg/L
Chromium, mg/L
Chlorine, mg/L
Bromine, mg/L
Phosphorus, mg/L
Sulfur, mg/L
PCB, mg/L
Phenols, pg/L
Aromatic solvent, mg/L
Aliphatic solvent, mg/L

Ammonia. %
n-Butyl acetate, %
Copper, %
Formaldehyde, %
Formic acid, %
Hydrochloric acid, \
Methylene chloride, %
Nickel. %
Oil and grease, %
Perchloroethylene, %
     64
     15
     21
    6.8
   0.02
    8.7
    2.1
    0.9
  0.008
   0.12
   0.10
  1,100
     12
   50.8
  2,100
   24.3
    2 8
   21.2
   59.0

 0.0040
<0.0013
0.00075
  <0.01
  <0.01
   0.02
<0.0044
0.00014
   31.4
 0.0447
B
                                                                                                              (continued)

-------
 TABLE  A-2  (continued)

Process and/or waste description
Oily waste generated from the machin-
ing of metal parts (continued)






Emulsified oil coolant from machine
shop







"
Spent water soluble oil from tapping.
roll mill, etc., operations

Spent can forming lubricant

Waste composition3
Polychlorinated biphenyls, %
Sodium hydroxide, %
Sodium metasilicate (as total
silica), %
Sulfuric acid, %
Toluene , %
Trichloroethylene, %
Xylene (total), %
PH
Oil. %
Water, %
Lead, mg/L
Zinc, mg/L
Nickel, mg/L
Copper, mg/L
Cadmium, mg/L
Chromium, mg/L
Phosphorus, mg/L
Water soluble mineral oil. %
Water, %
Iron and aluminum fines, %
Quakerol #539, %
Water. %

<0.005
0.045

<0.001
0.73
<0.0013
<0.0052
<0.0028
7.9
2
98
2.0
7.13
<0.03
0.25
<0.03
0.95
590
5-100
0-95
0-2
5
95
Data
quality








B









C


C

Quakerol 41539  is composed of amine soap, polyglycol, min-
  eral oil,  and petroleum sulfonate chlorinated ester
                                                       (continued)

-------
                                           TABLE A-2 (continued)
     Process and/or waste  description
                   Waste composition
                Data
               quality
   Oily waste generated from the machin-
     ing of metal parts
K>
oo
   Waste lubricant from a cold forming
     operation
   Machine coolant
Ammonia, mg/L
n-Butyl acetate, mg/L
Copper, mg/L
Formaldehyde, mg/L
Formic acid, mg/L
Free isocyanate, mg/L
Hydrochloric acid, mg/L
Methylene chloride, mg/L
Naphtha, mg/L
Nickel, mg/L
Oil an.-i grease, '„
Perchloroethylene, mg/L
Polychlorinated biphenyls, mg/L
Sodium hydroxide, mg/L
Sodium metasilicate (as total
  silica), mg/L
Sulfuric acid, mg/L
Toluene, mg/L
Trichloroethylene, mg/u
Xylene  (total), mg/L

Mineral oil and fatty oil, %
Lead oleate, %
Lead, %
Water

Water, %
Paraffjnic oil, %
     12
   0.42
    2.7
    100
    100

  1,800
    1.4

    0.5
   3.62
    1.9
      1
  5,200

     10
  5,100
   0.42
    1.6
   0.84

  10-95
   3-10
    2-8
Balance

  70-90
   5-10
                  B
                                                                                                   (continued)

-------
                                           TABLE A-2  (continued)
     Process and/or  waste  description
                   Waste composition
             Dat'i
            quality
   Emulsified oil from metal  grinding
     operation
   Waste coolant and lubricant  frcm
     grinding and machining operation
K>
oo
vj
Oil and grease (up to),  %
Water (up to), %
Total solids, %
Chlorine. mg/L
Phosphorus, mg/L
Sulfur, mg/L
1,1,1-Trichloroethane.  mg/L

Flammable liquid
  Flash point, °F
  Solids, %
  Water, %
Trim sol, \
DuBois C-1575A. %
Trim 7030, %
Hydraulic oil, %
Mineral spirits, %

Trim Sol Components
  Petroleum oil, chlorinated wax,
  emuluifieia, odorant3, and dye

Trim 7030 Components
  Mixture of amine and potassium
  oleates, borates, and nitrites

DuBois C-1575A Components
  Cyclohexanol, %
  Aromatic petroleum solvent, %
   5
  97
1.53
 570
 8.1
 130
  28
>200
   1
  60
   2
   2
   2
  10
   1
                                                                                             3
                                                                                            40
                                                                                                   (continued)

-------
                                      TABLE A-2 (continued)
CD

Process and/or waste description
Waste oil and coolant from machining
operations














Water soluble die spray hydraulic oil










Spent oil from die casting machines


Waste composition
PH
Solids, %
Oil, %
Coolant, %
Water, %
Lead, mg/L
Zinc, mg/L
Nickel, mg/L
Copper, mg/L
Mercury, mg/L
Beryllium, mg/L
Cadmium, mg/L
Total chrome, mg/L
Arsenic, mg/L
Sulfur, mg/L •
Cyanide , mg/L
pH
Oil, %
Water, %
Ash, mg/L
Cadmium, mg/L
Chromium, mg/L
Copper, mg/L
Lead, mg/L
Nickel, mg/L
Zinc, mg/L
Chloroform, mg/L
Mineral oil, %
Water, %
Iron, %

8.7
10
0-30
0-10
80
0-250
0-1,500
0-40
0-5C
<0.0002
0-0.02
0-4.0
0-500
0-0.05
0-300
0-1.0
5.1
76
24
538
2.5
0.08
9.3
0.55
0.39
0.83
22
65-69
31-35
0-2
Data
quality
C















8










C


                                                                                         (continued)

-------
                                           TABLE A-2 (continued)

Process and/or waste description
Oil, grease, and water from die cast-
ing process
Waste composition
Oil and grease, %
Water, %

30-40
60-70
Data
quality
C
   Emulsifier
ts)
oo
   Rustproofing oil
   Machine cutting fluid
Completely water-soluble
  PH
BOD5, mg/L
COD, mg/L
Iron, mg/L
Nickel, mg/L
Potassium, mg/L
Chromium, mg/L
Cobalt, mg/L
Ash, %

Oil, %
Water, %
Oil pha?;e composition
  Paraffinic oil, %
Suifonatcd petroleum hydrocarbons,  %
Dutyl ccllouolve, %
Oxidized hydrocarbons, %

Petrochem 130, %
Water, %
    6.83
  32,955
>900,000
    6.88
     1.2
     8.3
   <0.01
   <0.01
    0.01

      20
      80

   55-65
    5-15
    5-10
   20-30

       5
      95
                                           Petrochem  13>  composition:  soft water, sodium nitrite,
                                             triethanoJcnine, diethylene glycol, butyl carbitol,
                                             Petronate L, Acintol D20LR
                                                                                                   (continued)

-------
                                           TABLE A-2 (continued)
     Process and/or waste  description
                   Waste composition
             Data
            quality
   Chemical coolant
   Waste machining oil
vo
o
   Heat treating quench solution
PH
Amine b'orates, %
Sodium nitrite, %
Glycol, %
Water, %
Non-ionic surfactants, %

Mineral oil, %
Ethylene glycol, %
Sulfonate, %
Acrylate copolymer, %
Lead, mg/L
Zinc, mg/L
Nickel, mg/L
Copper, mg/L
Cadmium, mg/L
Chromium, mg/L
Mercury, mg/L
Chlorine, mg/L

Water, %
Polyacrylate, %
  (Aque-Quench 120 from E. F.  Houghton
  and Company)
 9.0
                                                                                          1-10
1-10

  45
  45
   5
   4
  51
 150
 1.2
 5.9
0.72
 1.2
0.32
 220

  90
  10
    Data are reported as found in State files.  Percentages given are by volume or weight are not known.

-------
                           APPENDIX B

            SOLVENT DESCRIPTION AND COMPOSITION DATA


Composition data for new (raw material) and waste degreasing
solvents are listed in this appendix.  Brief descriptions of
degreasing solvents and composition data for solvents and
hydrocarbon stabilizers are listed first (Tables B-l through B-3)
followed by waste composition data (Table B-4).  Also, raw mate-
rial applications and the type of operation generating the waste
are identified wherever they are known.

Data were scrutinized and assigned a data quality rating based
on an A-B-C quality system.  Data with an "A" quality are those
found to have been sampled »:id analyzed with some QA/QC protocol
attached; e.g., demonstrated comparison with analytical standards,
use of splits, blanks, etc.  "B" quality is assigned to data with
documented sampling and analysis procedures but no evidence of
QA/QC.  "0" quality data are these values for which no documenta-
tion has been provided and/or the accuracy is undeterminable.
                                291

-------
                                 TABLE B-l.  DECREASING  SOLVENTS
                   Compound
         Characterization and applications'
      Halogenated Solvents

        Trichloroethylene
K>
VO
        Fluorocarbons
        Methylene chloride
Trichloroethylene (C1CH=CC12) is a stable,  color-
  less liquid with a chloroform-like odor.   It
  has been used because of its high solvency
  power and its low cost.  For 1976, trichloro-
  ethylene  sold for $0.435/kg.

Trichloroethylene can be vaporized with low-pressure
  (135.7 kPa to 204.6 kPa) steam because of its low
  boiling point (87.2°C).  Stabilized trichloro-
  ethylene is used for degreasing applications.

In addition to trichlorotrifluoroethane, trichloro-
  fluoromethane and tetrachlorodifluoroethane are
  also'used in solvent cleaning processes on a
  small, specialized scale.  All three have high
  density (1.5 times that of water), low boiling
  point (0°C to 50°C), low viscosity, low surface
  tension, and acceptable stability.  Fluorocarbons
  are principally used as aerosols.  Trichloro-
  trifluoroethane is also used as a solvent in dry-
  cleaning operations.

Methylene chloride (CH2C12) is a colorless, vola-
  tile liquid.  It is a low-volume degreasing
  solvent with an estimated annual consumption
  of 5.6 x 104 metric tons.  Methylene chloride
  is the most active of the degreasing solvents
  (high solvency power).  The low boiling point
  requires refrigerated water (12.7°C to 15.5°C)
                                                                                  (continued)

-------
                                       TABLE  B-l  (continued)
                   Compound
         Characterization and applications'
        Methylene chloride  (continued)
        1,1,1-Trichloroethane
K)
vO
        Perchloroethylene
  on the degreaser condensing coils,  and the high
  latent heat of vaporization requires removal of
  more heat than other solvents.   Methylene chlo-
  ride is stable under degreasing conditions.  In
  1976, the cost was estimated to be $0.435/kg.
  I*ethylene chloride consumption in metal vapor
  cegreasing has more than doubled since 1972,
  indicating a switch from other solvents such as
  trichloroethylene.

1,1,1-Trichloroethane (methyl chloroform (CH3CC13)
  is a colorless liquid.  It is the largest volume
  vapor degraasing solvent,  with 1.68 x 105 metric
  tons/yr being consumed.  1,1,1-Trichloroethane
  is the degreasing solvent most like trichloro-
  ethylene in its degreasing properties.  It must
  be stabilized for degreasing applications be-
  cause it decomposes in the presence of water to
  form hydrochloric and acetic acids.  Improperly
  stabilized, 1,1,1-trichloroethane can als;> de-
  compose in the presence of aluminum or magnesium.
  Stabilizers for 1,1,1-trichloroet'iane (0.05 g/
  100 g @ 2Ji°C) require a special saparator and
  dessicant to remove water from the system.  The
  estimated 1976 cost was $0.467/kg.

Perchloroethylene (C12C=CC12) is a colorless
  liquid with a chloroform-like odor.  It is the
  third largest volume vapor degreasing solvent,
  with 1.1 x 10s metric tons consumed each year.
                                                                                   (continued)

-------
                                      TABLE  B=l  (continued)
                   Compound
         Characterization and applications'
        Perchloroethylene (continued)
        Carbon tetrachloride
to
      Nonhalogenated Solvents

        Acetone
  The boiling point (121.1°C) of perchloroethylene
  is beneficial for two reasons:  (1)  it aids in
  the removal of high melting waxes and greases
  and (2) it allows the solvent to condense on the
  work for a longer period of time, thereby giving
  a longer cleaning cycle.  Perchloroethylene is
  also stabilized for degreasing use.   In 1976,
  the cost was estimated to be $0.377/kg.

Carbon tetrachloride (CC14) is a heavy, colorless
  liquid with an ethereal odor.  It is used occa-
  sionally as a solvent and diluent, dry cleaning
  agent, or degreaser.  It is miscible in all
  proportions with alcohol, benzene, chloroform,
  ether, and pettoleum ether.  If ingested or in-
  haled, it will cause injury depending on the
  dose.   Death can result from prolonged exposure
  to high concentrations.   The cost in 1976 was
  estimated to be $0.372/kg.
Acetone (CH3COCH3) is a colorless liquid giving off
  a fragrant, mintlike odor.   Acetone generally is
  rated moderately toxic.  It is widely used in
  industry as a solvent for fats, oils, waxes,
  nitrocellulose, and other cellulose derivations.
  The cost in 1976 was estimated to be $0.110/kg.
                                                                                  (continued)

-------
                                       TABLE B-l (continued)
                   Compound
         Characterization and applications'
        Butanol
Ki
V0
in
        Methyl ethyl  ketone  (2-butanone)
        Naphthas  (petroleum distillates,
          Stoddard solvents)
Butyl alcohol (CHaCHjCHgCHzOH) is a colorless liq-
  uid emitting a choking odor resembling that of
  isoamyl alcohol.  It is used as a solvent in the
  manufacture and preparation of various materials
  such as airplane dopes,  lacquers,  and plastics.
  In industry, it is used primarily because of
  its ability as an extender (making substances
  soluble in each other).   For example, a mixture
  of acetone, butyl alcohol, methyl or ethyl alco-
  hol, and methyl ethyl ketone in methylene chlo-
  ride is used as a paint stripper.   The 1976 cost
  of butanol was estimated to be $0.485/kg.

Methyl ethyl ketone (CH3COCH2CH3) is a colorless
  liquid discharging an odor resembling acetone.
  Methyl ethyl ketone has a slight to moderate
  toxicity rating.  Maximum allowable concentration
  is 250 ppm in air or 735 mg/m3.  The estimated
  1976 cost was $0.440/kg.

Petroleum naphthas are composed of approximately
  65% hydrocarbons in the five to eic,ht carbon
  range, while 35% have nine or more carbon atoms.
  They contain approximately 2% tol»ene and a max-
  imum of 0.5% benzene.  Naphthas consist of
  approximately 10% aromatics, from ^0% to 60%
  naphtheiies, and from 70% to 30% pcira^fins, do-
  pending on whether the naphtha is low r.apr.*"c»;
  ic or high naphthenic.
                                                                                   (continued)

-------
                                       TABLE B-i  (continued)
                   Compound
         Characterization and applications'
        Toluene
K>
vO
        Hexane
        Mineral spirits
        Xylene
Toluene (C6H5CH3) (methylbenzene or toluol) is a
  colorless liquid exuding a benzene-like odor.
  Its boiling point is 110.4°C and its flash point
  is 4.4°C.  Ic is moderately toxic;  the maximum
  allowable concentration is 200 ppm in air.  Tol-
  uene is derived from coal tar, and commercial
  grades usually contain small amounts of benzene
  as an impurity.  Its cost in 1976 was estimated
  to be $0.187/kg.  It is used as a solvent for
  the extraction of various materials, as a dilu-
  ent in cellulose ether lacquers, and in the
  manufacture of benzoic acid, benzaldehyde, ex-
  plosives, dyes, and other organic compounds.

Hexane [CH3(CH2)4CH3] is a colorless liquid having
  a low toxic hazard rating.  Maximum acceptable
  concentration is 100 ppm in air and 360 mg/m3 of
  air.  Its cost in 1976 was estimated to be
  $0.167/kg.

Mineral spirit is also called turpentine substi-
  tute, white spirit, or petroluem spirit.  It is
  a clear, water-white refined hydrocarbon solvent
  with a minimum flash point of 21°C.  Its toxic
  hazard rating is considered to be slight to
  moderate.

The xylenes [C6H4(CH3)2] are colorless liquids with
  toxicity comparable to toluene.  The maximum
  allowable concentration of xylene is 200 ppm in
  air.  It is used as a solvent for gums and oils
                                                                                   (continued)

-------
                                       TABLE  B-l  (continued)
                   Compound
         Characterization and applications'
        Xylene (continued)
        Cyclohexane
to
vO
-4
  and in the manufacture of dyes and other organic
  substances.  The cost of xylene in 1976 was es-
  timated at $0.182/kg.  It is slightly soluble
  in water and is miscible with absolute alcohol
  and other common organic solvents.

Cyclohexane (C6H12), also known as hexahydrobenzene
  or hexamethylene, is a colorless mobile liquid
  giving off a pungent odor and is moderately
  toxic.  In high concentrations, it may act as a
  narcotic and/or skin irritant.  Maximum allow-
  able concentration is 400 mg/m3 of air.  Cyclo-
  hexane is a solvent for resins and rubber.  It
  is also used as a degreasing agent and a paint
  thinner.  It is insoluble in water but is com-
  pletely miscible with alcohol, ethers, hydro-
  carbons, chlorinated hydrocarbons,  and most
  other organic solvents.  Its cost was estimated
  to be $0.288/kg in 1976.
       Chemical  Marketing Reporter.   209(12):46-56,  1976  September 20

-------
                                 TABLE B-2.  SOLVENT COMPOSITION
       Process
       and/or
      material
     description
Material composition	
                   Weight
Ingredient	percent
   Physical characteristics
Volatile
 volume    Weight,    Flammable    Data
 percent   Ib/gal	liquid	quality
00
Solvent     Mineral spirits         >10
            Petroleum naphtha       >10
            Methylene chloride      >10

Solvent     Xylene                   31.34
            Toluene                  20.54
            Ethylene glycol
              Ethyl ether acetate    29.55
            Isopropyl alcohol        13.27
            Ethyl cellosolve
              Acetate ester           5.30
                                                       100
                                         7.40
                        yes

-------
                  TABLE  B-3.   STABILIZERS  USED  IN  HAl.OGF.NATED  HYDROCARBONS
Typical Gol'jto
concentrat ion ,
Ctobllizimi coniolv«nt vt t
Organic m_Tco|.tnnn and dlnulfldeo HC
(Aonyl aercaptan, 2-cncrcaptocthyl methyl ether.
bis (di-alkoxyphosphinothionyl) disulf ide.
bis (1-piperazinylthiocarbonyl) disulf ide.
cyclohexyl mercaptan, 2-nercaptoethanol,
2,3-diraercapto-l-propanol, dimethyl disulfide.
di-£ert-butyl disulfide, 4 ,4 '-dithiodimorpholine.
2,2 '-dithiobis (bcnzothlazole) , dibenzyl
disulfide, decamcthylene dithiol, furfuryl
Mercaptan)
With butylene oxide
Diakyl sulfoxides KC
(Glycidol (2,3-cpoxy-l-propanol) , dimethyl
Su If oxide, J-'methylaninolpropionitnle,
3- (dlmcthylamino)propionitrile.
nothylethanolamine, norphol i.ie, acetonltrile.
butylene oxide)
^ 1,3,5-Cycloheptatriene PERC, TCENE
vD
1,3,5-Cycloheptatriene PERC, TCENE
With 1- (dimeth/lanino)propene-2
Dipcntene (terpene) ACR
Indene AER
p-Mentha-l,5-diene AER
a-Methylstyrene AER
Trinethyl orthofornate (TMOF) MC
With nitromethane
TMOF MC
With acetonitrile
TMOF MC
with trloxjne
TMOK MC
With 1,4-dioxine
TMOF MC
With acetonitrile
And tert-butyl alcohol
0.1









0.3






O.OS
0.1
O.OS
0.5
0.30
0.30
0.30
0.75
0.75
0.5
0.5
1.0
1.0
0.75
0.75
0.50
0.25
0.25
Kangc of
concentration, TI.V, U.S. patent
wt * 'J/a- niinl.=-r
3.041,10V









3,641,169
O.OS to 6 3,535,392





3,642,645
3,642,645
3,642,645
3,352,789
0.450 3,352,789
3,352,789
3,352,789
0.250 3,564,061
3, 564, Obi
3,564,061
0.070 3,564,061
3,564,001
3,tiC4,Of,l
3,564,061
0.180 3,564.061
3,564,061
0.070 3,564,061
0.300 3,564,061
PatcntD
lanuT)
lo
uow









DOW
PPC





WCGG
WCCG
WCGG
ALL
ALL
ALL
ALL
PCPSG
PCPSG
PCPSG
PCPSG
PCI'fiG
l-cr:.cj
PCPSG
PCPSG
PCPSG
PCPSG
PCPSG
footnotes at end of  table
                                                                                                           (cont inued)

-------
                                                    TABLE  B-3  (continued
Stabilizing compound
THOF
with mcthanol
AnJ methylfornate
Bcnzotrlazole
Oxazole
Polyoraines (ethylcnediamino, tr iethylencdianine,
4,4'-ethylene<3iB>orpholino, pyrrole, 1, 1* -ethyl -
encdipiper idine , diicopropylaminc, diethylcne-
triamine, tetraethylencpentaoiine, n-mcthyl-
pyrrole
N.N-Dioethyl -p-phenylenediamine
N.N.N'.N'-Tctracwthyl-o-phenylenediamlne
N.N.N' ,N-Tetraaethylbenzidine
Quaternary aramoniun compounds
With volatile epoxy compounds
W And organic anlnos
~~ (pyridine. picoline. trief "lylamine, anilino,
dinethylanlllne, nalKylinorpholineo,
dlisopropylaaine, N-methylpyrrole)
2-Hethy 1-2-oxazol ino
2-Phenyl-2-oxazol ine
2-(l-Azlridinyl)-2-oxazolJ number
MC
PFRC
MC
PtRC, TCENE,
CH
MC
MC
MC
MC, TCENE, CH
MC
MC
MC
TCENE, CH
2.10
O.60
0.30
0.5
2
0.004
0.13
1.1
0.22

0.44
0.65
0.25
6.8
i, 564, 061
0.260 3,564,061
0.250 3,564,001
0.1 to 2.5 3,337,471
1 to 4 3,676,155
0.001 to 0.02 3,424,805
3,546,125
3,546,125
3,546,125
0.005 to 0.2 3,314,892
0.01 to 1.0 3,314,892
0.005 to 0.2 3,314.892
3,494,968
3,494,968
3,494,968
3,551,505
ir.oued
to
pcrsc
PCPSG
PCPSG
DOW
UKF
WCGG
DOW
DOW
DOW
CI
CI
CI
DOW
DOW
DOW
SCB
  (1.2-diethyldiaslridlno,  M-nothylpyrrolo)
a*Mothyl-l-azlri<.llncathanol                           KC
2-(l-Azirldinyl)ethyl acetate
Lac turns (Caprolactact)                                 MC, CH
  With glycldol(2,3-epoxy-l-propanol)
(2,3, and 4)-Pyridinecarboxaldchydo                    MC
(2,3. and 4)-Acetylpyridino                           MC
(2,3. and 4)-Cyanopyrldino                             MC
p-Nltrolxinionltri lo                                   MC
0-Nltrobenzoiiltrile                                   MC
  (2-nltro-p-tolunitril«, 4-nltro-m-
  tolunitrile,  2,3-dincthyl-4-nitrobenzonitrile)
See  footnotes at end of table
0.5
0.25
0.25
0.50
0.35
0.33
0.77
               1.0 to 4.0

              0.05 to 5
0.36 to 0.54
0.31 to 0.39
3,328,474

3,496,241
3,496,241
3.444.24H
3,444,248
3,452,108
3,454,659
3,454,659
    DOW

    KMC
    FMC
    DOW
    DOW
    DOW
    DOW
    DOW

(continue

-------
                                           TABLK  B-3  (continued)
Stabilizing compound
(3 and 8) -Aminoquinol ino
Acotaldohyile dlraothylhydrozono
With tnltylono oxldo
with butylcne oxide
And propyleno oxide
And thyswl
(or formaldehyde dinetJiylhydraione)
Crotonaldehyde dimethylhydrazone
With bv^'lene oxide
And nitromethane
With p-tcrt-^«ntylphenol
f-( Dice thy laainolbenzaldehyde
Kethoxyacctonitrile
And butylene oxide
And nitrcxnetliane
Or propargyl alcohol
U)
O Acetonitrilc
f-1 Arxi tert-butyl alcohol
And 1,4-dioxano
Acttonitrlla
And nitromethane
And 1,4-dioxane
Acetonltrile
And Ceirt -butyl alcohol
And nitromc'thjsne
Nit rom«thAnc
With butylene oxide
With 2-propanol
3-Mcthoxy-l ,2-epoxypropane
With 1,4-illoxane
And nl t r ocve thane
And nclliyl ijlycidyl ether
Propylcne oxido
With nitrooctruine
3-Hethoxyoxetane
1 ,2-Dimethoxyethylene
l-ypicai uuiui.6 K^ncjc: of
concentration, ..oncontrat Ion,
Solvent wt » wt »
MC 0.32
TCtNE, CH 0.025
0.2
0.1
0.1
0.05

TCENE 0.025
0.2
O.OS
0.002
MC 0.11 to 11.1
MC 2.9
0.32
0.44
0.35

MC 1.0
5.0
0.7
MC 3.0
1.0
0.8
MC 0.5
3.0
0.7
MC 3.0
1.0
3.0
MC O.S
2.5
0.5
O.S
CTA O.S O.S to 3.0
0.05
MC 3.0
N: 2.0 1 to 5
TLV,
q/oj




0.240




0.240




r
0.0'2

0.07C
0.300
0.180
0.070
0.250
0.180
0.070
0.300
0.250
0.250

0.980
r
o.uo
0.250


0.250


U.S. Patent
numlxsr
3, 47;, 901
1,417,15.'
3,417,1V
3,417,152
3,417,152
3,417,152

3,403,190
3,403,190
3,401,190
3,403,190
3,444,247
3,565,811
3,565,811
3.565.811
3,565,811

3,590.000
3,445,532
3,445,532
3,445,532
3,445,532
3,445,532
3,445,532
3,445,532
3,445,532
3,549,715
3.549,715
3,549,715
3,536,766
3,536,766
3,516,706
3,536,706
3,445,527
3,445,527
3,532,761
3,549,547
P.it«-ntb
i GSUOll
to
LOW
Ml •'
Mr:,
HI S
KCS
MES

MES
MES
MLS
MES
KM
DOW
DOH
DOW
DOW

DNAC
DNAG
DNAG
DNAC
DNAG
DNAG
DNAC
DNAG
DNAG
PPG
PPG
Pl'G
DOW
DOW
low
D(JW
OKKK
DKKK
PPC.
OCW
Sec footnotes at end o(  table
                                                                                                      (con» inuod)

-------
                                          TABLE B-3 (continued)
Stabilizing compound
2-Metho«y-2 , 3-dihydropyran
Or 2-ethoxy-2,3,-dihydropyran
And isop.ropyl nitrato
4,7-Dihydro-l,3-dloxepin
And nitromethane
Or propargyl alcohol
And butyler.e oxide
Or epichlorhydrin
Furfuryl alcohol
Furfuryl cercaptan
5-Forraylfurfuryl alcohol
2-Thiophenmethanol
2 , 5-Tetrahydrof urandimethanol
i-<2 and 3)-Pyridyl ethanol
o-Aminobenzyl alcohol
p-Mcthoxybenzyl alcohol
3-Mtithyl-2-thiophenemethanol
1 , 3-Dioxolane
With phenolic antioxidants
(p-tert-butylphenol, 2,6-di-tert-butyl-p-cresol,
nonylphenol, 4,4 '-thiobis(6-tart-butyl)ra-cresol)
1,4-Dioxane
With nitromethane
With butylene oxide
With N-methylpyrrole
With diisopropylamine
3-Mcthylpropionaldehyde
4-Methyl-2-butanone
laobutyric acid, oethyl ester
And ni tromethane
4-Hetiiyl-4-n»ethGxy-2-pcntanone
With acetonltrile
And tert-butyl alcohol
With tert-butyl alcohol
And mathyl ethyl ketone
a
Solvent
MC

.
MC




MC
MC
MC
MC
MC
MC
MC
MC
MC
MC



MC




MC
MC
MC

HC




Typical nolutc I:anyo of
concentration, conc-rntration,
Wt * rft \
1 .4
0.5 0.5 to 2
2
4 2 to 10
1 0.25 to 2
O.5 0.25 to 0.5
0.5 0.25 to 1.0
0.5 0.25 to 1.0
0.066
0.11
0.19
0.47
0.29
0.32 0.28 to 0.35
0.37
0.21
0.33
1 to 3
0.01 to 0.1


2.84
0.3921
0.2601
0.005
0.003
2
2
1
1
I
0.5
0.5
1
1
TLV,
g/m3




0.250
0.002

0.019C
0.020












0.180C
0.250






0.250

0.070
0.300
0..100
0.590
U.S. Potent
Pumlx-r
3,661,78B
3,661,788
3,601,7Ub
3,518,202
3,518,202
3,518,202
3,515-202
3,518,202
3,475,503
3,475,503
3,475,503
3,475,503
3,475,503
3,475,503
3,475.503
3,475,503
3,475,503
Reissue
26,025


3,629,128
3,629,128
3,629,128
3,629,1?8
3,629,128
3,505,415
3,505,415
3,505,415
3,105,415
3,505.415
3,505.415
3,505,415
3,505,415
3,505,415
Patcntb
issued
to
ICI
ICI
ICI
DOW
DOW
DOW
DOW
DOW
DOW
DOW
DOW
DOW
DOW
DOW
DOW
DOW
DOW
AR



ETH
ETH
ET1I
ETH
ETH
DNAG
DNAG
DNAG
DJIAC
DtlAG
DHAG
DNAG
DNAG
DN\G
See footnotes at en'J of table
                                                                                                  (continued)

-------
                                         TABLE B-3  (continued)
Stabilizing compound
1 , 4-Cyclohexanod ione
1, 2-Cyclohexanedione
2,5-Butanedione
2 , 5-Butanedione
p-Bcnioquinono
2, 3-Dihydro-l, 4-dithiin
(al so S-me thy 1-2 , 3-dihydro-l , 4-dithiin)
Polysulfones
Trimethylene sulfide
3-Hydroxytrimethylene sulfide
Isopropyl nitrate
With acetonitrile
And nitromethane
And butylene oxide
With acrylonitrile
Any butylene oxide
Iron benzoate
Sodium benzoate
Zinc benzoate
Sodium didecyl phosphate
(or sodium dioctyl phosphate)
Benzyl fluoride
Benzotrifluoride
Ethyl prppargyl ether
Propargyl be:izoatc
2-Butync-l ,4-diol-dlbenzoate
With ir.oeuyonol
l'io|>ar-jyl alcohol
Nitromethane
Nitroethane
2-Ntttopropano
I'ropargyl alcohol
With pyrrole
And diisopropylaraine
Typical solute Range of
concentration, concentration, TLV,
Solvent wt \ wt » g/"1'
MC
MC
MC
MC
MC
MC, TCENE
PERC
MC
MC
MC
TCENE, PERC
TCENE, PERC
TCENE, PERC
PERC
MC
MC
PERC
PERC
PERC
AERO
AER
AER
AER
TCENE
0.25
0.33
0,17
0.28
0.24

0.092
0.17
0.20
2
2
1
0.25
2
0.25
12
0.025
10
1.5
O.14
4.9
0.25
0.25
0.25
0.01
0.01
2
1
2
0.1
0.05
O.001




O.OC04
0.2 to 4.5



2 to 4
0.75 to 1
0.1 to 1
0.5 to 4
0.1 to 1 0.045
10.2 to 14.3
0.020 to 0.027
0.41 to 38.3

0.82 to 8."


0.002C
0.1 to 5
0.1 to 5
0.1 to 5
0.05 to 0.5 0.002°
O.C1 to 0.05
0.0005 to 0.01
U.S. Patent
ntimlxjr
3,546,305
3,546,305
3,546,305
3,5<6,305
3,546,305
3,439,051
3,396,115
3,467,722
3,467,722
3,609,091
3,609,091
3,609,091
3,609,091
3,609,091
3,609,091
3,527,703
3,527,703
3,527,703
3,441,620
3,681,469
3,681,469
British
773,447
773,447
773,447
771,447
2,092,720
3,085,116
3,085,116
3,005,116
2,803,676
2,802,676
2,803,676
Patcntb
issued
to
DOW
DOW
DOW
DCW
DCW
ICI
DCW
DOW
DCW
ICI
ICI
ICI
ICI
ICI
ICI
DCW
DOW
DCW
STA
DOW
DOW
DIA
DIA
DIA
DIA
DUJ>
DUP
DtIP
DOW
DOW
DOK
Sco footnoten at end of table
                                                                                                 (continu"'D

-------
                                                   TABLE B-3  (continued)


MahlllKiuj c'xnj'Ouri'1
Hothyltrutynol (nfi'l 2 prior)

1,4-Dioxane

Nitromethane
Vinylidene chloride
2-Butyn-l,4-diol
3-Methyl-l-butyn-3-ol
3-Methyl-l-bjtyn-3-ol
(with thymol, di-tcrt-butyl-p-cresol.
cpichlorohydrin, butylene oxide, amines,
dioxane)
Typical U'llti'u
OOll'/'tillll'ol Ion,

TCtllB 0-1

CH *


0.5
AERO, CH 0.5
CH
•JH



i'ali'jl of
fio«'i« ration, T/.V. 1/,/J
wl I -j/«
0.05 to 0.5 2
2

2

2
2
0.1 to 0.5 i
0.005 to 0.3 . 2



	
. Put rration
 STA   —  Stauffer Chemical Corporation
 DIA   —  Diamond Alkali Company
 DUP   —  E.  I. Du Pont de Nemours and Company
 CEL   —  Celanese Corporation
 RH    --  Rohm & Haas Co.
 AIR   --  Air Reduction Corporation

 TLV for skin contact.
CFA  —- Chloro-fluoro alkanea
CH   —- Chlorinated hydrocarbons
AERO — Methylone chloride and  methanol  (aerosols)

-------
                                TABLE B-4.  WASTE COMPOSITION DATA
       Process and/or waste name
               Waste composition1
 Data
quality
      Degreasing solvent
      Parts degreasing operation
u>
o
en
      Degreasing operation
      Vapor degreasing operation
Liquid oil, %                                 10
Grease, %                                     60
Perchloroethylene, %                        5-10
Hy-Flo (diatomaceous earth), %
Soap, %                                    20-25
Dirt, %

Alcohol,  %                                    77
Perchloroethylene, %                          12
Wax and grease, %                             11
Lead, mg/kg                                   70
Cadmium,  mg/kg                               0.8
Nickel, mg/kg                                4.9
Antimony, mg/kg                              6.9
Cobalt, mg/kg                                0.4
Mercury,  mg/kg                               7.4
Chromium, mg/kg                              5.4
Copper, mg/kg                               30.6
Zinc, mg/kg                                   83
Lithium,  mg/kg                               0.2
Si1ver, mg/kg                                2.4
Flash point, °F                               95
Noncombustible material (600°C), mg/kg       750

Trichloroethylene, %                          90
Oil, %                                        10

Trichloroethylene, %                       80-90
Polymerized vinyl plastisol fragments, %    5-10
Oil and grooucj, %                            2-5
                                                                                   (continued)

-------
TABLE B-4 (continued)

Process and/or waste name Waste composition9
''apor degreasing operation Freon, %
Trichloroethylene, %
Oil. %
Solids, %
Degreasing 1, 1, 1-Trichloroethane, %
Oil, %
Degreasing 1, 1, 1-Trichloroethane, %
Oil and grease, %
Water, %
Residue, %
w
o Degreasing Trichloroethylene, %
Water, %
Oil and grease, %
Noncombustible ash, rag/kg
Lead, mg/kg
Cadmium, mg/kg
Nickel, mg/kg
Chromium, mg/kg
Copper, mg/kg
Zinc, mg/kg
Chlorine, mg/kg
Degreasing Trichloroethylene, %
Water, %
Oil and grease, %
Data
quality
25 ± 5
40 ± 20
27 ± 13
7 ± 3
60
40
50-65
35-45
<2
2.5

37
35
24
28,000
435
0.8
185
4.5
18
1,116
296,000
10
82
5
C



B

B




B










B


                                            (continued)

-------
                                      TABLE D-4  (continued)
       Process  and/or waste name
Warte co
OJ
o
Degreasing (continued)       Noncombustible ash,  mg/kg,
                             Lead,  mg/kg
                             Cadmium,  mg/kg
                             Nickel, mg/kg
                             Chromium, mg/kg
                             Copper, mg/kg
                             Zinc,  mg/kg
                             Chlorine, mg/kg

Degreaser                    High flash naphtha,  %
                             Ethylene chloride, %
                             Oil, %
                             Zinc,  mg/kg
                             Nickel, mg/kg
                             Copper, mg/kg
                             Chromium, mg/kg

Aircraft equipment cleaning  Trichloroethylene, %
                             Other solvents, %
                             Oil, %
      Aircraft parts  cleaning
      Cegreasing
                             Chlorinated hydrocarbons
                             Phenoic compounds
                             Oil
                             Water
                             PH

                             Water, %
                             Toluene and xylene, %
                             Grease, %
                                                          Lon
 Data
quality
                            7,700
                               54
                              0.4
                              3.0
                              1.3
                              0.9
                              430
                           80,000

                               60
                               16
                             6.17
                              179
                           53,053
                            4,980
                           25,444

                               30
                               40
                               30
                             10.0

                               80
                               17
                                3
   B
                                                                                   (continued)

-------
                                       TABLE  B-4  (continued)
       Process  and/or waste  name
               Waste composition*
        Data
       quality
      Degreasing
      Degreasing
      Parts cleaning
u>
o
o>
      Degreasing
Acetone
Alcohol
Water
Grease
Oil

Freon, %
Oil and grease, %

Acetone, %
1,1,1-Trichloroethane, %
Isopropanol, %
Methanol, %
Trichloroethylene, %
Freon, %
Transene 100, %
Toluene, %
MEK, %
Bromides and solvent, %
Paint solvent, %
Xylene, %
Dimethyl formamide, %
De SOLV 8090, %
Oil, water, impurities, %

Oil, %
Tetrachlorethene, %
1,1,1-Trichloroethene, %
MEK, %
90-95
 5-10

 24.2
 13.5
 10.5
  6.5
  2.4
  7.9
  0.7
  9.1
  0.5
 18.2
  0.4
  0.3
  0.1
  0.6
  5.1

 5-10
60-65
10-20
  2-5
B
                                                                                   (continued)

-------
                                       TABLE B-4 (continued)
o
VO
Process and/or waste
Parts cleaning
Degreasing
Degreasing
Degreasing
Degreasing
name Waste composition3
1,1, 1-Trichloroethane, %
Alcohol, %
Oil, %
1,1, 1-Trichloroethane, %
Oil and grease, %
Oil, %
Mineral thinners, %
Freon, %
Chloroethanc: VG, %
Trichloroethylene, %
Oil and grease, %
I,l,l-Tric1iloroe thane, %
Grease and solids, %
Data
quality
3-5
10-15
75-80
80
20
39
10
24
27
90-95
5-10
10-40
50-70
C
B
B
B
C
       Data are reported as found in State files.   Whether percentages  given are by volume
       or weight is not known.

-------
                           APPENDIX C

       COMPOSITION DATA FOR NEW AND WASTE SURFACE COATING?


Composition data for new (raw material) and waste surface coat-
ings are listed in this appendix; raw material data (Tables C-l
and C-2) are followed by waste data (Table C-3).   The type of
operations generating the waste are identified wherever known.

Data were scrutinized and assigned a data quality rating based
on an A-B-C quality system.  Data with an "A" quality are those
found to have been sampled and analyzed with some QA/QC protocol
attached; e.g., demonstrated comparison with analytical standards,
use of splits, blanks, etc.  "B" quality is assigned to data with
documented sampling and analysis procedures but no evidence of
QA/QC.  "C" quality data are those values for which no documenta-
tion has been provided and/or the accuracy is undetermined.
                                310

-------
                   TABLE C-l.   PRODUCT SURFACE COATING  COMPOSITION DATA

Physical characteristics



Coating description
Lacquer, yellow tracer














Material composition

Ingredient
Pigments
Chrome yellow
Titanium dioxide
Vehicle
Vinyl resin
Plastici^ers
Ketones
Aromatic hydrocarbon
solvents
Other
Aliphatic hydrocarbon
iolvent
Alcohols
Additives


Weight
percent

11.25
1.25

8.00
3.50
39.00

25.75


8.25
2.25
0.75
Volatile
by
volume
percent

89.00












Weight,
Ib/gal or
(specific Flammable
gravity) liquid

(0.9459) Yes














Data
quality

B












Lacquer,  white tracer
Pigments
  Titanium dioxide
Vehicle
  Vinyl resin
  Placticizer
  Ketones
Other
  Aromatic hydrocarbon
    solvents
  Additives
                                                     10.00


                                                     10.50
                                                     7.50
                                                     43.00
                                                     28.50
                                                      0.50
83.20     (0.9627)     Yes
                                                                                         (continued)

-------
                                              TABLE  C-l  (continued)
                                                                          Physical  characteristics
                                        Material composition
         Coating  description
       Ingredient
Weight
percent
Volatile
   by
 volume
 nercent
 Weight,
Ib/gal or
(specific
 gravity)
Flammable
 liquid
 Data
quality
       Lacquer,  orange tracer
to
       Lacquer,  green  tracer
Pigments
  Molybdate orange
  Chrome yellow

Vehicle
  Vinyl resin
  Plasticizer
  Ketones

Other
  Aromatic hydrocarbon
    solvents
  Additives

Pigments
  Chrome yellow
  Phthalocyanine blue
  Titanium dioxide
  Extender pigments

"chicle
  Vinyl resin
  Plasticizer
  Ketones

Other
  Aromatic hydrocarbon
    solvents
  Additives
                                                              4.50
                                                              3.50


                                                              9.00
                                                              4.75
                                                             45.00
 32.50
  0.75
                                                              5.00
                                                              0.25
                                                              0.50
                                                              0.60


                                                              9.00
                                                              5.00
                                                             45.00
                                                             34.00
                                                              0.65
            88.00
           (0.9447)
                                   Yes
            88.00
           (0.9243)
              Yes
                                                                                                   (continued)

-------
                                       TABLE C-l  (continued)
                        	Material composition
  Coating description
       Ingredient
Weight
percent
   Physical characteristics
Volatile   Weight,
   by     Ib/gal or
 volume   (specific  Flammable    Data
 percent   gravity)   liquid    quality
Lacquer, black tracer
Lacquer, red tracer
Pigments
  Channel black

Vehicle
  Vinyl chloride/vinyl
    acetate copolymer
  Aromatic hydrocarbon

Other
  Ketone
  Plasticizers

Pigments
  Molybdate orange
  B.O.N. red

Vehicle
  Vinyl resin
  Plasticizer
  Aromatic hydrocarbon
    solvents
                                                       1.15
                                                      10.60
                                                      37.75
                                                      49.00
                                                       1.50
                                                       7.50
                                                       3.50
                                                       9.50
                                                       7.00

                                                      32.50
            91.50
            83.50
           (0.8764)
Yes
           (0.9723)
Yes
                         Other
                           Ketones
                           Additives
                              39.50
                               0.50
                                                                                            (continued)

-------
                                              TABLE  C-l  (continued)
                                                                          Physical  characteristics
         Coating descri- tion
         Material composition

       Ingredient	
Weight
percent
          Volatile
             by
           volume
           percent
 Weight,
Ib/yal or
(specific
 gravity)
Flammable
 liquid
 Data
quality
       Lacquer, pink  tracer
u>
       Ink.  blue  tracer
Pigments
  Titanium dioxide
  Lithol red
  B.O.N. red

Vehicle
  Vinyl resin
  Plasticizers
  Ketones
Other
  Aromatic hydrocarbon
    solvents
  Additives

Pigments
  Titanium dioxide
  Phthalocyanine blue
Vehicle
  Vinyl resin
  Plasi .tcizers
  Ketones
Other
  Aromatic hydrocarbon
    solvents
  Additives
 3.75
 1.25
 0.25

10.00
 7.50
42.00
                                                             35.00
                                                              0.25
  .50
  .10

  .00
  .00
                                                             46.50
                                                             33.00
                                                              0.90
                                                                        84.40
                      (0.9303)
   Yos
                                                                        87.20
                      (0.9267)
   Yes
                                                                                                   (continued)

-------
                                         TABLE  C-l (continued)
co
M
in

Material composition
Coating description
Ink, tan tracer












Alkyd enamel, black
gloss

Alkyd enamel, black
semi-gloss
Tank coating



Ingredient
Pigments
Red and brown iron
oxides
Titanium dioxide
Vehicle
Vinyl resir.s
Plasticizcr
Cresols
Other
Ke tones
Aromatic hydrocarbon
solvents
Nitroparaffin
Mineral spirits
Aromatic naphtha
Xylene
Mineral spirits
Xylene
Xylene
Petroleum distillate
Petroleum distillate
Zinc chromate pigment
Weight
percent


5.00
3.00

16.50
4.50
6.00

41.50

23.25
0.25
55
<5
<5
45
<5
25
15
5
5
Physical characteristics
Volatile Weight,
by lb/gal or
volume (specific Flammable
percent gravity) liquid

82.40 (0.9807) Yes











63.9 7.45 Yes


60.4 8.29 Yes

64 9.84 Yes



Data
quality

B











B


B

B



                                                                                         (continued)

-------
                                              TABLE C-l  (continued)
                                                                          Physical characteristics
                                        Material composition
         Coating description
       Ingredient
Weight
percent
Volatile
   by
 volume
 percent
 Weight,
Ib/gal or
(specific
 gravity)
Flammable
 liquid
 Data
quality
       Primer,  rust  protective
CJ
       Tank coating
       Paint,  gray primer
Alkyd resin
Linseed oil

Pigments
  Zinc/chromate
  Red iron oxide
  Inert additives
  Solvent:  aliphatic
    hydrocarbon   '

Epoxy resin and aiaine
Pigments - unspecrfied
  chemical resistant

Solvents
  Ketones
  Aromatic hydrocarbons
  Glycol ether

Paint composition, % of
  volatile volume
  Xylene
  Aromatic naphtha
  Ethylbenzene
  Mineral spirits
    TOTAL
                                                             66.6
                                                             27.8
                                                              4.3
                                                              1.3
                                                            100.0
            39.32
           10.35
              Yes
                                                                                                   (continued)

-------
                                       TABLE C-l  (continued)
                                                                   Physical characteristics
                                 Material composition
  Costing description
       Ingredient
Weight
percent
Volatile
   by
 volume
 percent
 Weight,
Ib/gal or
(specific
 gravity)
Flammable
 liquid
 Data
quality
Paint, gray primer
  (contin'.ed)
Acrylic enamel
Aromatic hydrocarbon with
  8 or more carbon atoms
  except ethyl benzene,
  94.47% of volatiles
Ethylbenzene and/or toluene
  and/or trichloroethylene,
  4.31% of volatiles

Paint composition, % of
  volatile volume
  Xylene
  n-Butyl alcohol
  2-Ethoxyethyl acetate
  Ethylbenzene
  Toluene
  2-Butoxyethyl acetate
  Mineral spirits
  Diethylaminoethanol
    TOTAL

Aromatic hydrocarbon with
  8 or more carbon atoms
  except ethyl benzene,
  75.56% of volatiles

Ethylbenzene and/or toluene
  and/or trichloroethylene
  8.05% of volatiles
                                                      73.1
                                                       7.1
                                                       5.2
                                                       4.0
                                                       4.0
                                                       3.9
                                                       2.2
                                                       0.5
                                                     100.0
            43.35
            9.05
              Yes
                                                                                            (continued)

-------
                                         TABLE C-l (continued)
CO



00

Material composition
Coating description
Acrylic enamel, tan




Acrylic enamel, white




Modified acrylic primer

Enamel, modified alkyd
green machinery
coating










Ingredient
Diethylene glycol mono-
butyl ether
Ethylene glycol
N,H-Dimcthyleth9riolaminc
Lead an % nonvolatile
Diethylene glycol mono-
butyl ether
Ethyiene glycol
N,N-Dimethylethanolamine
Lead as % nonvolatile
Strontium chr ornate pigment

Pigments
Phthalocyanine blue
Yellow iron oxide
Extender pigment
Titanium dioxide
Other
Alkyd resin
Aromatic hydrocarbon
solvents
Aliphatic hydrocarbon
solvents
Tinting, driers and
additives
Weight
percent

<5
<5

-------
                                              TABLE C-l (continued)
                                                                          Physical characteristics
                                         Material  composition
         Coating description
       Ingredient
  Weight
  percent
Volatile
   by
 volume
 percent
 Weight,
Ib/gal or
(specific
 gravity)
Flammable
 liquid
 Data
quality
       Paint, black water
         reducible baking
         epoxy
w
M
vo
       Epoxy primer
Water
Solids
Pigments
  Carbon black
  Lead silicochromate
  Urea formaldehyde
  Methylated mclnmine
Vehicle
  Epoxy ester
Solvents
  See below
Additives
  Ammonium compounds
    (i>s NH, OH)
Others
  Talc
  Butyl cellosolve
  n-Butanol
  Methyl cellosolve

Xylol
Toluol
Methyl ethyl ketone
Methyl isobutyl ketone
Butanol
Butyl cellosolve
   49
   39


    2.4
    4.0
    4.0
    3.9


   12.7
    1.5


    7.9
    4.8
    0.5
    3.7

   30
   10
    5
Less than 5
Less than 5
Less than 5
 70
9.45-9.65
    No
                                                                          B
 70.72
  9.57
   Yes
                                                                                                   (continued)

-------
                                         TABLE C-l  (continued)
K)
o

Physical characteristics
Material composition
Coating description
Epoxy primer, zinc rich


Epoxy primer

Paint, guide coat






Paint, gray primer






Inqredient
Xylol
Mineral spirits
Zinc (metal)
Xylol
Cobaltous napthenate
Ethylene glycol ethyl
ether acetate
Xylene
Methyl ethyl ketone
Diethylene glycol butyl
ether
Toluene
Xylene
Toluene
Lactol spirits
Long range VM&P naphtha
Isopropanol
n-Butanol
Mineral spirits
height
percent
20
Less than 5
35
60
0.010

19.60
6.70
27.17

4.01
10.45
15.07
10.61
3.23
10.99
5.25
0.64
0.09
Volatile
by
volume
percent
59.1


76.89


81.76





67.21






Weight,
Ib/gal or
(specific Flammable
gravity) liquid
20.5 Yes


9.06 Yes


8.75 Yes





9.97 Yes

e*>




Data
quality
B


B


B





B






                                                                                        (continued)

-------
                                             TABLE  C-l (continued)'
t\>
Material composition
Costing description
Paint, black primer
Ingredient
Xylene
Diacetone alcohol
Isopropanol
Toluene
Aromatic hydrocarbon 150
Weight
percent
47.24
5.44
5.13
11.33
0.31
Physical characteristics
Volatile Weight,
by Ib/gal or
volume (specific Flammable Data
percent gravity) liquid quality
77.78 8.62 Yes B
        Solids, volume percent:   63.
        Flashpoint, minimum:   (83°F).
        Solids, volume percent:   50.
        Flashpoint, minimum:   (60°F).

-------
     Reproduced from
     best available copy.
                         TABLE C-2.   CLASSIFICATION  AND  COMPOSITION OF  PAINTS  [   ]
(A)
to
PAINT CLASS
IA* - SPRAY. Air drying.
•olvent born*




lAw - SPRAT. Atr dk-ylng.
woter born*
IB* - SPRAT. Bak* cured.
•olv*t>t born*


PAINT DF'icRiptKM
(FOPMUIAllcrl)
1. Medlii. Ml Alkv.l While
Enanel (Anhl.nd P-ll)
1. Ho.Hflrd Alkyd Red PrUer
(AnhUnJ Q-t05a)
). Nodldled Alkyd Brnvn Prlaier
(Aahland Q-llia)
4. Modified Alkyd Green Prl«er
(AlhUnd P-lll)
5. Urcthane lac>^
etltanol /water aolutlon ..
(Arolnn Ihl) *
1
SeKcroaallnk acrylic In etho4jr
ethcnol/iylene (Aro.*t 701X11-50
Acrylic rettn In Xyltne crova-
llnk/«»U»lne (Aruaet 4110X60)
Acrylic realn In Xylene croaa-
llnk/«UBlne (Aroael 4IIOXAO)
J2I Tall Oil. 40Z Phlh. Anh. In
Xyltne (Aropl. t UilXVi)
l^S (ix-orul Oil. »II Phlh. Anh.
In Xylene (AroRlai 2MU1X60)
MI4.rv>» USf.
TTRZftBd - Type IV.
Inw vl« . . color fast
rtFiH 4 TTP»>*4c
(jit ilty. ltd rettat.
Ruat l.ihlbttlns, Ucq.
rcalat Ing
Fant drylnjt. It. colnrf
Druaia. Marhlneryt etc.
Fur (leu Inn part* !vy
~"h,iy ~
2.09
(17.4)
1.09
(9.10)
1.1*
(11.6)
1.6*
(14.1)
1.17
(2*. I)
1.50
(12.5)
1.24
(10.1)
1.10
(9.20)
0.51
(4..'»>)
1.6}
(11.6)
1.01
(8.60)
1.06
(8.80)
1.22
(10.2)
o.«o
(7.V»
III NV
E'L-WJ 	
u
-------
TABLE  C-2 (continued)
; 	 ! 	 • •; 	 "«
J t KAIN1 llr'.mirlli'\ M/l'l
] 	 ?-My "AS*. ) IH'K'II 1 \l In'.' ( limpii>.|||.>\ HI HIM'IM | '.IM ISIII) IM [ (th/g.il)
Inn - (riMil Imii'il) h. \ MI-">|.||/|>I>- '. U-. .1 >.ll.iw. i7 1 i-lnr nil, f I'l.i'i. An). S.nl-.lr\ Aid .1 1 n <|m r 4 ' .'.IS

I • » t
^,,,'s.ra, ' *.,•*., I*.M^ .wW, i.Kp., «„ ,,,..,.., ,.„,„..,.., J ' J ..i.,)
' ' ' 1
' ! 2. MiJIun M.i-rl AIH>.I i'r inc. ' Vilfl.>v. r nil Alk\d In t.it.r/1. | Fxt.-il.-r. durable, bare ' 1.92
' InrtU-'l (Ashl ni.l P-.VS) h.il ./|MI|O«\ 1 , llnn..| witir ' "I Jlr dr\ • (lh..M


( ^,.|-il Ion 1 \r..lon I.M ! ]
! 1. 1i.ll.uo Sliurt Alk .1 Rot ' l.illli'wr nil AU d In wu. .lutl.m (Ar..|..n Oh) |
!l . P
4. Mtdlu* sl.ort .Mk)d l.rein S il 1 \,-v, t nil AlVt.l In wit.r/l.



*" 	 r "
?A« . nrp. ^inu IIHIAIK
to
ro
W



Air drying, 'nlvmi
bornr




1















2Au - DIP. now. CURTAIN,
Air drying. wa«r
bornt


2Bs - DIP. nXJW. OJHTAIK.
bnrn«
_ .*
rulirlnr, ilnrible, hake ' I.S'.
kx ov/iu :\-
't _ db ov/«,.ti .-.v) _
." hvr 	 ,. •"* ...
;';" • i:l
i *" * ' i
« - *.. —
: ,":^, ; «":^7> ;

O.Bi [ U.t4 !
(7.0D) (7.00)
,
O.76 0.76
fit in) '•> lnk '
ID. ju;
« »• . *••/
0.84 0.84
t j nn\ i 7 n*t ft
i .
I

(Ird Rusln tray ti.dncl . (Ar..| In/ .' lOJI'iO)
(AsliUnd T-114)



2. McOluB 4 Shnri Modified
Ron In Slick Fnmrl
(A>hUnd P-IH)



1. Short, Mr.dlflcd Alkyd Oran«i
EnalMl (Aihlnnd P-2)l«)

2. Sh..rl. Modified Alkyd Uhltr
Fnanrl (Athlaiid P-238)
I. Short Alkrd Yrllow Fnnncl
(Ashland P-140)
\Y '....hi in. in I'hlh. Anil.
(Aropla; 7i.".xVi)
Phrn.'1-Ri.^ In (Aro« hrn ID)
5i: Snvbr.in. 101 Phlh. Anh.
(Aroplaz 7)07rl)0)

1'jJ Soybean, IM Phrli. Anh.
(Arcplat 7424XV1)
fhtnol-totln (Arochm ))S)
Jflfftinifr oil ton In - waicr dla-
piT*lon lypv (Arolnn Ml))

Sam.iwrr Oil Ronln - walrr dU-
t»ersli»n ivpe (Arnlnn i85)
IS? Tnll Oil, IHt Phth. In ly-
Ienf/Allpli9
•Ion 4 loughncnx (14.1)

fin. trotlat l< aprav (10.6)
(ronllnurd)
• • r 	
1 . 3h 1 Qf>
(11.11
(16.3)




,.*»
(12.1)




0.11
(0.90)

0.12
(1.00)
I.M
(14.4)



2.09
(17.4)




0.11
(O.«0)

0.12
(1.00)
2.09
(17.4)

 '"Produce^

-------
                Reproduced trom    ty*f%
                best available copy. \gjf^
                                                   TABLE  C-2  (continued)
K>
	 PAiNT_CLAjs_ ._, 	
2la - (continued)
2Bv - DIP, FLOW, CURTAIN,
born*
lAa - COIL t ROLL. Air or
•lid heat drying,
solvent borne
Us - COIL 4 ROLL, tok*
cured, solvent borne
PAINT HI •:( Kin IdV
2. oil Free Alkyd

(A^nland P-241)
2. Short Oil Alkyd White Fnaael
(Anhlarvl P-2)))
3. Short Oil Alkyd Ulark Fnaael
(A.ht.nd P727)
4. Mo.Jll.ed Oil Halelnlzed
BUck rclaec (Ashland Q-510)
5. Nedlixi Short Alkyd Orange
PrUrr (Ashland P-234)
6. Modified Alkyd Cray Prli.tr
(Aahland 8o)SFIIS4)
7. Halelnlzed OH Resin Black
Prlaer (Aahland Q-SI9)
PrUer (Aahland Q-515)
1. Medium Oil Alkyd Red Shop
Coat (Aahland Q-U)
2. Nedlun Oil Alkyd Flat White
Ena.cl (Aahland H-in5«>
1. Short Oil A 11. yd Wlilte Enanel
(AshUnd B-15)
1. Oil Free Polyester White
(Ashland P-87)
< (IMPOSITION lit MNIIIR

dl*.pir4l->n (Arnlun MIS)
S*ffl»wi-r Oil Resin In Wllrr
illnpirslon (Arolnn 'i(*5)
dl^pirKlnn (Aro)pn SRS)
Llns,,.|/ravti.r (Ml lesln In rth-
o«y tlloniil 1 Ivcol butyl
\jril. .wn 1)11 Kisln In Hul.i.y
linn (Ar. li>n K7)
Mel. I..I/.-.I Oil Rmln In B.il.'iv
solnl Ion (Arol'in SII7)
tl.'n (Arolnn S2S)
tlon (Aroli.n S25)
52S High Soya. 147 Ptith. Anh. In
Mln. Spirits (Aroplar 108 21 SO)
S2Z High toy*, lit Phth. Anh. In
Mln. Spirits (Aroplas I082NSO)
I".; Sovahejn OH. 411 Phtli. Anh.
In Xvl.ne/Mln. Spirits (Aroplaz
71IOXSO)
Non-onldlrlnj Alkyd In Aroo./
•elhyl-hcptyl setnne (Aroplas
6022Rh5)
	 1
SIIU.r.STfD US_K 	
hllltv
High slofis, hlRh sollJs.
Inluctrlal use
Hl(>i Klov^, high solids.
High glf«». high solids.
Industrial UHC
Rust Inhlbltlv*
High gln««, hard fleilblr
Tot'^tt r**ntn( uur*t«ndlnn
plR*rnt tiiiitprnAloi for
•UtfMBOC (VC U( *•
rconovlr.il

li^« vUiOatity Tl*266d-IV,
lil|lh color rrtrntlon
Low viv^ohlty m»2*.M-IV.
hlRh color retention
Very flmlhlc, high
veathrr durability
Exterior coll co«i
-,, /•'"„"
1.71
(lo.n)
1.12
2.04
(17.0)
1.46
(12.2)
2.17
I.S2
(12.7)
1.92
(16.0)
1.14
(11.2)
1.46
(17.2)
l.nO
(1).))
(17.2)
2.24
(18.7)
1.79
(14.9)
k< nv/iit NV
1.16
(9.70)
0.48
(t.OO)
0.2«
(2. JO)
0.29
(2.40)
0.64
(5.10)
1.01
(8.40)
O.K1
(5.00)
(7i90)
0.76
(6.30)
1.10
(9.70)
1.27
(10.6)
0.79
(t.M)
1.16
(9.70)
0.48
(4.00)
0.28
(2.30)
0.79
(2.40)
0.64
(5.10)
1.01
(8.40)
0.60
(5.00)
0.95
(7.90)
0.76
(6.30)
1.10
1.69
(Ik. I)
1.57
(13.1)
0.79
<6.*0)
          
-------
                                          TABLE C-2  (continued)
w
M
tn
PAINT CLASS
IBs - (continued)
)Bw . COIL 4 ROLL. Bake
cured, water borne
4Bw - ELKTROCOATS. Bake
cured, water borne
PAINT OPSUtmiON
(FOItrll'LATlON)
2. Slllcone mpdlllvr Polve«l*r
White Cninel (AOil m.l P-77)
Gloss F.naael (Alhlind P-84)
4. Oil Fr«« Polyretcr White
Cloaa Enuel (A«hl.i.«) P-8S)
3. Oil Free Polyrater While
Clou Elaawl (Ashl.nJ P-S»)
6. Oil free Polyemer Whllr
Cloia tnuel (Anhlend P-81)
I. Oil Free Polyester White
Cluit Fnaael (AihUnd P-240)
I. Medium Short Alkyd Rrd
Prlaer (A.hUnd Q-SH)
3. Hedluei Short Alkyd Green
Eiuael (Aihland P-22Jc)
1. Short Oil Alkyd Red Prlner
(Alhlcnd Q-60I)
2. Short Oil AlVyd FUt Black
(Alhlanj P-702)
). Snort Oil Alkyd Cloae Black
(A.hl.nd P-:u4)
4. Short Oil Alkyd Cray PrUcr
(A.hl.nd 0-601)
>. Short Oil Alkyd White
Istfssl {fohl.nd f-JOl)
	 	 " 1
(OPPOSITION 01 KINDfR ' SUCOtSTLD USE
70! nil Frrr Alkyd, 1'U 'Illtorr
In AriNBJt lf/polv»'i»tet /htitnitol
(Arnplai t7IIA'!hO)
8» Oil Frre Alkyd, 151 Sllicone
In Aron./bnt. ac . (Aroplaz
fiO25R70)
Oil Fnlblllty, color
retention, adhealon
Encellrnt color retention
HlRh gloat, adhealon.
corrosion reatetnnt.
f»««lbl»
High floea, adhealoa.
flexible
Autoontlve t other high
qual Ity uaea
Autonotlve 4 other high
quality uaea
Automotive 4 ether high
quality uaaa
Automotive 4 othei high
quality uaea
Automotive 4 otWr high
quality «a«a
sv
kR/Itt
0)
1.4)
(11.*)
I.JJ
(II. 1)
k. OV/lIt KV
(Ib OV/gal NV)
buy
0.70
(i.eo)
0.66
(5.50)
0.7)
(6.10)
0.85
(7.10)
0.66
(5.50)
0.)2
(2.70)
0.76
(6.30)
0.84
(7.00)
0.31
(1.60)
0.30
(2.80)
0.47
(3.vO>
O.)l
(1.60)
O.H
(2. BO)
utc
0.70
(5.80)
0.66
(3.50)
0.73
(6.10)
O.E5
(7.10)
0.64
(5. 5l>)
0.32
(2.70)
0.76
(4.30)
O.S4
(7.00)
0.31
(.'.60)
o. :o
(2.8C)
0 47
(S.»0)
0.31
(2.60)
0.34
(2.00)
        (coot lo

-------
                                            TABLE C-2 (continued)
w
to
o»
— 	 	 .
PAINT CIASS
51 - fCUDUS. Buki- cur.-J



































......... _._ . .....
fAIST DrSlKIPIIllN
(IORHI I.ATIOS)
1. rpovy. Convent lnn.il



2. Epo>y. low Ttapvrtture



). Tlienaojvt Polyester, Hcla-
nlne « «ir»-«1







thine cured






5. TnernopUitlc Polyester



6. Theraoiet Acrylic







~
CmPnSITION 01 BINTIIH ,




































siHx.rsrrci tsi.
Indoor or prtArr^







Ourdoor netal*







t
OwiJ.iut •ctal






furniture, fencing*



Outdoor nel*l t
equipment1






NV
k»/lll
1 VO-
1.10
(10.0-
1J.O)
1.16-
1.79
(9.60-
I* 9)
1.16-
1.79
(9.tO-
14 »)




11 A
. lo-
1.79'
(9.60-
14.9)




I.IJ-
l.ll
(9.60-
10.9)
1.20-
1.52
(10.0-
12.7)




db m/
o.ou-
o.nia2
(O.IZO-
0.150)'
O.O07-
o me1
(O.MO-
0 OHO) '
0.042-
0 078'
(O.J50-
0 640) '
0 0)0-
." OtH*
(0.250-
0.4OO)11

0.01,0
(0 400-
O.iOO)1
0.054-
0.0705
(0.4SO-
0.5«C)S
0.001-
0.0046
(0.010-
O.OJO)'
O.OWV-
0.04J*
(0 250-
O.J50)'
0.0)»-
0.124'
(0.820-
I.OJO)2
111 N.'
(*t "VI
ute
0.012-
o.oi»:
^3f I jo_
O.I5C)'
O.CO7
0 010'
tO.O".C»-
0.080)'
0.04?-
O.OJB^
(O.)50-
0 640) !
0.030-
0.048*
(0 250-
0.400)*

0.060'
(0 400-
0.500)>
0.054-
0.0705
(0.450-
0.580)4
0 001-
O.OO*1
(0.010-
O.OJC)'
0.0:0-
' 0.0473
(0.2V)-
0.1501'
0.098-
0.124'
(0.820-
I.OJO)'
         (conlInurd)

-------
                                       TABLE C-2 (continued)
u>
PAINT flJlSS
59 > (continued)


6eh - RADIATION. Electron
brim cured



6uv - RADIATIO*. Ultra
violet ray cured


7Aa - MICH 5011 W. Air
drying, eolvent borne
(ceellaurd)
PAIKT nf MXIPTII l.ili-i
907 Acr>l4t>-n. A" Slyrtne
jnt r..|vni|i-r. lot Slyrene. 10*
(Urvrll, SlliiiAitv. 101 Methyl
Keiacr yl ite



591 Acrylic otl(OBer. 4IX Itn-
•od*-r N In ethomy athanol
aretate •oletenrr

Reproduced from /ffl&
bes» available copy. &jj
•HHSI'TIU US^ 	
OntJmir lurnliure,
hlrvcln1
Fencing, vlret. under-
Rroiiml u«e^7
NV
1 «/!(«
1.20-
I.WI
(10.0-
14.0)
Furniture1 ' 1.14-
j 1.1:
(9.50-
; II. 0)
'
1
Wood 4 Betal
Wood 4 vela!
Wood 4 vrtal
Wood 4 aieial
Printed decoration!
Clear oveicoata
Elevated teaperature
coata. aMKAellc wire
large equlpnent. beat
•eMaltlve lleva, *ho»
rednlahlni
0.91'
0.91-
0.911
(7.fcO)'
0.911
(7.60)1
link
(Unk.)
link
(Unk)
link
(I'rk)
1.58
(13.2)
">« ov'/

-------
                                                                   TABLE  C-2  (continued)
to
CD

PAINT C1.A3S
;je - MICH SOUDJ. leke


ilw - UM SOLVtXT. leke
cured, veter borne
«RV - POk-ori stum, aeke
cured, water bot*te
PAINT Dtsriimo*
(rOIM'LATION)
1. Acrylold OL 4} While rru»el
2. Acrylic UMte Canrl (Eoh»
4 «•-.•)

1. Acrylic Whit* tn*e>el
(Aehlend CF-II)
1. Acrylic White t>.»el
t 	 ..

riMK>sfTi^t Kit
Arcyll. rvutelun In weter
(Arolon I-BOI)
Acrylic powder In weler

SUCCKSTfD I'^C
Indoor 4 outdoor furnl-
etc.
Low rneriy porcelela

Cenerel Induelrtel or
outdoor over prle>er
Cenerel Induetrlel
NV
l|/llt
(Ib/Ael/
l.«
!.«.»
(14.1)

,l:lo,
I.J4
(11.1)
k| 0V/
(Ib 0V/
buy
O.VO
0.5«

0.11
(1.10)
O.OIIf
lit NV
uer
O.W
0.1*

0.11
O.OIII
              1  C.
              '  i.
              »  0.
              »  T.
              »  r.
              • s.

              » A.
nlcetloD.
t. Cole.  Jr.:  SKI peper. FC 74-16O. *nd direct co»-unlcelIon.
D. Nirdy  4 T. U. Selti:  .
              t Oeie  |lven ere eetlnetee.
              t Oeia  gleea lactude liberated orgenlc coreectent*.

-------
                                TABLE C-3.   WASTE  COATING COMPOSITION DATA
        Process and/or waste  desc. iption
                   Waste  composition
              Data
             quality
      Paint sludge from spray  painting at
        truck assembly plant
      Paint sludges from auto assembly
        plant
to
K*
VO
Pigments, %
Resin,  %
Moistme, %

Toluene, %
Ethyl alcohol.  %
Diacetone alcohol,  %
Isopropyl alcohol,  %
N-Butyl alcohol, \
Cellosolve acetate, %
Xylene, \
MEK, \
Ethylene glycol monoethyl ether, %
V.M. & P. naphtha,  %
Aromatic naphtha, %
N-Butanol, %
Iso-butanol, %
Ketones, %
Esters, %
Crotonsldehyde, %
Diethylbenzene, %
Turpentine, %
Pigments, %          |
  Barium sulfate
  Aluminum silicate  (
  Titanium dioxide
  Hontmorillonite clay
  Magnesium silicate,
  Carbon black      »
   20
   60
   20

 5-33
 2-11
  1-4
 1-15
 1-16
  1-6
3-100
 1-16
  1-4
  1-2
 9-30
  1-2
  1-2
 1-20
10-20
 0-25
 0-25
 0-11
 1-60
                                                                                                  (continued)

-------
                                               TABLE   -3  (continued)
        Process and/or waste des' ~iv>
                   Waste compositiona
      Paint sludges from auto tu.'.embly
        plant (continued)
Pigments, %
  Copper
  Lead
  Nickel
  Chrome
      Paint sludge from tractor manufactur-   Nonvolatiles, %
        ing operations                       Volatiles, %
                                             Water, %
                                             Ogranic  solvents
                                               Xylene, %
                                               Naphtha, %
u>
u>
o
      Paint sludge from a tank plant
Composition of nonvolatile portion
  Alkyd type grey bake enamel,  %
  Alkyd type blue bake enamel,  %
  Alkyd type yellow bake enamel,  %
  Alkyd type black air-dry enamel, %
  Alkyd type primer, %

Total chromium, mg/L
Lead, mg/L
Zinc, mg/L
Mercury
Arsenic
Copper, mg/L
PH
Solid paint, heterogeneous mixture
                                            70.18
                                            29.82
                                               >25


                                                <4
       14
       34
       37
        A.
       11

600-2,000
      1-3
  400-600
       ND
       ND
   60-100
     6.35
                  Data
                 quality
                                                                                                  (continued)

-------
                                              TABLE  C-3  (continued)
        Process and/or waste description
                   Waste composition
              Data
             quality
      Paint primer sludge
      Finish paint sludge
u>
      Paint sludge
      Acrylic based paint residue  (solids)
Alkyd resin
Xylene
Toluene
Naphtha
Zinc
Iron

Alkyd resin
Xylen.
Toluene
Naphtha
Mineral spirits
Titanium
Iron
Carbon

Silicone resins
Cellosolve acetate (acetate esters of
  ethylene glycol monoethyl ether)
Isobutyl acetate
Xylene
Toluene
Aluminum

Resin, %
Moisture, %
Pigments (primarily carbon black), %
Solvent (trace of toluene), %
40-60
25-30
15-20
0.5-2
                                                                                                  (continued)

-------
                                             TABLE C-3  (continued)
        Process and/or waste  description
                   Waste composition
                Data
               quality
      Solvent based paint  sludge
w
u>
N>
      Acrylic copolymer based dewatered
        paint residue
      Electrolytic paint sludge
Flammable, volatile
Alkyds. %
Nitro cellulose, %
Organic solvent, %
Organic resin, %
Organic and inorganic pigment,  %
Toluol, %
Xylol, %
Butyl acetate, %
MIBK, %
Isopropanol, %
Lead, %
Chromium, %

Odorless waxy solid
Softening point, °F
Flash point, °F

Moisture, %
Resin, %
Free oil, %
Pigments, %
Solvent
                                                                                            15
                                                                                            10
                                                                                            13
                                                                                            4
                                                                                            25
                                                                                            24
                                                                                            3
                                                                                            2
                                                                                            1
                                                                                            3
                                                                                          <0.5
                                                                                          <0.5
   >160
   >250

   <0.5
  60-62
    3-4
  34-37
     ND
                                            Pigments consist of titanium dioxide and some carbon
                                              black.  No acrylic monomer present.
Deionized water, %
Alcohols, %
Pigments, %
PH
   85.5
    4.5
   10.0
6.6-7.6
                                                                                                  (continued)

-------
                                              TABLE C-3  (continued)
        Process and/or waste description
                   Waste composition
 Data
quality
      Solvent based scrap automotive paint
u>
w
u-
The minimum and maximum are ranges one would expect to
  find" from one drum (55 gallon) to another.  The aver-
  age represents what one would expect by mixing one
  truck load (approx. 4,000 gallons) of scrap paint.
General analysis
  Resin, %
  Solvent, %
  Water
  Pigment, %
  pH, %

Detailed analysis
  Resin
    Acrylic copolymerc, %
    Melamine, %
    Helamine copolymers, %
    Epoxy ester resin, %

  Solvents
    Acetone, %
    Xylene, %
    Toluene, %
    Acetate esters of ethylene
      glycol mono ethyl ether, %
    Hisc. hydrocarbons, %
    Water
                                                                                     Kin/Avg/Hax
                                                                                          10/25/40
                                                                                          10/50/95

                                                                                           5/2r>/30
                                                                                         6.5/7/8.5
                                                                                          20/30/40
                                                                                            0/5/10
                                                                                            0/5/10
                                                                                            0/3/12
                                                                                           5/10/15
                                                                                           0/10/20
                                                                                           0/10/15

                                                                                           0/10/15
                                                                                            0/8/12
                                                                                                      (continued)

-------
                                              TABLE  C-3  (continued)
        Process and/or waste  description
                   Waste composition
                Data
               quality
      Solvent based scrap automotive paint
        (continued)
w
      Paint and water from paint  spray
        booth-auto assembly plant
Heavy metals in pigments
  Lead, mg/L
  Mercury, mg/L
  Nickel, mg/L
  Arsenic, mg/L
  Chromium, mg/L
  Silica, mg/L
  Copper, mg/L
  Zinc, mg/L
  Bromine, mg/L
  Chlorine, mg/L

Total solids (pigments and resins
  left after heating at 250°F),  %

PH
Paint, %
Water, %
Lead,, mg/kg
Zinc, mg/kg
Nickel, mg/kg
Copper, mg/kg
Chromium, mg/kg
Phenolics compound (by leach
  test), mg/kg
                                        Min/Avg/Max
                                                                                        50/150/300
                                                                                             1/1/5
                                                                                           2/10/15
                                                                                            1/1/10
                                                                                      50/400/2,000
                                                                                         50/50/200
                                                                                      50/100/3,000
                                                                                    50/3,000/6,000
                                                                                       10/16/3,000
                                                                                       10/80/3,000
    5/12/45

    8.1
   61.5
   38.5
<10,000
 <1,000
   <100
 <1,000
 <1,000

    4.7
                                                                                                  (continued)

-------
                                              TABLE  C-3  (continued)
        Process and/or waste description
                   Waste composition
             Data
            quality
      Cray epoxy low bake primer sludge
U)
      Liquid water base aluminum paint
        sludge
      Solid water base aluminum paint
        sludge
      Liquid solvent base aluminum paint
        sludge
Pigments, %
  Barium sulfate
  Titanium dioxide
  Silica
  Carbon black

Vehicle solids. %
  Epoxy ester resin, %
  Nitrogen resin, %

Solvents, %
  Aromatic hydrocarbons
  Aliphatic hydrocarbons
  Ethylene glycol monobutyl ether
  Butyl alcohol

Metallic aluminum pigment, %
Alkyd resin, %
Driers and stabilizers, %
Cosolvents, %
Water, %

Metallic aluminum pigment, %
Alkyd resins, %
Driers and stabilizers, %

Metallic aluminum, %
Suspending and tinting pigment, %
Phenolated alkyd resin, %
Aromatic and aliphatic hydrocarbon
  blend, %
  37
                                                                                            16
                                                                                            93
                                                                                             7

                                                                                            47
 6.2
19.4
 0.4
12.6
61.4

23.8
74.6
 1.6

12.7
 0.5
25.2

61.6
                                                                                                  (continued)

-------
                                       TABLE  C-3  (continued)
  Process and/or waste  description
                   Waste composition
                Data
               quality
Solid solvent base aluminum paint
  sludge
Liquid zinc rich welding primer
  sludge
Metallic aluminum,  %
Suspending and tinting pigment,  %
Aromatic and aliphatic hydro-
  carbon blend, %

Metallic zinc, %
Suspending agent, %
Epoxy ester, %
Rubber, %
Aromatic and aliphatic hydro-
  carbon blend, %
Solid zinc rich welding primer  sludge  Metallic zinc, %
                                      Suspending agent, %
                                      Epoxy ester, %
                                      Rubber. %
Dip paint sludge
Overspray and drippings from spray
  paint booth
PH
2-Butoxyethanol, %
N-Dutoxypropanol, %
Triethylamine, %
Chromiumin pigment, %
Water

Lead, %
Chrome, %
Anodized aluminium, %
Carbon black, %
Iron oxide, %
Iron blue, %
   33.1
    1.3

   65.6

   71.2
    2.7
    4.6
    1.1

   20.4

   89.4
    3.4
    5.8
    1.4

    7.2
     15
   <5.0
   <0.5
   0.29
Balance

      5
      3
      3
      1
      6
      2
B
                                                                                            (continued)

-------
                                        TABLE C-3  (continued)
  Process and/or waste description
                   Haste composition
              Data
             quality
Overspray and drippings from spray
  paint booth (continued)
Paint spray booth sludge
Dip prime sludge
Paint sludge
Solvents
  Xylol, %
  Toluol. %
  NapJ'tha, %
  MEK. %
Vehicle (resin;, %

Flammable
Flash point, °F
Vinyl toluenated alkyd resin,  %
V. H. & P. naphtha, %
Calcium carbonate, %
Titanium dioxide, %
Lead, rng/kg
Nickel, mg/kg
Cadmium, :ng/kg
Chromium, mg/kg
Mercury, mg/kg
Arsenic, mg/kg
Amines, mg/kg
Nitro-phenols, mg/kg
Quinones, mg/kg

Pigments, %
Xylol, HIBK, cellosolve acetate, %
Zinc, mg/L

PH
Water, %
Sodium silicate, %
                                                                                      10
                                                                                      70
                                                                                      53
                                                                                    33.5
                                                                                    51.7
                                                                                    11 5
                                                                                     3.0
  100
  100

15-20
80-85
  247

  7.0
70-95
 5-10
                                                                                            (continued)

-------
                                              TABLE C-3  (continued)
        Process and/or waste description
                   Waste composition
                Data
               quality
      Paint sludge (continued)
      Paint residue from productive paint-
        ing operations
      Solvent based paint sludge
u>
CO
oo
      Paint sludge from spray booth
Sodium phosphate,  %
Sodium hydroxide,  %
Paint resin, %
Pigments, %

Ketones and alcohols, %
Toluene, %
Pigments, %
Xylene, %

Flammable
Flash point. °F
PH
Noncombustible ash, %
Aliphatic alcohols, cs
Toluene, %
Aliphatic petroleum distillate, %
Triethylamine, %
Xylene, %
Manganese, %
Nickel. %
Chromate, %
Copper, %
Lead, %

Noncombustible ash, %
Resins, fillers, pigments, %
Lead, %
   5-10
    1-5
   5-10
    1-5

  10-20
  70-80
   5-10
    200
8.0-9.0
      6
   9-13
      1
  34-42
    0.4
   0.03
   0.06
     <2
   0.25

    6.1
   87.7
    2.7
                                                                                                   (continued)

-------
                                              TABLE C-3  (continued)
        Process and/or waste description
                   Haste composition'
              Data
             quality
      Paint sludge from spray booth
        (continued)
      Paint sludge from painting automobile
        accessories
10
vO
Zinc, mg/L
Nickel. mg/L
Copper, mg/L
Mercury, mg/L
Beryllium, mg/L
Cadmium, mg/L
Hexavalent chromium,  mg/L
Arsenic, mg/L
Phosphorus, mg/L

Flammable
Flash point, °t-
Oil and grease, %
Pigments, %
Solvents, %
Aromatic hydrocarbons,  \
Alcohol, %
Water, %
Naphtha, %
Ketones, %
Glycol, %
Esters. %
Phosphorus, mg/L
Phenol, mg/L
PCB
  Aroclor 1242, mg/L
  Aroclor 1280, mg/L
Lead, mg/L
Zinc, mg/L
  260
    2
  220
   16
    2
    1
9,100
    8
4,760
  <32
  3.6
 30.4
 66.0
 17.9
 13.5
 11.4
  9.8
  9.2
  1.7
  0.8
   37
  4.4

   <2
   <2
  190
   11
                                                                                                  (continued)

-------
                                        TABLE  C-3  (continued)
  Process and/or waste  description
Haste composition"
                                                          Data
                                                         quality
Paint sludge from painting automobile  Nickel, mg/L
  accessories (continued)              Copper, mg/L
                                      Beryllium, mg/L
                                      Cadmium, mg/L
                                      Chromium, mg/L
                                      Mercury, mg/L
                                      Chlorine, mg/L
                                      Bromine, mg/L
                                      Arsenic, mg/L
                                      Sulfur, mg/L
                                      Cyanide, mg/L
Paint sludge from painting automobile
  accessories
Water base paint residue-water
  reducible baking epoxy paint
Flash point,  °F
PH
Water, %
Resins, %
Metals and dirt,  %
Noncombustible ash,  %
Lead, mg/L
Zinc, mg/L
Nickel, mg/L
Copper, mg/L
Cadmium, mg/L
Chromium, mg/L

Toxic
PH
Water, %
Carbon black, %
Lead silicochromate, %
                            8.8
                             12
                           <0.2
                           <0.2
                          <0.05
                          <0.01
                         10,570
                             74
                           0.31
                            710
                            0.8

                           >200
                            8.4
                             45
                             40
                             15
                           57.2
                          3,345
                          2,651
                             70
                          1,682
                            0.8
                            120
                                                                                 64
                            8.0
                           ± 10
                            2.4
                            4.0
                                                                                            (continued)

-------
                                       TABLE  C-3  (continued)
  Process and/or waste description
                   Waste composition
               Data
              quality
Water base paint residue-water
  reducible baking epoxy paint
  (continued)
Paint sludge
Urea formaldehyde.  %
Methylated melamine, %
Epoxy ester, %
Ammonium compounds, %
Talc, %
Butyl cellosolve, %
n-Butanol, %
Methyl rellosolve.  %
Noncombustible ash, %
Lead, mg/kg
Trivalent chromium, mg/kg

Flammable
Flash point, CF
PH
Solids (paint), %
Noncombustibl'i ash, %
Lead, mg/kg
Zinc, mg/kg
Nickel, mg/kg
Copper, mg/kg
Beryllium, mg/kg
Cadmium, my/ky
Chromium (totnl), mg/kg
Chromium (hcxnvalent), mg/kg
Mercury, mg/Xg
Arsenic, mg/kg
Kjeldahl nitrogen,  mg/kg
Phenol, mg/kg
   4.0
   3.9
  12.7
   1.5
   7.9
   4.8
   0.5
   3.7
12 ± 1
 1,640
    15
                                                                                    <140
                                                                                     4.5
                                                                                    54.3
                                                                                    28.7
                                                                                  43,000
                                                                                     540
                                                                                     8.1
                                                                                     195
                                                                                   <0.06
                                                                                     4.3
                                                                                  10,300
                                                                                  <0.005
                                                                                  <0.004
                                                                                    0.41
                                                                                   3,390
                                                                                     1.2
                                                                                            (continued)

-------
                                              TABLE  C-3  (continued)
        Process and/or waste  description
                   Waste composition
      Paint sludge (continued)
w
*»
to
      Waste enamel from wire coating
        process
      Primer paint sludge from paint spray
        booth
Total halogens reported as
  Chlorine, mg/kg                               62
  Bromine, mg/kg                                33
Organic halogens reported a.
  Chlorine, ng/kg                               59
  Bromine, mg/kg                                32
Sulfur, mg/kg                                  140
Phosphorus, mg/kg                            2,100
Oil and grease, mg/kg                      143,000
Cyanide, mg/kg                                  35
PCB reported as
  Aroclor 1242. mg/kg                           <1
  Aroclor 1260, mg/kg                            7
Solvents
  V.M.P. naphtha, mineral spirits,  and alcohol.
Toxic
Flammable
Cresylic acid (cresols-xylenols),  %
Aromatic hydrocarbons (xylene),  %
Resins (polyamide-polyester
  urethanes-amide-imides),  %
Zinc, mg/L
Copper, mg/L
Cadmium, mg/L
Lead, nickel, beryllium, chromium

Pigments and resins
Water
                                                                                         30-50
                                                                                         20-40

                                                                                         15-30
                                                                                          63.5
                                                                                          3.17
                                                                                          1.00.
34.5
65.5
             Data
            quality
                                                                                                  (continued)

-------
                                              TABLE  C-3  (continued)
        Process and/or waste  description
                   Waste  composition
                                                                                a
                                                                                                 Data
                                                                                                quality
      Primer paint sludge  from paint  spray
       ! booth (continued)
Scrap enamel and solvent  fp
  wire coating process
                                      gnet
u>
      Waste enamel and solvents from magnet
        wire coating process
Lead, mg/kg
Zinc, mg/kg
Nickel, mq/kcj
Copper, "ig/kg
Chromium, mg/kg
Phosphorus, mg/kg

Flammable
Flash point, °F
Toxic, corrosive

Polyester amide (maximum), %
Xylene (maximum),  %
Cresylic acid (maximum), %
Trivalent chromium (maximum), mg/L
2,3,5-Trimethyl phenol, mg/L
                                                                       %
Flash point,  °F
Toxic, odorous, irritant
Enamel resins in solution.
Xylene, %
Cresylic acid,  %
Ethyl alcohol,  %
Phenol , %
Hydraulic oil,  %
Helamine, mg/kg
Trivalent chromium, mg/kg
                                                <1.000
                                                <1,000
                                                  <100
                                                  <100
                                                <1,000
                                        1,000 to 10,000
                                                    81

                                                  M.O
                                                    4C
                                                    40
                                                    40
                                                    200
                                                  0.01
                                                                                       £4-110

                                                                                          1-5
                                                                                        40-60
                                                                                         8-15
                                                                                         5-15
                                                                                          3-6
                                                                                          1-5
                                                                                          350
                                                                                        10-12
                                                                                                       (continued)

-------
                                        TABLE  C-3 (continued)
w
Process and/or waste description
Paint sludge



Waste solvents and resins from
magnetic wire coating operation

Waste paint




Aluminum can painting process-
solvent oil and paint sludge


Paint sludge




Waste dip coat


a
Waste composition
Pigments, %
Solvents and resins, %
Lead, %
Chromium, %
Xylene, %
Phenol, %
Cresylic acid, %
Paint pigments, %
Xylene, %
Toluene, %
High boiling naphtha (such as
SP-100 or kerosene), %
Methyl ethyl ketone, %
Paint sludge, %
Oil, %
Water, %
Paint, %
Solvents, %
Latex, %
Water
PH
Solids, %
Liquid, %
PH

35
65
0.22
0.06
•V40
~35
•v-25
31
17
17

35
15
15
40
30
45-50
10-15
2-5
Balance
7.0
73
27
9.6
Data
r"'ality
B






B




B



C




B


                                                                                       (continued)

-------
                                             TABLE  C-3  (continued)
        Process and/or waste  description
                   Waste composition0
              UaL<>
             qua]ity
      Waste dip coat (continued)
      Off-spec paint thinners
      Off-spec spray paint
*>
en
      Off-spec water base paint
      Off-spec primer
Silica (colloidal). %
Silica (Si02). %
Aluminum oxide,  %
Isopropyl alcohol,  %

Acetone (90%)/Toluol (10%). %
Butyl cellosolve. %
Butyl carbitol,  %

Water, %
Aliphatic hydrocarbons, %
Fatty acids, %
Aluminum oxides, %
Titanium oxide,  %

Water, %
Resin and solvent,  %
Talc, %
Carbon black, %

Flammable
Flash point, °F
Aromatic hydrocarbons (toluene.
  xylene, MEK),  %
Resin, %
Noncombuotible material (600°C), %
Lead, mcj/kg
Cadmium, mg/kg
Nickel, mg/kg
Lithium, mg/kg
 26.2
 12.4
 37.0
   62

30-70
20-30
10-30

50-60
25-30
10-15
  3-4
  2-3

   55
   30
   12
    3
                                                                                           <70
                                                                                          63.7
                                                                                          36.7
                                                                                          24.9
                                                                                          18.0
                                                                                           2.6
                                                                                           1.2
                                                                                           2.0
                                                                                                  (continued)

-------
                                              TABLE  C-3  (continued)

Process and/or waste description
Off-spec primer (continued)




Waste composition3
l.ercury, ing/ kg
Chromium, mg/kg
Copper, mg/kg
Zinc, mg/kg
Silver, mg/kg

6.0
1.1
2.9
.38.2
0.2
Data
quality





      Waste paint thinner
OJ
4*
cr>
Flammable
Flash point,  °F
Toxic, irritant
Pigments,--%- .  . _
Aromatic hydrocarbons,  %
Alcohol, %
Waterr %
Naphtha, %
Ketones, %
Glycol ethers,  %
Esters, %
Noncombustible  ash,  %
Lead, mg/L
Zinc, mg/L
Nickel, mg/L
Copper, mg/L
Cadmium, mg/L
Chromium, mg/L
Antimony, mg/L
Cobalt, mg/L
Lithium, mg/L
Silver, mg/L
 <65

 2.1
27.7
20.5
17.2
14.9
13.9
 2.5
 1.
 0.
 152
  37
 1.4
13.3
  29
  23
 5.3
44.0
 1.4
 2.3
                                                                                            .2
                                                                                            .5
                                                                                                  (continued)

-------
                                        TABLE  C-3  (continued)
Process and/or woste doncription
Waste lacquer thinner from paint shop Flammable
Wnntc romponltlon

Data
quality
C
Paint filters and paint  dust from
  clean-up of paint  booths
Grease and paint scraped  from paint
  booth walls
Flash point, °F
Methyl ethyl ketone, %
Isopropyl acetate, %
Toluene, %
Acetone, %
Methyl isobutyl ketone,  %
Isopropyl alcohol, %
Isobutyl, %
Methanol, %
XyieneV % "'
Solvent, %
Pigments and resins, %
Zinc, mg/L
Chromium, mg/L

Pigments, %
Resin, %
Filter and dust, %
Diethylamine, mg/kg

Paint solids, %
Grease, %
Cadmium, mg/L
Chromium, mg/L
Copper, mg/L
Nickel, mg/L
Lead, mg/L
Zinc, mg/L
                                                                                      21
                                                                                    •vSO
                                                                                    MO
     56
     44
  1,005
     73

     44
     51
      5
<10.000

   92.5
    7.5
   0.15
    449
    5.7
    0.5
  1,940
   10.9
                                                                                            (continued)

-------
                                              TABLE  C-3  (continued)
        Process and/or waste  description
                   Waste composition
 Data
quality
      Waste paint thinners and paint  solids
        from paint clean-up operations
CD
      Waste generated during cleaning of
        paint spraying equipment
      Waste from clean up of painting
        operation
Aromatic hydrocarbons,  %                      62.4
Oxygenated hydrocarbons, %                    30.1
Butyl ester/glycol ether, %                    3.1
Paint solids, %                                4.4
Noncombustible material (600°C),  mg/kg       2,520
Lead, mg/kg                                  1,920
Cadmium, mg/kg                                 0.3
Nickel, mg/kg                                  5.9
Cobalt, mg/kg                                 11.8
Iron, mg/kg                                   32.1
Chromium, mg/kg   _     _                      160
Copper, mg/kg                                 ~3T9~
Zinc, mg/kg                                     54
Antimony, mg/kg                                1.2
Silver, mg/kg                                  O.Q

Toluene, %       -                               62
Hexane, %                                       13
Trichloroethylene, %                            11

Flammable
Flash point, °F                              20-80
Volatile
Aliphatic petroleum distillate, %               48
Toluene, %                                      43
Paint solids, %                                  9
Noncombustible ash, %                         0.35
Lead, mg/L                                   1,225
Zinc, my/I,                       ,             30.3
Nickel, 'fng/L                                  49.3
                                                                                                         B
                                                                                                  (continued)

-------
                                              TABLE  C-3  (continued)
Id
Process and/or waste description
Waste from clean up of painting
operation (continued)
Waste solvent generated during clean-
ing paint brushes or guns
Waste composition
Copper, mg/L
Cadmium, mg/L
Chromium, mg/L
Flammable
Flash point, °F
Xylenoi/toulene, %

27.5
<0.1
47.0
81
85-95
Data
quality

C
      Alcohol rinse for waste enamel for
        wire coating process	
      Acid rinse for waste enamel from
        wire coating process
Dirt, paint, and other material
  from cleaning, %

Flammable
Denatured-ethyl-alcohol,  %-
Cresylic acid, %
Water, %
Lead, mg/L
Zinc, mg/L
Copper, mg/L
Nickel, cadmium, chromium

Flammable
Irritant
Solids, %
Xylenols, %
Cresols, %
Mixed resins (polyamides, etc.),  %
Phenol, %
Lead, mg/L
Zinc, mg/L
Copper, mg/L
                                                                                          0-15
70-95
 5-25
 1-10
  0.8
  1.6
 19.0.
   ND
                                                                                             5
                                                                                         40-50
                                                                                         30-40
                                                                                          2-15
                                                                                           0-3
                                                                                           0.8
                                                                                           2.8
                                                                                          29.0
                                                                                                  (continued)

-------
                                             TABLE C-3  (continued)
1/1
o

Process and/or waste description Waste composition8
Acid rinse for waste enamel from Cadmium, mg/L
wire coating process (continued) Nickel
Chromium
Paint 'sludge from water wash air Noncombustible material (600°C), %
pollution control device Paint resins and pigments, %
Water, %
pH
Lead mg/kg ~ ~ — ~
~ Cadmium, mg/kg
Nickel, mg/kg
Cobalt, mg/kg
Chromium, mg/kg
Copper, mg/kg
Zinc, mq/kg
Lithium, mg/kg
Silver, mg/kg
. Chlorine
Bromine
Antimony

Data
quality
1.8
NDb
ND°
32.7 B
70-96
4-30
8.0 	 	 __
7,695
0.7
7.5
2.4 t
238
6.8
1,095
1.8
°'5b
N$

NDb
       Data are reported as found in State files.  Whether percentages given are by volume or weight is not

       known.               •                                                                       ••


      bNot detected.

-------