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
^
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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EPA Form 2220-1 (Rev. 4-77) PHKVIOUS EDITION is OBSOLETE ±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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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.
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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
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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
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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.
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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.
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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.
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(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.
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(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.
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(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.
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(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
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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
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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
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This report was printed specifically for your
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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
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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
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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
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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
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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
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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
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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
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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.
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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
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'-.'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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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]37. Control of volatile organic emissions from organic solvent
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133. Monahan, R. Vapor degreasing with chlorinated solvents.
Metal Finishing. 26-31, 1977 November.
139. Control of hydrocarbons from tank truck gasoline loading
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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-
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146. Fair, J. R.; and Bolles, W. L. Modern design of distilla-
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378 p.
148. Tierney, D. R.; and Hughes, T. W. Source assessment: re-
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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.
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Clyde Paint and Supply Company, Inc., Clyde, Ohio.
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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.
-------
|