EPA
Group I, Phase II
Development Document for
Effluent Limitations Guidelines and
New Source Performance Standards
for the
SYNTHETIC POLYMERS
Segment of the
PLASTICS AND SYNTHETIC
MATERIALS MANUFACTURING
Point Source Category
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
JANUARY 1975
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*
I*
f - '
»
*
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DEVELOPMENT DOCUMENT
for
EFFLUENT LIMITATIONS GUIDELINES
and
NEW SOURCE PERFORMANCE STANDARDS
for the
SYNTHETIC POLYMER SEGMENT OF THE
PLASTICS AND SYNTHETIC MATERIALS MANUFACTURING
POINT SOURCE CATEGORY
Russell E. Train
Administrator
James L. Agee
Assistant Administrator for Water and Hazardous Materials
i
a
Allen Cywin
Director, Effluent Guidelines Division
David L. Becker
Project Officer
January 1975
Effluent Guidelines Division
Office of Water and Hazardous Materials
U.S. Environmental Protection Agency
Washington, D.C. 20460
For sale by the Superintendent of Documents, U.S. Government Printing Office
Washington, D.C. 20402 - Price $3.55
-------
ABSTRACT
This development document presents the findings of an
extensive study of the synthetic polymers segment of the
plastics and synthetics industry for the purposes of
developing effluent limitations guidelines, and standards of
performance for the industry to implement Sections 304, 306,
and 307 of the Federal Water Pollution Control Act of 1972
(PL 92-500). Guidelines and standards were developed for
the following major products:
Ethylene-Vinyl Acetate Copolymers
Polytetrafluoroethylene
Polypropylene Fiber
Alkyds and Unsaturated Polyester Resins
Cellulose Nitrate
Poly amides (Nylon 6/12)
Polyester Resins (thermoplastic)
Silicones
Effluent limitations guidelines contained herein set forth
the degree of reduction of pollutants in effluents that is
attainable through the application of best practicable
control technology currently available (BPCTCA) , and the
degree of reduction attainable through the application of
best available technology economically achievable (BATEA) by
existing point sources for July 1, 1977, and July 1, 1983,
respectively. Standards of performance for new sources are
based on the application of best available demonstrated
technology (BADT) .
Annual costs for this segment of the plastics and synthetics
industry for achieving BPCTCA control by 1977 are estimated
at $5,000,000, and costs for attaining BATEA control by 1983
are estimated at $12,000,000. The annual cost of BADT for
new sources in 1977 is estimated at $3,300,000.
Supporting data and rationale for the development of
proposed effluent limitations guidelines and standards of
performance are contained in this development document.
11
-------
TABLE OF CONTENTS
Section Page
I CONCLUSIONS 1
II RECOMMENDATIONS 3
III INTRODUCTION 13
Purpose rand Authority 13
Methodology 14
General Description of the Industry 16
Product and Process Technology 25
Acrylic Resins 27
Other Pollutants 33
Alkyd Molding Compounds 34
Cellulose Derivatives 35
Cellulose Nitrate 38
Chlorinated Polyethylene 41
Diallyl Phthalate Resins 44
Ethylene-Vinyl Acetate copolymers 47
Fluorocarbon Polymers 50
Nitrile Barrier Resins 58
Parylene Polymers 62
Poly-Alpha-Methyl Styrene 67
Polyamides 69
Polyaryl Ether (Arylon) 70
Polybenzimidazoles 74
Polybenzothiazoles 79
Polybutene 82
Polycarbonates 86
Polyester Resins (Thermoplastic) 91
Polyester Resins (Unsaturated) 94
Polyimides 99
Polymethyl Pentene 104
Polyphenylene Sulfide 107
Polypropylene Fibers 112
Polysulfone Resins 117
Polyvinyl Butyral 122
Polyvinyl Carbazole 126
Polyvinyl Ethers 128
Polyvinylidene Chlorides 133
Polyvinyl Pyrrolidone 135
Silicones 138
Spandex Fibers 145
Other Pollutants 151
Urethane Prepolymers 152
111
-------
TABLE OF CONTENTS Contd
Section Page
IV INDUSTRY CATEGORIZATION 157
V WASTE CHARACTERIZATION 161
Raw Waste Loads 161
VI SELECTION OF POLLUTANT PARAMETERS 167
Selected Parameters
BODS I67
COD 168
Total Suspended Solids 163
Other Pollutant Parameters 170
Phenolic Compounds 171
Nitrogenous compounds 171
Flour ides 172
Phosphates 173
Oil and Grease 174
Dissolved Solids 175
Toxic and Hazardous Chemicals 176
Alkalinity, Color, Turbidity, and the 176
Metals Listed in Table V-3
VII CONTROL AND TREATMENT TECHNOLOGY i79
Presently Used Waste ^Water^ Treatment I80
Technology
Copper 188
Lead 188
Mercury I89
Flouride 189
Cyanide 190
Oil and^ Grease 191
VIII COST, ENERGY, AND NONWATER QUALITY 193
ASPECTS
Cost Models of Treatment Technologies 194
CostrEf fectiveness Perspectives 194
AJQQU£i_c.°.st_P.ei:s|2§c.£ive.§ 194
Cost Per Unit Perspectives 195
Waste Water Treatment „ Cost Estimates 195
Industrial Waste Treatment Model Data 196
Energy cost Perspectives 196
Non Water Auality Effects 197
Alternative Treatment Technologies 197
IV
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TABLE OF CONTENTS Contd
Section Page
IX BEST PRACTICABLE CONTROL TECHNOLOGY 237
CURRENTLY AVAILABLE GUIDELINES AND
LIMITATIONS
Definition of Best Practicable Control 237
Technology Currently Available (BPCTCA)
The Guidelines 238
Attainable Effluent Concentrations 239
Demonstrated Waste Water Flows 243
Statistical Variability of a Properly
Designed and Operated Waste Water 243
Treatment Plant 243
X BEST AVAILABLE TECHNOLOGY ECONOMICALLY 251
ACHIEVABLE
Definition of Best Available Technology 251
Economically Achievable (BATEA)
The Guidelines 252
Achievable EfTluent Concentrations 252
Suspended Solids' 252
Oxygen-Demanding Substances 253
Waste Load Reduction Basis 255
Variability 257
XI NEW SOURCE PERFORMANCE STANDARDS - BEST 261
AVAILABLE DEMONSTRATED TECHNOLOGY
Definition of New Source Performance 261
Standards Best Available Demonstrated
Technology (NSPS BADT)
The Standards"261
Achievable Effluent Concentration 261
Waste Load Reduction Basis 261
Variability 263
Alkyds and Unsaturated Polyesters 263
XII ACKNOWLEDGMENTS 267
XIII REFERENCES 271
XIV GLOSSARY 277
v
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LIST OF FIGURES
Figure No. Page
III-l Typical Reactions to Form Poly(Methyl
Methacrylate) Including Monomer
Manufacture 28
III-2 Acrylic Resin Production - Bulk Poly-
merization Process 29
III-3 Acrylic Resin Production - Emulsion
Polymerization Process 31
III-4 Acrylic Resin Production - Suspension
Polymerization Process 32
III-5 Typical Reactions to Form Cellulose
Derivatives 36
III-6 Cellulose Ethers Production 37
II1-7 Typical Reaction to Form Cellulose
Nitrate 39
III-8 Cellulose Nitrate Production 40
III-9 Typical Reaction to Form Chlorinated
Polyethylene 42
111-10 Chlorinated Polyethylene Production 43
III-ll Typical Reactions to Form Diallyl
Phthalate 45
111-12 Ethylene-Vinyl Acetate Copolymer
Production 48
III-l3 Polytetrafluoroethylene (PTFE) Pro-
duction - TFE Monomer Process 52
II1-14 Typical Reactions to Form Fluorocarbon
Polymers 53
111-15 Polytetrafluoroethylene (PTFE) Pro-
duction - PTFE Polymer Process 54
111-16 Nitrile Barrier Resin Production - »
Emulsion Polymerization Process 61
VI
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LIST OF FIGURES Contd
Figure No. Page
III-17 Typical Reactions to Form Parylene
Polymers 63
111-18 Parylene Production 65
111-19 Typical Reaction to Form Alpha-Methyl
Styrene 68
III-20 Typical Reactions to Form Polyaryl Ether 71
111-21 Typical Reactions to Form Polybenzimid-
azoles 75
III-22 Typical Reactions to Form Polybenzo-
thiazoles 80
III-23 Typical Structures Produced in the
Synthesis of Polybenzothiazoles 81
III-24 Typical Reaction to Form Polybutene 83
111-25 Polybutene Production - Huels Process 84
III-26 Typical Reaction to Form Polycarbonate 87
111-27 Polycarbonate Production - Semi
continuous Process 89
III-28 Thermoplastic Polyester Resin Production 93
III-29 Typical Reaction and Raw Materials Used
to Form Unsaturated Polyester Resins 95
III-30 Typical Reactions to Form Polyimides 100
111-31 Typical Reactions to Form Polymethyl
Pentene 105
III-32 Typical Reaction to Form Polyphenylene
Sulfide 108
III-33 Polyphenylene Sulfide Production 110
VI1
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LIST OF FIGURES Contd
Figure No. Page
III-34 Polypropylene Fiber Production 113
III-35 Polypropylene Monofilament Production 114
III-36 Typical Reactions to Form Polysulfone
Resins 118
III-37 Polysulfone Resins Production 120
111-38 Typical Reaction to Form Polyvinyl
Butyral 123
III-39 Polyvinyl Butyral Production - DuPont,
Inc. Process 124
III-40 Polyvinyl Butyral Production Monsanto,
Inc. Process 125
III-41 Typical Reaction to Form Polyvinyl
Carbazole 127
111-42 Typical Reactions to Form Polyvinyl
Ethers - Including Monomer Manufacture 129
III-43 Polyvinyl Ether Production - Solution
Polymerization Process 130
III-44 Polyvinyl Ether Production - Bulk Poly-
merization Process 131
111-45 Typical Reaction to Form Polyvinylidene
Chloride 134
111-46 Typical Reactions to Form Polyvinyl
Pyrrolidone 136
111-47 Production of Silane Monomers, Oligomers,
and Dimethyl Silicone Fluid 139
111-48 Production of Silicone Fluids, Greases,
Compounds Emulsions, Resins, and Rubber 140
111-49 Typical Reactions to Form Silicones 141
vin
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LIST OF FIGURES Contd
Figure No. Page
III-50 Typical Reactions to Form Spandex Fibers 146
III-51 Spandex Fiber Production - Dry Spinning 147
Process
III-52 Spandex Fiber Production - Wet Spinning
Process 148
III-53 Spandex Fiber Production - Reaction
Spinning Process 150
III-54 Typical Reactions to Form Urethane Pre-
polymers 153
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LIST OF TABLES
Table No. Page
II-l Best Practicable Control Technology
Currently Available Effluent Limitations
Guidelines 6
II-2 Best Practicable Control Technology
Currently Available Effluent Limitations
Guidelines (Other Elements and Compounds) 7
II-3 Best Available Technology Economically
Achievable Effluent Limitations Guidelines 8
IT-H Best Available Technology Economically
Achievable Effluent Limitations Guide-
lines (Other Elements and Compounds) 9
II-5 Best Available Demonstrated Technology -
New Source Performance Standards 10
11-6 Best Available Demonstrated Technology -
New Source Performance Standards (Other
Elements and compounds) 11
III-l Plastics and Synthetics for Consideration 18
III-2 Products to be considered for Development
of Effluent Guideline Limitations 22
III-3 Products Eliminated From Consideration for
Establishment of Effluent Guideline
Limitations 24
III-U Manufacturers of Products to be Considered
for Development of Effluent Limitations
Guidelines 26
II1-5 Commercial Fluorocarbon Polymers 57
III-6 Properties of Polyaryl Ethers 72
II1-7 Acids Whose Derivatives Are Used in
Polybenzimidazole Synthesis 76
IV-1 Industry Subcategorization 159
x
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LIST OF TABLES Contd
Table No. Page
V-l Waste Water Loading for Synthetic Polymers 162
Production
V-2 Synthetic Polymers Production Raw Waste
Loads 163
V-3 Other Elements, Compounds, and Parameters 165
VI-1 Other Elements and compounds Specific to
the Resins Segment of Plastics and
Synthetics Industry 177
VII-1 Operational Parameters of Waste Water
Treatment Plants (Metric Units) 181
VII-2 Operational Parameters of Waste Water
Treatment Plants (English Units) 183
VII-3 Performance of Observed Waste Water
Treatment Plants 185
VII-4 Observed Treatment and Average Effluent
Loadings From Plant Inspections 186
VIII-1 Perspectives on the Production of Syn-
thetic Polymers - Water Usage 199
VIII-2 Perspectives on Synthetic Polymers
Production - Annual Treatment Costs 200
VIII-3 Perspectives on Synthetic Polymers
Production - Cost Impact 201
VIII-U summary of Water Effluent Treatment
Costs - Cost Per Unit Volume Basis 202
VIII-H/1 Water Effluent Treatment Costs: Ethylene
Vinyl Acetate (Small Plant - Large
Industrial Complex) 203
VIII-4/2 Water Effluent Treatment Costs: Ethylene
Vinyl Acetate (Large Plant - Industrial
Complex) 204
XI
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LIST OF TABLES Contd
Table No.
VIII-4/3
VIII-U/4
VIII-4/5
VIII-4/6
VIII-4/7
VIII-4/8
VIII-a/9
vin-a/io
VIII-4/11
VIII-U/12
VIII-4/13
VIII-U/14
VIII-4/15
VIII-4/16
Page
Water Effluent Treatment Costs:
Fluorocarbons (Small Plant - Free
Standing) 205
water Effluent Treatment Costs:
Fluorocarbons (Small Plant - Municipal
Discharge) 206
WETC: Fluorocarbons (Large Plant -
Free Standing) 207
WETC: Fluorocarbons (Large Plant -
Municipal Discharge) 208
WETC: Polypropylene Fibers (Free
Standing Treatment Plant) 209
WETC: Polypropylene Fibers (Municipal
Discharge) 210
WETC: Polyvinylidene Chloride (Small
Plant - Industrial Complex) 211
WETC: Polyvinylidene Chloride (Large
Plant - Industrial Complex) 212
WETC: Acrylic Resins (Small Plant -
Industrial Complex) 213
WETC: Acrylic Resins (Large Plant -
Industrial Complex) 214
WETC: Cellulose Derivatives (Small
Plant - Industrial Complex) 215
WETC: Cellulose Derivatives (Large
Plant - Industrial Complex) 216
WETC: Alkyds and Unsaturated Polyester
Resins (Large Plant - Once-Through
Scrubber - Free standing) 217
WETC: Alkyds and Unsaturated Polyester
Resins (Small Plant - Recirculating
Scrubber - Municipal Discharge) 2.18
XII
-------
LIST OF TABLES Contd
Table No.
VIII-4/17
VHI-4/18
VIII-4/19
VIII-4/20
VIII-4/21
VIII-4/22
VIII-4/23
VIII-4/24
VIII-U/25
VIII-4/26
VIII-4/27
VIII-4/28
VIII-U/29
VIII-4/30
Page
WETC: Alkyds and Unsaturated Polyester
Resins (Large Plant - Recirculating
Scrubber - Free Standing) 219
WETC: Alkyds and Unsaturated Polyester
Resins (Large Plant - Recirculating
Scrubber - Municipal Discharge) 220
WETC: cellulose Nitrate (Plant in
Industrial Complex) 221
WETC: cellulose Nitrate (Plant with
Municipal Discharge) 222
WETC: Polyamides (Nylon 6/12) Pro-
duction in a complex 223
WETC: Thermoplastic Polyester Resins
(Large Plant - Industrial Complex) 224
WETC: Polyvinyl Butyral (Free Standing
Treatment Plant) 225
WETC: Polyvinyl Ether (Plant in
Industrial Complex) 226
WETC: silicones (Fluids Only - Free
Standing) 227
WETC: Silicones (Fluids Only - Indus-
trial Complex) 228
WETC: Silicones (Multi-product -
Free Standing) 229
WETC: Silicones (Multi-product -
Industrial Complex) 230
WETC: Nitrile Barrier Resins (Plant
in Industrial Complex) 231
WETC: spandex Fibers (Plant in
Industrial Complex) 232
Xlll
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LIST OF TABLES Contd
Table No. Page
VIII-5/1 Industrial Waste Treatment Model Data
Synthetic Polymers Production 233
VIII-5/2 Industrial Waste Treatment Model Data
Synthetic Polymers Production 234
VIII-5/3 Industrial Waste Treatment Model Data
Synthetic Polymers Production 235
IX-1 COD/BOD5 Ratios 240
IX-2 Demonstrated Waste Water Flows 244
IX-3 Variability Factors for BOD5 247
IX-U Best Practicable Control Technology
Currently Available Effluent Limita-
tions Guidelines 248
IX-5 Best Practicable Control Technology
Currently Available Effluent Limita-
tions Guidelines (Other Elements
and Compounds) 250
X-1 BATEA Waste Water Flow Rates 256
X-2 Variability Factors BATEA 257
X-3 Best Available Technology Economically
Achievable Effluent Limitations Guide-
lines 258
X-4 Best Available Technology Economically
Achievable Effluent Limitations
Guidelines (Other Elements and Compounds) 260
XI-1 Lowest Demonstrated Waste Water Flows 262
XI-2 Best Available Demonstrated Technology
New Source Performance Standards 264
XI-3 Best Available Technology Economically
Achievable Effluent Limitations
Guidelines 266
XIV-1 Metric Units Conversion Table 285
xiv
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SECTION I
CONCLUSIONS
In this segment of the plastics and synthetics industry,
approximately 160 company operations are responsible for the
manufacture of products which have been grouped into fifteen
product subcategories. Annual production for the fifteen
products was estimated to be 1.2 million kkg (2,6 billion
Ibs) per year or about one-tenth of the volume of the
eighteen larger-volume resins surveyed earlier. The volume
of effluents currently discharged was estimated to be 90
thousand cu m/day (24 MGD) . Water usage (at current
hydraulic loads) was projected to increase at 10 percent per
year through 1977, while production was projected to
increase at 14 percent in the same period.
For the purpose of setting effluent limitations guidelines
and standards of performance, the industry parameters giving
the most effective categorization were found to be waste
water characteristics, specifically, raw waste load, with a
BOD5 value of more than or less than 10 kg/kkg of product
separating high and low waste load subcategories; and
attainable BOD5 concentrations as demonstrated by plastics
and synthetics plants using technologies which are defined
herein as the basis for BPCTCA. Three groupings were
defined with average effluent concentrations under 20
mg/liter (low attainable BOD5 concentration) , from 30 to 75
mg/liter (medium attainable BOD5 concentration), and over 75
mg/liter (high attainable BOD5 concentration.
Based on these two dimensions of categorization, four major
subcategories were defined.
Major Subcategory I - low waste load, low attainable
BOD5 concentration (4 products: ethylene vinyl
acetate, polytetrafluoroethylene, polypropylene fiber,
and polyvinylidene chloride).
Major Subcategory II - high waste load, low
attainable BOD5 concentration (2 products:
acrylic resins and cellulose derivatives).
Major Subcategory III - high or low waste load,
medium attainable BOD5_ concentration (7 products:
alkyd and unsaturated polyester resins, cellulose
nitrate, polyamides, saturated thermoplastic
polyesters, polyvinyl butyral, polyvinyl ethers,
-------
and silicones).
Major Subcategory IV - high or low waste load,
high attainable BOD5 concentration (2 products:
nitrile barrier resins and spandex fibers).
Additional subcategorization within the above four major
subcategories was necessary to account for the waste water
generation which is specific to individual products and
their various processing methods. The separation of each
individual product into separate subcategories simplifies
the application of the effluent limitations guidelines and
standards of performance by providing a clearly defined
context for application of the numerical values. The
advantages of this double-layered (by waste characteristics
and by product) subcategorization appear to outweigh the
advantages that might be connected with product group
characterization alone.
Annual costs of treatment for the synthetic polymer segment
of the plastics and synthetics industry were estimated at
$1.8 million. By 1977, under BPCTCA guidelines and assuming
full payment of user charges by this industry for municipal
treatment, it was estimated that the synthetic polymers
industry segment should expect annual costs of $5.0 million
- an increase of 23 percent per year. By 1983, under BATEA
guidelines, existing plants would be expected to have annual
pollution control costs of $12.0 million - an increase of 20
percent per year between 1977 and 1983. By 1977, under
BADT-NSPS and projected product growth, the annual costs for
new plants are estimated at $3.3 million. The estimated
average cost of treatment over the industry for BPCTCA,
BATEA, and BADT-NSPS technologies respectively was: $0.16
($0.63), $0.t»0 ($1.52), and $0.17 ($0.66) per cubic meter
(per thousand gallons).
The average range of water pollution control costs under
BPCTCA was estimated at 0.3 to 1.3 percent of current sales
price. On average, the range of costs for applying BATEA to
existing plants was 0.6 to 3.3 percent of sales price. The
cost of BADT-NSPS was estimated at 0.5 percent of sales
price over the fifteen product groups.
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SECTION II
RECOMMENDATION S
BOD!5r COD, and total suspended solids and pH are recommended
as the critical parameters requiring effluent limitations
guidelines and standards. Other pollutant parameters are
specific to product subcategories as indicated in the
following list. Some of these pollutants are identified as
being of potential concern, and others as being ones for
which effluent limitations guidelines and standards are
recommended.
Subcategory
Alkyd compounds and
unsaturated polyester
resins
Pollutant
Parameters
lead
cobalt
Guidelines
Recommended
Polytetrafluoroethylene fluorides
Spandex fibers
x
x
Acrylic resins
Polypropylene fibers
Nitrile barrier resins
Polyamides
Cellulose derivatives
Cellulose nitrate
Silicones
cyanides
oils and grease
organic nitrogen
oils and grease
oils and grease
phosphates
organic nitrogen
cyanides
organic nitrogen
inorganic nitrogen
inorganic nitrogen
polychlorinated organics
copper x
fluorides
Polyvinylidene chloride polychlorinated organics
Polyester resins
(thermoplastic)
cobalt
manganese
cadmium
-------
Effluent limitations guidelines and standards of performance
are proposed for those parameters noted above as based on
analogy with other industries, since there were insufficient
data available to determine the magnitude of the raw waste
loads or their concentration in treated waste waters.
However in most cases where metals are used, the combination
of neutralization and biological waste water treatment is
expected to reduce or remove them to low concentrations
which are within the recommended guidelines. In the case of
mercury, cyanides, and cadmium the standards for toxic and
hazardous chemicals should apply.
Best practicable control technology currently available
(BPCTCA) for existing point sources is based on the
application of end-of-pipe technology at the production site
or the utilization of municipal sewage treatment by
facilities with appropriate pretreatment methods. End-of-
pipe technologies are considered to be based on biological
treatment systems for BOD5 reductions (typified by the
activated sludge process, trickling filters, aerated
lagoons, aerobic - anaerobic lagoons, and so on) . These
biological systems are presumed to be preceded by
appropriate treatment such as equalization basins to dampen
shock loadings, settling, clarification and chemical
treatment for removal of solids and adjustment of pH, and
subsequent treatment such as clarification or polishing
ponds for additional removal of BOD5 and suspended solids.
Also, in-plant application of technologies and operational
methods which may be helpful in meeting BPCTCA standards
include segregation of process contact waste waters from
noncontact water, elimination of direct condensers, control
of leaks, minimization of housekeeping water usage and
establishment of nonwater using housekeeping practices.
Best available technology economically achievable (BATEA)
for existing point sources is based on the best in-plant
practices of industry which minimizes the generation of
waste water pollutants. These are typified by complete
segregation of contact process waters from noncontact waste
water, maximum recycle and reuse of treated waste water,
elimination of all possible contact of water with the
processes (for example, by the elimination of barometric
condensers), preventing leaking materials from getting into
waste water streams, and the application of other methods of
removing pollutants (such as the reduction of COD through
the use of adsorptive floes, granular media filtration,
chemical treatment, or activated carbon) . In some
instances, preventing wastes from becoming waterborne
-------
results in small volume, highly concentrated streams which
can be treated selectively or incinerated.
Best available demonstrated technology (BADT) for New Source
Performance Standards (NSPS) is based on BPCTCA technologies
and the maximum possible reduction in process waste
generation and minimization of waste water flows as outlined
for BATEA. The application of granular media filtration and
chemical treatment for additional suspended solids and other
pollutant removal may be required as well as more than one
stage of biological treatment.
The levels of technology considered above as BPCTCA, BATEA,
and BADT-NSPS are the bases for effluent limitations
guidelines and standards of performance. (Tables II-l, II-
2, II-3, II-4, II-5, and II-6) . The tables are based upon
documented effluent concentrations attained by the
techniques outlined above or upon the engineering judgment
that available technologies from other industries can be
transferred to this one.
Variations in flow rates and the variabilities normally
inherent in well designed and operated treatment facilities
have been taken into consideration.
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TABLE II-I
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE EFFLUENT LIMITATIONS GUIDELINES
[kg/kkg (lb/]000 Ib) of production]
Foot-
note
No.
1
. 2
3
4
5
6
7
8
9
10
ii
12
13
14
Sub category
Ethylene-Vinyl Acetate Copolymers
Folytetr£fluoroethylene
Polypropylene Fiber
yolyvinylldene Chloride
Acrylic Resins
Cellulose Derivatives
Alkyds and Unsaturated Polyester Eeains
Cellulose Nitrate
Polyanides (Nylon 6/12 only)
Polyester Resins (thermoplastic)
Polyvinyl Butyral
Polyvlnyl Ethers
Silicons
Fluid
Greases, Emulsions,
Rubbers, Resins
Coupling Agents
Ultrile Barrier Resina
BOD
Maximum Average of Maximum for Anv
Daily Values for Any One Day
Period of Thirty
Consecutive Days
0.20 0.39
3.6 7.0
0.40 0.78
No numerical guidelines-sec discussion
in footnote
ii ii
"
0.33 0.60
14 26
0.66 1.20
0.78 1.4
No numerical guidelines-sea discussion
in footnote
it t«
1.0 1.9
13.2 "
8.2 15
No numerical guidelines-see dia -
CUSSion in footnote
SUSPENDED SOUDS
Maximum Average of Kaxiffiun for Any
Daily Values for Any Otve Bay
Period of Thirty
Consecutive Davs
0.55 1.0
9.9 18.0
1.1 2.0
No numerical guidelines-see discussion
la footnote
..
0.22 0.40
9.4 17
0.44 0.30
0.52 0.95
No numerical guidelines-see discussion
in footnote
"
0.69 1-25
8.8 It
5.4 10
No numerical guidelines-see dis-
15
Spandex Fibers
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TABLE II-2
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE EFFLUENT LIMITATIONS GUIDELINES
(Other Elements and Compounds)
Product
Parameter
kg/kkg (lbs/1000 Ibs of production)
Maximum average of daily
values for any period of
thirty consecutive days
Maximum
For Any
One Day
Alkyds and unsaturated
polyester resins
Mercury
Polytetrafluoroetbylene Fluorides
Spandex fiber Cyanides
Nitrile barrier resins Cyanides
Polypropylene fibers Oils & grease
Silicones
Fluids
Toxic and hazardous chemicals guidelines to apply
0.6 1.2
Toxic and hazardous chemicals guidelines to apply
Copper
0.5
0.005
1.0
0.010
Greases, Emulsions,
Rubbers and Resins Copper
Coupling Agents Copper
Polyester resins Cadmium
(Thermoplasti c)
0.067
0.042
0.13
0.084
Toxic and hazardous chemicals guidelines
to apply
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TABLE II-3
BiST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE EFFLUENT LIMITATIONS GUIDELINES
[kg/kkg (lb/1000 Ib) of production]
Foct-
r.ot«
So.
1
2
3
A
5
j
B
CO,
•°
12
13
14
15
Subcategory
Ethylene-Vinyl Acetate Copolyoers
Polytetr«fluoro«thylen«
Polypropylene Fiber
PMyvinylidere Chloride
Acrylic Resins
Colluiose Nitrate
?clyaai,!es (Nylon 6/12 only)
Polyester Resins (thermoplastic)
Pclyvinyl Ethers
SilLcones
Fluid
Greases, Euldons,
Rubbers, Resins, and
Coupling Agents
Nitrile Barrier Resins
Spaadex Fibers
gpj)
Maximum Average of Maximum for Any
Dally Values for Any One Day
Period of Thirty
Consecutive Davs
0.19
2.2
0.22
No numerical guidelines-see
in footnote
0. 10
6.9
0.37
0.44
in footnote
0.57
6.4
No nuaerical guidelines-see
in footnote
"
0.29
3.3
0.33
discussion
0.14
9.4
0.50
0.59
"
0.28
8.8
discussion
"
COD Sl'srEMiD' SOL;3S
Maximum Average of Maximum for Any Maxiaura Avernge of Maj:}-ui f:r A">
Dally Values for Any One Day Daily Vnluc? fcr Any Coe L'-;y
Period of Thirty Period of Thirty
Consecutiye Davs Crn^i'cut ivc IV.v~
1.65
4.0
0.40
No numerical
0.52
34
1.9
2.3
No numerical
3
33.4
No numerical
l.U °'1* 0.16
5-9 1.6 1.?
J-59 0.16 C':JV
gujdeliin-a-see discussion No nunerical gu: j*.-l i:> =-:-... •, - -
in footnote in ni't.'.- tv
0.74 0.03 <-••<:«
47 2.1 * f
2-6 o.n «->J
3.1 0.14 Cjt
guidelines-see discussion No numerical guid-'.-i i •:^-~ •'•<:• .. - :
in footnote in Is ir.i. tt
4 0.21 0.18
*5'5 2.0 2.3
guidelines-see discussion No numerical gu;dolir.cs-s*:t: J; ;•
in footnote in footnote
*l M "
-------
TABLE II-4
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE EFFLUENT LIMITATIONS GUIDELINES
(Other Elements and Compounds)
Product
Spandex fibers
Nitrile barrier resins
Polypropylene fibers
Silicones
Fluids
Greases, ^mulsions,
Rubbers, Resins and
Coupling Agents
Polyester resins
(thermoplas tic)
Parameter
Alkyds and unsaturated
polyester resins
Mercury
Polytetrafluoroethylene Fluorides
Cyanides
Cyanides
Oils and grease
Copper
Copper
Cadmium
kg/kkg (lbs/1000 Ibs of Production)
Maximum average of daily Maximum
values for any period of For Any
thirty consecutive days One Day
Toxic and hazardous chemicals guidelines to apply
0.6 1.2
Toxic and hazardous chemicals guidelines to apply
0.092
.0026
0.18
.0052
.029 .058
Toxic and hazardous chemicals guidelines to apply
-------
TABLE II-5
BEST AVAILABLE DEMONSTRATED TECHNOLOGY NEW SOURCE PERFORMANCE STANDARDS
[kg/kkg (lb/1000 Ib) of production]
Foot-
note
Bo.
1
2
3
4
5
6
7
£ 0
10
11
12
13
14
IS
Subcstegory
Ethylene-Vinyl Acetate Copolymers
Poly tetrafluoroethy lens
Polypropylene Fiber
Polyvlnylidene Chloride
Acrylic Resins
Cellulose Derivatives
Alkyds and Unsaturated Polyester Resins
Cellulose Nitrate
PoIysMides (Hrlon 6/13 only)
Polyester Resins (thermoplastic)
Polyvinyl Butyral
Polyvinyl Ethers
Silicon**
Fluid
Creases, Emulsions,
Rubbers, Resins, and
Coupling Agent*
Hltrlle Barrier Eeains
Spudex fibers
BOD,
Maximum Average of Maximum for Any
Dally Values for Any One Day
Period of Thirty
Consecutive Days
0,18
0.80
0.04
No numerical guldellaes-see
In footnote
**
»
0.02
6.0
0.37
0.44
No numerical guidelines-see
.57
e C
J « J
No nu-wrical guide lines- a e»
in footnote
n
0.35
1.60
0.08
discussion
"
"
0.03
11
0.67
0.80
discussion
1.0
10
di«cu«lon
n
COD
Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Pays
1.8 3.5
1.4 2.9
0.07 0.14
Mo numerical guidelines-see discussion
in footnote
M It
.,
00.11 0.20
30 54
1.9 3'*
6.5 12
No numerical guidelines-see discussion
In footnote
4.7 8.5
45 82
No numerical guidelines-see discussion
In footnote
Suspended Solids
Minimum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Days
0.13
0.57
0.03
No numerical guidelines-see
in footnote
"
"
0.0 06
1.8
0.11
0.14
No numerical guidelines-see
0.18
* 7
i. '
Ho numerical guidelines-see
In footnote
»
0.19
0.83
0.04
discussion
"
"
0.008
2.7
0.17
0.20
discussion
0.26
2 5
discussion
"
-------
TABLE II-6
BEST AVAILABLE DEMONSTRATED TECHNOLOGY - NEW SOURCE PERFORMANCE STANDARDS
(Other Elements and Compounds)
Product
Parameter
kg/kkg (lbs/1000 Ibs of Production)
Maximum average of daily
values for any period of
thirty consecutive days
Maximum
For Any
One Day
Alkyds and unsaturated
polyester resins
Mercury
Polytetrafluoroethylene Fluorides
Spandex fibers
Nitrile barrier resins
Polypropylene fibers
Cyanides
Cyanides
Oils and grease
Silicones
Fluids Copper
Greases, Emulsions,
Rubbers, Resins and
Coupling Agents Copper
Polyester resins Cadmium
(thermoDlaPtic)
Toxic and hazardous chemicals guidelines to apply
0.6 1.2
Toxic and hazardous chemicals guidelines to apply
0.017
0.0026
0.034
0.0052
0.025 0.050
Toxic and hazardous chemicals guidelines to apply
-------
FOOTNOTES FOR TABLES II-l, II-3, II-5
1. Ethylene-Vinyl Acetate (EVA) Copolymer. Two of the five
known producers were contacted* All plants are located
at polyethylene production facilities. Water use and
vastewater characteristics for EVA are essentially iden-
tical to those for low density polyethylene. However*
an emulsion polymerization process Is known and produce*
a distinctly different waste load which Is essentially
that of polyvinyl acetate emulsion polymerization
reported in EPA 440/1-73/010. Both multi-plant and
municipal sewage treatment la used.
2. Polytenrafluoroethylene. Three of the seven manufacturing
plants were visited. A wide range of products are produced.
The most important is polytetrafluoroethylene (PTFE) and
these guidelines are recommended for PTFE granular and
fine powder grades only. The wastewater discharges differ
considerably depending upon the process recovery schemes
for hydrochloric acid and the disposal of selected streams
by deep well, ocean dumping or off-site contract methods.
The use of ethylene glycol in a process can significantly
affect the waste loads. Fluoride concentrations in
untreated wastewaters are generally below lev Is attain-
able by alkaline precipitation.
3- Polypropylene Fibers. Tvo of the three producers were
contacted. The volumetric flow ranges per unit of pro-
duction vary widely depending upon the type of cooling
system used. The waste loads are for plants where selec-
ted concentrated wastes are segregated and disposed of
by iandfilling, etc. Primary treatment at one plant site
was observed while the other plant discharges to a
municipal sewage system.
*• P-Ql^yJ-nxlldene Chloride. The two major manufacturers
were contacted. Both plant sites send wastewaters to
multi-plant treatment plants of which the polyvlnylidene
chloride is a snail portion. Consequently, there was
insufficient data to develop recommended guidelines.
5. Aery11^__Resj.ns^, Three of the four manufacturers were
contacted. Large numbers of product grades are produced
by bulk, solution, suspension and emulsion polymeriza-
tion. The widely varying hydraulic loads for the large
number of products In addition to treatment of the waste-
waters by multi-plant wastewater treatment facilities
prohibited obtaining sufficient meaningful data to
recoamend effluent limitation guidelines.
6. pellulose Pertvatlyes. Cellulose derivates Investigated
included ethyl cellulose, hydroxyethyl cellulose, methyl
cellulose and carboxymethyl cellulose. Wide variations
in unit flow rates for two plants producing the aame
product, differences In manufacturing techniques and the
availability of data prevented recommending guidelines.
The wastewaters from the three manufacturers are being
treated in multi-plant wastewater treatment facilities
or will enter municipal sewage systems*
7. Alkyda and Unsaturated Polyester Regjjia. Six carefully
•elected plants were visited to provide a cross-section
of the industry for size of operation, type of manufac-
turing process and wastewater treatment methods. Hydrau-
lic loads vary widely depending upon the process designs.
Similarly, raw waste loads vary widely because some
plants segragate wastes foi disposal in other manners.
Generally, the industry discharges wastewaters into
municipal sewage systems ard should continue. Also, the
type of air pollution contiol, e.g. combustion or scrub-
bing, has a significant effect on the wastewater loads.
The recommended guidelines are for plants having their
own wastewater treatment system - a very infrequent
occurrence.
9* Cellulose Nitrate, The two major manufacturers of the
four manufacturers were contacted. These wastes require
pH control and contain large amounts of nitrates. One
plant discharges to a municipal sewage system while the
other goes into a multi-plant treatment complex.
'• jPolxajBijg3• Various polyamides are produced but only
Nylon 6/12 produces significant amounts of wastewater,
e.g. Nylon 11 uses no process water. Consequently, the
guidelines are restricted to Nylon 6/12 and were develop-
ed on the basis of similarity with waste loads from
Nylon 66 production*
\Q. Poji^^er The^ There are three manu-
facturers, two of which produce poly(ethylene, terephtha-
late) in quantities less than 21 of their total thermo-
plastic production. The guidelines are recommended for
polyfethylene terephthalate) since the other product
poly(butylene terephthalate) Is produced at only one
plant and the wastewater goes into a municipal sewage
system, so no data on performance could be obtained.
11. Polyvinyl Butyral. Of three production sites,two have
processes beginning with vinyl-acetate monomer which ~~
generates much larger wastewater volumes than the pro-
cess beginning with polyvinyl alcohol. Since the manu-
facturing sites where production starts with a monomer
discharge into municipal sewage systems, there waa no
data available*. Consequently, there are no recommended
guidelines since they would be tantamount to establishing
a permit for the direct discharger production site.
12* Po 1 yviny 1___gth
-------
SECTION III
INTRODUCTION
Purpose and Authority
Section 301 (b) of the Act requires the achievement by not
later than July 1, 1977, of effluent limitations for poiut
sources, other than publicly owned treatment works, which
are based on the application of the best practicable control
technology currently available as defined by the
Administrator pursuant to Section 301 (b) of the Act.
Section 301 (b) also requires the achievement by not later
than July 1, 1983, of effluent limitations for point
sources, other than publicly owned treatment works, which
are based on the application of the best available
technology economically achievable which will result in
reasonable further progress toward the national goal of
eliminating the discharge of all pollutants, as determined
in accordance with regulations issued by the Administrator
pursuant to Section 305 (b) of the Act. Section 306 of the
Act requires achievement by new sources of a Federal
standard of performance providing for the control of the
discharge of pollutants which reflects the greatest degree
of effluent reduction which the Administrator determines to
be achievable through the application of the best available
demonstrated control technology, processes, operating
methods, or other alternatives, including, where
practicable, a standard permitting no discharge of
pollutants.
Section 301(b) of the Act requires the Administrator to
publish within one year of enactment of the Act, regulations
providing guidelines for effluent limitations setting forth
the degree of effluent reduction attainable through the
application of the best practicable control technology
currently available and the degree of effluent reduction
attainable through the application of the best control
measures and procedure innovations, operation methods and
other alternatives. The regulations proposed herein set
forth effluent limitations guidelines pursuant to Section
304 (b) of the Act for the lower volume products of the
plastics and synthetic materials manufacturing source
category.
Section 306 of the Act requires the Administrator, within
one year after a category of sources is included in a list
published pursuant to Section 306 (b) (1) (A) of the Act, to
propose regulations establishing Federal standards of
performances for new sources within such categories. The
13
-------
Administrator published in the Federal Register on January
16, 1973 (38 F.R. 1624), a list of 27 source categories.
Publication of the list constituted announcement of the
Administrator's intention of establishing, under Section
306, standards of performance applicable to new sources
within the plastic and synthetic materials manufacturing
source category, which was included within the list
published January 16, 1973.
Methodology
The effluent limitations guidelines and standards of perfor-
mance proposed herein were developed in the following manner
for this second group of specialty plastics and synthetics
that are generally produced in smaller volumes than the
first group.
Because establishing guideline limitations for one or two
plants would be tantamount to prescribing the limitations
for the plants' discharge permit and because plants with
less than one million pounds per year of production are
nearly always installed at multi-product facilities, it was
decided to include only those products being produced at
three or more plants in quantities of at least one million
pounds per year. The products were examined for categoriza-
tion on the basis of raw material, products, manufacturing
processes, raw waste characteristics, and the demonstration
or availability of waste water treatment technology.
The raw waste characteristics for each subcategory were
identified through analyses of (1) the sources and volumes
of water and waste waters emitted from the processing plants
and (2) the thermal conditions and pollutants including
toxic or hazardous substances and other constituents which
might result in taste, odor, or color problems or toxicity
to aquatic organism. The constituents within each sub-
category which should be subject to effluent limitations
guidelines and standards of performance were identified from
information on process operating conditions and data on
waste water analyses.
The types of waste water control and treatment technologies
existing in the industry were identified. This includes an
identification of each distinct control and treatment
technology for both in-process and end-of-process techno-
logies which are existent or capable of being engineered for
each subcategory. It also includes an identification of the
pollutants in terms of chemical, physical, and biological
characteristics, and the effluent concentration levels
resulting from the application of each of the treatment and
14
-------
control technologies. The problems, limitations, and
reliability of each treatment control technology were also
identified as well as the time required for implementation.
In addition, certain other nonwater environmental impacts
were discussed, such as the effects of control technologies
on other pollution problem areas (e.g., air, solid wastes,
noise, and radioactivity) . Energy demand requirements for
each of the control and treatment technologies were
developed, and the cost of applying such technology was
estimated.
The information outlined above was then evaluated to
determine what levels of waste water treatment technologies
constituted the "best practicable control technology
currently available (BPCTCA)," the "best available
technology economically achievable (BATEA)," and the "best
available demonstrated control technology, processes,
operating methods, or other alternatives." In identifying
such technologies, various factors were considered. These
include the total cost of applying the technology in
relation to the age of both the equipment and the facility
involved, the processes employed, the engineering aspects of
applying various types of control techniques through process
changes, nonwater quality environmental impact (including
energy requirements), the treatability of waste water, water
use practices, and other factors.
The data for identification of industry segments, analyses
of waste water generation rates, evaluation of process
control technology and determination of waste water
treatment technologies were developed from a number of
sources. These sources included public information from the
U.S. EPA research and development efforts, data from permits
filed under the 1899 Refuse Act permit program, records of
selected state agencies, published literature, surveys of
waste water treatment practices by the Manufacturing
Chemists Association and by EPA contractors, qualified
technical consultants, interviews with industry personnel,
and on-site inspection of manufacturing processes and waste
water treatment facilities. References used in developing
guidelines for effluent limitations and standards of
performance of new sources reported here for this segment of
the plastics and synthetics industry are essentially the
same as those reported in EPA 4UO/1-73/010 (16) and are
listed in Section XIII of this document. Because this
segment of the industry represents generally less well known
and smaller volume products, significant amounts of
information on manufacturing processes were obtained from
the companies and are included in files developed to support
this Development Document.
15
-------
General Description of the Industry
The plastics and synthetics industry is composed of three
separate segments: the manufacture of the raw materials or
monomers, the conversion of these monomers into a resin
plastic material, and the conversion of the plastic
materials into products such as toys, synthetic fiber,
packaging film, adhesives, and so on. The development
document for the first group of plastics and synthetics (EPA
440/l-73/010a) was concerned primarily with the manufacture
of the basic plastic or synthetic resins (SIC 2821);
however, also included were the production of synthetic
fibers such as nylon (SIC 2824), man-made fibers such as
rayon (SIC 2823), and cellulose film or cellophane (SIC
3074). The first industry grouping dealt with 16 of the
major resins, most of the major synthetic fibers, and all of
the cellulose fibers and cellophane film, that is, over 90
percent of the total volume of the industry. Consequently,
this group of plastics and synthetic products deals with the
remaining less than 10 percent of the industry. The large
number of products (45) encompassed in this segment of the
industry is indicated in Table III-l, which lists the
plastics and synthetics fibers to be considered in the
second phase of the work on development of effluent
limitations guidelines and new source performance standards.
The total production of this segment of the industry is
approximately 1.2 million kkg (2.6 billion Ibs) of which
approximately 0.7 million kkg (1.5 billion Ibs) is accounted
for in the production of unsaturated polyesters by over 40
producers. The remaining products are generally produced by
less than four manufacturers. Because many of the products
are manufactured to end use specifications, it is not
possible to categorize the industry commercially except in a
very general way, such as price range, size product, size of
market, or potential growth. From a commercial point of
view, this segment of the synthetics and plastics industry
can be divided into four generally distinct groups. The
first group is the relatively new, high performance, low
volume and high priced materials, e.g., selling generally at
over $6.60/kg ($3.00/lb)r such as chlorinated polyethers,
methyl pentene, phenoxy resins, parylene phosphonitrilic
resins, polyaryl ether, polybenzothiazoles, polyethylene
amines, polybenzimidazoles, polyimides, polymethyIpentene,
polyphenylene sulfide, poly alpha-methyl styrene, and
polyvinyl carbazol. A second group is the older materials
which have a significant market and, being medium priced,
are generally produced by a limited number of companies.
These are the cellulosics, polyvinyl butyral, diallyl
phthalates, polytetrafluoroethylene, silicones,
16
-------
pyrrolidines, and vinylidene chloride. A relatively new and
fast growing third group encompasses ionomers, nitrile
barrier resins, polyphenylene oxide, and polybutenes. The
fourth group is those relatively large volume resins which
can anticipate good growth such as methacrylates,
polyesters, polycarbonates, and ethylene-vinyl acetate.
17
-------
TABLE II1-1
PLASTICS AND SYNTHETICS FOR CONSIDERATION
Alkyd Molding Compounds
Amine Resins
Cellulose Acetate Butyrate
Cellulose Acetate Propionate
Cellulose Butyrate
Cellulose Nitrate
Cellulose Propionate
Chlorinated Polyethers
Chlorinated Polyethylene
Diallyl Phthalate Compounds
DuPont Nitrile Barrier Resins (NR-16)
Ethyl Cellulose
Ethylene-Vinyl Acetate
Fluorocarbons
CTFE (Kel-F) Chlorotrifluoroethylene
FEP
TFE - Teflon Polytetrafluoroethylene
PVDF - Polyvinyldifluoride
lonomers. Acrylics - Surlyn
LOPAC (Monsanto) + BAREX (Sohio) (Nitrile Barrier Resin)
Methyl Cellulose
Parylene (U.C.)
Phenoxy Resins
Phosphonitrilic Resins
Polyallomer (PE/PP Copolymer)
Poly-alpha-methyl Styrene
Polyamides
Polyaryl Ether (Arylon)
Polybenzimidazoles
Polybenzothiazoles
Polybutene
Polycarbonate
Polyethylene Imines
Polymethacrylonitrile Resins
Polymethylacrylate
Polymethyl Pentene (ICI's TPX)
Polyphenylene Oxides (Noryl)
Polyphenylene Sulfide (Ryton-Phillips)
Polypropylene Fibers
Polysulfones
Polyvinyl Butyral
Polyvinyl carbazoles
Polyvinyl Ethers
Polyvinyl Pyrrolidone
Silicones
Unsaturated Polyesters
18
-------
The basis for selecting products from this segment of the
industry for the development of effluent limitations
guidelines was set as follows: at least 454 kg (1 million
Ibs) of the material must be produced at a single
manufacturing site, and three or more manufacturers must
produce the material. These criteria were chosen because
location or production facilities for lesser quantities
would be very difficult to establish, and developing
guidelines for products manufactured in only one or two
plants would be tantamount to writing the permits under the
National Pollution Discharge Elimination System for the one
or two plants, which is not within the scope of this work.
With these prerequisites, an extensive survey of the
following literature sources was made to determine names and
numbers of manufacturers, and production rates.
Chemical Economics Handbook, Stanford Research
Institute.
Directory of Chemical Producers, 1973, USA,
Chemical Information Services, S.R.K.
Modern Plastics Encyclopedia, 1972-1973,
Suppliers-Resins and Molding Compounds.
Plastics World. 1972-1973, Directory of the Plastics
Industry.
Chemical Horizons File, Predjcast, including
updates to July 1973 (this includes references
to journals such as chemical Week) .
Chemical Marketing Reporter, "Chemical Profile"
Section, from June 26, 1972, through July 23, 1973.
An exhaustive review of this information indicated it was
often impossible to delineate between basic producers and
distributors of compounds or products, and many
discrepancies were found in reported production capacities.
Consequently, the literature sources were supplemented with
information from both the contractor's files and direct
contact with companies in order to establish that there were
three or more plants producing a specific product or that
there were two or less producers. In those product
categories where only two producers were listed in the
original searches, the companies were contacted to ascertain
whether or not there were other producers. Where only three
producers were found originally, we contacted any companies
we were uncertain of to confirm that they were indeed basic
19
-------
producers and not distributors. Products selected for the
development of effluent limitations guidelines are listed in
Table III-2. These include 13 from the original list of
Table III-l plus the following three additional products,
which were found to meet the selection criteria and which
were not considered in the Phase I work of this contract or
by other EPA contractors:
Polyamides (other than Nylon 6 and 66)
Thermoplastic polyesters
Spandex fibers
Therefore, 29 products were eliminated between the two
lists. The principal reasons for elimination of these 29
products are summarized below.
1. Misnomer or duplicates 4
2. Families of compounds or further 5
generic groupings
3. Insufficient number of production 20
sites
TOTAL ELIMINATED 29
A short discussion of the rationale for eliminating the nine
products in categories (1) and (2) above follows.
(1) Misnomers or duplicates
Amine resins - not a meaningful designation for
a specific or generic group of products.
Cellulose butyrate - not an article of commerce -
probably meant to apply to cellulose acetate
butyrate.
Polymethacrylonitrile resins - combined with the
more general category of nitrile barrier resins.
Methyl pentene - another name for polymethyl
pentene.
(2) Families of compounds or further generic
groupings.
20
-------
The product, category "cellulose derivatives" was created by
combining methyl cellulose, ethyl cellulose, cellulose
propionate, cellulose acetate propionate, and cellulose
acetate butyrate from the original list plus two additional
materials, hydroxymethyl cellulose and carboxy methyl
cellulose (CMC). This category was established because the
total production of these cellulose derivatives was judged
to be important for the development of effluent limitations
guidelines, although none of the individual products is made
by more than two companies. These products are regrouped
below into general processes and the specific products are
shown.
21
-------
TABLE III-2
PRODUCTS TO BE CONSIDERED FOR DEVELOPMENT OF
EFFLUENT GUIDELINE LIMITATIONS
Acrylic resins
Alkyd molding compounds
Cellulose derivatives
Cellulose nitrate
Ethylene-vinyl acetate copolymers
Nitrile barrier resins
Polyamides (other than Nylon 6 and 66)
Polyester resins (thermoplastic)
Polyester resins (unsaturated)
Polypropylene fibers
Polytetrafluoroethylene
Polyvinyl butyral
Polyvinyl ethers
Polyvinylidene chloride and copolymers
Silicones
Spandex fibers
22
-------
Derivative
Alkali Processes
(a) methyl cellulose,
(b) ethyl cellulose,
(c) carbomethyl cellulose,
(d) hydroxyethyl cellulose
Acid Processes
(e) cellulose acetate butyrate,
(f) cellulose acetate propionate,
(g) cellulose propionate
Items (a) through (d) are made by dissolving cellulose in
alkali and reacting with CH3C1, C2H5C1, C1CH2COOH or C~,C
respectively NaCl being in most cases the biggest by-
product. The esters (e) through (f) are synthesized in acid
medium, rather than alkali, using acetic, propionic and/or
butyric acids.
Nitrile barrier resins were chosen as the generic grouping
for the following products:
DuPont's NR-16 (R)
Monsanto*s Lopac (R)
Sohio1 s Barex (R)
Although these products are only produced in limited
quantities at the present time, they are believed to be
potentially large volume products,
(3) Insufficient number of production sites.
The remaining 20 products were eliminated from consideration
because no more than two manufacturing plants could be found
or because they are manufactured in less than one million
pounds per year quantities at a plant. The products are
listed in Table III-3.
23
-------
TABLE III-3
PRODUCTS ELIMINATED FROM CONSIDERATION
FOR ESTABLISHMENT OF EFFLUENT GUIDELINE LIMITATIONS
Product
Chlorinated Polyethers
Chlorinated Polyethylene
Diallyl Phthalate Compounds
lonomers
Parylene
Phenoxy Resins
Phosphonitrilic Resins
Polyallomer
Poly-alpha-Methyl styrene
Polyaryl Ethers
Polybenzimidazoles
Polybenzothi azoles
Polybutylene (called polybutene
in Table I)
Polycarbonates
Polyethylene Imine
Polymethyl Pentene
Polyphenylene Oxides
Polysulfone
Polyvinyl Carbazole
Polyvinyl Pyrrolidone
Urethane Prepolymers
24
-------
In addition, three of the original product names were
changed, i.e., (1) polybutenes are more correctly listed as
polybutylenes (in the plastics and synthetics field
polybutenes are tars whereas polybutylene is a specific
isomer of polybutylene used in film and pipe formation) , (2)
poly (vinyl and vinylidene) chloride was reinterpreted to
mean polyvinylidene chloride since effluent limitations
guidelines for polyvinyl chloride were developed in the
Phase I study, and (3) polymethyl methacrylate was placed
into the more generic category "acrylic resins."
Those companies which were determined to be manufacturers
(not suppliers or distributors only) of the products
selected for consideration in the development of effluent
limitations guidelines are shown in Table III-4.
Product and Process Technology
Brief descriptions of the chemical nature of the products
and the manufacturing process technology are presented in
this section with special emphasis on indicating those
process operations which generate waste waters. These
descriptions are presented in alphabetical order for the
products regardless of whether guidelines are established or
not. In some instances the only available information was
from patents and the literature since manufacturing
processes remain proprietary; in some instances no
information was available.
25
-------
TABLE III-4
MANUTACTURERS OF PRODUCTS TO BE CONSIDERED FOR DEVELOPMENT OF EFFLUENT LIMITATION GUIDELINES
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^
•«
B
rt
rH
^3
0)
<
1 Electric
rt
l-i
0)
C
-------
Acrylic Resins
Polymers have been produced commercially from a wide variety
of different esters of both acrylic acid and methacrylic
acid. Specialty plastics have been produced from 2-
haloacrylic esters and 2-cyanoacrylic esters. In recent
years the production of methacrylate polymers has exceeded
production of acrylic polymers. Since production methods
are similar, methyl methacrylate polymers will be discussed
here as representative of the acrylate resins.
Methacrylic acid, CH2 C(CH3)COOH, can be considered as the
parent substance from which methyl methacrylate monomer and
poly (methyl methacrylate) and all other methacrylate com-
pounds are derived. In one process, methyl methacrylate
monomer is manufactured starting with acetone cyanohydrin
and 98 percent sulfuric acid. The methacrylamide sulfate
formed as an intermediate is not isolated but reacts with
methanol to produce methyl methacrylate. Both steps are
carried out continuously. The reaction sequence is shown in
Figure III-l, Equation 1.
Polymerization of methyl methacrylate produces poly(methyl
methacrylate). The clarity, outstanding weather resistance,
light weight, formability, and strength of poly(methyl
methacrylate) have led to extensive use of acrylic plastics
in aircraft glazing, signs, lighting, construction, trans-
portation, appliances, and merchandising. Because of
excellent suspending, rheological, and durability character-
istics, acrylic emulsions have wide use in paints for
exterior and interior applications on wood, masonry, metals,
etc.
Manufacture - Monomer is delivered to the polymerization
manufacturer usually in tank car quantities. Low concen-
tration (5-15 ppm) of inhibitor is often adequate for safe
handling and storage of methyl methacrylate. Low inhibitor
content is desirable, since subsequent polymerization
without first removing the inhibitor is possible.
The polymerization of methyl methacrylate shown in Figure
III-l, Equation 2, may be conducted in a variety of ways.
In commercial casting of sheets of poly(methyl methacrylate)
each sheet is cast in a mold assembled from two sheets of
plate glass spaced apart at the edges by a gasket (see
Figure III-2). The mold is filled by pouring in a charge of
monomer with exact amounts of catalyst, colorant if desired,
or other additives for special effects. The closed mold
then goes through a controlled temperature cycle, generally
27
-------
(1)
(CH3)2C(OH)(CN) + H2SO4 CH2 = C(CH2 )CONH2 • H2S04
CH2 =C(CH2)CONH2 • H2SO4 + CH2OH —CH2 = C(CH2 )COOCH3 + NH4HSO4
(2) n
PPiOTH
1
_ CH3 _
COOCH3
pu p
— onT — *-* — ^— — ^~
OH ^
n
(where n is 500 to 3000)
FIGURE 111-1 TYPICAL REACTIONS TO FORM POLY (METHYL METHACRYLATE)
INCLUDING MONOMER MANUFACTURE
28
-------
REUSED MOLDS
MONOMER _
MIYIMf! _^_to*
f ATAI Y'lT
ADDITIVES
PARTING
AGENT
J
1 '
,.A. n POLYMERIZATION
MOLD » BATH OR
FILLING QVFW
i
AIR
OR
WATER
(CONTROLLED
I
CAST
SHEET
PRODUCT
i
MOLD
CLEANING
\
WASTE
WATER
TEMPERATURE)
FIGURE 111-2 ACRYLIC RESIN PRODUCTION - BULK POLYMERIZATION PROCESS
-------
between 40 and 75°C (113 and 158°F). Annealing often
follows the casting process.
Homo- and copolymers can also be conveniently prepared by an
emulsion technique. In a representative procedure shown in
Figure III-3, methyl methacrylate is emulsified with an
anionic emulsifier and deionized water containing a little
ferrous sulfate and ammonium peroxysulfate. The emulsion is
flushed with nitrogen and then treated at 20°C (68°F) with
small quantities of sodium metabisulfite and t-butyl
hydroperoxide. The temperature rises spontaneously to 70°C
(158°F) and the polymerization is completed at this
temperature in about 15 minutes. After the batch is cooled
to room temperature, the product typically contains 35
percent total solids with a viscosity of about 6 cp and a pH
of 2.5.
In suspension as well as in emulsion polymerization, water
is used as a heat transfer medium in the reaction zone, but
the methods differ in the state in which the polymer is
obtained. Suspension polymerization (see Figure III-U)
yields discrete beads, granules, or particles ranging in
size from a few microns to a fraction of an inch in
diameter.
With water as the reaction medium, the following factors
have to be controlled for successful suspension
polymerization methods:
1. The initiator should be soluble in the monomer and
insoluble in water. This prevents the
polymerization from occurring in the aqueous phase
and is especially necessary when the monomer is
appreciably soluble in water.
2. Suspending agents may be used to prevent droplet
contact and merging and to aid in the suspension of
polymerizing droplets. Such agents may be soluble
products such as cellulose derivatives, starches,
gums, and salts of acrylic polymers; polyvinyl
alcohol, or they may be insoluble materials such as
clay or talc. Thickeners such as polyoxyalkylene
derivatives may also be present to prevent droplet
contact.
3. Inorganic salts are often added to increase the
density of the aqueous medium, to reduce the water
solubility of the monomers, and to increase the
interfacial tension of the system.
30
-------
VENT
MONOMER
HOLD
TANK
MIX
TANK
AIR POLLUTION r
DEVICES L
WATER
SCRUBBER
ADDITIVES
REACTION
KETTLE
WASTE
WATER
FILTER
WASHING
VENT
DRIED
MOLDING
POWDER
EMULSION
PRODUCTS
FIGURE 111-3 ACRYLIC RESIN PRODUCTION -EMULSION POLYMERIZATION PROCESS
-------
ACRYLIC
MONOMERS
.COOLING WATER
-DRIVER
INITIATOR,
GRANULATING AGENT,-
MISC. ADDITIVES
WATER
WATER
WATER
POLYMERIZATION
•DEMIN. WATER
RECYCLE
TO EXTRUDERS
COOLING WATER* STEAM
•*• RIVER
CENTRIFUGE
DEMIN. WATER
DRYING
•COOLING WATER'
•RIVER
-^-ACRYLIC BEAD POLYMER
EXTRUSION
I
• WATER
ACRYLIC MOLDING POWDER
•* NON-CONTACT WATER
FIGURE 111-4 ACRYLIC RESIN PRODUCTION - SUSPENSION
POLYMERIZATION PROCESS
32
-------
Waste Water Generation - The primary waste water streams are
obvious from inspection of the process schematic diagram.
Upon cooling, the polymer product is washed, usually within
the cooling vessel, and the water or brine leaving this
vessel will be contaminated with some monomer, some polymer,
and the various stabilizing, emulsifying, and chain-
regulating agents as well as the catalyst. Final dewatering
occurs in the centrifuge, and the waste water stream from
this equipment will contain the same type of contaminants
listed above.
If the monomer is assumed to be present at its saturation
concentration in the wash water, it will comprise
approximately 1.5 percent in the waste stream. If two
volumes of water per volume polymer are used to wash the
product beads, then 1335 mass units of water will be
released per 1000 mass units of polymer product (spec. gr. =
1.5).
There is no water of reaction for the polymerization of
methyl methacrylate (25) .
Other Pollutants
Oil and grease are due to the presence of lubricants used
for the extrusion process. Depending on the specific waste
water chemical conditions and the analytical methods used,
cyanides may be detected due to the presence of cyanoacrylic
esters and acetone cyanohydrin.
33
-------
Alkyd Molding Compounds
Alkyd molding compounds are mixtures of unsaturated
polyester or polyalkyd resins with various fillers and
additives which are incorporated to obtain the specific
physical characteristics required for the compression
molding of parts. The terms alkyd and polyester are often
used interchangeably, and indeed alkyds are chemically very
similar to unsaturated polyesters (see Unsaturated Polyester
Resin section of this report). The primary difference is
that in alkyds the acid component is supplied by long chain
unsaturated acids rather than the phthalic and maleic
anhydrides which are used in unsaturated polyesters. The
primary use of alkyd resins is for paint formulations, but
they are also used in molding compounds. The alkyds used
for paints are often made in the same plant as unsaturated
polyesters. When used for paints, the alkyds are diluted
with the appropriate paint solvent and sold as a liquid in
drums. In this form they contain no monomeric reactive
diluent.
Manufacture - Alkyd molding compounds are sold in the form
of free flowing powder, gunk, and pastes. They are usually
prepared in two steps. The resin producer carries out the
polymerization and sometimes adds a reactive diluent, such
as diallyl phthalate or styrene, and sells the resin to a
compounder in liquid form. The compounder then adds the
appropriate fillers such as glass, fiber, asbestos, clay,
calcium carbonate or alumina, and packages the alkyd molding
compound in a form appropriate to be sold to a molder. The
process description and guidelines developed for the resin
manufacturer should be applicable to the manufacture of the
liquid alkyd resins which are used to make molding compounds
as well as for alkyds for paints (which are not covered by
this study) and unsaturated polyester resin manufacture.
Waste Water Generation - Waste water production in the poly-
merization process is similar to that described in the
section on Polyester Resins. The compounding steps are all
mechanical and do not generate liquid waste
34
-------
Cellulose Derivatives
This group of materials includes ethyl cellulose, methyl
cellulose, carboxymethyl cellulose, and hydroxyethyl cellu-
lose. All are ethers of cellulose.
The first three of these derivatives are made by reaction of
an alkyl chloride — ethyl chloride, methyl chloride, and
chloracetic acid — with cellulose. Hydroxyethyl cellulose
is made by reaction of ethylene oxide with cellulose.
Several of the commercial grades of methyl cellulose are
mixed ethers, made by reaction of propylene oxide as well as
methyl chloride with cellulose. Equations (1) through (4) in
Figure III-5 express the general reactions involved.
All of the reactions are run using alkali cellulose — a
mixture of cellulose with sodium hydroxide. In the course
of the reactions involving alkyl halides ±(1), (2), (3)1,
the alkali is neutralized by formation of sodium chloride.
This salt, and excess alkali, must be removed from some of
the products to provide materials that are usable.
Manufacture - Figure III-6 on the following page shows a
block flow diagram for production of cellulose ethers. The
use of a solvent in the process maintains the cellulose as a
relatively easy-to-handle slurry. Depending on the
cellulose derivative involved, the solvent may be either an
alcohol or a hydrocarbon.
Proprietary processes appear to be widely used in production
of cellulose ethers. Manufacturers refuse to discuss the
processes in any detail.
Uses of the cellulose ethers are varied. Ethyl cellulose is
a plastic. Methyl cellulose, carboxymethyl cellulose, and
hydroxyethyl cellulose are water soluble and are generally
used in applications involving water solubility. Carboxy-
methyl cellulose may be used as a suspending agent. Methyl
cellulose is used as a film former. All three ethers are
used in certain foodstuffs.
Waste Water Generation - Wastes generated in production of
cellulose derivatives constitute alkali, salt, solvent
residues, pulp, and treatment chemicals. These wastes
indicate relatively high BOD, COD, and dissolved solids
levels (41). Organic nitrogen may be present in the waste
waters of facilities where nitrogen containing cellulose
derivatives (other than cellulose nitrate) are produced.
35
-------
(1) (C6Hi0Os)n + CH3CI + NaOH methyl cellulose + NaCI + H20
(2) (C6H1005)n + C2H5CI + NaOH ethyl cellulose + NaCI +H2O
(3) (C6H10O5)n + CIC2H3O2Na+NaOH carboxymethyl cellulose + NaCI + H2O
(4) (C6H100,L + H2C-CH2 -hydroxyethyl cellulose
\ /
0
FIGURE 111-5 TYPICAL REACTIONS TO FORM CELLULOSE DERIVATIVES
36
-------
FRESH
SOLVENT
I
SOLVENT
RECOVERY
WASTE
CELLUOSE' ALKALI
REACTION
PURIFICATION
DRYING
PACKING
REACTANT
{ ETHYL CHLORIDE,
-METHYL CHLORIDE,
CHLORACETIC ACID,
ETHYLENE OXIDE)
-w-WASTE
.WASTE
FIGURE 111-6 CELLULOSE ETHERS PRODUCTIOIM
37
-------
Cellulose Nitrate
Cellulose nitrate is produced by reaction of fibrous
cellulose with a mixture of nitric and sulfuric acids. The
equation of reaction is shown in Figure III-7.
Manufacture - From the equation in Figure III-7 one may
calculate that cellulose nitrate contains 1U.1 percent
nitrogen. The commercial product contains about 12 percent
nitrogen; this level is attained by using mixtures
containing carefully controlled amounts of nitric acid,
sulfuric acid and water. These liquids are present in the
mix in the approximate proportion 1:3:0.75.
The fibrous nature of the original cellulose is essentially
unaltered by the reaction. In order to provide a commer-
cially useful product, the initially obtained nitrate is
taken through the following processes:
1. Washing with water to remove all acid.
2. Stabilization by boiling with water to remove small
amounts of combined sulfuric acid.
3. Digestion (heating in the presence of water) to
reduce viscosity of the product to a useful level.
U. Dehydration or exchange of the water, by alcohol.
The steps listed above are shown in Figure III-8, which also
indicates waste water streams.
Waste Water Generation - Aqueous wastes generated in the
manufacture of nitrocellulose constitute primarily acids
(both nitric and suit uric) and alcohol lost in the
dehydration process. Spent acids are recovered as far as
possible, but some are inevitably lost. Alcohol is
recovered and recycled. Suspended solids in the wastes
include a small amount of cellulosic material. The strongly
acidic wastes are handled by neutralization with lime. The
calcium sulfate which is formed may be removed by settling
38
-------
(C6H1005)n + 3HN03 + H2S04^n±(C6H-,02 (IMO3)3)n + H20 + H2SO4
FIGURE 111-7 TYPICAL REACTION TO FORM CELLULOSE NITRATE
39
-------
NITRICACID - AC|D M|J(
TANKS *
OLEUM >
f
SPENT ^
ACID
f
1
SPENT
ALCOHOL
RECOVERY
SI ILLS "* '
1
1
WASTE
WATER
DRYFR
\
NITRATING
POTS
1
CFNTRlFUGF
BOILING TUBS
(STABILIZATION)
1
DIGESTER
(VISCOSITY
CONTROL)
1
BLENDING
\
DEHYDRATING
PRESS
\
PACKAGING
(ALCOHOL
WET)
^.WASTE
WATER
FIGURE 111-8 CELLULOSE NITRATE PRODUCTION
40
-------
Chlorinated Polyethylene
Polyethylene may be chlorinated either in solution or more
commonly as a suspension in an inert diluent such as water,
acetic acid, or cold carbon tetrachloride. When water is
used, reaction temperatures between 50-65°C (122-1U9°F) are
used, and a suitable catalyst is necessary to establish
economic reaction rates at atmospheric pressure. Artificial
light of wavelength below U785 A and certain azo compounds
are effective for accelerating the reaction. No catalyst is
needed, however, at reaction temperatures when pressures are
greater than 7 atmospheres (100 psig) or greater. The
reaction equation is given in Figure III-9.
The chlorinated polyethylenes are currently used
commercially to improve the impact strength and
processibility of polyvinylchloride, as an elastomer having
good chemical resistance, as a blending agent with PVC in
the manufacture of floor tile, and as a blending agent in
other multi-component plastic compositions.
Manufacture - A flow chart for a typical chlorination is
shown in Figure 111-10. Feed materials are polyethylene in
hot carbon tetrachloride solution and chlorine. These are
fed into a liquid phase tubular reactor. The reaction
temperature is between 50-150°C (122-302°F) at pressures as
high as 20 atmospheres (300 psig). The reaction time for
the exothermic reaction is about 5 minutes (44). After
reaction, the polymerized product is separated from HCl, a
by-product of the reaction.
Waste Generation - The primary waste generated is the by-
product hydrogen chloride. Recovery or other disposal of
hydrogen chloride (or hydrochloric acid vapor or solution)
would be the primary environmental concern. About 590 mass
units of HCl (dry basis) would be generated per 1000 mass
units of product (5t 10, 11, 40, 44, 45).
41
-------
-f- CH2 — CH2 -b + CI2—*--(- CHCI— CH2 -b + HCI
FIGURE 111-9 TYPICAL REACTION TO FORM CHLORINATED POLYETHYLENE
42
-------
POLYOLEFIN
SOLUTION CHLORINE
SEPARATOR
HCL
PRODUCT
SOLUTION
CONDENSER
FEED MATERIALS
POLYETHYLENE
CHLORINE
kg/1000kg PRODUCT
450
1140
SOURCE; u.s. PATENT 2,954,509 BY D.M.HURT (TODUPONT)
(DECEMBER 13, 1960).
FIGURE 111-10 CHLORINATED POLYETHYLENE PRODUCTION
43
-------
Diallyl Phthalate Resins
Diallyl phthalate was one of the earliest unsaturated
polyester resins. It is a member of the allyl family of
resins. The basis for this family of resins is allyl
alcohol (Figure III-ll, Equation 1). The vinyl group in the
allyl alcohol provides the unsaturation through which
subsequent free radical initiated crosslinking or chain
extension can take place in order to cure the resin. When
allyl alcohol is reacted with phthalic anhydride, the
resulting product is diallyl phthalate (Figure III-ll,
Equation 2). This product is manufactured in the United
States by the FMC Corporation, Princeton, New Jersey.
The allyl alcohol can be condensed with either the ortho-
phthalic anhydride to produce diallyl orthophthalate
(trademark Dapon 35, FMC Corp.) or with the isophthalate
acid. The isophthalate ester is identified as Dapon M, FMC
C orporati on.
The product can be used as either a low viscosity monomer or
as a higher molecular weight thermoplastic prepolymer. The
allyl monomers and, in some cases, the prepolymers find
utility as crosslinking agents for other unsaturated poly-
ester resins, either in conjunction with or as a substitute
for styrene monomer which is the conventional reactive
diluent. The low vapor pressure at molding temperatures
(2.4 mm of mercury at 149°C or 300°F) favors the use of
diallyl phthalate over styrene, particularly for larger
parts. This low volatility permits allylic polyesters to be
molded at higher temperatures than styrene polyester, and,
as a result, faster molding cycles can be achieved (30).
Another advantage of using the allylic monomers or prepoly-
mers as the reactive diluent in unsaturated polyesters is
that they result in formulations with lower volume shrinkage
on curing.
A major use of the diallyl phthalate compounds when used by
themselves is critical electrical/electronic applications
which require a high degree of reliability under long-term,
adverse environmental conditions. Examples are electrical
connectors used in communications, computer, aerospace, and
other systems, as well as insulators, potentiometers, and
circuit boards.
Diallyl phthalate prepolymer is also used as a surfacing
medium for decorative laminates and in combination with
polyester resin systems to meet the growing demand for
economical, low pressure laminates.
44
-------
(1)
CH2 = CH-CH2 -OH
(2)
-COOCH2 CH = CH2
- COO CH2 CH = CH2
FIGURE 111-11 TYPICAL REACTIONS TO FORM DIALLYL PHTHALATE
45
-------
Manufacture - Conventional polycondensation batch reactor
type technology is used to form the diallyl phthalate.
Conventional free radical methods are used in extending the
molecular weight of the monomeric diallyl phthalate (30).
46
-------
Ethylene-Vinyl Acetate Oopolymers
Manufacture - Ethylene-vinyl acetate (EVA) copolymers with
vinyl acetate contents in the range of about 7-40 percent by
weight are manufactured in the same facilities as low
density polyethylene (LDPE) and often with high density
polyethylene (HOPE). A process flow diagram is shown in
Figure 111-12. The same equipment is used for EVA
copolymers as for LDPE except for additional facilities
needed for recovery of unreacted vinyl acetate and ethylene.
This equipment consists of a separator downstream from the
polymerization autoclave, where the solid EVA particles are
sent to the pelletizing operation and the liquid phase is
distilled to recover ethylene and vinyl acetate. The
distillate wastes consist of a waxy residue that is incin-
erated or used as fuel.
In the overall process, shown in Figure 111-12, vinyl
acetate and ethylene monomers are fed to a compressor to
build up the pressure necessary for polymerization.
Polymerization is carried out in an autoclave using a
peroxide type initiator. Following polymerization, the
pressure is reduced and the mixture of unreacted vinyl
acetate and ethylene, together with EVA copolymer, is sent
to a separator. The separated EVA copolymer is fed to an
extruder (where residual ethylene gas is removed and
returned to the compressor) which extrudes continuous
strands into a water chill bath where they are mechanically
cut into pellets. The polymer pellets are screened from the
water and spin dried.
The liquid phase from the separator is distilled for
recovery of monomers, and the final residue incinerated as
described above.
As the final process step, the EVA pellets are remelted,
combined with additives and repelletized. Examples of addi-
tives are diatomaceous earth, amides, butylated hydroxy
toluene, and various cyclic organic compounds. Since many
of the end uses for the product involve direct contact with
foods, it is produced to meet FDA requirements.
An EVA copolymer with distinctly different characteristics
from those described above is produced by an emulsion poly-
merization process. The emulsion copolymer has a very high
vinyl acetate content. It is made at only one plant, which
is unrelated to those plants using the LDPE process. The
emulsion polymerization process and associated waste water
loads are essentially the same as those reported for poly-
47
-------
PEROXIDE
INITIATOR
VINYL
ACETATE'
ETHYLENE-
COMPRESSOR
T
l
VINYL ACETATE
RECYCLE
ETHYLENE
RECYCLE
AUTOCLAVE
SEPARATOR
OIL LEAKAGE AND
SPILLS TO
PROCESS SEWER
EVA POLYMER
a 450-500°C
PLUS ENTRAINED
GASES
MONOMER
RECOVERY
OILS & WAXES
- TO BOILER
AS FUEL
ETHYLENE
RECYCLE
WET PELLETS
DRIED
EVA PELLETS
(7-40% VA byWt.)
MAKE-UP WATER
REFRIGERATION
COOLING
PURGE TO PROCESS SEWER
(VINYL ACETATE AND
POLYMER FINES
CONTAMINATION)
FIGURE 111-12 ETHYLENE-VINYL ACETATE COPOLYMER PRODUCTION
-------
vinyl acetate homopolymer emulsion in EPA Development
Document No. EPA 440/1-73/010 (61).
Waste Water Generation - In plants using LDPE equipment for
EVA production, the pelletizer cooling water is generally
recirculated through the refrigeration cooling system. A
continuous purge is maintained to control vinyl acetate and
polymer fines contamination in the recirculated water.
Vinyl acetate which enters the waste waters from the purge
stream is biodegradable both as the intact compound and in
the form of its hydrolysis products, acetaldehyde, and
acetic acid.
Other waste sources are oil leakage and spills from compres-
sors and pumps which enter area surface water drainage
ditches. Washdown water from processing and loading areas
also flows to the drainage ditches and is another source of
vinyl acetate contamination. The waste stream from the
ditches is skimmed to recover oil and EVA particles. The
oil is incinerated and the EVA is either land-filled or sold
to scrap reprocessors (16, 25) .
49
-------
Fluorocarbon Polymers
The term Mfluorocarbon polymers" as used in this report
refers to addition type polymers in which all, or a
significant portion, of the substituent groups on the carbon
atoms in the polymer chain are fluorine. Typically, the
balance of the substituents are chlorine and/or hydrogen.
The fluorocarbon polymer family encompasses a range of
homopolymer, copolymer, and terpolymer compositions as
indicated by the list shown in Table III-5. Most of the
products are in the plastics category, but elastomer grade
polymers have also been included.
Polytetrafluoroethylene (PTFE) is by far the most important
commercial polymer in this group and accounts for an
estimated 75 percent or more of the total production. PTFE
is produced in two dry product forms (granular and fine
powder) and as an aqueous dispersion. It is the only
fluorocarbon polymer produced in three different plants. In
view of the relative significance of PTFE, the process des-
criptions below have been divided to separate PTFE from the
other fluorocarbon polymers.
Practice varies widely from plant to plant in this industry.
Some plants produce only one type; more commonly several
types of fluorocarbon polymers are made at the same plant.
However, since most of the polymers are proprietary, the
product mix differs from plant to plant. All existing
plants are located within larger chemical complexes. The
practice with respect to production of monomer and monomer
feedstock varies. TFE monomer is produced on-site in all
cases. Production of other monomers and monomer feedstocks
(chlorodifluoromethane in the case of TFE) may or may not be
carried out at the same plant. From examination of
available waste load data related to production of the
various polymers and in view of the widely varying practices
from plant to plant, we have concluded that waste water
guidelines should be limited to the dominant products -
granular and fine powder grades of PTFE - and that aqueous
dispersion grade and all other fluorocarbon polymers must be
considered as unique products.
It is also characteristic of this industry that process
technology is considered highly confidential. The process
descriptions that follow, therefore, are necessarily general
in nature.
A. Polytetrafluoroethylene (PTFE)
1. TFE Monomer Process
50
-------
Since TFE monomer is produced on-site in all cases, we have
included monomer synthesis as part of the overall polymer
process.
Manufacture - TFE monomer is produced by continuous process
based on pyrolysis of chlorodifluromethane (Refrigerant 22)
as indicated by the flowsheet shown in Figure 111-13. The
main reaction involved is shown at the top of Figure III-1U.
Various other fluorinated side products may also be formed
in minor amounts.
The process stream from the reaction furnace is scrubbed
first with water, then with dilute caustic solution to
remove by-product HC1 and other soluble components. After
the caustic scrub, the gas stream is dried either with
concentrated sulfuric acid or with ethylene glycol. The dry
gas stream is compressed and distilled to recover purified
TFE monomer. Extremely pure monomer is required for
subsequent polymerization.
Waste Water Generation - The sources of waste water
generation from the TFE monomer process are indicated in
Figure 111-13. The effluent from the water scrubber is a
dilute solution of HCl. This stream is the only significant
source of fluoride discharge from the process. In general,
waste waters from TFE monomer and polymer processes do not
contain appreciable amounts of fluoride. (However, greater
amounts of fluoride are generated in the production of the
monomer precursor. Refrigerant 22.) The effluent from the
caustic scrubbers contains very dilute caustic and dissolved
salts. In those cases where sulfuric acid is used for
drying the gas stream, strong acid solution is recovered
from the drying tower. Where ethylene glycol is used for
the drying step, a small amount of glycol is lost in the
glycol recycle operation and contributes a minor BOD load in
the waste water stream.
2. PTFE Polymerization
Manufacture - Polymerization of TFE to the homopolymer,
PTFE, proceeds by free-radical addition polymerization
typical of olefins. The polymerization is carried out under
pressure in aqueous media in batch reactors. The literature
suggests initiators such as sodium or potassium peroxydi-
sulfates may be employed. The polymerization reaction is
indicated in Figure 111-14 and a generalized flowsheet of
the process is shown in Figure 111-15.
PTFE is produced for sale in several forms: a granular or
pellet form, a fine powder, and aqueous dispersion. The dry
51
-------
FURNACE
REACTOR
Oi
K)
ALTERNATIVE
DRYING
METHODS
DILUTE
HC*
GLYCOL LOSS
AQUEOUS WASTE
DISTILLATION
PURE
TFE
FIGURE 111-13 POLYTETRAFLUOROETHYLENE (PTFE) PRODUCTION - TFE MONOMER PROCESS
-------
Feedstock
Monomer
Polymers
2CHF2CI »-2HCI +
heat
(chlorodifluoromethane)
\
CF2CI-CH3 »- HCI
heat
(chlorodifluoroethane)
pr PI pr PI b»
" Metal Cat.
(trichlorotrifluoroethane)
CF2 =CF2
(TFE)
CH2 — (_,H2
(ethylene)
CF3
CF2 = CF
(HFP)
, pc pu
(VDF)
CI2 + CF: = CFCI
(CTFE)
+ CH2 =CH2
(ethylene)
. ^-fCF2-CF2-)-n
(PTFE)
»» / ri i pi i rr
(ETFE)
*--fCF2-CF2-CF2
(FEP)
0— <-CF2~CH2-CF2
(VDF-HFP)
> ( CF CH )
(PVDF)
*— (-CF2-CH2-CF2
(CTFE-VDF)
»•- <-CF,-CFCI1-n
(PCTFE)
-CF2-)-n
CF3
-CF^n
CF3
-CF+n
-CFCI-hn
»--(-CH2-CH2-CF2-CFCI4-n
(ECTFE)
HC=CH
(acetylene)
HF
(hydrogen
fluoride)
-*- CH2 = CHF
VF
-t-CH2-CHF-hn
(PVF)
Source: Chemical Economics Handbook, Stanford Research Institute.
FIGURE 111-14 TYPICAL REACTIONS TO FORM FLUOROCARBON POLYMERS
53
-------
TFE
INITIATORS
WATER STABILIZERS
1 1
BATCH
POLYMERIZATION
if i
DISPERSION
GRADE
POLYMER
RECOVERY/ WASH
1
WASH
WATER
AQUEOUS WASTE
(SUPERNATE LIQUOR)
GRANULE
EXTRUSION/
PELLETIZING
CHILL WATER
FINE
POWDER
FIGURE 111-15 POLYTETRAFLUOROETHYLENE (PTFE) PRODUCTION -
PTFE POLYMER PROCESS
-------
product forms, granular and fine powder, account for the
major portion of PTFE production. Guidelines have been
proposed for these dry product forms only. Dispersion grade
is made by only two of the three plants presently producing
PTFE.
Waste water Generation - Water is used as the polymerization
medium in producing all forms of PTFE, but subsequent
process water use and waste water discharge varies with the
form being produced. High purity, demineralized process
water is required in all cases.
For granular or pellet grades, process water use in addition
to polymerization medium includes polymer wash water and,
for pellets, chill water for extrusion/pelletizing
operations. The process water discharged from these
operations is very clean. In one plant, all the process
water is collected and recycled through a purification
system. In the production of fine powder grade PTFE, wash
water is required to purify the polymer particles. The
conditions required to produce fine powder grade are such
that the water discharged from the polymerization and
washing steps may contain a higher level of suspended and
dissolved solids than in the case of granular product.
In the production of the dispersion form of PTFE, the
polymerization batch is concentrated after addition of a
surfactant to stabilize the dispersion. The supernate
liquor from the concentrating step is discharged as a waste
stream. This stream has a BOD load due to presence of the
surfactant.
B. Other Fluor ocarbon Polymers
The nature of other fluorocarbon polymers produced is
indicated by the list presented in Table III-5. Since most
of these polymers are proprietary and process technology is
considered highly confidential, it is not possible to give
detailed process descriptions. Reactions taken from the
literature, indicating the routes to most of these polymers,
are given in Figure
The polymerization step is comparable to that used for PTFE
in that the polymerization is carried out in aqueous
(purified water) medium in batch kettles. Subsequent steps
may vary significantly with the type of polymer and form of
product made. These steps may include concentration and
stabilization of a dispersion form of the product;
filtration or coagulation to recover polymer particles;
polymer washing with water or solvent; conversion to final
55
-------
product, form by drying granules or powder, extrusion of
pellet or film forms, or solvent casting. Recovery
operations to recover organic solvents or other proprietary
additives may also be associated with some of the polymer
processes (6, 29, 30).
56
-------
TABLE III-5
COMMERCIAL FLUOROCARBON POLYMERS
Polymer Abbreviation
Polytetrafluoroethylene PTFE
Fluorinated Ethylene - Propylene FEP
Poly (ethylene - tetrafluoroethylene) ETFE
Chlorotrifluoroethylene CTFE
Poly(ethylene - chlorotrifluoroethylene) ECTFE
Poly (chlorotrifluorothylene - vinylidene fluoride) CTFE-VDF
Polyvinyl Fluoride PVF
Polyvinylidene Fluoride PVDF
Poly(vinylidene fluoride - hexafluoropropylene) VDF-HFP
57
-------
Nitrile Barrier Resins
This class of resins has assumed importance primarily
because nitrile barrier resins are transparent polymers with
good resistance to passage of gases and solvents. They are
in the early stages of being utilized for beverage
containers. The nitrile group is the source of these good
barrier properties. The nitrile group originates from the
presence of either acrylonitrile or methacrylonitrile in the
final polymeric structure. The nitrile content was
previously restricted to below 30 percent in order to
produce resins with acceptable processibility. At this
level, the barrier properties were not exceptional. Recent
developments have been in the direction of producing resins
which have higher nitrile content while still retaining
adequate processibility by conventional thermoplastic
methods (i.e., extrusion, injection molding, blow molding,
thermoforming) .
The exact details of resin composition are considered pro-
prietary by the resin manufacturers. The general structure
however may be viewed as a butadiene backbone to which
acrylonitrile/ methylaerylate or acrylonitrile/styrene
copolymers are attached by grafting.
The exact nature of the technical developments which have
resulted in this breakthrough is closely held proprietary
knowledge by the three U.S. resin suppliers competing in
this field.
Any of the generally known polymerization methods (such as
bulk, solution, or emulsion) could be used to prepare these
resins. Emulsion polymerization is undoubtedly the prefer-
red method. The final composition may result from a two-
step polymerization scheme in which a copolymer (such as
aerylonitrile/acrylate) is polymerized by emulsion
techniques in the presence of a previously formed graft
copolymer (such as acrylonitrile/ butadiene).
The polymerization scheme described below is speculative and
is based on a review of in-house information and published
literature. It is believed, however, that it is a
reasonable representation of a typical polymerization
process.
A typical polymerization procedure would involve a two-step
process in which the acrylonitrile butadiene graft copolymer
is made by batchwise emulsion polymerization of a recipe
such as that listed below (U8) .
58
-------
Typical Latex Recipe Parts A^
~~ ~ ^/J!
Acrylonitrile I3" ^ 40
1,3-butadiene 60
Emulsifier 2.4
Azodiisobutyronitrile 0.3
t-dodecyl mercaptan 0.5
Water 200
Before starting the reaction, pH is adjusted to about 8
using potassium hydroxide. Conversion of 92 percent can be
obtained in 22-1/2 hours at 45°C (113°F) giving a total
solids content of 33.1 percent.
The final resin is then prepared by mixing the following:
Latex (from reaction above) 31.9
Acrylonitrile (or methacrylonitrile) 70
Ethyl acrylate 30
Potassium persulfate 0.06
Emulsifier 3.0
n-dodecyl mercaptan 1.0
Ethylene diamine tetracetic acid 0.5
Water 200
Adjust to pH7 using potassium hydroxide. Twenty hours
polymerization time (absence of oxygen) at 60°C (140°F)
results in 97 percent conversion to 33 percent solids.
The polymer is then coagulated using aluminum sulfate,
washed and dried. At this point the dried polymer chips are
then probably densified and passed to an extruder for
processing into pellets.
Manufacture - The generalized batch process description for
emulsion polymerization shown below is taken from EPA.
Development Document No. 440/1-73/010 (16) along with a
generalized flowsheet shown as Figure III-16.
59
-------
A batch process, as shown in Figure 111-16, is commonly
used. Typical reactor size is 19 cu m (5000 gal.). The
batch cycle consists of the continuous introduction of a
water-monomer emulsion to the stirred reactor.
Polymerization occurs at about the rate of monomer addition;
the heat of reaction is removed to cooling tower water
circulated through the jacket. The reactor is vented
through a condenser for monomer recovery; and the
condensate, including any water, is returned directly to the
vessel. On completion of the batch, a short "soaking" time
is allowed for completion of the reaction, and water is then
added to dilute to the desired end composition. The batch
is drawn off through a screen to product storage. Oversize
screenings (a very small amount) are disposed of to
landfill.
Monomers, the principal raw materials, are often protected
during shipping and storage by an inhibitor, such as
catechol, which may be removed prior to polymerization by
washing. This contributes to the waste water load.
Waste Water Generation - Sources of waste water from a
typical emulsion polymerization include the following:
o Reactor cooling water
o Cooling tower and boiler blowdown
o Monomer washing
o Liquid or solid waste from monomer stripping
or recovery operations
o Discarded Latex batches
o Coagulant wastes
o Startup, spills, etc.
o Demineralizer wastes
o Possible liquid wastes from monomer scrubbing
(16, 51, 48).
Other Pollutants
Organic nitrogen occurs as a result of losses from
dissolution and emulsification of reactants.
Cyanides will be detectable by analytical
methods due to the presence of acrylonitrile.
60
-------
EMULSIFIER
PROCESS
WATER
CATALYST
i
MONOMERS'
COOLING
WATER
WASH WATER
BATCH
REACTOR
CYCLE
0*0
RECYCLED
MONOMER
WASTE
WATER
SOLID
WASTE
COAGULATION
TANK
c>o
WASTE
WATER
DRY
PRODUCT
FIGURE 111-16 NITRILE BARRIER RESIN PRODUCTION - EMULSION POLYMERIZATION PROCESS
-------
Parylene Polymers
Parylene is produced by vapor-phase polymerization and
deposition of paraxylylene (or its substituted derivatives).
The polymers are highly crystalline, straight-chain
compounds with a molecular weight of approximately 500,000.
It is extremely resistant to chemical attack, exceptionally
low in trace metal contamination, and compatible with all
organic solvents used in the cleaning and processing of
electronic circuits and systems. Although parylene is
insoluble in most materials, it will soften in solvents
having boiling points in excess of 150°C (302°F). It is
also being used for moisture barrier coatings on discrete
components such as resistors, thermistors, thermocouples,
fast responding sensing probes, and photocells.
Unlike most plastics, parylene is not produced and sold as a
polymer. It is not practical to melt, extrude, mold or
calender it as with other thermoplastics. Further, it
cannot be applied from solvent systems since it is insoluble
in conventional solvents.
Parylene polymers are prepared from di-p-xylylene and
dichlorodip-xylylene, through a process called pyrolytic
vapor deposition polymerization. Di-p-xylylene and the
chloro derivative dichlorodi-p-xylylene are white, high
melting crystalline solids. Di-p-xylylene has a melting
point of 28<4°C (543°F) and a density of 1.22 g/cm3.
Dichlorodi-p-xylylene has a melting point of 1UO-160°C (284-
320°F) and a density of 1.3. Both are insoluble in water.
The reactions are illustrated in Figure 111-17, Equation 1.
Unsubstituted di-p-xylylene can be readily purified by
recrystallization from xylene. Dichlorodi-p-xylylene is a
mixture of isomers as prepared by chlorination of di-p-
xylylene. It is not necessary to separate these isomers
since, after pyrolysis, only chloro-p-xylylene results
regardless of which isomeric dimer is used as starting
material.
The polymerization process is exceptional in that it takes
place in two completely distinct and separate steps. The
first involves the cleavage of the two-methylene-methylene
bonds in di-p-xylylene by pyrolysis to form two molecules of
the reactive intermediate, p-xylylene. This latter molecule
is stable in the vapor phase but, in the second step,
spontaneously polymerizes upon condensation to form high
molecular-weight poly(p-xylylene) .
62
-------
(1)
X = H
or
X = Cl
2CH,
X
:CH2
-CH-
CH
( )\—CH2 CH2
CH2' + CH2
(2)
• CH-,
CH2 —f-CH2
V
CH2J— CH2.
' n
FIGURE 111-17 TYPICAL REACTIOWS TO FORM PARYLENE POLYMERS
63
-------
The polymerization step proceeds by a free-radical mechanism
in which, as a first step, two molecules of p-xylylene
condense on a surface and react to form a diradical
intermediate.
The first step is probably reversible. However, subsequent
reaction with p-xylylene by addition to either end of the
reactive diradical of the intermediate results in the form-
ation of stable species (Figure 111-17, Equation 2) in which
n is 1, 2, or 3. Growth then progresses by addition of p-
xylylene to each end of the radical. Growth is terminated
by reaction of the radical end groups with reactive sites in
other growing polymer chains, by reaction of the free-
radical sites with chain transfer agents (e.g., oxygen or
mercaptans), or by the reactive sites becoming buried in the
polymer matrix.
This proposed method of polymerizing p-xylylene suggests
that the rate of polymerization should be markedly increased
by lowering the temperature of the deposition surface to
increase the rate of condensation and, therefore, the
concentration of molecules of p-xylylene in the condensed
phase. This has also been shown to be the case, and
relative polymerization rates of 1, 10, and 100 were
observed for p-xylylene on surfaces maintained at 30, 0, and
-UO°C (86, 32, and -<40°F) , respectively, and at equivalent
monomer concentrations in the vapor phase. These data
provide strong evidence that the rate determining step in
the polymerization is condensation of a p-xylylene molecule
in the vicinity of a growing free radical, and that addition
of the condensed molecules to the reactive site is very
rapid in comparison.
Manufacture - Manufacture is accomplished in a batch process
requiring relatively simple equipment (see Figure ITT-18).
For example, the reactions may be carried out in a 61 cm (24
in.) section of 28 cm (11 in.) I.D. Vycor tubing. The first
15 cm (6 in.) of the tube serves as a distillation zone, and
the following 46 cm (18 in.) section as the pyrolysis zone.
The pyrolysis tube is connected to a glass deposition
chamber. System operating pressure is in the range of 1
Torr. The distillation zone is maintained at temperatures
ranging from 140-220°C (284-428°F), depending upon the
derivative. The pyrolysis zone is heated to 600°C (1112°F)
and the deposition chamber is usually held at room
temperature. With some derivatives, it is heated as high as
160°C (320°F) to permit deposition of polymer over a fairly
broad area.
64
-------
DI-P-XYLYLENE
VAPORIZER
PYROLYSIS
DEPOSITION
CHAMBER
COLD TRAP
FIGURE 111-18 PARYLENE PRODUCTION
65
-------
Deposition chambers of virtually any size can be
constructed. Those currently in use range from 0.0082-0.459
cu m (500-28,000 cu in.). Large parts up to 1.5 m (5 ft)
long and 46 cm (18 in.) high can be processed in this
equipment. The versatility of the process also enables the
simultaneous coating of many small parts of varying
configurations.
Waste Water Generation - The waste water generation from the
manufacture of parylene is minimal since it requires no
catalysts or solvents. Any waste water generated will be
that from the washing and cleaning of processing equipment,
which with housekeeping and operational procedures can be
contained in the process area. Provided the cold trap is
efficient, air pollution would be minimal (27, 34) .
66
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Poly-Alpha-Methyl Styrene
The poly(alpha-methyl styrene) homopolymer is apparently of
little commercial importance. The homopolymer has a low
ceiling temperature (61°C or im.8°F), and thus
depolymerization can occur easily during fabrication. In
addition, the homopolymer is difficult to fabricate because
of its high melt viscosity.
Radical polymerization of the pure monomer, alpha-methyl
styrene, proceeds very slowly and is not a practical
technique for production of this product. Homopolymers are
instead prepared by anionic catalysis of the monomer.
Polymerizations by free alkali metals are included in this
category since a free radical propagation is apparently not
involved. The polymerization of alpha-methyl styrene is
readily catalyzed by metallic potassium. The polymerization
proceeds as shown in Figure 111-19.
Recent literature articles report additional polymerization
techniques, including: radiation- and photo-induced poly-
merization of pure alpha-methyl styrene; increased polymeri-
zation rate and slightly increased degree of polymerization
upon the application of an electric field for pure alpha-
methyl styrene; and grafting by irradiation of alpha-methyl
styrene to other polymers for the purposes of physical
property modification. It is doubtful that these techniques
have yet been applied on a commercial scale, however. Those
copolymerizations utilizing alpha-methyl styrene which are
carried out on commercial scale are accomplished by radical
polymerization. In styrene copolymers or terpolymers the
presence of alpha-methyl styrene results in a stiffening of
the polymer chain. Usually, higher polymer fabrication
temperatures are required (and can be tolerated) for these
materials.
Manufacture - Adequate information is not available on
commercial methods used, if any. Presumably, small batch
processing may be employed (25).
67
-------
CH3
I
""5 0 ~ OH2
Cll
ens
c —
FIGURE 111-19 TYPICAL REACTION TO FORM ALPHA-METHYL STYRENE
-------
Polyamides
Materials considered to fall in this category include nylons
other than Nylon 66 or 6, which were covered in EPA Develop-
ment Document No. EPA 4UO/1-73/010 (16). Thus, the category
would include Nylon 6/12, Nylon 11, and other polyamides
having special structures. Among resins produced in the
U.S.A. are Nylon 6/12 (DuPont) and Nylon 11 (Rilsan, Inc.).
Manufacture and Waste Water Generation - Nylon 6/12 is pro-
duced in equipment used regularly for production of Nylon
6/6. The product is based on sebacic acid rather than
adipic. The process is operated under slightly different
conditions than those used for Nylon 6/6. Wastes from the
two processes are similar.
Nylon 11 is produced by polymerization of 11-amino
undecanoic acid in a process that is comparable to that used
for Nylon 6. In the production of Nylon 11, the reaction is
such that very little free monomer remains when
polymerization is complete. Wastes developed in the process
are negligible
69
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Polyaryl Ether (Arylon)
The polyaryl ethers, also known as the polyphenyl ethers or
polyphenylene oxides are a new class of polymers. They have
the structure shown in Figure 111-20, Equation 1, where Ar
is an aromatic radical and R may be aromatic or aliphatic.
The best known examples of this type of polymer are the
thermosetting epoxy resins. Recently, several new polymeric
ethers have become commercially important as thermoplastics.
These polymers have outstanding hydrolytic resistance, and
most of them are unaffected by corrosive environments.
The polyaryl ether resins are made by the oxidative coupling
of hindered phenols. The reaction of 2,6-dimethyl phenol to
produce polyphenylene oxide is illustrated in Figure 111-20,
Equation 2. The di-substituted phenol, copper salt, and
amine are dissolved, and oxygen is passed through the
solution producing the polyphenylene ethers and a minor
amount of diphenyl quinone (Figure 111-20, Equation 3). The
polymer obtained is an extremely high molecular weight
material, has a useful temperature of -170°C to -H90°C (-
274°F to +374°F), and is chemically inert.
An alternative method of producing the polyphenylene ethers
is the oxidation of p-bromophenol. A solution of 2,6-
dimethyl-U-bromophenol in aqueous potassium hydroxide is
reacted with potassium-ferricyanide, producing poly-2,6-
dimethyl-1,4-phenylene ether.
One manufacturer produces poly-2,6-dimethy1-1,t-phenylene
ether by another method, the copper-catalyzed oxidation of
2,6-xylenol. The polymer product is marketed under the
trademark PPO. The commercial polyphenylene ether is a
linear polymer having a molecular weight of 25,000 to
30,000. The electrical properties of PPO (R) are such that
the material has been used extensively for high-frequency
insulation of electrical equipment. Because PPO (R) can be
autoclaved in medical sterilizers, it is used to replace
glass and stainless steel in a variety of medical and
surgical instruments in hospital utensils. It is also
employed in household appliances, in food processing
equipment and in plumbing fittings.
A modified form of polyphenylene oxide resins has been
introduced under the trademark NORYL, also by General
Electric. This material is based on polyphenylene
technology and is intended for applications not requiring
performance of polyphenylene oxide. The properties of PPO
(R) and NORYL (R) are given in Table III-6.
70
-------
(1)
-f ArO-R-04-n
(2)
O2, R., N
Cu+
(3)
= O
FIGURE III-20 TYPICAL REACTIONS TO FORM POLYARYL ETHER
71
-------
TABLE III-6
PROPERTIES OF POLYARYL ETHERS
Property 2F.OJR1. NORYL (R)
Density 1.06 1.06
Tensile strength, psi 111,000 9,600
kg/sq cm 740 675
Elongation, % 80 20
Tensile modulus, psi x 10s 3.8 3.55
kg/sq cm x 10 0.27 0.25
Impact strength notch, ft-lb/in. 1.5 1.3
Joules/cm 0.8 0.7
Heat deflection temp., °F at
26H psi fiber stress 375 265
Heat deflection temp., °C at
18.6 kg/sq cm 190.5 129.5
Dielectric constant, 60 cycles 2.58 2.64
72
-------
A typical synthesis from the literature is as follows.
Oxygen was passed for 10 minutes into a reaction mixture
containing 5 g of 2,6-dimethy1 phenol, 1 g of Cu2Cl2 and 100
ml of pyridine. During the course of the reaction, the
temperature rose to a maximum of 70°C (158°F) and no water
was removed. The product was precipitated by pouring the
reaction mixture into about 500 ml of dilute hydrochloric
acid and was separated by filtration. The product, poly-
2,6-dimethyl-l,4-phenylene ether, was produced in
substantially quantitative yields.
This product had a molecular weight in the range of 300,000
to 700,000 and did not melt at 300°C (572°F). The powder
produced on precipitation could be molded, calendered, or
extruded under pressure.
Manufacture - Manufacturing processes for polyaryl ethers
have not been discussed in the literature. By analogy to
the bench-scale syntheses, solution polymerization in water
is probably practiced for polyphenylene oxides.
Waste Water Generation - Waste water effluents will contain
small fractions of all components of the reaction mixture,
including monomers, catalysts (copper-salts), and amine and
possibly the by-product diphenyl quinone, or other reactants
and catalysts depending upon the process of interest. In
general, there is one mole of water of reaction produced per
mole of oxide linkage or, for poly-2,6-dimethy1-1,4-
phenylene ether, 159 mass units of water per 1000 mass units
of polymer product (23).
73
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Polybenzimidazoles
The polybenzimidazoles are polymers incorporating the benzi-
midazole ring into the polymer backbone as shown in Equation
1 of Figure 111-21. These polymers are notable for their
stability to oxidative attack at high temperatures. They
have high molecular weights and excellent resistance to
hydrolytic attack in acidic or basic media.
Essentially, the benzimidazole is formed by the reaction of
a 1,2-aromatic diamine with a carboxyl group. The reaction
may be written as shown in Equation 2 of Figure 111-21.
The first polybenzimidazoles, described in a patent in 1959,
were synthesized by condensation of aromatic bis-o-diamines
with aliphatic dicarboxylic acids in a manner analogous to
the preparation of benzimidazoles. This polymer, which
incorporated an aliphatic linkage, gave the first indication
that high temperature resistance might be achievable in
these polymers. This synthesis was followed by that of
completely aromatic polybenzimidazoles in the belief, later
justified, that thermal and oxidative properties would be
improved in a totally aromatic system.
The initial work with the aromatic polybenzimidazoles
involved reaction of an aromatic tetraamine with a diphenyl
ester of an aromatic dicarboxylic acid — in particular, the
reaction of 3,3'-diaminobenzidine and the phenyl ester of
isophthalic acid. The reaction is illustrated in Equation 3
of Figure III-21. Subsequent work extended to the synthesis
of a number of polymers from other acid derivatives. From
this initial exploratory work, 3,3•-diaminobenzidine and
isophthalic or blends of isophthalic and terephthalic
derivatives were selected as most promising. These acids
are illustrated in Table III-7.
Polybenzimidazoles have been synthesized to high molecular
weight by solution, melt, or solid state polymerization.
Solution condensation can take place in either an organic
solvent having a boiling point sufficiently high for the
reaction to proceed, or in polyphosphoric acid. A typical
high-boiling organic solvent is either phenol or m-cresol.
Phenol has the ability to provide an easier, more complete
polymerization than most solvents. It is necessary to
conduct all condensations under inert atmosphere to prevent
oxidation of the tetraamine. Condensations have been
reported in which solvents such as dimethylacetamide.
74
-------
(Equation 1)
N
H
benzimidazole
NH2
NH,
HC02H
HNOCH
H20 (Equation 2)
o-Phenylenediamine Formic acid
NH2
Amide intermediate Water
HNOCH
A
NH2
Amide intermediate
NH
+ H,O
Benzimidazole Water
H, N
Generalized Synthesis of Polybenzimidazole
NH2
H2N NH2
3,3'-Diaminobenzidine
C0,(
Diphenyl isophthalate
Polybenzimidazole
(Equation 3)
0OH
Phenol
FIGURE 111-21 TYPICAL REACTIONS TO FORM POLYBENZIMIDAZOLES
75
-------
0
II
HOC
COM
Isophthalic Acid
Terephthalic Acid
TABLE 111-7 ACIDS WHOSE DERIVATIVES ARE USED IN POLYBENZIMIDAZOLE SYNTHESIS
76
-------
dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone,
phenol, and cresol were used. Polyphosphoric acid has been
investigated because the oxidation sensitivity of the tetra-
amines could be circumvented by use of the
tetrahydrochloride salt. Upon heating in an inert
atmosphere, hydrogen chloride is evolved at about mO-150°C
(284-302°F), giving a solution of tetraamine and
polyphosphoric acid.
Melt condensation for preparation of polybenzimidazoles has
been investigated in some detail. Upon application of heat,
the mixture of monomers melts, and shortly thereafter the
evolution of phenol becomes noticeable and rapid. Continued
heating results in increasing viscosity until the reaction
mixture solidifies. At this point vacuum is applied to
remove as much evolved phenol as possible. After the
polymer has been cooled to room temperature, it is
pulverized, replaced in the polymerization tube, and the
polymerization is completed by slowly heating to 350-400°C
(662-752°F) in vacuo. Thus, the critical phase of the
polymerization, in which high molecular weight is achieved,
takes place as a solid state reaction.
Many polybenzimidazoles have been synthesized since the
original disclosures. The greatest impetus was provided by
the work involving the fully aromatic systems.
In general, if equimolar quantities of reactants are
employed, the polymerization will continue with heating to
produce high molecular weight polymers soluble only in
formic or sulfuric acids. These cannot conveniently be
processed further. Accordingly, the reaction may be
interrupted at some intermediate stage to produce soluble,
low-melting compounds which can be applied in the liquid
phase. Alternatively, through the use of an excess of
amine, an amine-terminated prepolymer may be produced, which
is then combined with an acid-terminated prepolymer, with
the remainder of the polymerization being subsequently
conducted either from solution or as a hot melt. During the
final polymerization, there will be the evolution of
considerable volumes of volatiles, which must be removed
from the polymerizing structure. Thus, at high pressures,
low molecular weight polymers may be developed as a result
of entrapped volatiles. For some purposes, high volatile
content is desirable. For example, porous laminates provide
better strength properties than do the more dense
structures. For other purposes, systems with low volatile
contents have been developed. The envisioned applications
for polybenzimidazoles are as high temperature adhesives and
laminating resins for the aerospace industry. They may be
77
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employed as secondary structural members in supersonic
aircraft, and as adhesives for honeycomb bonding and similar
applications. Among the civilian potential of these
materials are their use as ultrafiltration and
hyperfiltration membranes.
Manufacture - Specific process information on this subject
has not been reported in the literature. However, processes
are probably scale-ups of the original laboratory synthesis,
i.e., solution polymerization in high-boiling organic
solvents or in polyphosphoric acid. Melt condensation is
practiced for several of the products, wherein processing
may proceed only to the low molecular weight, low-melting,
soluble compounds which are used in the liquid state.
Alternatively, prepolymers may be produced for later
polymerization in solution or in bulk.
Waste Water Generation - Process wastes will include the
water and the phenol evolved in polybenzimidazole synthesis:
2 moles of each per mole of benzimidazole group. For the
condensation with the isophthalic or terephthalic ester,
this corresponds to 120 mass units water and 610 mass units
of phenol per 1,000 mass units of polymer product. In the
solution polymerization process in polyphosphoric acid,
hydrogen chloride is evolved during the condensation.
The quality of water effluent will depend upon pretreatment,
but some dissolved phenol and/or HCl and some monomer
reactant will likely be present (29).
78
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Polybenzothiazoles
Similar to the polybenzimidazoles are the
polybenzothiazoles. These polymers are prepared from 3,3'-
dimercaptobenzidine and a diacid, a diphenyl ester, a diacid
chloride, etc. The reaction sequence is as shown in
Equation 1 of Figure III-22 for use in diphenyl esters.
Typical of the structures synthesized by this procedure are
those shown in Figure 111-23. The hydrochloric acid salt of
3,3'-dimercaptobenzidine may also be used along with the
diacid chloride, overcoming the problem of sensitivity to
air oxidation of the parent mercaptoamine. This is
illustrated in Equation 2 of Figure 111-22. Many other
syntheses of various polybenzothiazoles have also been
attempted, some with success. Many of the problems
associated with the synthesis of the polybenzimidazoles are
common to the synthesis of the polybenzothiazoles and thus
synthesis approaches are frequently similar.
Typical reaction conditions for the polymerization to poly-
benzothiazoles are temperatures of 160-250°C (320-U82°F) and
times of one to 25 hours.
Waste Water Generation - As with the polybenzimidazoles, the
polymerization leads to the release of 2 moles of water per
mole of benzothiazole group and 2 moles of phenol if the
diphenyl ester is used. For the condensation of the
isophthalic ester, this corresponds to 110 mass units water
and 550 mass units phenol per 1000 mass units of polymer
product (29).
79
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(1)
SH
Polybenzothiazole
(2)
HCI • H2N
NH, • HCI + CIOC .,
HS SH
3,3'-Dimercaptobenzidine dihydrochloride
-HCI
--HN
NH OC
I n
FIGURE III-22 TYPICAL REACTIONS TO FORM POLYBENZOTHIAZOLES
80
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HO2C C02H
NH2 +
HS SH
3,3'-Dimercaptobenzidine
Isophthalic acid
H,N
Poly-2,2'-(m-phenylene)-6,6'-bibenzothiazole
H2N
NH2
o-
CO2H
HS SH
3,3'-Dimercaptobenzidine
p-Oxydibenzoic acid
Poly-2,2'-[p,p'-oxybis(phenylene)] -6,6'-bibenzothiazole
Poly-2,2'-[p,p'-oxybis(phenylene)-6,6'-bibenzothiazolyl] -2,2'-(3,5-pyridinediyl)-
6,6'-bibenzothiazole
FIGURE 111-23 TYPICAL STRUCTURES PRODUCED IN THE SYNTHESIS OF POLYBENZOTHIAZOLES
81
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Polybutene
Polybutene can be produced by the polymerization of 1-butene
in the presence of catalysts as shown in Equation 1 of
Figure III-24. Usually Ziegler-type catalysts are employed.
Manufacture - Polybutene or polybutylene is currently being
produced by either of two processes. In the United States,
Mobil Chemical Company uses a polymerization process which
starts when fresh feed and recycle monomer are combined and
passed through a distillation and drying step to remove
volatile impurities and water prior to polymerization. The
reaction is carried out in the presence of Ziegler-Natta
catalysts, and the product stream from the reactor is
contacted with water to remove catalyst residues. Water is
then separated, the polymer phase is heated and flashed to
remove 1-butene for recycle, and the molten polymer is
cooled and extruded into pellets. Another process for
polymerization of polybutene is utilized by Chemische Werke
Huels AG and is also based on the use of Ziegler-type
catalysts. In this process, a C-U feed stream along with
recycled butenes from the process is fed to the monomer
purification section where butadiene is removed. The
resultant 50 percent 1-butene stream (with only trace
quantities of butadiene and isobutylene) is then passed to
the first of two distillation towers where the high boiling
components are removed as bottoms. In the second column low
boilers are removed at the top, and the reactants are
recovered at the bottom.
The monomer stream next goes to two stainless steel
continuous polymerization reactors. Catalyst and solvent
are added in the first reactor.
The polymer/solvent slurry from the second step is then
washed with water to remove catalyst. The wash water is
directed to the waste treatment facility, while the
remaining slurry is sent to a centrifuge as a first step in
removing the atactic isomer which is produced in the Huels
process. Liquid from the centrifuge goes to a distillation
column where a waxy substance, atactic polybutylene, is
removed as bottoms. (This atactic polybutylene is often
used as a carpetbacking material.) The overhead liquid
butene stream is cooled and sent to monomer purification and
then recycled to the process.
Solid polymer is recovered from the centrifuge, dried, and
sent to bins where additives are added prior to extrusion
and pelletizing. A flow chart is shown in Figure 111-25.
82
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CH2 - CH =
CH—CH2~-
CH2
I
CH3
FIGURE 111-24 TYPICAL REACTION TO FORM POLYBUTENE
83
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DISTILLATION
COLUMNS
03
-P-
EXTRACTION EXTRACTOR
SOLVENT AGENT
WATER
FRESH BUTENE
(C4 CUT)
POLYMERIZATION REACTORS
ATACTIC
POLYBUTYLENE
FIGURE 111-25 POLYBUTENE PRODUCTION - HUELS PROCESS
-------
There are several important differences between the Mobil
and HueIs processes. The Mobil process, which is based on a
relatively pure 1-butene monomer stream, is carried out in
the presence of excess butene monomer. This enables the
reaction to be carried out without the need for solvent.
The Huels process is based on a raw C-H cut, which requires
purification prior to polymerization. The Mobil process
does not produce atactic isomer, a portion of the polybutene
produced by the Huels process is atactic.
Waste Water Generation - The major aqueous wastes are likely
to be minimal in both processes, and especially so in
Mobil's process. In the Huels process, liquid residues from
columns and some aqueous wastes from C-4 washing are likely
(25).
85
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Polycarbonates
Polycarbonates are a special variety of linear thermoplastic
polyesters in which a derivative of carbonic acid is substi-
tuted for the acid and a diphenol is substituted for the
glycol. Polycarbonates are end products in themselves,
undergoing thermoplastic processing utilizing the
conventional equipment of the plastic industry. By far the
most important polycarbonates from the commercial point of
view are aromatic polycarbonates derived exclusively from
the reaction of bisphenol A with phosgene. In addition,
aliphatic or aliphatic-aromatic polycarbonates may be
derived, but indications are that they find little
industrial usage. Thus they will not be discussed.
Phosgene is a liquefied gas, boiling at 7.6°C (45.7°F), and
is only very slightly soluble in water. Bisphenol A is a
solid melting at 152°C (305°F) and is soluble in water to
the extent of 3000 mg/liter at 85°C (185°F). The
polymerization may be carried by means of the following
mechanisms: condensation, interfacial, and
transesterification. Of the three, condensation is
preferred. Interfacial polymerization is seldom used for it
is inconvenient and slow, and in order to achieve
sufficiently high rates of transesterification, the reaction
conditions must be so drastic that a portion of the
polycarbonate is decomposed.
The reaction between the two raw materials takes place under
alkaline conditions in the presence of catalyst and pyridine
as shown by Equations 1 and 2 in Figure III-26.
In contrast to base-free condensation, which proceeds only
at high temperatures in the presence of special catalysts
and yields polymers with insufficient molecular weights,
condensation in the presence of basic substances proceeds at
high rates at room temperature to give high molecular weight
polycarbonates. As shown in the above equation, two moles
of hydrochloric acid are formed per mole of phosgene
consumed. To maintain basic conditions in the reactant mix,
the hydrochloric must be either neutralized or consumed.
Pyridine is added, usually in excess, to act as an acid
acceptor and so that the resulting polycarbonate forms a
more or less viscous solution. Alternatively, a good
portion of the pyridine may be replaced by an organic
solvent in which the polycarbonate is soluble. The reactant
is strongly catalyzed by Lewis acids such as aluminum
chloride, aluminum isopropoxide, stannic chloride and
titanium tetrachloride. Suitable reaction media solvents
are the chlorinated aromatic hydrocarbons, such as
86
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C5 H5 N + (CHsh + C(C6H4OH)2 + COCI2
Solvent
Pyridine Bisphenol A Phosgene
(1)
CSH5N +-4-OC6H4C(CH3)2 C6H4Of4- + 2 HCI
Pyridine Polycarbonate Unit
(2) [C5H5N] +HCI -CSH6NCI
FIGURE 111-26 TYPICAL REACTION TO FORM POLYCARBONATE
87
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chlorobenzene, methylene chloride, or o-dichlorobenzene. A
typical catalyst is benzyl triethyl ammonium chloride. It
is important to use equimolar quantities of phosgene and
bisphenol A, since the molecular weight of the product will
depend on the ratio of the starting materials. It is also
important to avoid the presence of substances such as
monofunctional alcohols or phenols which act as chain
terminators. The molecular weight is also indirectly
dependent on possible concurrent side reactions, which in
turn depend on the usual parameters such as temperature,
time, and reactants. In choosing the solvent, chlorobenzene
is preferable since the pyridine hydrochloride formed is
insoluble in this medium and may be readily separated by
filtration. Traces of the hydrochloride that are in
solution may be removed by distillation.
Manufacture - The process scheme is shown in Figure 111-27.
The bisphenol A is charged with excess pyridine and a
solvent such as methylene chloride into the vessel.
Phosgene is vaporized in a still, and then bubbled through
the reaction mixture,. Total moles of phosgene fed are in
slight excess of the moles of bisphenol A charged. Phosgene
and bisphenol react to form the carbonate monomer, which in
turn polymerizes. Reacting mixture is kept under UO°C
(104°F); residence time in the vessel is 1 to 3 hours. The
reaction can be controlled through any of several variables,
including residence time, temperature, and proportions of
the components introduced. Component purity also has great
effect on the reaction.
Reacted mixture, consisting of the polymer, pyridine hydro-
chloride, and unreacted pyridine in solvent, is fed to water
wash tanks. Wash water and hydrochloric acid are added
here, the acid reacting with residual pyridine. Additional
solvent may also be introduced at this stage to lower the
viscosity of the mixture.
The next step is the removal of water and pyridine hydro-
chloride by decantation or the equivalent. The aqueous
phase goes to pyridine recovery; the solvent phase,
containing the dissolved polymer, goes to an agitated
precipitation tank.
Here the polymer is precipitated by addition of an organic
11 an ti sol vent" such as an aliphatic hydrocarbon. This forms
a solution with the carrier solvent and causes the polymer
to precipitate. The resulting slurry goes to a rotary
filter, and the separated polymer goes to a hot air dryer
where the remaining solvent is removed. The polymer leaves
the dryer as a powder and is sent to blending, extrusion.
88
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POLYCONDENSATION
PYRIDINE
RECOVERY
SODIUM
CHLORIDE
SOLUTION
WATER
HYDROCHLORIC
ACID
SEPARATION
ORGANIC PHASE
PRECIPITATION
PRECIPITANT
FILTRATION
1
DRYING
I
PELLETIZING
FIGURE 111-27 POLYCARBONATE PRODUCTION - SEMI-CONTINUOUS PROCESS
89
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and pelletizing. Aqueous pyridine hydrochloride solution is
combined with caustic solution in a mix tank for removal of
chloride ions as sodium chloride. The stream then goes from
the mix tank to a fractionating column where steam strips
out any solvent present.
The stripped solution goes to an azeotropic distillation
column, and the sodium chloride solution is removed as
bottoms and discarded. The overhead stream is an azeotrope
consisting of about 43 percent water, 57 percent pyridine.
The azeotrope is condensed and then combined with a breaking
agent. The mixture goes to a pyridine distillation column
where water-free pyridine is removed overhead. The bottoms
are treated to recover the breaking agent.
Waste Water Generation - The waste water originating from
the process is principally due to polymer washing. The
major substance present in the waste water stream will be
sodium chloride. The amount and concentration of sodium
chloride will depend upon the excess of pyridine required
and the dilution necessary to effect adequate washing. It
is expected that the waste waters will be alkaline from
excess sodium hydroxide used in the recovery of pyridine.
Also, the waste water stream would be expected to contain
traces of pyridine, solvents, breaking agents, bisphenol,
polycarbonate, and side reaction products (25, 28, 36, 40,
46) .
90
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Polyester Resins (Thermoplastic)
The most common polyester is derived from the linear
polymer, poly(ethylene terephthalate) . The other
homopolymer to achieve this polymer, the dihydric alcohol is
butanediol rather than ethylene glycol*
The term thermoplastic polyester resin as used in this
report refers to the saturated polyester polymers based on
poly (ethylene terephthalate) or poly(butylene
terephthalate). These polymers are quite different in
method of manufacture, chemistry, and areas of application
from the unsaturated polyester resins in which a site of
unsaturation is incorporated into the polymer chain for
subsequent reaction to form a crosslinked structure.
The saturated polyester resins comprise a rapidly growing
market of molding materials. These resins are produced by
the same polymerization process used to polymerize resin for
fiber production. Resin chips are often taken as a side
stream from integrated polyester fiber plants. There are,
however, some U.S. polyester resin facilities which produce
resin alone and are not integrated to fiber production. In
addition, there are polyester film facilities which are
integrated back to resin production.
The dihydric alcohol most frequently used in the polyester
condensation reaction is ethylene glycol. Specific require-
ments for the dihydric alcohol are that it be quite pure and
particularly free from color-forming impurities and traces
of strong acids and bases.
The other component can be either dimethyl terephthalate
(DMT) or terephthalic acid (TPA). The use of DMT as a
polyester raw material is more common. There is a
difference in waste products generated during polymerization
depending on whether DMT or TPA is used. The use of DMT
results in the generation of methyl alcohol either as a
waste or by-product stream, whereas the TPA-based
polymerization process does not. In either case a waste
stream containing unreacted glycol is generated.
The exact nature of the catalysts used in the polymerization
process varies somewhat and is regarded as proprietary
information. They are, however, known to include acetates
of cobalt, manganese, and cadmium.
Manufacture - Many plants still use the batch polymerization
process. A typical continuous polymerization process based
on DMT consists of a DMT melter, ester exchange vessel, and
91
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a polymerization reactor(s). This process is shown
schematically in Figure 111-28. The alternative system
based on TPA involves a direct esterification rather than
ester interchange.
In the case of plants producing both resin and fiber, the
molten polymer stream from the final reactor is divided.
Polymer destined to become resin is chilled by once-through
cooling water during a band casting operation and broken up
into chip form for shipping. The figure shows polyester
resin production from ethylene glycol or butanediol.
Waste Water Generation - Liquid wastes result from the
condensation of steam ejector vapors (suction and discharge
sides). Process materials present in these streams are
methanol and ethylene glycol when ethylene glycol is the
diol feed, and methanol and tetrahydrofuran in the case of
butanediol feed. In the latter case, when unreacted
(excess) butanediol is removed from the process under
vacuum, it spontaneously dehydrates to produce
tetrahydrofuran (25).
92
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EJECTOR
STEAM
DMT - DIMETHYLTEREPHTHALATE
EG-ETHYLENE GLYCOL
TMG-TETRAMETHYLENE GLYCOL
(BUTANEDIOL)
THF-TETRAHYDROFURAN
MATERIALS DENOTED ( )
RELATE TO PROCESS WHERE
DIOL IS BUTANEDIOL (TMG),
STEAM
DMT-
DIRECT
OR
INDIRECT
COOLING
WATER
CATALYST
AND
ADDITIVES
COMBINED
WASTEWATER
RESIN PRODUCT
TO BANDING
METHANOL
RECYCLE
FIGURE 111-28 THERMOPLASTIC POLYESTER RESIN PRODUCTION
-------
Polyester Resins (Unsaturated)
Onsaturated polyester resins are made by an esterification
reaction involving a glycol and both an aromatic dibasic
acid and an unsaturated dibasic acid. The unsaturated
dibasic acid is used to incorporate an ethylenic linkage
into the polymer and is a compound such as maleic acid or
fumaric acid. The aromatic dibasic acid can be phthalic
acid, isophthalic acid or the like. The glycol is commonly
propylene glycol. The basic polyester resin is made
typically by a batchwise reaction process in stirred, glass-
lined, or stainless steel vessels and is later dissolved in
a reactive monomer such as styrene which can crosslink with
the ethylenic bonds in the main polymer. The resultant
viscous liquid, diluted with styrene, is the current item of
commerce known as polyester resin.
The chemical structure of the various materials involved in
polyester resin fabrication are shown in Figure 111-29,
along with a representation of the basic reactions involved.
All of the starting materials for polyester resin
manufacture are derived from petroleum fractions. The
aromatic acids are made from xylenes, and the unsaturated
acids are made from benzene by oxidation. The most common
glycol, propylene glycol, is made from propylene via
oxidation. Styrene is made from benzene and ethylene.
Phthalic acid and maleic acid are both easily dehydrated and
are therefore used in the form of anhydrides rather than as
acids in order to avoid the costs associated with shipping
water.
The major use for unsaturated polyester resins is in the
manufacture of reinforced plastics. They constitute about
80 percent of all the materials used for reinforced plastic
applications. Glass fiber is the most common reinforcing
agent, although other reinforcements such as metallic fibers
and natural fibers are occasionally used. Typically, glass
fiber averages about 35 percent of the weight of the rein-
forced polyester. Nonreinforced applications for
unsaturated polyester resin include molded plastic and
resins used for castings, surface coatings, and putty-like
compounds used as body solder on automobiles.
Manufacture - There are two somewhat different procedures
for carrying out the polyester polymerization reaction. The
differences are related to the manner in which the water of
reaction is removed. The fusion process removes the water
by passing an inert gas, usually nitrogen, through the
94
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HYDROCARBON STARTING MATERIALS
H
HC CH
I II
HC. CH
H
ACIDS
Benzene
COOH
COOH
COOH
COOH
Ortho-phthalic Acid Iso Phthalic Acid (IPA)
CH,
CHs
Toluene
Ortho-xylene
CH,
CH3
Meta-xylene
HC-COOH HC-COOH
II II
HC - COOH HOOC -CH
MaleicAcid Fumaric Acid (FA)
CO
CO
Phthalic Anhydride (PA)
GLYCOLS
HOCH (CH3)CH2 OH
Propylene Glycol (PG)
REACTIVE SOLVENT
CH =CH2
HCCO
II >
HCCO
Maleic Anhydride (MA)
HOCH2 C (CH3)2 CH2 OH
Neopentyl Glycol (NPG)
Styrene (S)
POLYESTERS
HOOC - R-COOH + HO - Ft' - OH *> (- OOC - R - COOR' -)p + H2O
Note: Some of the R groups contain the reactive ethylenic linkage.
RESIN
PA + MA + PG = Base Resin (Solid)
Base Resin + Styrene = Polyester Resin (liquid)
FIGURE 111-29 TYPICAL REACTION AND RAW MATERIALS USED TO FORM
UNSATURATED POLYESTER RESIN
95
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reaction mixture. In the second technique, which is
referred to as the solvent or azeotropic process, a solvent
(usually xylene or toluene) is added to the reaction mixture
and forms a constant boiling azeotrope with the water of
reaction. This azeotrope is distilled off during the
esterification reaction and the solvent is recovered.
After carrying the polymerization reaction to the desired
molecular weight and removing the water of reaction, the
polymer is transferred to another vessel containing the
reactive monomer which is typically styrene, although methyl
methacrylate and vinyl toluene are sometimes used. After
mixing in the thinning tank, the final composition
containing reactive monomer is either discharged to a
filtration press prior to being loaded into 208.2 1. (55
gal.) drums or bulk tanks. Discharge from the thinning tank
is sometimes carried directly to drums or bulk without
filtration. The concentration of reactive monomer can vary
considerably (from 20 to about 55 percent by weight). A
typical formulation contains about 35 percent styrene.
Although the vast majority of polyester reactions are
carried out in batch reactors, there are several plants in
the U.S. which have continuous esterification reactors.
This mode of operation can usually only be justified when a
large quantity of a specific type of polyester resin is
desired. The continuous reactor undoubtedly generates less
waste per pound of product as compared to batchwise
production due to more infrequent cleanout, more efficient
operation, and more careful control of operating parameters.
Waste Water Generation - In addition to boiler and cooling
tower blowdown, the sources of effluent are as follows:
Water of Reaction
The water of reaction which is passed out overhead is
condensed by some means and is either removed directly
from the condenser, or more typically from the decanter
following the condenser. This condenser also serves as
a means for separating the solvents used in azeotropic
distillation and sending them back to the reactor. The
water of reaction may contain a variety of contaminants,
including glycols, acids, and minor quantities of
dissolved solvent.
Scrubber Waste
Scrubbers are used on the overheads leaving the reactor
in crder to reduce the concentration of entrained
96
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liquids and solids. Both recirculating and once-through
scrubbers are used. The scrubber operation usually
consists of passing the gaseous stream leaving the top
of the reactor through a column into which water is
sprayed. The scrubber may either use a recirculating
water stream or once-through water. In the latter case,
although the water use is quite high, the effluent
concentration in the water stream leaving the scrubber
is not high and the stream can therefore be passed to a
treatment system. In the case of a recirculating
scrubber, however, the BOD and COD concentration can
often be 200,000 to 400,000 ppm. Such high
concentrations could upset the operation of conventional
biological or municipal waste treatment plants, and
therefore it is common practice in the industry to
either discharge such concentrated recirculating
scrubber wastes to a landfill or to incinerate the
wastes.
Caustic Cleanout of Reactors
Concentrated caustic solution is typically used to clean
out the polymerization reactors. The frequency of
reactor cleanout is highly variable depending on the
grades and types of resin produced by the manufacturer,
Cleanout periods ranging from once every three weeks to
once a year were encountered during our interviews. The
caustic solution is also used to clean out tank cars and
tank trucks. Generally, some form of recycling is
practiced on this caustic cleanout solution.
Alkyd Resins - Although there are some notable exceptions,
most polyester resin plants also manufacture the alkyd
resins which are used in paint manufacture. These resins
are quite similar to polyester resins with the exception
that the acid portion of the polymerization recipe contains
a significant quantity of a long chain of unsaturated fatty
acid, and the polymerized resin instead of being diluted
with a reactive monomer such as styrene is diluted with a
solvent such as xylene or naptha.
With these two exceptions, the processes used to manufacture
alkyd resins are quite similar to those used for
manufacturing unsaturated polyester resins. Both azeotropic
and fusion cook processes are used for manufacturing alkyd
resins and, in many cases, identical reactors are used.
The nature of the effluents in alkyd resin and unsaturated
polyester resin manufacture is also quite similar, with the
notable exception of an increased amount of an oily material
97
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which originates from the long chain, unsaturated fatty
acids used in the alkyd recipe. The presence of this ma-
terial often appears as a high "oil and grease" analysis in
the discharge. It is also worthy to note that although a
typical polyester reaction gives off about 12 percent of the
original weight of the reactants as water of reaction, the
alkyds, because of the high molecular weight of the
reactant, typically give off 5 percent of the weight of the
original reactants as water of reaction.
Litharge (lead oxide) and other catalysts such as lithium
compounds are often used as alcoholysis catalysts in the
reaction vessel in concentrations of a few ppm.
Occasionally benzene sulfonic acid is used as an esterifica-
tion catalyst. Most of these catalysts go out with the
polymer or are trapped in the filtration step.
Various additives are often mixed with the resin in the
thinning tank. These are color stabilizers such as
triphenyl phosphate, amines, fire retardants such as
chlorophthalic anhydride, curing accelerators such as cobalt
naphthenate, and thixotropic agents such as Cab-o-Sil (R) .
All these components appear to go out with the resin.
Discharge to municipal waste is the waste treatment method
utilized by 90 percent of the polyester/alkyd resin
industry. There are some notable exceptions, however, who
carry out their own biological treatment or who truck all of
the wastes to a large, centralized municipal treatment
plant. The exact nature of the wastes can be highly
variable depending on such factors as:
o The use of once-through vs. recirculating scrubbers.
o The extent to which cooling water is recycled.
o The frequency of reactor washout.
o The product mix (polyesters vs. alkyds).
o Whether or not polymerization catalysts are used.
o Whether or not wastes are incinerated (U1).
98
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Polyimides
The development of thermally-stable polymers has for many
years been one of the important tasks in the chemistry of
high molecular compounds. Such polymers ideally combine the
properties of heat resistance and thermal stability. One of
the greatest successes in this direction was the synthesis
of polyimides -cyclic chain polymers with the structure
shown in Figure 111-30, Equation 1. The greatest heat
resistance and thermal stability was obtained by the
production of completely cyclic polymers with no aliphatic
units in the chain.
Polyimides may be divided into two broad groups according to
their structure and method of preparation: (1) polyimides
with aliphatic units in the main chain; and (2) polyimides
with aromatic units in the main chain. Polyimides
containing aliphatic units in their main chains of the
general formula shown in Figure 111-30, Equation 2, are
obtained by thermal poly-condensation by heating salts of
aromatic tetracarboxylic acids and aliphatic diamines. The
preparation of an aliphatic polyimide in this manner is that
illustrated in Figure 111-30, Equation 3. After heating at
110-138°C (230-280°F), an intermediate low molecular weight
product (salt) is formed. This is converted into the
polyimide by additional heating at 250-300°C (482-572°F) for
several hours.
The melt polycondensation method for the preparation of
polyimides has limited applicability. The melting points of
the polyimides obtained must be below the reaction
temperature so that the reaction mixture will be in the
fused state during the polycondensation process. Only in
this case is it possible to achieve a high molecular weight.
Melt polycondensation can therefore be used successfully
only for aliphatic diamines containing at least 7 methylene
groups. Aromatic polyimides are generally infusable, so
that when aromatic diamines are used, the reaction mixture
solidifies too early to permit the formation of a high
molecular weight product. Furthermore, aromatic diamines
are not basic enough to form salts with carboxylic acid,
Polyimides with aromatic units in the main chain (of the
general formula shown in Equation 4, Figure 111-30) are
generally synthesized by a two-stage poly-condensation
method. This method has recently found very widespread use,
since soluble products are obtainable in the first stage of
the reaction. This first stage, carried out in a polar
solvent, consists of the acylation of a diamine by a
dianhydride of a tetracarboxylic acid, leading to the
99
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(1)
fco co ~i
-N< >R< \N-R'- .
^C0/ ^CO/ J n
(2)
CO CO
>R< >N-(CH2)m-
COX ^CO'
(3)
HOOC /^. COOH
+ H2N-(CH2)m-NH2-
A
CH3OOC ^^ COOCH3
HOOC ^\ ,COONH3-(CH2)m-NH2
A
CH3OOC COOCH3
,CQ
CO'
N-(CH2)m-
(4)
CO. CO. ~|
-N/ \R< \N-R- ,
\COX NCOX J n
where R' = Ar
(5)
CO CO
' ">R< \0 +H2N-R'-NH2
"C0_ CO
HOOC. „ CO-NH-R'-
(6)
CO-NH-R'-
-2nH20
cov
CO CO
FIGURE 111-30 TYPICAL REACTIONS TO FORM POLYIMIDES
100
-------
formation of a polyamic acid according -to Equation 5 of
Figure 111-30. The second stage of the reaction — the
dehydrocyclization of the polyamic acid (imidization) —
proceeds according to Equation 6, and is carried out
thermally or chemically.
The first stage of the synthesis of polyimides — the
preparation of polyamic acid — is effected as follows. To
a solution of an aromatic diamine in a suitable solvent
there is added in small portions, with agitation, an
equimolar quantity or a slight excess of the dry
tetracarboxylic dianhydride. The reaction is carried out at
temperatures of -20-70°C (-U-158°F), with the optimum
reaction temperature in most cases being 15-20°C (59-68°F).
The reaction is carried out in polar solvents, the best of
which are N,Ndimethylacetamide, N,N-dimethylformamide,
dimethylsulfoxide, and N-methyl-2-pyrrolidone. The polyamic
acids as a rule apparently have a low molecular weight
(below 100,000) and a low degree of polymerization (110 or
lower) .
The conversion of polyamic acids to polyimides, imidization,
consists of the intramolecular evolution of water from the
polyamic acid to form a cyclic polyimide. The imidization
reaction can be carried out in two ways, thermally or
chemically. The thermal imidization generally consists of
heating the dried polyamic acid with a continuous or step-
wise increase of temperature. Thermal treatment at high
temperatures (above 200°C or 392°F) is carried out in vacuum
or an inert medium.
The chemical imidization method consists of a treatment of
polyamic acid film or powder with dehydrating agents.
Acetic anhydride or anhydrides of other lower aliphatic
acids, such as propionic acid, can be used for this purpose.
Most polyimides, particularly the thermally stable aromatic
polyimides which are of great practical significance, are
inert toward organic solvents and oils. They are also
little affected by dilute acids, but dissolve in strong
acids such as fuming nitric or concentrated sulfuric acid.
Polyimides have a relatively low stability toward alkalis
and superheated steam, and under the action of both they are
hydrolyzed.
Polyimides have been used as electrical insulating films,
for wire enamel, for testing compounds, and for adhesives.
They are being produced for the most part on a semi-
industrial scale.
101
-------
Polyimide Films - The compounds of primary industrial signi-
ficance are the aromatic polyimides. The DuPont Company
started the production of polyimide film in experimental
quantities in 1962. At the present time this company is
producing two types of film under the general trademark
Kapton: H-Film made from the pure polyimide, and H-F-Film
made from the polyimide and coated on one or both sides with
Teflon.
The main area for application of polyimide film at this time
is as a heat resistant insulating, gasketing, and winding
material for electric machines, and also for electric
cables. The use of polyimide films for flexible printed
circuits is of great interest. Thin polyimide film can be
used for condenser insulation for operating temperatures up
to 250°C (U82°F) .
Polyimide Plastics - Production of polyimide plastics, in
which all advantages of these polymers are completely
realized, involves greater technological problems than the
production of films. The difficulties are caused primarily
by the necessity for the removal of large quantities of
salt. Polyamic acid solutions generally contain no more
than 20-30 percent of dry material. In addition, the water
of imidization must be removed. The direct conversion of a
concentrated polyamic acid solution into a polyimide block
in a manner similar to that used for epoxy resins has not
been achieved so far. The preparation of polyamic plastics,
therefore, generally requires isolation of the polyamic acid
from solution in the form of thin films, powders, coatings
on glass, tape, or the like, followed by complete or partial
imidization of these intermediate products by a chemical or
thermal method. Processing into articles by molding,
sintering, or other methods then follows.
Actual consumption of polyimides for the period since 1970
are not known. However, prior to 1970 one estimate
predicted a meteoric rise in consumption of polyimides
rising to 50 million pounds per year by 1972 or 1973.
Manufacture - Specific information on manufacturing
processes has not been reported in the literature, probably
for proprietary reasons in this relatively new field.
Patents largely refer to bench-scale syntheses, as described
previously.
Waste Water Generation - The generation of water wastes
during polyimide manufacture is not documented. The general
synthesis of interest, that represented by Equations 5 and 6
in Figure III-30, leads to the generation of two moles of
102
-------
water per mole of imide linkages. If R and R« refer to
phenyl groups, then this corresponds to generation of 125
mass units of water per 1000 mass units of polymer products.
In this two-stage polycondensation reaction, water is either
removed thermally in the vapor state under vacuum, or
chemically through the use of dehydrating agents. In the
former case, the water may be quite pure when condensed. In
the latter case, the condition of the effluent water will
depend upon the method of regeneration of the dehydrating
agent.
The melt polycondensation method is now obsolete for most
purposes. However, it is worth noting that this
polymerization and related polymerization methods lead to
the release of two moles of methanol per mole of imide
linkage (25).
103
-------
Polymethyl Pentene
Methyl pentene (or 4-methyl-l-pentene) is made by the alkali
metal catalyzed dimerization of propylene as shown in
Equation 1 of Figure 111-31. The polymerization of 4-
methyl-1-pentene to produce poly(methyl pentene) can be
carried out with ZieglerNatta catalysts in inert hydrocarbon
diluents such as cyclohexane, heptane, and commercial
saturated aliphatic hydrocarbon fractions. It can also be
homopolymerized in bulk. The polymerization reaction is
shown in Equation 2 of Figure 111-31. The typical
polymerization product contains a mixture of the crystalline
isotactic polymer (which is almost insoluble in warm
aliphatic hydrocarbons) and an amorphous, atactic polymer
which is soluble in the diluent. The relative proportion of
these two products in the polymer mix depends on such
factors as the type of transition metal-halide catalyst plus
organometallic activator used and the temperature of
polymerization (high temperatures favor the formation of
atactic polymer). The catalyst most frequently used is
based on titanium trichloride activated by diethyl aluminum
chloride.
In a typical polymerization, the diluent serves as a solvent
for monomer, activator, and the atactic product which is
carried out in the temperature range of 20-80°C (68-176°F).
The titanium trichloride and the isotactic polymer remain
insoluble. Thus, the monomer polymerizes at the titanium
trichloride-liquid interface, and the isotactic polymer
precipitates out on the TiCl# crystals forming a slurry of
catalyst-polymer particles in the diluent. To isolate the
isotactic polymer, the slurry of catalyst-isotactic polymer
particles in the diluent is treated with agents which kill
the catalyst activity and solubilize the catalyst residues
so that they can be washed out. An alcohol is usually
employed for this purpose. The polymer is separated from
the wash liquors by filtration or centrifugation. Residual
liquor held in the polymer particles can then be removed by
steam distillation and/or drying. An important feature of
the H-methy1-1-pentene polymer is its optical clarity which
can only be attained by the almost complete removal of
catalyst residues. In order to obtain this high degree of
catalyst residue removal, aqueous washings (as used in
polypropylene manufacture) are inadequate, and more complex
systems involving washing with hydrocarbons or with alcohols
are required.
Waste Water Generation - The waste water generation occurs
during washing, and solid/liquid separations since the
polymerization reaction does not produce water. The polymer
104
-------
(1) CH2=CH-CH3 " CH3 -CH-CH2 - HC = CH2
CH3
(2) n CH3-CH-CH2-CH = CH2
CH3
-J_CH-CH2- —
CH2
I
CH
A
CH3 CH3
FIGURE 111-31 TYPICAL REACTIONS TO FORM POLYMETHYL PENTENE
105
-------
washing step may use water or, in some cases, hydrocarbon or
alcohol. Consequently, the wash liquids may contain
dissolved metals. The volume of waste waters per unit of
production is expected to vary widely depending upon the
specific operations, and the waste waters may also contain
hydrocarbons or alcohols from other washing operations (25).
106
-------
Polyphenylene Sulfide
Polyphenylene sulfide polymers possess recurring units of
sulfur which provide linkage for aromatic compounds. Poly-
phenylene sulfide (PPS) is a finely divided light-colored
powder and is insoluble in any known solvent below 190°C
(375°F). Above this temperature it has limited solubility
in some aromatic and chlorinated aromatic solvents and
certain heterocyclic compounds. It is highly crystalline
with a melting point near 285°C (550°F). Although curing in
air at elevated temperatures is required to effect chain
extension and crosslinking, the resin remains thermoplastic
in nature. It can be processed through conventional
equipment for compression and injection molding.
Polyphenylene sulfide is a recent thermoplastic on the
market; therefore only a small amount of information on its
synthesis is available in the literature. It is believed
that the process employs p-dichlorobenzene, sodium sulfide,
and polar organic material such as n-methyl pyrrolidone to
yield PPS which may or may not have crosslinking agents
added to the reaction medium.
P-dichlorobenzene is solid with a melting point of 53.1°C
(127.5°F) , a specific gravity of 1.46, and is insoluble in
water. Sodium sulfide in the hydrated form contains 9 moles
of water and is very soluble in water. N-methyl pyrrolidone
is a liquid which boils at 197°C (387°F) and is soluble in
water.
The reaction between the two raw materials takes place in
the presence of a polar organic solvent as shown in Figure
111-32.
The reaction is carried out at a temperature in the range of
130-175°C (266-3U7°F). The mole ratio of p-dichlorobenzene
to sodium sulfide should be in the range of 0.9:1 to 1.3:1.
If ratios above this range are employed, the amount of
unreacted dichlorobenzene will be increased, requiring
separation and recycle. Larger excess of either reagent
leads to lower molecular weight polymers, and still shorter
polymers are produced by an increase in the reaction
temperature.
In general, the synthesis reaction is carried out by
reacting a polyhalo-substituted compound with an alkali
metal sulfide which has been partially dehydrated by the
polar organic compound that also serves as the solvent for
the reactants. The solvent should be stable at the elevated
temperatures for the reaction. The polymer formed may be
107
-------
+ Na2S
C,H9NO
-+2NaCI
FIGURE 111-32 TYPICAL REACTION TO FORM POLYPHENYLENE SULFIDE
108
-------
heat treated in the absence of oyxgen to yield a higher
molecular weight polymer. Molecular weight control may be
achieved by introducing a monohalo-substituted aromatic com-
pound to the reaction medium, which causes termination of
the chain growth. Yields of finished polymer are higher if
a catalyst such as copper or a copper compound is added to
the reaction medium.
It is possible to obtain a cross-linked polymer through
addition of a polyhalo-substituted aromatic compound which
contains substituents through which crosslinking can be
effected by further reaction.
Manufacture - A typical process scheme is shown in Figure
111-33.
The hydrated sodium sulfide in n-methyl-pyrrolidone is
charged to a stainless steel autoclave. The temperature is
brought up to 190°C (37U°P) while flushing with nitrogen to
remove the water of hydration. Upon removal of water, the
p-dichlorobenzene is charged to the autoclave and the
temperature raised to approximately 250°C (482°F) for the
desired reaction time after which the polymer and reaction
medium is dropped to a stainless steel tank. The contents
are washed with water and then with acetone, which carries
along unreacted reaction media. The finished polymer is
dried and packaged.
Waste water Generation - Aqueous wastes would be generated
from two sources:
1. Water of hydration.
2. Process wash water. The primary contaminant would
be sodium chloride, of which two moles would be
generated per mole of feedstock.
The water of hydration is associated with the water bound to
the sodium sulfide which is removed in a pre-reaction step
by heating. It is likely that the water removal would carry
along traces of sodium sulfide and n-methyl pyrrolidone
which may or may not be recovered. Process wash water is
used to wash sodium chloride from the reaction mass. Due to
the high solubility of n-methyl-pyrrolidone and sodium
sulfide in water, the waste generated from this source is
most apt to contain a large waste loading. It is likely
that solvent extraction and subsequent further recovery
operations will be applied to this stream to recover the raw
materials for recycle.
109
-------
N-METHYL
PYRROLIDONE
LLE
P-DICHLORO-
BENZENE
RECOVERY
SEPARATION
WATER
AQUEOUS
WASTES
FIGURE 111-33 POLYPHENYLENE SULFIDE PRODUCTION
110
-------
If it is assumed that the sodium chloride is removed in a
water solution at a concentration of about 10 percent by
weight, then about 10,000 mass units of water per 1,000 mass
units of product would be required (24, 47) .
Ill
-------
Polypropylene Fibers
Manufacture - The polymerization of polypropylene was
described previously in EPA Development Document No. EPA
140/1-73/010 ±161. Polypropylene fibers are made by melt
spinning. The general process, shown in Figure 111-34,
consists of coloring polypropylene flake by some type of dry
blending of the flake with pigments followed by a melting
and extrusion process that regenerates the colored
polypropylene as pellets. The pellets are then extruded
through a spinnerette into a column of air which solidifies
the molten filaments. The filaments are subsequently
stretched or spun and crimped, depending on the applications
of the final fiber.
As in most melt-spun fibers, drawing is the critical step in
fiber manufacture. The quenched filaments are heated and
drawn to develop molecular orientation along the fiber axis.
To relieve internal stresses and provide dimensional
stability, the filaments are heat set. This last step also
aids in development of a higher degree of crystallinity.
Fibers with degrees of crystallinity of about 70 percent can
be obtained under optimum quenching and annealing
conditions.
There are three basic types of polypropylene filaments.
These include monofilaments, which may be round or flat or
have special cross-section; fibers; and fibrillated or slit
film.
Monofilaments
A typical extrusion and orientation arrangement for
monofilament is shown in Figure 111-35, in which can be
seen that extruded filaments coming from the spinnerette
are quenched in a water bath (quench tank) and then hot
stretched to several times their original length between
a series of heated Godet rolls and ovens. The source of
heat can be hot water, steam or hot air. After leaving
the orientation oven, the filaments must then be
annealed by heating to a specific temperature (heat set
temperature) while maintaining an essentially constant
length but permitting a limited amount of retraction.
This procedure stabilizes the filament against shrinkage
up to the heat set temperature.
Fibers
Polypropylene fibers are produced from 1-1/2 denier up
to about 15 denier by a technique basically resembling
112
-------
DRY PIGMENT OR
"COLOR MASTERBATCH
PINERETT
CLEANING
WASTE
PP FIBER PRODUCTS
IN BALES OR
ON TUBES
FIGURE 111-34 POLYPROPYLENE FIBER PRODUCTION
-------
EXTRUDER
QUENCH TANK
PULL-OUT
ROLLS
DRAW OVEN
WIND-UP
RELAX
ROLLS
RELAX OVEN
DRAW
ROLLS
SOURCE; POLYPROPYLENE FIBERS AND FILMS. A.U. GALANTI and C.C.MANTELL,
PLENUM PRESS, NEW YORK (1965).
FIGURE 111-35 POLYPROPYLENE MONOFI LAMENT PRODUCTION
-------
that used for nylon and polyester fibers. After
extruding the filaments downward and quenching by air
under carefully controlled conditions, the now undrawn
filaments are collected on bobbins in bundles and then
passed to the stretching operation. There are two
different methods of stretching depending on the desired
end product: one for continuous multifilament yarn and
another for staple fiber. For continuous multifilament
yarn, the bundles are removed from the individual
bobbins and are drawn under heat to four to eight times
their original length (stretch ratios of 1:4 to 1:8).
Typical drawing equipment consists of heated metal shoe
over which the bundles are run; occasionally steam or
hot air heating is used.
In many cases the multifilament is used in the form of a
twisted yarn. This is made in a draw twister, which
combines a twisting motion with the stretching
operation.
Staple fiber is produced from tow containing several
hundred thousand filaments which are combined from
creels. These tows are usually stretched in successive
steps to stretch ratios of 1:3 or 1:4. After drawing,
the tow is normally crimped (or deformed) by heat using
specially shaped rollers to give bulk to the fiber
(approximately that of wool, for example). The crimped
tow is then cut to staple fiber in lengths ranging from
1.3-12.7 cm (1/2-5 in.).
Fibrillated or Slit Film
This product is made by extruding or casting the
polypropylene into a thin film, which is then stretched
to obtain a high degree of orientation of the crystal-
line structure. This highly-oriented film is then
fibrillated by applying various kinds of forces
perpendicular to the machine direction. The fibril-
lation splits the sheet into fibers which are then
processed into the final product.
Slit film is made in a similar manner with the exception
that the extruded film is slit into thin widths prior to
the stretching step. In making slit film, lower stretch
ratios are used in order to avoid fibrillating the film.
The applications of polypropylene fiber include carpet face
yarns, carpet backing, and various industrial yarn
applications.
115
-------
Waste Water Generation - Water is used as a heat exchange
medium in the extruders and in the air conditioning system
of the plant. Water is also used as a rinsing medium for
various equipment and kettles associated with the blending
step.
Sources of waste include rinse water from the blending step,
extensive quantities of cooling and air conditioning water,
and the spin and crimping finish waste. These are
lubricants that will contribute to an oil and grease
analysis. The crimping finish wastes are sometimes directly
drummed and sent to landfill rather than being put into the
waste water stream because of their high BOD's. Some
dissolved solids are generated by the rinsing of gear pump
parts that are periodically removed from service and cleaned
in a molten salt bath. In common with other fiber
production plants, polypropylene plants have a large number
of employees due to the number of hand operations associated
with the handling of the product, and therefore sanitary
wastes account for a significant portion of the total
effluent load from the plants (41). Phosphate can be
present in the wastes due to phosphate containing
surfactants.
116
-------
Polysulfone Resins
Polysulfones are high-molecular-weight polymers containing
sulfone groups and aromatic nuclei in the main polymer
chain. The term "polysulfone" is also used to denote the
class of polymers prepared by radical-induced co-
polymerization of olefins and sulfur dioxide. The latter do
not have commercial significance, and will not be discussed.
Among the aromatic polysulfones synthesized, the polysulfone
derived from dihydric phenols (bisphenol A) and 4,4»-
dichlorodiphenyl sulfone have achieved commercial
application under the trade name of Bakelite polysulfone.
This is a rigid, strong thermoplastic which can be molded,
extruded, or thermoformed into a variety of shapes. It is
both stable and self-extinguishing in its natural form.
Bakelite (R) polysulfone is prepared from the two raw
materials under alkaline conditions according to the
equations listed in Figure 111-36, Equations 1 and 2.
The disodium salt is prepared in situ by reaction of
bisphenol A with exactly two moles of aqueous sodium
hydroxide. A solvent is required for this polymerization,
dimethyl sulfoxide being the most suitable. Very few others
are effective. The reaction must be carried out at 130-
160°C (266-320°F), primarily because of the poor solubility
of the disodium salt at lower temperatures. Polymerization
is, however, very rapid at these temperatures, leading to
molecular weights as high as 250,000 in an hour's time. As
these molecular weights are too high for commercial
processing, chain growth must be regulated by the addition
of terminators. A variety of monohydric phenolic salts or
monohalogen compounds have been found to be effective.
In the polymerization, the highest molecular weights will be
obtained when the mole ratio of co-monomers approaches
unity. Since the co-monomers contain two functional groups
per molecule, as is required for this type of
polycondensation, addition of a compound containing one
functional group per molecule will result in an overall
imbalance in functionality, terminating chain growth.
All but traces of water must be removed from the reaction
mixture before polymerization. Hydrolysis of the dihydric
phenol salt occurs otherwise, resulting in the formation of
sodium hydroxide, which reacts very rapidly with the
dichlorodiphenyl sulfone, forming the monosodium salt of 4-
chloro-4•-hydroxydiphenyl sulfone (Figure 111-36, Equation
3).
117
-------
(1)
HO
CH
I
C
CH3
OH+ 2 NaOH
NaO
CH3
I
C
I
CH3
ONa + 2H,0
(2)
NaO
CH3
C
I
CH3
CH3
ONa + Cl
O--Q
CH3 x '
O
SO,
0
+2NaCI
(3) Cl Ca H4 S02 C6 H4 Cl + 2 NaOH—Cl C6 H4 S02 C6 H4O Na + NaCI + H2O
(4)
CH3
CH3
SO2 + OH~
CH3
- C
CH3
O-'
+ HO
o
SO,
FIGURE 111-36 TYPICAL REACTIONS TO FORM POLYSULFOIME RESINS
118
-------
Two moles of caustic soda (from 2 moles of disodium salt)
are used per mole of dichlorodiphenyl sulfone, which creates
an imbalance in functionality between the co-monomers.
Consequently, it becomes impossible to obtain high molecular
weight.
Another, somewhat less important, side reaction may occur if
caustic soda is present during polymerization. Cleavage of
polymer chains para to the sulfone groups results in the
formation of two phenoxides, as shown in Figure III-36,
Equation 4, for polysulfone.
Other bisphenol A-derived polysulfones are prepared by using
various combinations of dihydric phenol sodium or potassium
salts and dichlorodiphenyl sulfone. Use of certain other
aromatic dihalides besides dichlorodiphenyl sulfone expands
the list considerably.
Manufacture - A typical process scheme is shown in Figure
III-37, Polymerization of bisphenol A and 4,4»-
dichlorodiphenyl sulfone (DCDPS) is carried out batch-wise
by first forming the disodium salt of bisphenol A. This is
done by charging bisphenol A and an excess of dimethyl
sulfoxide (DMSO) to a reactor where the temperature is
brought up to 60-80°C (140-176°F). Sodium hydroxide as a 50
percent solution is added stoichiometrically to the mixture
over a period of about 10 minutes. Water is removed from
the system, the DMSO that co-distills being returned
continuously. In so doing, the temperature of the contents
rises from about 120°C (248°F) initially to 140°C (284°F) at
the conclusion of this step, when this point is reached,
most of the water originally present has distilled, and the
disodium salt of bisphenol A appears as a precipitate.
Excess azeotrope solvent is distilled from the system until
the temperature of the contents reaches 155-160°C (311-
320°F). At this point the precipitate will redissolve with
the formation of a very viscous solution. It is assumed
that at this point only traces of water remain,
A 50 percent solution of 4,4»-dicholordiphenyl sulfone
(DCDPS) in DMSO maintained at 110°C (230°F) is fed
stoichiometrically to the polymerizer. The temperature must
not drop below about 150°C (302°F) until the polymerization
is well along, since sodium-ended low polymer may
precipitate on the walls of the reactor. Too high a
temperature during addition of the sulfone and subsequent
polymerization is to be avoided, as the reaction is mildly
exothermic, extremely rapid over 160°C (320°F), and
119
-------
BISPHENOL A
SODIUM
HYDROXIDE
DIMETHYL
SULFOXIDE
COAGULANTS
TO
RECOVERY
1
REACTION
DICHLORO
DIPHENYL
SULFONE
1
» POLY*^
DISODIUM
SALT
FILTRATION
COAGULATION
I
SEPARATION
I
SOLIDS
DRYING
PELLETIZING
WATER
I
FIGURE 111-37 POLYSULFONE RESINS PRODUCTION
120
-------
excessive solvent decomposition and/or discoloration or even
gelation of the reaction mass may occur.
The polymerization may be terminated in a variety of ways,
one of which is to pass methylene chloride into the
polymerizing mixture when the desired degree of
polymerization is reached.
Additional DMSO is added to the reactant mixture to reduce
the viscosity to a workable level. The mixture is then
passed through a rotary drum filter to remove sodium
chloride. The process stream is fed to a coagulation vessel
where an alcohol such as ethanol is added to coagulate the
polysulfone. The solvent and unreacted feed materials are
separated from the polymer and sent to recovery. The
polymer is then dried and pelletized while the vented
solvent is recovered and recycled.
Waste Water Generation - The reaction products include 810
mass units of water per 1000 mass units of the disodium
salt, and an estimated 1800 mass units of water is added
with the sodium hydroxide for a total of 2610. The waste
water from the azeotropic distillation are likely to contain
DMSO and traces of bisphenol. In addition, appreciable
concentrations of sodium chloride are expected to occur.
The waste waters are expected to be alkaline because of the
excess sodium hydroxide required for pH control. The volume
of waste water generated is highly dependent upon operating
conditions, especially those associated with the washing
operations (25, 27).
121
-------
Polyvinyl Butyral
Polyvinyl butyral is formed by condensation of polyvinyl
alcohol with butyraldehyde in the presence of an acid cata-
lyst (Figure 111-38).
Manufacture - Two processes, shown in Figures 111-39 and
111-40, are used for production of polyvinyl butyral.
The process shown in Figure III-39, which is used by E. I.
DuPont de Nemours and company. Inc., Fayetteville, N.C.,
starts with powdered polyvinyl alcohol. The alcohol is dis-
solved in water and reacted with butyraldehyde according to
the equation in Figure 111-38. The butyral is washed and
slurried in water. The slurry is treated with a plasticizer
(triethylene glycol di-2-ethyl butyrate is one)f and the
mixture is sheeted to give the product that is sandwiched
and heat sealed between pieces of glass to produce safety
glass.
The process shown in Figure III-40 is practiced by Monsanto
Co., Indian Orchard, Mass., and Trenton, Michigan. At these
plants, vinyl acetate monomer is polymerized in suspension
to give polyvinyl acetate. This polymer is separated,
dissolved in ethyl alcohol and hydrolyzed in the presence of
a mineral acid. The polyvinyl alcohol is centrifuged and
condensed with butyraldehyde in the presence of ethyl
alcohol and acid. The butyral solution is filtered,
precipitated with water, washed and dried.
The dry product may be sold as such, or transferred to
another area of the Monsanto plant for sheeting. In this
operation, the polymer is combined with plasticizer and
sheeted on rolls. The sheeting process uses very little
water, and wastes are negligible.
Waste Water Generation - Wastes generated in the DuPont
process are indicated in Figure III-39. The acid catalyst,
small amounts of the reaction components, and a small amount
of the plasticizer are anticipated wastes.
Wastes generated by the Monsanto process, shown in Figure
III-40, are considerably more complex than those generated
by the DuPont process. The Monsanto process requires
ethanol, which is not needed in the DuPont process; the
ethanol combines with acetic acid which is liberated in the
hydrolysis step to give ethyl acetate, which is recovered
(31,
122
-------
x-
[CH2CHOHCH2CHOHln + C3H7C ^ - [CH2CH CH2CH] n + H20
H
o o
\ /
c
/ \
C3H7 H
FIGURE 111-38 TYPICAL REACTION TO FORM POLYVINYL BUTYRAL
123
-------
DEMIN. WATER & STREAM
PVA
CATALYST
BUTYRALDEHYDE
DEMIN. WATER
PLASTICIZER
POLY VINYL
ALCOHOL (PVA)
DISSOLVING
BIOTREATMENT-*
EXTRUSION
SHEETING
FINISHED
PRODUCT
5% BOD 30% OF BOD
(MISC. SOURCES)
POWDERED ROLLS
\
REFRIGERATED ROLLS
I
TINTED ROLLS
r:
DEMIN. WATER
FIGURE 111-39 POLYVINYL BUTYRAL PRODUCTION - DU PONT INC. PROCESS
-------
VINYL
ACETATE
1
\
SUSPENDING AGENT
1 WATER
r CATALYST
LIME ^
POLYMERIZATION
SLURRY
i— »-TO WASTE WATER TREATMENT
NEUTRALIZING
FACILITY
A
OTHER
M PLANT
WASTE
STORAGE
ETHYL
ALCOHOL
MINERAL
CATALYST
CENTRIFUGE
DISSOLVING
0.9% FLOW
WATER-
PV
ACETATE
HYDROLYSIS
30.6% FLOW
MISC.
DRYING
68.5% FLOW
CENTRIFUGE
STEAM
SOLVENT
RECOVERY
SYSTEM
PV
ALCOHOL
CENTRIFUGE
ETHYL
ALCOHOL-
LT
BUTYRALDEHYDE
WATER
•r
WATER
WASHING
WATER
~1
PRECIPITATION
BUTYRALDEHYDE
ACETAL
REACTION
FILTRATION
PV BUTYRAL
FIGURE 111-40 POLYVINYL BUTYRAL PRODUCTION - MONSANTO INC. PROCESS
125
-------
Polyvinyl Carbazole
Polyvinyl carbazole is a thermoplastic which can be molded
at temperatures of 210-270°C (410-518°F) into sheets which
are clear and stiff, resembling mica. The polymer is
soluble in chloroform, trichloroethylene, aromatic
hydrocarbons, etc. Despite its excellent dielectric
properties, the polymer has not been used to any great
extent for electrical insulation, mainly because of the high
cost of the monomer.
Poly(N-vinyl carbazole) can be prepared via the use of a
Lewis acid catalyst. The polymerization is illustrated in
Figure III-U1.
Substitution of other solvents such as toluene, carbon
tetrachloride, etc., or the use of higher polymerization
temperatures, all lead to lower molecular weight products.
Alternatively, very highly purified monomer may be heated in
the absence of catalyst at temperatures of 85-120°C (185-
248°F), to give a nearly colorless clear product similar in
appearance to polystyrene. Even small amounts of impurities
lead to low molecular weight products, however.
The literature reports successful polymerization with zinc
bromide initiated by passing an electric current. The
yields increased with increased applied current density and
were high after short times. Molecular weights were low
(2000 to 5000), but the distribution was very narrow. It is
doubtful that this technique will reach commercialization in
the near future.
Manufacture - It is presumed that batch processing is
employed. Further information is unavailable in published
literature.
Waste Water - While the reaction itself does not produce
wastes, washing of the product polymer would produce aqueous
wastes containing the catalyst (such as boron trifluoride)
and small amounts of the solvent. Adequate information is
unavailable to make projections of quantities involved (25,
29).
126
-------
FIGURE 111-41 TYPICAL REACTION TO FORM POLYVINYL CARBAZOLE
127
-------
Polyvinyl Ethers
The various vinyl alkyl ether monomers (the reactants) are
normally colorless liquids or low melting solids. All
readily add halogens across their double bonds. The lower
alkyl vinyl ethers are sparingly soluble in water. These
monomer ethers hydrolyze slowly in water at room temperature
(and more rapidly in the presence of mineral acids),
producing acetalydehyde, as shown in Figure 111-42, Equation
1,
Hydrolysis of the monomers is avoided by adding alkaline
stabilizers (for example 0,1 percent of triethanolamine) to
the stored vinyl ethers. Stabilizers and impurities such as
alcohol, acetaldehyde, and acetals are then removed before
polymerization by washing with water or very dilute KOH.
Vinyl ethers produce high molecular weight homopolymers when
reacted in the presence of Lewis acid catalysts. The
catalysts used are related to Zeigler catalysts, for
example, diethyl aluminum chloride or Grignard reagents.
The propagation step proceeds as shown in Figure 111-42,
Equation 2, thereby producing a head-to-tail structure. The
more highly branched the alkyl groups are, the greater the
reactivity of monomer. Long chain alkyl ethers are
generally less reactive than the short chain homologs.
Aromatic vinyl ethers do not polymerize readily and are
susceptible to side reactions such as rearrangements and
condensations.
Vinyl ethers do not copolymerize readily with other vinyl
ethers, but they readily form copolymers with a wide variety
of ether monomers including dibutyl maleate, maleic
anhydride, acrylonitrile, vinylidene chloride, vinyl
chloride, vinyl acetate, and methyl acrylate.
Polyalkyl vinyl ethers are utilized primarily for their
ability to serve as plasticizers for coatings, or because of
their tackiness for use in adhesives. The methyl
homopolymer is used as a plasticizer for coatings and is an
aqueous adhesive tackifier. The vinyl methyl ether-maleic
anhydride copolymer is used as a water thickening agent,
suspending agent, and an adhesive.
Manufacture - Commercial processes are typical for the
various polymerization techniques. Solution or bulk
techniques are presently used in the U.S. Typical flow
diagrams for these processes are shown in Figures III-U3 and
III-4U. In the solution polymerization process, when a
solvent-free product is desired, it is dried by heating
128
-------
H+ H+
(1) CH2 =CHOR + H20 [CH2 = CHOH] CH3CHO
(2)
H
1
1
VW-CH-,-CH +
1
1
O
1
R
H
1
1
+ CH2 =CH-OR -M/CH2-C-Ch
I
I
O
II
R
H
1
i
1
I
O
1
R
FIGURE III-42 TYPICAL REACTIONS TO FORM POLYVINYL ETHERS
INCLUDING MONOMER MANUFACTURE
129
-------
COOLING WATER
OR REFRIGERATED
BRINE (INDIRECT)
STEAM
COOLING WATER
(INDIRECT)
MONOMERS'
CATALYST
SOLVENT
(ORGANIC)
VACUUM
STEAM
EJECTOR
POLYMERIZER
STEAM FOR
INDIRECT
HEATING
COOLING
WATER
BAROMETRIC
CONDENSER
WASTE
WATER
SOLUTION
PRODUCTS
SOLVENT-FREE
PRODUCTS
FIGURE 111-43 POLYVINYL ETHER PRODUCTION - SOLUTION POLYMERIZATION PROCESS
-------
STEAM
VACUUM
FOR AQUEOUS
OPERATION
MONOMER CATALYST
ORGANIC
OR AQUEOUS
SOLVENT
ORGANIC
OR AQUEOUS
SOLVENT
STEAM
EJECTOR
1
1
1
POLYMERIZER
FINAL
REACTOR
DILUTION
ADJUSTMENT
BAROMETRIC
CONDENSER
COOLING
WATER
WASTE
WATER
PRODUCT TO
PACKAGING
FIGURE 111-44 POLYVINYL ETHER PRODUCTION - BULK POLYMERIZATION PROCESS
-------
under vacuum. In the bulk process, aqueous or organic
solvent is sometimes added to the product depending on
desired properties.
Waste Water Generation - Sources of waste water will depend
upon the polymerization process employed. In solution
polymerization, when no drying step is employed, there are
no direct contact waste waters. When drying is employed,
some contamination of the water from the steam ejector
barometric condenser results.
There is no water of reaction in the polymerization of poly-
alkyl vinyl ethers (25).
132
-------
Polyvinylidene Chlorides
Polyvinylidene chloride latex is commonly used for paper and
film coatings. The latex is produced by emulsion
polymerization of vinylidene chloride, frequently in the
presence of another monomer. The equation in Figure 111-45
expresses the reaction involved.
Manufacture - The polymerization is performed in water using
an emulsifier, a peroxide, and a reducing agent such as
sodium bisulfite. The reaction is conducted in an inert
atmosphere, and after several hours it is complete.
Following the polymerization, the emulsion may be heated
with steam to destroy components in the mixture that might
generate odors on standing or in use, and is then ready for
sale.
Waste Water Generation - Wastes developed in the process
consist of tank washings. These wastes include a low level
of all of the ingredients used, and suspended solids
corresponding to the polymer produced (41) .
133
-------
CClI]
(CH2-CCI2)
n
FIGURE 111-45 TYPICAL REACTION TO FORM POLYVIIMYLIDENE CHLORIDE
134
-------
Polyvinyl Pyrrolidone
Polyvinyl pyrrolidone is a water soluble polymer
characterized by unusual complexing and colloidal
properties. It is available in pharmaceutical grades, a
beverage grade, and in a grade suitable for textile leveling
and stripping.
The monomer reactant is N-vinyl-2-pyrrolidone, shown in
Figure 111-16, Equation 1. This is a colorless liquid with
a freezing point of 13.6°C (56.5°F), a boiling point of 96°C
(204.8°F) at 50 mm, and 123°C (253. H°F) at 114 mm. It is
completely miscible with water and most organic solvents.
The monomer is manufactured by the vinylation of 2-pyrroli-
done with acetylene in the presence of alkali metal salts of
pyrrolidone.
The polymerization to the product polymer (shown in Figure
111-46, Equation 2) is accomplished by ionic catalysis using
boron trifluoride or potassium amide. The polymerization
may also be catalyzed with free radical catalysts such as
hydrogen peroxide, benzoyl peroxide, or
azobisisobutyronitrile. Also, highly purified vinyl
pyrrolidone combines with atmospheric oxygen to give
peroxide-type compounds which themselves act as
polymerization catalysts. Since the vinyl amides are
hydrolyzed under acidic conditions, polymerizations are best
carried out at neutral or basic pH in water. The
polymerization reaction is as shown in Equation 3 of Figure
111-46.
A typical batch solution process for homopolymerization
which was applied on a semi-industrial scale is as follows.
One-half of a 30 percent solution of purified vinyl
pyrrolidone in water was added to the reaction vessel. The
remainder was added slowly during the reaction. Catalysis
was accomplished by addition of 0.2 percent hydrogen
peroxide and 0.1 percent ammonia. The reaction was complete
in 2 to 3 hours. It was found that molecular weight
increases with ammonia concentration and is directly
proportional to monomer concentration up to about 30
percent. Above 30 percent, molecular weight was found to be
inversely proportional to catalyst concentration.
Copolymerization of N-vinyl-2-pyrrolidone has been success-
fully accomplished with a number of co-monomers. Among
these are ethylene glycol monovinyl ether, ethylene,
laurylacrylamide, C12 to C1J3 methacrylate, divinyl
carbonate, cinnamic acid, and crotonaldehyde. A typical
process utilizes solvents such as alcohol or benzene, a
135
-------
(1)
Monomer
N-Vinyl-2-Pyrrolidone
CH2
CH2
\
— CH2
I
c = o
N
I
CH = CH2
(2)
Polymer
CH2 - CH2
1 I
CH2 C = O
CH-CH2
NH4OH
H202 2HO-
HO- + CH2= CH—-HO-CH2-C'
HO-CHj-C- + nCH2=CH
I I
(3)
V
H
HO-CH2- C— (CH2 - CH)nl -CH2- CH-
I I I
FIGURE 111-46 TYPICAL REACTIONS TO FORM POLYVINYL PYRROLIDONE
136
-------
reaction temperature of 50-75°C (122-167°F), and catalyst at
concentrations 0.1 to 1 percent. Typical catalysts are
benzoyl peroxide, lauroyl peroxide, and
azobisisobutyronitrile.
Graft polymerization has also been readily accomplished in a
number of cases.
The homopolymer polyvinyl pyrrolidones are produced in four
viscosity grades corresponding to average number molecular
weights: 10,000, 40,000, 160,000, and 360,000. Pharmaceu-
tical grades, beverage grades, and textile leveling and
stripping grades are produced domestically. Copolymers with
vinyl acetate of varying proportions are also marketed
domestically.
Manufacture - Polyvinyl pyrrolidone is produced on
commercial scale by polymerization in water at 20-60 percent
concentration, depending upon the desired product viscosity.
Reaction is carried out with catalysis by hydrogen peroxide
and ammonia in the temperature range 50-80°C (122-176°F).
The product is spray dried. An alternative commercial
process is polymerization in water using
azobisisobutyronitrile at 50-60°C (122-140°F).
Waste Water Generation - The typical solution polymerization
in water would yield only a small waste water stream since
the solvent is recycled whenever possible. The polymer
product is probably washed, depending upon its end use, and
the wash water would contain small fractions of all agents
in the reaction mix including some catalyst. There is no
water of reaction (25).
137
-------
Silicones
Manufacture - Plants producing silicones typically produce a
wide variety of chemicals incorporating silicone. Silicone
chemistry is complex, and the discussion here is limited to
indicating the processes conducted and the types and scope
of wastes generated. Figures III-47 and III-18 are
simplified flowsheets which suggest the complexity of
silicones plants. Figure 111-47 shows processes used for
production of several different chlorosilanes and hydrolysis
of dimethyl dichlorosilane to dimethyl silicone fluid.
Figure III-U8 shows transformation of the dimethyl silicone
fluid to finished fluids, greases, emulsions, rubber, and
resins. These figures do not include several processes
conducted at the plants.
All of the plants we have examined purchase silicon metal
and react it with a wide range of chemicals, used in several
steps. The following processes may be conducted at a
silicone plant:
1. Production of methyl chloride, generally by
reaction of methanol and hydrogen chloride. Figure
III-U9, Equation 1.
Methyl chloride is used in production of methylated
chlorosilanes. Other organic chlorides, alkyl or
aryl, are used also; e.g., phenyl chloride.
Methyl chloride may be purchased by a silicones
plant rather than being manufactured there. As far
as we are aware, other organic halides are always
purchased.
2. Chlorosilane production. For the methyl fluids,
methyl chlorosilanes are produced by the reaction
shown in Figure III-49, Equation 2.
Other organic chlorides (see above) would be used to
generate other chlorosilanes. The mixture of products
produced in the direct process are separated by
fractional distillation to provide each component;
dimethyldichlorosilane must be very pure for use in
subsequent syntheses (see below). Some of the
chlorosilanes (probably methyl trichlorosilane) have
limited use, and are wasted.
The above equation represents the "direct" process for
making chlorosilanes; it is widely used for the methyl
compounds, the phenyl compounds, and perhaps others.
138
-------
>. Transistor-grade silicon
vo
Benzene,
olefins,
acetylene, and
other reagents
T
Fluids,
rubber
FIGURE 111-47 PRODUCTION OF SILANE MONOMERS, OLIGOMERS AND
DIMETHYL SILICONE FLUID
-------
Catalyze
and use
Blends of
chlorosilanes
s
— *i
Water
"* t
'/
Catalysts
,
/ /
/
" 7
Hydrolysis
kettle "
Bodying
' kettle
I
Hydrochloric
acid
^Silicone
resins
Room temperature
curing rubber
Silicone
emulsions
FIGURE 111-48 PRODUCTION OF SILICONE FLUIDS, GREASES, COMPOUNDS,
EMULSIONS, RESINS AND RUBBER
-------
(1) CH3OH + HCI -CH3CI + H20
Cu
(2) CH3CI + Si + HCI SiCI4 + CH3SiHCI2 + CH3SiCI3 + (CH3)2SiCI2
300°C
(3) CH3CI + Mg
Cl
i
(4) 2CH3MgCI + SiCI4 ^2MgCI2 + CH3-Si-CH3
i
Cl
(5) (CH3)2SiCI2 + H20 -(CH3)j Si{OH)2 + 2 HCI
(6)
-------
Chlorosilanes may also be made by a Grignard process,
represented by Equations 3 and 4 in Figure III-49. The
Grignard process finds limited use, in part because
large amounts of solvent are required, and the metal
salts go into a waste stream. We believe that it is
used only for special chlorosilanes.
Trichlorosilane (HSiCl3) is produced by reacting
directly silicon and hydrogen chloride. For production
of still other chlorosilanes, olefins or acetylene may
be reacted with appropriate silane monomers,
3. Hydrolysis. For production of the methyl fluids,
dimethyl dichlorosilane is hydrolyzed with water as
shown in Figure 111-49, Equations 5 and 6.
The cyclic siloxane may be further processed to the
linear polymer. The linear products are manufactured in
a broad viscosity range to give the well-known fluids.
Silicone fluids are often sold as emulsions in water;
production of these mixtures involves use of emulsifiers
and special equipment. In addition, the viscosity of
certain fluids may be substantially increased, probably
by cross-linking, to provide silicone greases.
4. Silicone resin production. The resin products are
branched and cross-linked siloxane polymers, generally
sold as solutions in organic solvents.
The resins are manufactured by hydrolysis of mixtures of
chlorosilanes in solvents. The mixtures may be complex,
including mono-, di- and trichloro-silanes having
different organic radicals, alkoxysilanes, and other
silanes bearing special functional groups. After
hydrolysis, the aqueous layer is separated and the
organic phase is neutralized. A catalyst may be added
to the organic solution, and the mixture may be heated
to polymerize the dissolved chemicals.
5. Elastomer production. Silicone elastomers are
produced from high molecular weight fluids, fillers, and
curing agents. The mixtures are often called compounds.
Two types of polymer-filler mixtures are produced, those
which cure to rubber by application of heat and those
which are cured at room temperature. Catalysts used for
products cured at room temperature may be tin or
organotin salts.
142
-------
6. Specialties production. For our purposes,
specialties constitute materials which are produced in
significant amounts at a single silicones plant but in
minor amounts, if at all, at others. We have included
surfactants, coupling agents and fluorosilicones as
specialties, but other products may also be classified
in this group. It is characteristic of silicones plants
that new products are constantly being developed and
offered commercially.
Surfactants are produced by reaction of silicone fluids
with polyethylene oxide, or polyethylene oxide-
polypropylene oxide. The products are water soluble.
Coupling agents are monomeric silanes which serve as
glass surface primers to increase the adhering strength
of a resin subsequently applied. The typical final
composition is glass-silane-resin. The resin may be
epoxy, polyester, melamine, or other. One coupling
agent which has been used is aminopropyl triethoxy
silane. Production of such chemicals generally involves
reaction of a chlorosilane with an appropriate organic
compound, followed by exchange of the halogen atoms with
alcohol groups. Coupling agents are produced in
significant quantities at one manufacturing location.
These resins require a vacuum to be applied to the batch
reactor kettle during the hydrolysis reaction (5) in
Figure U9. Existing plants employ once-through
barometric condensers to achieve the vacuum; use of such
condensers increases the process water flow from the
vicinity of 17,000 to 27,000 gallons per 1000 pounds of
product. These extra waters cannot be recycled until
concentrated, as is practiced in the manufacture of
polyesters and alkyds, for instance, since the materials
of construction of the process equipment will not
withstand the more concentrated hydrochloric acid. New
plants, however, could incorporate such a change without
undue penalty. On existing plants, this additional
condenser water may be used as scrubber water for
incineration, thereby not adding to the total hydraulic
load by the addition of incineration. Surface
condensers of current design are very expensive for this
application due to the need for hastalloy type alloys
for the metal parts in contact with the process waters,
and are also subject to frequent plugging from the
products of reaction.
Waste water Generation - Resin production generates
significant amounts of acid wastes due to the liberation of
hydrogen chloride in the hydrolysis step. The acid may be
143
-------
recycled, for example in the production of methyl chloride,
but in many cases it is impractical to recover it. Organic
solvent wastes, such as naphtha or toluene, are also
produced. Most of the solvents are recovered, but trace
quantities may appear in the waste water. Quantitative
information on the waste water generated in silicone
polymerization processes is not documented in the literature
(25, HI).
Source of heavy metals - copper catalyst used for the
chlorosilane production process enters the waste water
during the hydrolysis step and in subsequent water of
reaction produced during polymerization. Fluorides may be
present in the waste water where fluorosilicones are being
manufactured.
144
-------
Spandex Fibers
Spandex fibers are made from conventional polyurethane
ingredients. Textile Organon C*3) defines spandex fibers as
being composed of "at least 85 percent by weight of a
segmented polyurethane.11 In common with other fiber
processing reactions, extremely careful control must be
maintained in raw materials specifications and reaction
techniques to insure adequate quality of fiber.
The rubber-like qualities of the spandex fibers result from
the formation of a polyurethane composed of alternating
sections of soft and hard segments. The hard segments are
considered to be rigid and impart elasticity by limiting the
viscous flow which results from the soft segments. The soft
segments are long-chained molecules terminated with hydroxyl
groups. Common examples are polyadipate which is the
reaction product of adipic acid and a glycol (Figure 111-50,
Equation 1), polytetramethylene glycol (Equation 2), and
polycaprolactone (Equation 3). These soft segments are then
reacted with a diisocyanate, most generally toluene
diisocyanate (TDI) (Equation 4), or methylene bis (4-phenol
isocyanate) (MDI) (Equation 5) , to give an isocyanate-
terminated prepolymer containing urethane linkages. The
structure of a typical MDI-terminated polyadipate prepolymer
is shown in Figure 111-50, Equation 6. This prepolymer is
then reacted with either a diamine (such as ethylene
diamine) or hydrazine to form the final spandex fiber; the
reaction is shown in Figure 111-50, Equation 7. Various
additives such as delusterants (titanium dioxide),
ultraviolet absorbers, and antioxidants are also added to
obtain various properties.
Manufacture - Spandex fiber can be produced by wet or dry
solution spinning processes, reaction spinning, or melt
spinning.
One major U.S. fiber producer, uses the dry spinning
process. In this the heated polymer, dissolved in a solvent
such as dimethyl formamide, is extruded through a
spinnerette into a column of circulating hot air which
serves to evaporate the solvent and thereby solidify the
filaments. A schematic diagram of the dry spinning process
is shown in Figure III-51.
Another U.S. producer produces spandex fibers by the wet
spinning process. This process is similar to that employed
by DuPont in that a spinning solution is used, but instead
of spinning into a column of circulating hot air, the
spinning solution is spun into a water bath which serves to
145
-------
(1)
HIOROCO CH2 CH2 CH2 CH2 CO)nOROH
(2)
H [0(CH2)3CH]nOH
(3)
H [0(CH2)5CO]nOROH
(4)
H,C
NCO
NCO
(5)
OCN—
— CH2-
— NCO
0
(6) OCN-0-CH2 -0-N-C-OCH2CH2O
H
O 0
• C-(CH2 )4 C-OCH2 CH2O
-N -0-CH2 -0NCO
H
(7) OCN- R -
Prepolymer
H2NCH2CH2IMH2
O 0
C-N-R-N-C-N-CH2-CH2-N4
H
H
H
H
FIGURE 111-50 TYPICAL REACTIONS TO FORM SPANDEX FIBERS
146
-------
MAKE UP
Dl ISOCYANATE
DIAMINE
POLYMER-
IZATION
VESSEL
BLOW-DOWN
RECYCLE
SOLVENT
PURIFICATION
(N-DIMETHYLFORMAMIDE)
SOLVENTS
WASTE SOLUTION
TO INCINERATION
WASTE TO INCINERATION
SOLVENT +
HOT AIR
SPINNING
SPINNING WASTE
TO INCINERATION
J
SOURCE: BASED ON DISCUSSION
WITH DU PONT.
T
HOUSEKEEPING WASTE WATER
TO BIOLOGICAL TREATMENT
FIGURE 111-51 SPANDEX FIBER PRODUCTION - DRY SPINNING PROCESS
-------
00
TOLUENE
Dl ISOCYANATE
POLYTETRAMETHYLENE
GLYCOL
LUBRICANT
COOLING
WATER FROM
CITY
POLYMER-
ZATION
VESSEL
WELL WATER
COOLANT
TO
SEWER
SOURCE: ADL, BASED ON DISCUSSIONS
WITH AMELIOTEX, INC.
TO
STORM
SEWER
REGENERATION
WASTES
PRODUCT
CITY
WATER
FIGURE 111-52 SPANDEX FIBER PRODUCTION - WET SPINNING PROCESS
-------
extract the solvent and coalesce a multifilament yarn. A
schematic of the process based on a discussion with
Ameliotex is shown in Figure 111-52.
Another U.S. producer produces spandex fibers by a variation
of wet spinning which is known as reaction or chemical
spinning. The isocyanate-terminated prepolymer is extruded
into a bath containing toluene and a diamine (ethylene
diamine). The diamine reacts with the prepolymer by
crosslinking or chain extending to convert it to a solid
elastomeric fiber. Although individual filaments are
produced in this way, usually the individual fibers are
brought together to form a coalesced, multifilament yarn.
After leaving the ethylene diamine/toluene spin bath, the
coalesced yarn is washed with water, dried, and lubricated
prior to winding. A schematic of the process based on dis-
cussions and communications with Globe is shown in Figure
111-53.
Waste Water Generation - In addition to cooling water
discharge, the producer which uses the dry spinning process,
reports the following sources of wastes and corresponding
handling methods:
1, Waste polymer — incinerated.
2. Waste solution from the solution preparation step
— incinerated.
3. Spinning waste — incinerated.
U. Normal housekeeping water and equipment washout —
biological treatment.
5. Waste from the solvent purification and recycle
step — biological treatment.
In the wet spinning process there are cooling water
discharges, regeneration wastes from the water deionizing
unit, and occasional wastes resulting from cleanout of
lubricant (spin finish) tanks. Note that the solvent water
mixture from the spinning bath is transferred to a recovery
unit from which both solvent and water are recycled to the
spinning bath. The company states that the only water loss
is by evaporation to the atmosphere.
The primary source of waste from the other producers1
reaction or chemical spinning process originates from the
washing step which follows the spinning bath. This stream
containing wash water, toluene, and ethylene diamine is
149
-------
RECYCLE.
POLYESTER
MDI
•ISOCYANATE
TOLUENE
I
DIAMINE
COOUNG
WATER "
POLYMER-
IZATION
VESSEL
tn
O
DECANTED
WASTE
H20
STREAM
DRUMMED AND
HAULED TO DUMP
. WASTE WATER TO
MUNICIPAL
FIGURE 111-53 SPANDEX FIBER PRODUCTION - REACTION SPINNING PROCESS
-------
passed to a continuous decanter which allows separation of
toluene and water by gravity. Toluene is removed and
purified by distillation prior to being recycled to the spin
bath. Solid dregs remaining after distillation are drummed
and hauled to a landfill. In the method used by Globe, the
continuous decanter has a retention time of 160 minutes.
This is said to be sufficient to give a water effluent (con-
taining a faint odor of toluene) which is subsequently
discharged to a municipal sewage system (41, ^3) .
Other Pollutants
Depending on the particular waste water chemical conditions
and the analytical methods used, cyanides may be detected
due to the presence of isocyanates. Oil and grease presence
is due to lubricants used in the spandex fiber after
extrusion. Organic nitrogen derives from the presence of
ethylene diamine.
151
-------
Urethane Prepolymers
The reaction of a compound containing a hydroxyl (-OH) group
with a compound containing an isocyanate (-NCO) group
produces a urethane linkage as indicated in Figure 111-54,
Equation 1.
Polyurethane resins are produced by the reaction of polyols
(which are compounds containing two or more hydroxyl groups)
with polyisocyanates (which are compounds containing two or
more isocyanate groups) to form a polymer network with many
urethane linkages. In the polyurethane there may also be
other types of chemical linkages. For instance, if water is
present in the reaction mixture either as a result of inten-
tional addition of a minor amount of water or accidental
presence as humidity, the -NCO group can react with a water
molecule to produce an amine plus carbon dioxide (Figure
III-54, Equation 2). Another isocyanate group can then
react with the amine to produce a biuret linkage.
Additional -NCO groups can also react with a hydrogen of the
urethane linkage (Equation 1, Figure III-54) to produce an
allophanate linkage. However, as long as the primary
linkages in the polymer network are urethane, the product is
known as a polyurethane. There is a wide range (literally
hundreds) of polyols and several polyisocyanates that can be
utilized to make polyurethanes with a wide range of
properties.
In some cases, prepolymers are utilized to make the poly-
urethane resin. A prepolymer in the common commercial form
is a liquid reaction product of a polyol with an excess of
isocyanate to produce a low molecular weight polymer
containing reactive isocyanate end groups as exemplified by
Equation 3 in Figure 111-54. This low molecular weight
polymer normally becomes one part of a two-component system
in which the second component is additional polyol with
which the prepolymer can react to form a cross-linked cured
urethane.
There are a number of reasons for using the prepolymer tech-
nique rather than the one-shot approach in which the iso-
cyanate, polyol, and other components of a formulation are
simply mixed together and allowed to react. The prepolymer
approach often provides better control of rate of reaction
and improved compatibility and mixing characteristics in the
components. Improved product properties can often be
obtained both through better control of the reaction and
through the use of different polyols in making the
prepolymer and for the final curing. Another important
reason for using the prepolymer technique in polyurethanes
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o
(I
(1) R-OH + R'-NCO ^R-0-C-N-R'
I
H
(2) R'-NCO + H20—~R'-NH2 + CO2
(3) 3R (NCO)2 + HO R'-OH -
OCN - R (NHCOO - R' - OCO IMHR)2 NCO
FIGURE 111-54 TYPICAL REACTIONS TO FORM URETHANE PREPOLYMERS
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which utilize relatively low molecular weight
polyisocyanates such as toleuene diisocyanate (TDI) is that
prereaction of the polyol with the isocyanate reduces the
isocyanate vapor pressure and therefore lowers the toxicity
of the formulation.
Most large volume polyurethane products such as flexible and
rigid foams are produced primarily by the one-shot technique
in which all components are blended together with no
prereaction. The one-shot approach is used for large volume
products because it is the most economical method to make
polyurethanes. Prepolymers are generally used where smaller
volumes and more specialized applications of polyurethanes
are involved. For instance, foam systems that are sold as
two-component liquid formulations for field spraying or
cast-in-place applications frequently utilize prepolymers.
Similarly, for other high value products where maximum
control of the reaction is necessary, prepolymers are
frequently used. Such applications include cast elastomers,
sealants, adhesives, and two-component and air cure
polyurethane coatings.
Manufacture - Prepolymers are commonly made by batch
procedures although continuous processing techniques have
been developed. In batch processing, a reactor jacketed for
steam heating and water cooling is the only basic equipment
required. Auxiliary equipment includes a feed system to
place materials in the reactor and, frequently, a holding
tank to which two or more batches of prepolymer can be
transferred from the reactor and blended as necessary prior
to transfer to a shipping container. The prepolymerization
reaction is a simple addition reaction with no water or by-
products produced. Throughout the process, the raw
materials and the prepolymer must be stored or processed
under a blanket of dry nitrogen or other inert gas because
the isocyanate will react rapidly with any moisture present
and will thus be converted to an amine and deactivated.
The continuous processes involve primarily the use of
scraped film heat exchangers as the primary processing
equipment but are analogous to the batch operation in other
ways including maintenance of a nitrogen blanket over the
raw materials and the prepolymer to eliminate any exposure
to atmospheric moisture.
Waste Water Generation - Basically there is no water
involved in the prepolymer production except for minor
amounts which may purposely be added to the mix to produce
some biuret linkages. In fact, every effort is made to
assure that all unwanted water is excluded both from the
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feed materials and the product because the isocyanate will
rapidly react with any water to form an unwanted amine.
Even a minor amount of such unplanned reaction drastically
changes the properties of the prepolymer and may even cause
it to gel in the reactor or drum. The only water used is in
the cooling jacket of the reactor, and this is completely
separated from the reaction mixture. It is unlikely that
any water would be used for cleaning a reactor between
batches because the water would produce a rapid cure of the
prepolymer and make the cleaning operation more difficult.
In addition, the reactor would have to be thoroughly dried
before processing of a new batch could begin. There is a
remote possibility that in some instances a water miscible
solvent might be used to clean the reactor and the solvent-
prepolymer solution then mixed with water in order to react
with the prepolymer, and that such contaminated water might
be discharged. We are not aware of any such operations, and
the possibility of such contamination occurring on any
significant scale is remote because of the significant loss
of raw materials that would be involved (25) .
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SECTION IV
INDUSTRY CATEGORIZATION
The most effective means of categorizing the resin segment
of the synthetics and plastics industry was to determine if
the two most relevant characteristics of the waste waters
(i.e., raw waste loads expressed as kg of pollutant per kkg
of product* and attainable BOD5 concentrations in treated
waste waters from plants using technologies taken as the
basis of BPCTCA) were comparable to the subcategories
established for the polymers segment of the industry. The
data obtained on raw waste loads and treated waste water
characteristics from the plants observed and from
discussions with industry representatives indicated that
four major subcategories would also represent the resins
segment of the industry.
Major Subcategory I - Low raw waste load (less than 10
units/1000 units of product) ; attainable low BOD5_
concentration (less than 20 mg/liter).
Major Subcategory II - High raw waste load (greater than
10 units/1000 units of product) ; attainable low BOD5
concentration.
Major Subcategory III - High or low raw waste load;
attainable medium BOD5 concentration (in the 30-75
mg/liter range).
Major Subcategory IV - High or low raw waste load;
attainable high BOD5_ concentration (over 75 mg/liter).
The attainable BOD5 concentration in the effluent is
influenced by both treatability and, for a specific waste
water treatment plant design, by variations in the influent
concentrations.
In Major Subcategory I where reported BOD5_ raw waste loads
are less than 10 units/1000 units of product and where
hydraulic flows ranged from O.U to 153 cu m/kkg (55 to
18,300 gal/1000 Ib), the influent concentrations ranged from
8 to 720 mg/liter. While the influent concentrations varied
over a 90-fold range, the effluent concentrations varied
over a 3-fold range, i.e., 8 to 25 mg/liter. This indicates
that practicable waste water treatment plants should be
capable of retaining effluent concentrations in the vicinity
of 15 mg/liter when using properly designed and well
operated biological systems.
* Production basis for establishing the unit effluent
guidelines has been on the basis of actual production, not
rated capacity of a plant.
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The plants in Major Subcategory II are characterized by high
raw waste loads, but the waste waters can be treated to low
attainable BOD5 concentrations. Hydraulic flows varied from
1H.2 to 116 cu m/kkg (1700 to 14,000 gal./lOOO Ibs).
Influent concentrations of from approximately 600 to 4,300
mg/liter were reported. Although only one treatment plant
was found in Category II and this was producing effluent
concentrations of approximately 25 mg/liter, it is known
that the waste waters from the other processes are readily
treated by biological methods.
Major Subcategory III plants are characterized by high raw
waste loads and observed flows from 0 to 170 cu m/kkg (0 to
20,400 gal./lOOO Ibs). Influent BOD5 concentrations from 0
to 45,000 mg/liter were found, and effluent concentrations
varied from 15 to 80 mg/liter indicating intermediate
treatability of the waste waters. One of the waste water
treatment facilities attained a BOD5 removal of about 97
percent in a four-stage aeration basin indicating that
medium BOD5_ concentrations are achievable.
Major Subcategory IV facilities have high raw waste loads
with concentrations reported to be 2,200 mg/liter at flows
of from 7 to 40 cu m/kkg (900 to 4,800 gal./lOOO Ibs).
Estimates of BOD5 concentrations from a one-stage biological
system were in the vicinity of 225 mg/liter. The
supposition is made that practicable waste water treatment
technology, e.g., two-stage biological treatment, might
reduce the effluent concentration of Category IV processes
to levels comparable with the plants appearing in Major
Subcategory III; however, attainable BOD5. concentrations
below these levels have not been documented. Table VII-3
summarizes the performance of observed waste water treatment
plants.
Additional subcategorization within the above major sub-
categories was necessary to account for the waste water
generation which is specific to the individual products and
their various processing methods. The separation of each
individual product into separate subcategories simplifies
the application of the effluent limitations guidelines and
standards of performance by providing a clearly defined
context for application of the numerical values. The
advantages of this subcategorization appear to outweigh
technical advantages that might be connected with product
group characterization alone. The resulting major
subcategories and component product subcategories are
summarized in Table IV-1.
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TABLE IV-1
INDUSTRY SUBCATEGORIZATION
Major
Subcategory I
Major Major Major
Subcategory II Subcategory III Subcategory IV
Ethylene-vinyl Acrylic resins Alkyds and un- Nitrile barrier
saturated poly- resins
ester resins Spandex fibers
Cellulose nitrate
Polyamids
(Nylon 6/12)
Polyesters (therm-
plastic)
Polyvinyl-
butyral
Silicones
acetate Cellulose
copolymers derivatives
Polytetrafluoroethylene
Polypropylene
fibers
Polyvinylidene
chloride
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Several other methods for subcategorizing the industry were
considered. These included plant size, plant age, raw
materials and products, and air pollution and solid waste
generation. The utilization of municipal systems was
considered as a method of characterization for the alkyd
molding and unsaturated polyesters category, however, since
the waste waters are generally accepted into municipal
systems and since pretreatment standards would be
applicable, it was decided to establish a guidelines
limitation as though the plants were treating waste waters
in private waste water treating facilities. The age of the
plants in this industry are determined largely by
obsolescence due to size or process changes and not physical
age. Similar raw materials are often used to make
dissimilar products. The impact of air pollution control
systems using water scrubbing and the disposal of solid
wastes are not sufficient to warrant segmentation. For these
reasons none of the aforementioned factors was judged to
have sufficient relationships with raw waste load generation
or effluent compositions to warrant their use as a basis of
categorization.
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SECTION V
WASTE CHARACTERIZATION
The general process flow diagrams in Section III indicate
the major waste water generation points for individual
processes where information could be obtained. Flow rates
and compositions of process waste water streams at points of
origin were not available since the companies surveyed have
rarely monitored these streams except where excessive losses
of a particular component have been of concern, such as in
the waste waters from a distillation unit. Not only do
waste water streams emanate from direct process operations,
from chemical reaction by-products and other contacts, but
also a significant portion of waste waters may come from the
washdown of process vessels - especially where batch
operations are preeminent as in the synthetic polymers
industry - from area housekeeping, utilities blowdown and
other sources such as laboratories and so on.
Raw Waste Loads
Raw waste water flow ranges are shown in Table V-l, and
waste loads of BODJ5, COD, and suspended solids are shown in
Table V-2. These data are based on information provided by
the companies contacted during the course of this study.
Much of the data was provided as units per unit of
production by the manufacturers and was not obtained from
daily production rates and waste water flows and
concentrations. Furthermore, it is known that much of the
data on waste water flows and raw waste loads has been
derived from limited numbers of samples over short time
periods. Because the synthetic polymers industry is based
to a large extent on batch production methods and often on
the commercial need to produce a large number of product
types of a basic polymeric material, the waste water flows
and raw waste loads per unit of production were reported to
vary from essentially no water use (water leaves with
product or no water is used in manufacture) to nearly 300 cu
meters/kkg (36,000 gal./lOOO Ibs). The major pollutant
parameters for which data were obtained are BOD5, COD, and
suspended solids. Inspection of the ranges recorded in
Table V-2 shows that these pollutants vary by factors of up
to 30 from low to high values for an individual polymer.
Other pollutants which may occur in the waste water from
various polymer manufacturing processes are listed in Table
V-3. These elements, compounds, and characteristics were
developed from information obtained from industrial
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TABLE V-l
WASTEWATER LOADING FOR SYNTHETIC POLYMERS PRODUCTION
Observed or Reported Ranges of
Wastewater Loading
Acrylic resins
Alkyd molding compounds and
unsaturated polyester resins
Cellulose derivatives
Cellulose nitrate
Ethylene-vinyl acetate copolymers
Fluorocarbon polymers
Nitrile barrier resins
Polyamides
Polyester resins (thermoplastic)
Polypropylene fibers
Polyvinyl butyral
Polyvinyl ethers
Polyvinylidene chlorides
Silicones
Spandex fibers
(gal/1000*)
1700 - 5600
38 - 1440
1700 - 14000
13300 - 20400
275 - 300
2200 - 18300
900 - 4700
N.A.
260 - 770
160 - 3700
7800 - 14200
0 - 6250
500(E)
1000 - 33500
1000 - 1700
(cu m/kkg)
14.2 - 46.7
0.3 - 12.0
14.2 -116.8
110.9 -170.2
2.3 - 2.5
18.4 -152.7
7.5 - 39.2
N.A.
2.2 - 6.4
1.3 - 30.9
65.1 -118.5
0 - 52.2
4.2(E)
8.3 -279.5
8.3 - 14.2
NA = Not available
E = Estimated
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TABLE V-2
SYNTHETIC POLYMERS PRODUCTION RAW WASTE LOADS
(All units expressed as kg/kkg (lb/1000 Ibs of production)
Observed, Reported, or Estimated (E) Ranges of
Average Waste Loads
BOD COD SS
Acrylic resins 2-30 3-55 5-10
Alkyd molding compounds and unsaturated
polyester resins 9-25 15-80 1-2
Cellulose derivatives 140 - 220 340 - 950 1-42
Cellulose nitrate 55 - 110 (E) 75 - 275 (E) 35 (E)
Ethylene vinyl acetate copolymers 0.44 - 4.4(E) 0.2 - 54 (E) 0 - 4.1
Fluorocarbon polymers 0 - 6.6(E) 4.4 - 44(E) 2.2 - 6.6(E)
Nitrile barrier resins 5 - 10(E) 10 - 30(E) 3 - 10(E)
Polyamides NA NA NA
Polyester resins (thermoplastic) 0-10 1 - 30 NA
Polypropylene fibers 0.4 - 1.1 (E) 1.8 - 2.6(E) 0.2 - 2.2(E)
Polyvinyl butyral 30 - 200 40 - 400 NA
Polyvinyl ethers NA 10(E) - 40(E) NA
Polyvinylidene chlorides 0(E) 8(E) 0.2(E)
Silicones 5 - 110 15 - 200 50(E)
Spandex fibers 20(E) 40(E) NA
E = Estimated
NA «• Not available
-------
representatives, literature sources. Corps of Engineers
Permit Applications for a number of plants in the plastics
and synthetics industry, reviews with personnel in Regional
EPA offices, and internal industrial consultants.
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TABLE V-3
OTHER ELEMENTS, COMPOUNDS AND PARAMETERS
PH
Color
Turbidity
Alkalinity
Temperature
Nitrogenous Compounds(organic, ammonia and nitrates)
Oils and Greases
Dissolved Solids - principally inorganic chemicals
Phosphates
Phenolic Compounds
Sulfides
Cyanides
Fluorides
Mercury
Chromium
Copper
Lead
Zinc
Iron
Cobalt
Cadmium
Manganese
Aluminum
Magnesium
Molybdenum
Nickel
Vanadium
Antimony
Numerous Organic Chemicals
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SECTION VI
SELECTION OF POLLUTANT PARAMETERS
The selection of pollutant parameters for the purpose of
effluent limitations guidelines and standards of performance
was based on the following general criteria:
a. Sufficient data on a parameter known to have
deleterious effects in the environment were
available for all of the product subcategories with
regard to the raw waste load and the observed
degree of removal with demonstrated technology.
b. The parameter is present in the raw waste load for
an individual product subcategory in sufficient
quantity to cause known deleterious effects in the
environment and there is demonstrated technology
available to remove the parameter.
Selected Parameters
The following parameters have been selected for the purpose
of establishing recommended effluent limitations guidelines
and standards of performance based on the criteria discussed
above.
BOD5
Biochemical oxygen demand (BOD) is a measure of the oxygen
consuming capabilities of organic matter. The BOD does not
in itself cause direct harm to a water system, but it does
exert an indirect effect by depressing the oxygen content of
the water. Sewage and other organic effluents during their
processes of decomposition exert a BOD, which can have a
catastrophic effect on the ecosystem by depleting the oxygen
supply. Conditions are reached frequently where all of the
oxygen is used and the continuing decay process causes the
production of noxious gases such as hydrogen sulfide and
methane. Water with a high BOD indicates the presence of
decomposing organic matter and subsequent high bacterial
counts that degrade its quality and potential uses.
Dissolved oxygen (DO) is a water quality constituent that,
in appropriate concentrations, is essential not only to keep
organisms living but also to sustain species reproduction,
vigor, and the development of populations. Organisms
undergo stress at reduced DO concentrations that make them
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less competitive and able to sustain their species within
the aquatic environment. For example, reduced DO
concentrations have been shown to interfere with fish
population through delayed hatching of eggs, reduced size
and vigor of embryos, production of deformities in young,
interference with food digestion, acceleration of blood
clotting, decreased tolerance to certain toxicants, reduced
food efficiency and growth rate, and reduced maximum
sustained swimming speed. Fish food organisms are likewise
affected adversely in conditions with suppressed DO. Since
all aerobic aquatic organisms need a certain amount of
oxygen, the consequences of total lack of dissolved oxygen
due to a high BOD can kill all inhabitants of the affected
area.
If a high BOD is present, the quality of the water is
usually visually degraded by the presence of decomposing
materials and algae blooms due to the uptake of degraded
materials that form the foodstuffs of the algal populations.
COD
Chemical oxygen demand (COD) provides a measure of the
equivalent oxygen required to oxidize the materials present
in a waste water sample under acid conditions with the aid
of a strong chemical oxidant, such as potassium dischromate,
and a catalyst (silver sulfate). One major advantage of the
COD test is that the results are available normally in less
than three hours. Thus, the COD test is a faster test by
which to estimate the maximum oxygen exertion demand a waste
can make on a stream. However, one major disadvantage is
that the COD test does not differentiate between
biodegradable and nonbiodegradable organic material. In
addition, the presence of inorganic reducing chemicals
(sulfides, reducible metallic ions, etc.) and chlorides may
interfere with the COD test. As a rough generalization, it
may be said that pollutants which would be measured by the
BOD5 test will also show up under the COD test, but that
additional pollutants which are more resistant to biological
oxidation (refractory) will also be measured as COD.
Total Suspended Solids
Suspended solids include both organic and inorganic
materials. The inorganic components include sand, silt, and
clay. The organic fraction includes such materials as
grease, oil, tar, animal and vegetable fats, various fibers,
sawdust, hair, and various materials from sewers. These
solids may settle out rapidly and bottom deposits are often
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a mixture of both organic and inorganic solids. They
adversely affect fisheries by covering the bottom of the
stream or lake with a blanket of material that destroys the
fishfood bottom fauna or the spawning ground of fish.
Deposits containing organic materials may deplete bottom
oxygen supplies and produce hydrogen sulfide, carbon
dioxide, methane, and other noxious gases.
In raw water sources for domestic use, state and regional
agencies generally specify that suspended solids in streams
shall not be present in sufficient concentration to be
objectionable or to interfere with normal treatment
processes. Suspended solids in water may interfere with
many industrial processes and cause foaming in boilers, or
encrustations on equipment exposed to water, especially as
the temperature rises. Suspended solids are undesirable in
water for textile industries; paper and pulp; beverages;
dairy products; laundries; dyeing; photography; cooling
systems; and power plants. Suspended particles also serve
as a transport mechanism for pesticides and other substances
which are readily sorbed into or onto clay particles.
Solids may be suspended in water for a time, and then settle
to the bed of the stream or lake. These settleable solids
discharged with man's wastes may be inert, slowly
biodegradable materials, or rapidly decomposable substances.
While in suspension, they increase the turbidity of the
water, reduce light penetration, and impair the
photosynthetic activity of aquatic plants.
Solids in suspension are aesthetically displeasing. When
they settle to form sludge deposits on the stream or lake
bed, they are often much more damaging to the life in water,
and they retain the capacity to displease the senses.
Solids, when transformed to sludge deposits, may do a
variety of damaging things, including blanketing the stream
or lake bed and thereby destroying the living spaces for
those benthic organisms that would otherwise occupy the
habitat. When of an organic and therefore decomposable
nature, solids use a portion or all of the dissolved oxygen
available in the area. Organic materials also serve as a
seemingly inexhaustible food source for sludgeworms and
associated organisms.
Turbidity is principally a measure of the light absorbing
properties of suspended solids. It is frequently used as a
substitute method of quickly estimating the total suspended
solids when the concentration is relatively low.
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pH, Acidity and Alkalinity
Acidity and alkalinity are reciprocal terms. Acidity is
produced by substances that yield hydrogen ions upon
hydrolysis and alkalinity is produced by substances that
yield hydroxyl ions. The terms "total acidity" and "total
alkalinity" are often used to express the buffering capacity
of a solution. Acidity in natural waters is caused by
carbon dioxide, mineral acids, weakly dissociated acids, and
the salts of strong acids and weak bases. Alkalinity is
caused by strong bases and the salts of strong alkalies and
weak acids.
The term pH is a logarithmic expression of the concentration
of hydrogen ions. At a pH of 7, the hydrogen and hydroxyl
ion concentrations are essentially equal and the water is
neutral. Lower pH values indicate acidity while higher
values indicate alkalinity. The relationship between pH and
acidity or alkalinity is not necessarily linear or direct.
Waters with a pH below 6.0 are corrosive to water works
structures, distribution lines, and household plumbing
fixtures and can thus add such constituents to drinking
water as iron, copper, zinc, cadmium, and lead. The
hydrogen ion concentration can affect the "taste" of the
water. At a low pH water tastes "sour." The bactericidal
effect of chlorine is weakened as the pH increases, and it
is advantageous to keep the pH close to 7. This is very
significant for providing safe drinking water.
Extremes of pH or rapid pH changes can exert stress
conditions or kill aquatic life outright. Dead fish,
associated algal blooms, and foul stenches are aesthetic
liabilities of any waterway. Even moderate changes from
"acceptable" criteria limits of pH are deleterious to some
species. The relative toxicity to aquatic life of many
materials is increased by changes in the water pH.
Metalocyanide complexes can increase a thousand-fold in
toxicity with a drop of 1.5 pH units. The availability of
many nutrient substances varies with the alkalinity and
acidity. Ammonia is more lethal with a higher pH.
The lacrimal fluid of the human eye has a pH of
approximately 7.0 and a deviation of 0.1 pH unit from the
norm may result in eye irritation for the swimmer.
Appreciable irritation will cause severe pain.
Other Pollutant Parameters
The quantitative identification of other pollutants from
analytical data was impossible to establish. However, the
following are identified as the major other pollutants or
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parameters which may have to be considered in the National
Pollution Discharge Elimination System permits.
Phgnolic Compounds
Phenols and phenolic wastes are derived from petroleum,
coke, and chemical industries; wood distillation; and
domestic and animal wastes. Many phenolic compounds are
more toxic than pure phenol; their toxicity varies with the
combinations and general nature of total wastes. The effect
of combinations of different phenolic compounds is
cumulative.
Phenols and phenolic compounds are both acutely and
chronically toxic to fish and other aquatic animals. Also,
chlorophenols produce an unpleasant taste in fish flesh that
destroys their recreational and commercial value.
It is necessary to limit phenolic compounds in raw water
used for drinking water supplies, as conventional treatment
methods used by water supply facilities do not remove
phenols. The ingestion of concentrated solutions of phenols
will result in severe pain, renal irritation, shock, and
possibly death.
Phenols also reduce the utility of water for certain
industrial uses, notably food and beverage processing, where
it creates unpleasant tastes and odors in the product.
Nitrogenous Compounds
Nitrogenous compounds can occur as a result of biological
activity in the waste water treatment and can also come from
manufacturing processes such as urea, melamine, nylon,
ABS/SAN, cellulose nitrate, cellulose derivatives, nitrile
barrier resins, and acrylics. Ammonia is a common product
of the decomposition of organic matter. Dead and decaying
animals and plants along with human and animal body wastes
account for much of the ammonia entering the aquatic
ecosystem. Ammonia exists in its non-ionized form only at
higher pH levels and is the most toxic in this state. The
lower the pH, the more ionized ammonia is formed and its
toxicity decreases. Ammonia, in the presence of dissolved
oxygen, is converted to nitrate (NO.3) by nitrifying
bacteria. Nitrite (NO2.) , which is an intermediate product
between ammonia and nitrate, sometimes occurs in quantity
when depressed oxygen conditions permit. Ammonia can exist
in several other chemical combinations including ammonium
chloride and other salts.
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Nitrates are considered to be among the poisonous
ingredients of mineralized waters, with potassium nitrate
being more poisonous than sodium nitrate. Excess nitrates
cause irritation of the mucous linings of the
gastrointestinal tract and the bladder; the symptoms are
diarrhea and diuresis, and drinking one liter of water
containing 500 mg/1 of nitrate can cause such symptoms.
Infant methemoglobinemia, a disease characterized by certain
specific blood changes and cyanosis, may be caused by high
nitrate concentrations in the water used for preparing
feeding formulae. While it is still impossible to state
precise concentration limits, it has been widely recommended
that water containing more than 10 mg/1 of nitrate nitrogen
(NO_3-N) should not be used for infants. Nitrates are also
harmful in fermentation processes and can cause disagreeable
tastes in beer. In most natural water the pH range is such
that ammonium ions (NH4+) predominate. In alkaline waters,
however, high concentrations of un-ionized ammonia in
undissociated ammonium hydroxide increase the toxicity of
ammonia solutions. In streams polluted with sewage, up to
one-half of the nitrogen in the sewage may be in the form of
free ammonia, and sewage may carry up to 35 mg/1 of total
nitrogen. It has been shown that at a level of 1.0 mg/1 un-
ionized ammonia, the ability of hemoglobin to combine with
oxygen is impaired and fish may suffocate. Evidence
indicates that ammonia exerts a considerable toxic effect on
all aquatic life within a range of less than 1.0 mg/1 to 25
mg/1, depending on the pH and dissolved oxygen level
present.
Ammonia can add to the problem of eutrophication by
supplying nitrogen through its breakdown products. Some
lakes in warmer climates, and others that are aging quickly
are sometimes limited by the nitrogen available. Any
increase will speed up the plant growth and decay process.
Fluorides
As the most reactive non-metal, fluorine is never found free
in nature but as a constituent of fluorite or fluorspar,
calcium fluoride, in sedimentary rocks and also of cryolite,
sodium aluminum fluoride, in igneous rocks. Owing to their
origin only in certain types of rocks and only in a few
regions, fluorides in high concentrations are not a common
constituent of natural surface waters, but they may occur in
detrimental concentrations in ground waters.
Fluorides are used as insecticides, for disinfecting brewery
apparatus, as a flux in the manufacture of steel, for
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preserving wood and mucilages, for the manufacture of glass
and enamels, in chemical industries, for water treatment,
and for other uses.
Fluorides in sufficient quantity are toxic to humans, with
doses of 250 to 450 mg giving severe symptoms or causing
death.
There are numerous articles describing the effects of
fluoride-bearing waters on dental enamel of children; these
studies lead to the generalization that water containing
less than 0.9 to 1.0 mg/1 of fluoride will seldom cause
mottled enamel in children, and for adults, concentrations
less than 3 or 4 mg/1 are not likely to cause endemic
cumulative fluorosis and skeletal effects. Abundant
literature is also available describing the advantages of
maintaining 0.8 to 1.5 mg/1 of fluoride ion in drinking
water to aid in the reduction of dental decay, especially
among children.
Chronic fluoride poisoning of livestock has been observed in
areas where water contained 10 to 15 mg/1 fluoride.
Concentrations of 30 - 50 mg/1 of fluoride in the total
ration of dairy cows is considered the upper safe limit.
Fluoride from waters apparently does not accumulate in soft
tissue to a significant degree and it is transferred to a
very small extent into the milk and to a somewhat greater
degree into eggs. Data for fresh water indicate that
fluorides are toxic to fish at concentrations higher than
1.5 mg/1.
Phosphates
Surfactants may be used in the proprietary formulations of a
number of manufacturing processes such as polypropylene
fibers, acrylic resins, nitrile barrier resins, thermo-
plastic polyesters, polyvinylidene chloride, and so on.
During the past 30 years, a formidable case has developed
for the belief that increasing standing crops of aquatic
plant growths, which often interfere with water uses and are
nuisances to man, frequently are caused by increasing
supplies of phosphorus. Such phenomena are assoc.ated with
a condition of accelerated eutrophication or aging of
waters. It is generally recognized that phosphorus is not
the sole cause of eutrophication, but there is evidence to
substantiate that it is frequently the key element in all of
the elements required by fresh water plants and is generally
present in the least amount relative to need. Therefore, an
increase in phosphorus allows use of other, already present,
173
-------
nutrients for plant growths. Phosphorus is usually
described, for this reason, as a "limiting factor."
When a plant population is stimulated in production and
attains a nuisance status, a large number of associated
liabilities are immediately apparent. Dense populations of
pond weeds make swimming dangerous. Boating and water
skiing and sometimes fishing may be eliminated because of
the mass of vegetation that serves as an physical impediment
to such activities. Plant populations have been associated
with stunted fish populations and with poor fishing. Plant
nuisances emit vile stenches, impart tastes and odors to
water supplies, reduce the efficiency of industrial and
municipal water treatment, impair aesthetic beauty, reduce
or restrict resort trade, lower waterfront property values,
cause skin rashes to man during water contact, and serve as
a desired substrate and breeding ground for flies.
Phosphorus in the elemental form is particularly toxic, and
subject to bioaccumulation in much the same way as mercury.
Colloidal elemental phosphorus will poison marine fish
(causing skin tissue breakdown and discoloration). Also,
phosphorus is capable of being concentrated and will
accumulate in organs and soft tissues. Experiments have
shown that marine fish will concentrate phosphorus from
water containing as little as 1 ug/1.
Oils and Greases
Although oils and greases are most frequently found to occur
as the result of equipment leaks and so on, and are not
usually of significant concern to this industry, some
manufacturing processes such as are used to produce sili-
cones, polypropylene, and spandex fibers may require that
oil and grease be considered a parameter.
Oil and grease exhibit an oxygen demand. Oil emulsions may
adhere to the gills of fish or coat and destroy algae or
other plankton. Deposition of oil in the bottom sediments
can serve to exhibit normal benthic growths, thus
interrupting the aquatic food chain. Soluble and emulsified
material ingested by fish may taint the flavor of the fish
flesh. Water soluble components may exert toxic action on
fish. Floating oil may reduce the re-aeration of the water
surface and in conjunction with emulsified oil may interfere
with photosynthesis. Water insoluble components damage the
plumage and coats of water animals and fowls. Oil and
grease in a water can result in the formation of
objectionable surface slicks preventing the full aesthetic
enjoyment of the water.
174
-------
Oil spills can damage the surface of boats and can destroy
the aesthetic characteristics of beaches and shorelines.
Dissolved Solids
Dissolved inorganic salts are an integral part of the
operation of many processes. Although no effluent guide-
lines have been established for dissolved solids, receiving
stream water quality standards should determine if
limitations are necessary. Manufacturing processes for the
following products are believed to produce the greatest
loads of dissolved solids:
Acrylic resins
Cellulose derivatives
Cellulose nitrate
Polytetrafluoroethylene
Silicones
In natural waters the dissolved solids consist mainly of
carbonates, chlorides, sulfates, phosphates, and possibly
nitrates of calcium, magnesium, sodium, and potassium, with
traces of iron, manganese, and other substances.
Many communities in the United States and in other countries
use water supplies containing 2000 to 4000 mg/1 of dissolved
salts, when no better water is available. Such waters are
not palatable, may not quench thirst, and may have a
laxative action on new users. Waters containing more than
-------
other aquatic life, primarily because of the antagonistic
effect of hardness on metals.
Waters with total dissolved solids over 500 mg/1 have
decreasing utility as irrigation water. At 5,000 mg/1 water
has little or no value for irrigation.
Dissolved solids in industrial waters can cause foaming in
boilers and cause interference with cleanliness, color, or
taste of many finished products. High contents of dissolved
solids also tend to accelerate corrosion.
Specific conductance is a measure of the capacity of water
to convey an electric current. This property is related to
the total concentration of ionized substances in water and
water temperature. This property is frequently used as a
substitute method of quickly estimating the dissolved solids
concentration.
Toxic and Hazardous Chemicals
The industry uses a large number of accelerators and
inhibitors which are considered proprietary and, conse-
quently, no information could be obtained. Some of these
compounds, especially cyanide, cadmium, and mercuric
compounds, may be on EPA's recently proposed list of toxic
substances as published in the Federal Register of December
27, 1973.
Alkalinity, Color, Turbidity, and the Metals Listed in Table
V-3
These pollutants may be present in waste waters from
selected processes in varying amounts; however, no data
could be obtained which would permit establishing raw or
treated waste loads. Therefore, they are listed so that
appropriate cognizance can be taken to determine whether or
not they are present in amounts requiring effluent
limitation because of receiving water quality standards.
Where appropriate the particular parameters are summarized
in Table VI-1.
176
-------
TABLE VI-1
OTHER ELEMENTS AND COMPOUNDS SPECIFIC TO THE
RESINS SEGMENT OF PLASTICS AND SYNTHETICS INDUSTRY
Alkyd Compounds and
Ester Resins
Polytetrafluoroethylene
Spandex Fibers
Acrylic Resins
Polypropylene Fibers
Nitrile Barrier Resins
Polyamides
Cellulose Derivatives
Cellulose Nitrate
Silicones
Polyvinylidene Chloride
Polyester Resins (Thermoplastic)
Lead
Cobalt
Fluorides
Cyanides
Oils and Grease
Organic Nitrogen
Oils and Grease
Oils and Grease
Phosphates
Organic Nitrogen
Cyanides
Organic Nitrogen
Inorganic Nitrogen
Inorganic Nitrogen
Polychlorinated
Organics
Copper
Fluorides
Polychlorinated
Organics
Cobalt
Manganese
Cadmium
177
-------
-------
SECTION VII
CONTROL AND TREATMENT TECHNOLOGY
Technology for the control and treatment of waste waters
from this segment of the plastics and synthetics industry is
not specific to the industry but can utilize any of the
broad spectrum of technologies found in waste water
treatment. These technologies can be divided into the same
three broad categories found in the rest of the synthetics
and plastics industry. These are:
1. Presently used waste water treatment technology.
2. Potentially usable waste water treatment
technology.
3. Control of waterborne pollutants by in-plant or in-
process practices.
The application of presently or potentially usable waste
water treatment technologies may be applied on selected
bases to segregated streams or may be incorporated into a
centralized waste water treatment plant. Although
categories 1 and 2, often denoted as end-of-pipe treatment,
may be applied regardless of the manufacturing process, in-
process control to prevent pollutants from entering water
streams has a great potential for reducing the load of
pollutants as well as the waste water flows. The
application of in-plant control technology falls into two
broad categories: (1) process requirements and (2) plant
practices. Process requirements for water usage depend upon
the types of reactions being carried out, the amounts of
unreacted raw materials or undesired by-products that must
be removed by water washing to attain product
specifications, the removal of catalyst activators or other
additives necessary to control the reaction or create the
appropriate chemical characteristics, and the use of water
for quenching, creating vacuum, or other operations that
contact process streams. The emission of pollutants into
waste streams outside of the direct process operations may
come from poor housekeeping practices or from the excessive
usage of water for cleaning up spills, leaks, and accidental
occurrences due to equipment failure or personnel error.
Water used to control accidental occurrences or hazardous
conditions, such as fires, etc., is employed very
occasionally, and usually is not considered as contributing
to the pollution loads in the waste waters. Recycle of
179
-------
treated waste waters for such uses as housekeeping, cooling
tower makeup and fire ponds is currently being practiced in
the industry. One plant reports reuse of up to 75 percent
of its treated effluent. (50)
As indicated earlier, the survey found no waste water
treatment technologies unique to this segment of the
plastics and synthetics industry. The waste water treatment
technology is similar to that found during the survey of the
first segment of the industry and is generally similar to
that of other industries. Obviously, application of
basically similar technology, e.g., activated sludge
biological treatment, often requires unique conditions for
specific waste water and results in considerable variation
in performance characteristics such as efficiency of
pollutant removal.
Presently Used Waste Water Treatment Technology
This segment of the plastics and synthetics industry was
found to have relatively few waste water treatment plants
devoted solely to the treatment of the waste waters from a
particular product. A major portion of the individual
manufacturing plants, except in the alkyd and polyester
resins categories, was visited or otherwise contacted to
determine if water treatment facilities were installed. It
was found that a large portion of the waste waters from the
various products enter either centralized treatment
facilities for multi-plant chemical complexes or municipal
sewage systems. The major portion of the waste waters from
the manufacture of silicones is treated or will be treated
in their own waste water treatment plants. Typical
operating data or design information on silicone waste water
treatment plants are included in Tables VII-1 and VI1-2;
however, one-half of the companies requested confidential
handling of the data provided and, therefore, those data are
not included. In addition, confidentiality was requested by
a polytetrafluoroethylene and a nitrile barrier resin
manufacturer. Although a significant portion of the design
and operating data shown in Tables VII-1 and VII-2 are from
waste water treatment plants receiving waste waters from a
number of different chemical manufacturing processes, the
inclusion of data from multi-process waste water treatment
plants was made to indicate the operating conditions and
efficiencies found even though the load of pollutants from
the particular process was a small portion of the total load
on the waste water treatment plant. It must be recognized
that the efficiency of pollutant removal from waste waters
would not necessarily be the same as that demonstrated by
the multi-process treatment plant unless the waste waters
180
-------
TABLE VII-1
OPERATIONAL PARAMETERS OF VASTEHATER TREATMENT PLANTS
(Metric Units)
00
Type of Plant Methyl* Polyvlnyl Thermoplastic*
Methacrylate Butyral P/E
Acrylic* Vinyl Acetate EVA Polypropylene
*1* 12*
1 Type of Treatment Neut, screen, Equal, aer Equal S neut (30-70Z of wastes Skin, oil sep skim, filter. Skim, oil aep Skim before
equalize, lagoon coag aer lagoons due to acrylic equal, bio-aer burn recovered clar, aoaerob discharge
cool, nutrient, add, clarlf mfg) equal, 2 clarif w/chem oil, recycle bio
bio Ox, clarify, trickling filters add, bio-anaer-recovered
Polyvinylidene*
Chloride
Aerated lagoon
settling basin
sludge aeration parallel or serial oblc polymer
& centrlfuglng clarlf 4 polish (primary only) (primary only)
lagoons (57 acres)
2 Hydraulic Load (cu m/day) 11,000(6800 actual) 1,135 43,906 3,936 409 4.807 30.280 1,890 4.656
3 Residence Time (hours) Cl) "' ~"
4 BODj (kg removed/ day /cu m)
5 COD (.kg removed/day/cu m)
6 Power (HP/cu m)
7 Suspended solids (mg/llter)
8 Clarlfler overflew (m/day)
9 Blomass (mg/llter)
10 BOD$ (kg removed/day/kg HLSS)
11 Typical Values KBy-H out (mg/lltar)
12 Typical Values TKH out (mg/litar)
13 BODj In (mg/llter)
14 BODj out (mg/ liter)
15 COD BODj In
16 COD in (mg/llter)
17 COD out (mg/llter)
18 COD/BODj out
19 Iff. BODj Removal
20 Eff . COD Removal
Contents I
194- 34 120(2904)
0.85+ 0.36 0.009
0.46
0.106+ 0.06 0.018
50* 135
24.5 7.7
30004- 2991
0.17
14.6
14.8
800+ 543 1.476
120+ 39.7 422
1.5
839
179
4.5
854- 92.7+ 71+
79+ -
+ Design Values
Submerged aerators
41.5(424) 36 0.3 ' 8760
°-l°9 1.0? (API type skimmer) -
0.58 _
* 0.007 - 40.7
42 28 23 - 33
24.4 & 57.0 o.20 - 51
1200-1800 -
- - - -
1-89 - .1 to 1.5
8.33 - _
!.'*6 1,562 - (154) +
11 17 13 -
0.6(TOC/BOD) . (4.2) +
904(TOC) - 20.000(100)
" 37(TOC) 47 SOO(TOC) 27
I'*5 2.2(TOC/BOD) 3.6
99.4 99+
96+(TOC) - 96(TOC)
-
-
"
~
35
-
-
***
"
—
59
22
13
776
251
11.4
63+
68+
Notes:
horsepower
calculated froa
size of blowers.
* Indicates wastewater plant serves a chemical manufacturing
(1J First value is residence time In aerobic biological system.
Values In ( ) is residence time in total system.
-------
TABLE VII-1
(Continued)
OPERATIONAL PARAMETERS OF HASIEUATER TREATMENT PLANTS
(Metril Unite)
1-1
CO
NJ
I
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Co
Type of Plant
Type of Treatment (Neut.)
municipal
treatment
Hydraulic Load (cu m/day) 5-'
Residence Time (hours)*1'
BOD- (f removed/day/ cu •) ~
COD (fremoved/day/cu a) ~
Power (HP/cu m)
Suspended solids (mg/liter) -
Clarlfier overflow (a/day)
Blomass (mg/liter) -
"BODj (kg removed/day/kg MLSS)
Typical Values NHyN out (mg/llter)
Typical Values TKN out (ag/lic«r) ~
BOD, in(mg/liter) -
BODj out (mg/llter)
COD BODj In
COD in (mg/llter)
COD out (ag/llter)
COD/BODj out
Eff. BODj Removal
Eff. COD Removal
•menu! +Deslgn Values
Submerged aerators
horsepower
calculated from
Alkyd/Polyester Resins
Settling, bio* Municipal
aerobic (4 treatment
»tage)clarify (neut) *
hold lagoon
170 2
252
0.28
0.36
0.034
64
12.7
4,000
0.7
(Nutrients added) -
-
2,960
28
1.36
3,890
146
5.2
99+
96.2+
Includes lagoon
separator -
skinner, sump
* pH controller.
Silicones
Neut screen Neut. clsrify Bio-aerobic,
sedimentation sludge dewster clarify
screen) , skia. basin
filtration
(proposed
(primary onlf) (priaary only) secondary)
1,022 25,740 25,740
1.3 3+
(clarlfier)
- -
-
_
20 100
43.2 24.4
6500+
0.04
-
1.12
276+
24 - 38+
2.5
688
13.9 - 205+
0.58 - 5.4+
86.2+
70.2+
Cellulose* Polyvinyl Ether Spandex
Nitrate
*1* »2*
Neut. aedlaent Equal, naut. Settle 6 neut Biological Municipal
spray oxidation process wastes coagulation, treatment
wastes act. atlon
sludge clarify
2.0 *.«0 34,440
8.4 - 7.5 plant
2 city
i 0.93
0.66
0.02 - -
40.6 60 208 120
52.3
_ -
- - -
156
- 16 - -
219 - 776 2.200 3,900
30 1,100 104 225
3.05 2.1
2,370 4,440
123 .4 • S40 * ~
4.1+ 1.6 6.2 6.4
86 - 8*. 6 73
73 65-70+
size of blowers,
* Indicates wastewater plant serves a
chemical manufacturing complex.
(1) First value Is residence tine In
aerobic biological systea.
Valuea in ( ) is residence tlaa in
total system.
-------
TABLE VI1-2
OPERATIONAL PARAMETERS OF MASTEWATER TREATMENT PLANTS
(English Units)
1
2
3
4
5.
6
7
8
9
00 10
11
12
13
14
15
16
17
18
19
20
Type of Plant
Type of Treatment
Hydraulic Load (MGD)
Residence Time (hours)
BODj (*removed/day/1000 ft3)
COD (fremoved/day/1000 ft3)
Power (HP/1000 ft3)
Suspended solids (mg/llter)
Clarifier overflow (CPD/ft2)
Biomaas (mg/llter)
BODS (1 renoved/day/IMLSS)
Typical Values NH.-ti out(mg/liter)
Typical Values TKN out (me/liter)
BODS in (mg/liter)
BODj out (mg/liter)
COD/BODj in
COD in (mg/liter)
COD out (mg/liter)
COD/BOD5 out
Eff. EODj Removal
Eff. COD Removal
Methyl*
Methacrylate
Neut, screen,
equalize,
cool, nutrient,
bio ox, clarify,
sludge aeration
& centrifuging
2.9+
(1.8 actual)
19+
53+
-
3.0
50+
600+
3,000+
0.23
-
-
800+
120+
-
-
-
85+
_
Polyvinyl
Butyral
Equal, aer
lagoon coag
add, clarif
0.3
34
22
29
1.7
135
189
2,991
0.17
14.6
14.8
543
39.7
1.5
839
179
4.5
92.7+
79+
Thermoplastic * Acrylic*
P/E
Equal & neut, (30-702 of wastes
aer lagoons due to acrylic
mfg) equal, 2
tricking filters
clarif 4 polishing
lagoonn (57 acres)
11.6 1.04
120(2904) 41.5(424)
0.54 6.8
-
0.5
42
600 t 1400
-
-
1.89
8.33
1,476 1,946
422 11
-
-
16
1.45
7Hf 99.4
-
Vinyl Acetate
EVA
tl 12
Skim, oil sep Skim, filter, Skim, oil sep
equal, bio-aer burn recoverd clar, aoaerob
clarif w/chem oil, recycle bio
add, blo-anaer-recovered
obic polymer
(primary only)
0.108
36
1.27 8
0-3 8.760
Polypropylene Polyvinylidene*
Chloride
Skim before Aerated lagoon
discharge settling basin
(primary only)
Q.5 1.23 MGD
-
64 (API type skimmer) -
36 (TOC)
0.2
28
5
1200-1800
—
—
"
17
0.6(TOC/BOD)
904 (TOC)
37 (TOC)
2.2(TOC/BOD)
99+
96+(TOC)
-
-
23
1,257
-
•- —
.1 to 1.5
~ ~
(154)+
13
(4.2)+
20,000(TOC)
47 800 (TOC)
3.6
* -
96 (TOC)
-
-
33 35
-
-
- -
- -
— —
59
22
13
776
27 251
11.4
63+
68+
+ Design value
Submerged aerators
horsepower
calculated from
size of blowers.
* Indicates wastewater plant serves a chemical
manufacturing complex.
(1) First value is residence time in aerobic biological syste
Values in ( ) is residence time In total system.
-------
00
TABLE VII-2
(Continued)
OPERATIONAL PARAMETERS OF WASTEWATER TREATMENT PLANTS
(English Units)
Type of Plant
1
2
3
4
5
6
7
8
»
10
11
12
13
14
15
J6
17
18
19
20
Type of Treatment
Hydraulic Load (MOD)
Residence Time (hours) (1)
BODj (*removed/day/1000 cu ft)
COD (fremoved/day/1000 cu ft)
Pover (HPAOOO =u ft)
Suspended solids (mg/liter)
Clarlfier overflow (m/day)
Biomass (mg/llter)
BODj ( I removed/day/ ' MLSS)
Typical Values NHyH out (mg/liter)
Typical Values TKN out (mg/lttar)
BOD. In (mg/llter)
BODj out (m«/llt«r)
COO BOD5 in
COD in (mg/liter)
COD out (mg/liter)
COD/BODj out
Eff. BODj Removal
Eff. COD Removal
Alkyd/Polyester Resins
Sllicones Cellulose* Polyvinyl Spandex
Nitrate Ether
ii
(Neut.) Settling, Municipal Neut screen Neut. clarify Bio-aerobic, Neut. sediment Equal. Settle & neut Biological
Municipal aerobic (4 treatment sedimentation sludge dewater clarify spray oxidation neut process wastes coagulation
treatment stage) (neut.) I hid screen, skim, basin chlorinate city centrifuga-
clarify lagoon filtration wastes act. tion
(proposed sludge clarify
(primary only) (primary only) secondary)
0.0015 0.045 0.00053
252
17.4
22.2
0.95
64 -
312.5
4,000
0.7
(Nutrients added)
-
2,960
28 -
1.36
3,890
146
5.2
99+ -
96.2+
0.27 6.8 6.8 2.0 1.3 9.1
1.3 3+ 8.4 - 7.5 plant
(clarifier) 2 city
- ... 58
- - - 41
- 0.6 -
20 100 - 40.6 60 208 120
1,060 6CO+ - - 1,283
r - 6,500+ - - -
0.04 - - -
156
1.12 - 16
276+ 219 - 776 2,200
24 - 38+ 30 1,100 104 225
2.5 3.05 2.1
- 688 - ,S70 4,400
13.9 - 205+ 123.4 1,800 640 1.440
0.58 - 5.4+ 4.1+ 1.6 6.2 6.4
86.2+ 86 - 86.6 90+
70.2+ - '* 65-70+
12
Municipal
treatment
_
-
-
-'
-
-
-
-
-
-
3,900
-
-
-
-
-
-
-
Kott*:
+Design Values
Submerged aerators
horsepower
calculated from
•lea of blowers.
^Indicates vastewater plant serves a cheaical
manufacturing complex.
(1) First v.lue la residence tliM la aerobic
biological system.
Values in ( ) is residence; tiste in total
eystea.
Includes lagoon
separator -
akissMr. sunp
ft pH controller*
-------
TABLE VII-3
PERFORMANCE OF OBSERVED WASTEWATER TREATMENT PLANTS
BOD.
COD
Suspended Solids
Inlet Outlet
mg/liter rag/liter
Inlet Outlet Inlet Outlet
mg/liter mg/liter mg/liter mg/liter
Major Subcategory I
Ethylene-Vinyl Acetate*
Ethylene-Vinyl Acetate*
Fluorocarbons
Polypropylene Fibers
Polyvinylidene Chloride*
Major Subcategory II
Acrylic Resins*
Acrylic Resins**
Cellulose Derivatives
Polyvinyl Butyral
Major Subcategory III
Alkyds & Unsat. Polyesters
Cellulose Nitrate
Polyamids (Nylon 6/12 only)
Polyesters (Thermoplastic)*
Polyvinyl Ethers***
Sillcones**
Major Subcategory IV
Nitrile Barrier Resins
Spandejc*
59
630
666
1476
776
276
20,000(TOC) SOO(TOC)
10 - 48
8
22
17
66
543 40
2960 28
251 34
422
104
38
27
776 251
24
839
3890
2370
688
179
146
124
640
205
21
360
42
135
64
41
208
2200 225
4400 1440
120
* Part of a multi-plant wastewater treatment facility : Polyester operations contribute app. 14Z of the
lo adin g
** Design values - facility not operable at time of visit
*** Combined industrial municipal treatment facility
185
-------
TABLE VII-4
OBSERVED TREATMENT AND AVERAGE EFFLUENT LOADINGS FROM WASTE WATER TREATMENT PLANT INSPECTIONS
Produce Acrylic Resinfl Acrylic Resins Alkyds and Cellulose Ethylene-
Unsaturated Nitrate* Vinyl Acetate'
Polyester
Ccscrol and Treat- Equalization, Neutralization, Settling. Four- Neutralization, Skianning
Currently in Use Polishing Lagoons Bio-oxidation oxidation Spray Oxidation
(design)
Polypropylene Polyvinyl
* Fibers Butyral Silicones
Skimming Equalization, (Multi-Product) (Fluid Product)
Sludge Bio-oxidation Sedimentation
(design) S timing, Fi It rati<
of Product]
BOD5
too
Suspended Solids
o.fo
3.1
30.8
0.09
0.47
0.21
Observed or Reported Effluent Loading
3.34 0.07
13.7 0.25
4.4 0.15
0.24
0.78
0.98
2.6
13.6
6.5
8.6
46.0
25.0.
•Multi-plant vastevater treatment facility
-------
represented the major portion of the hydraulic and pollutant
load. Because of the many variables that can influence
performance of a waste water treatment plant, the
performance of a multi-process waste water treatment plant
can only be taken as a qualitative indicator of the removal
efficiency that might be achieved when operating exclusively
on the waste waters from a single process. The paucity of
data on waste water treatment facilities, as recorded in
Tables VII-1, VII-2, VII-3, and VII-4, for this segment of
the industry is not surprising because of the relatively
small production capacities of the products and the use of
municipal sewerage systems or multi-process waste water
treatment plants.
Biological treatment of the waste waters from this segment
of the industry appears to be the method chosen for
effecting removal of soluble substances. Pretreatment
before biological systems is often required whether the
biological system is operated by the manufacturer or is a
municipal sewage treatment plant. This treatment is
predominantly neutralization for the control of pH prior to
biological treatment. Primary treatment such as required in
municipal treatment plants is not routinely necessary for
these waste waters; however, when significant amounts of
oils or solvents do occur, the use of oil separators,
skimmers, and settling basins or lagoons is used.
The effectiveness of a particular operational mode of the
biological processes for removal of biologically degradable
pollutants varies widely depending upon the characteristics
of the waste waters being treated. Consequently, it is
impossible to generalize regarding the operating conditions
applied in biological treatment other than to say that these
are based on well understood principles. The design and
operational characteristics of the biological waste water
treatment plants are paramount in determining the overall
success in removing biologically degradable pollutants.
.Operational parameters found for waste water treatment
plants in this segment of the plastics and synthetics
industry were generally within the range found earlier and
reported in EPA Document 440/1-73/010 (16). These are
recorded in Tables VII-1 and VII-2. Similar removal
efficiencies for COD were found and the ratios of COD/BOD5
were within the earlier ranges.
The applicability and limitation of biological treatment
processes as well as physico-chemical processes to this
segment of the plastics and synthetics industry are the same
as outlined for the first segment and will be found in
Section VII of EPA Document 440/1-73/010 (16).
187
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Copper
The most widely accepted and economically feasible method
for the removal of relatively low concentrations of soluble
copper from waste water streams is precipitation followed by
sedimentation and filtration.
Under alkaline conditions, copper will tend to precipitate
out of solution and form solid particles composed of the
various oxides, hydroxides, and carbonates of copper.
Alkaline conditions are generally accomplished by the
addition of lime to the waste water. Typically, a solids-
recirculation clarifier is employed to promote the
formation, growth, and sedimentation of the precipitated
particles, coagulants were often added to the waste water
in order to encourage the agglomeration of precipitated
particles to such a size where they may readily settle.
The theoretical minimum solubility for copper in the pH
range employed in the lime treatment process is on the order
to 0.01 mg/liter, but this level is seldom attained due to
slow reaction rates, poor separation of colloidal
precipitates, and the influence of other ions in solution.
Most reported effluent copper concentrations from the lime
precipitation process are on the order to 0.5 to 1.0
mg/liter. If lime precipitation is followed by filtration,
concentrations on the order of 0.25 mg/liter are attainable.
Lower levels can be achieved by subjecting the effluent from
the lime precipitation step to carbon adsorption.
Ion exchange can be employed as an alternative to the lime
precipitation process. While ion exchange has been reported
to produce lower effluent concentrations (0.03 mg/1) than
that achievable by lime precipitation, it usually entails
much higher capital and operating costs. Ion exchange
becomes more practical when the waste streams are relatively
small and contain high concentrations of copper.
Lead
The most commonly employed process for the removal of
soluble lead from waste water is precipitation under
alkaline conditions followed by sedimentation and
filtration.
Under alkaline conditions (usually created by the addition
of lime) lead will precipitate out of solution and form
solid particles of lead carbonate and lead hydroxide. As
with the removal of copper, it is often necessary to also
188
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add coagulants to produce precipitates of sufficient size.
Precipitation followed by sedimentation has been reported to
produce effluent lead concentrations on the order of 0.5
mg/liter. If the sedimentation step is followed by
filtration, an effluent lead concentration of 0.03 mg/liter
may be achieved.
Ion exchange, while reported to produce lower lead
concentrations, usually entails a much higher capital and
operating cost than lime precipitation.
Mercury
The most promising and technically proven processes
currently available for the removal of low concentrations of
soluble mercury from large waste water streams are ion
exchange or sulfide precipitation.
In the ion exchange process, the waste water, after
sedimentation for the removal of any free mercury, is passed
through a proprietary ion exchange resin. Mercury is
removed as the mercuric chloride complex anion. A second
stage ion exchange step serves as a polishing step and
reduces the mercury concentration down to very low levels.
Concentrations of less than 0.005 mg/liter have been
reported.
In the sulfide precipitation process mercurous and organic
mercury compounds must first be oxidized to the mercuric
ion. Lime and sulfide are then added along with coagulant
aids in order to promote the formation of mercuric sulfide
precipitates. The precipitates are removed from the waste
water stream by means of sedimentation and filtration, as in
the copper and lead removal processes. This process has
been reported to be capable of producing an effluent mercury
concentration of 0.1 to 0.3 mg/liter.
In addition to ion exchange and sulfide precipitate several
newly developed organic adsorbents and complexing agents
have shown promising results in laboratory tests.
The entire technology for the removal of mercury has not
been developed very far in terms of full scale actual plant
operation.
Fluoride
Precipitation with lime is the standard technique for the
reduction of high concentrations of soluble fluoride. The
fluoride is precipitated as calcium fluoride. While the
189
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theoretical solubility limit for calcium fluoride is
approximately 8 mg/liter at pHll, effluent concentrations of
less than 20 mg/liter are seldom achieved due to the slow
reaction rates, difficulty in separating colloidal particles
of calcium fluoride, and the interference of other ions.
The addition of alum and other coagulants encourages the
formation of larger and more readily removable precipitates.
Where effluents fluoride concentrations lower the 20
mg/liter are required, various adsorptive techniques must be
used.
In such processes the fluoride containing water is passed
through contact beds of hydroxylapatite or activated
alumina. Adsorptive on activated alumina has been reported
to be capable of producing effluent fluoride concentrations
as low as 1.0 mg/liter. The use of adsorptive techniques
has largely been confined to the treatment of municipal
drinking water containing undesirably high concentrations of
fluoride.
Cyanide
The process most frequently employed for the treatment of
waste water containing cyanide is destruction by
chlorination under alkaline conditions. In this process the
cyanide may be partially oxidized to cyanate or totally
oxidized to carbon dioxide and nitrogen, depending on the
chlorine dosage.
Theoretically, if sufficient chlorine is added and
sufficient contact time provided, complete oxidation of
cyanide should be achievable. In reality, the presence of
small quantities of soluble iron often causes the formation
of extremely stable ferrocyanide complexes which prevent the
complete oxidation of cyanide.
In recent years ozonation has shown to be effective in
oxidizing cyanides. There are indications that ozonation is
more effective than alkaline chlorination in attacking the
more difficult to oxidize metal complexes of cyanide.
Both the alkaline chlorination and ozonation processes can
become prohibitively expensive if the cyanide containing
waste water also contains large quantities of oxidizable
organic material which will unavoidably be oxidized along
with the cyanide.
190
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Oil and Grease
Oil and grease are usually present in waste waters both in
the suspended and emulsified form.
Particles of suspended oil and grease are generally removed
by means of gravity separators. Such separators can
typically remove 90-95 percent of the suspended oil, but are
totally ineffective in removing emulsified oil.
To remove emulsified oil, the emulsion must first be broken
by chemical means consisting of the addition of acids and/or
coagulant salts such as alum. After so treated, the oil can
be removed by flotation or filtration. The concentration of
oil and grease in the treated effluent depends largely on
the degree of success in breaking the emulsion. Generally
an oil and grease concentration of less than 30 mg/liter
should be achievable by emulsion breaking and gravity
separation. If filtration is employed, a concentration of
10 mg/liter should be achievable.
Depending on conditions, varying amounts of emulsified oil
may be removed along with other biodegradable material in
standard biological treatment processes.
191
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-------
SECTION VIII
COST, ENERGY, AND NONWATER QUALITY ASPECTS
Approximately 160 company operations participate in the
manufacture of the fifteen synthetic polymer products (see
Table VIII-1). The actual number of plants is not known.
Some of the 60 company operations include multi-plant
divisions; many more are part of multiproduct plants.
Total production in the 1972-1973 time frame was estimated
at 1.2 million kkg (2.6 billion Ibs) per year or about one-
tenth of the volume (26 billion Ibs) represented by the
larger-volume resins studies earlier. Together (i.e., these
fifteen polymers and the earlier eighteen resins) the
products covered in the two studies were estimated to
represent 99 percent of the total production of synthetic
and plastic materials.
Current discharge resulting from the production of synthetic
polymers was estimated at 90 thousand cubic meters per day
(24 MGD). Water discharges (at current hydraulic loads) was
projected to increase at 10 per cent through 1977, while
production was projected to increase at It percent in the
same period. Approximately 25 percent of current discharge
by the industry was estimated to be treated in municipal
plants.
The first part of this section (Tables VIII-1 to VIII-4)
summarizes the costs (necessarily generalized) of end-of-
pipe treatment systems either currently in use or
recommended for future use in synthetic polymers production
facilities. Costs have been estimated for all fifteen
product categories even though specific guidelines or
standards were not recommended. Lacking specific effluent
requirements, appropriate control technologies were assumed
which were consistent with existing knowledge of waste
composition.
In order to reflect the different treatment economics of
existing versus new plants, large versus small plants, free-
standing versus joint treatment facilities, or municipal
versus industrial facilities, costs have been developed
typically for more than one plant situation in each product
subcategory. These productspecific analyses are presented
in Tables VIII-H/I to VIII-^/30.
193
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Cost Models of Treatment: Technologies
Information on treatment, cost experience was more scarce in
the production of synthetic polymers than it was from the
resin facilities studied earlier. In large part this was
due to the small number of free-standing plants in this
industry. There is also much greater dependence upon
municipal treatment for these smaller-volume products than
was true for resin production. More important, much of the
wastes resulting from these products are treated in the
central facilities of the large chemical complexes in which
they are located. Many times the main production in these
multi-product plants includes the resins covered earlier.
Consequently, the basic data for estimating the costs of
treating the wastes from synthetic polymers was that
developed in the first study. These cost models were
developed around standard waste water treatment practice and
compared to actual data from a dozen resin plants. That
comparison resulted in deviations within ± 20 percent of
model values. For details on the basis of the cost models
and their assumptions, see the cost section of the
development document for the resins industry segment (16).
Cost-Effectiveness Perspectives
Rough estimates were made of the existing degree of BOD5
removal by either industrial or municipal systems in the
fifteen product groups. A 7U percent weighted average
removal of BOD5_ was calculated for these synthetic polymers
in 1972. This is substantially higher than the H2 percent
removal for resin products because of the higher use of
municipal systems for polymer wastes and the availability of
larger central industrial treatment systems to handle the
lower volumes of these wastes. By 1977, the average removal
implicit in BPCTCA requirements is estimated at 90 percent.
This is lower than the 95 percent to be required of resin
production because, again, of the larger proportion of
municipal treatment - for which 85 percent removal is
expected.
Annual cost Perspectives
Annual costs for existing plants were roughly estimated at
$1.8 million. The expected annual costs for existing
synthetic polymers plants in 1977 consistent with best
practicable technology was estimated at $5.0 million. This
estimate (Table VIII-2) was the result of the following
considerations: the production volumes and waste loads for
each of the fifteen product groups; the average costs of
treatment for different plant sizes; or the costs to be
expected from handling these wastes as part of a larger
194
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municipal or industrial system. Similarly, by 1983, the
estimated costs (Table VIII-2) for existing plants using
best available technology were $12.0 million. It is noted
that these costs were associated with endof-pipe treatment
only. Costs for in-plant additions or modifications were
not included.
The above annual cost estimates for existing plants for
1972, 1977, and 1983 indicate average increases of 23
percent per year between 1972 and 1977, and 20 percent per
year between 1977 and 1983. Much of the estimated increase
in costs between 1972 and 1977 was tied to the assumed full
payment of charges for the use of municipal facilities.
User charges for treatment services beyond secondary
biological treatment in municipal systems were not
considered appropriate before 1983. To the costs for
existing plants must be added the costs associated with new
plants, governed by BADT-NSPS. Assuming the production
volume of new plants to be equal to the expected growth in
production, the potential annual cost associated with new
plants in 1977 was estimated at $3.4 million (Table VTII-2).
Altogether, that means that the industry's annual costs are
expected to increase 36 percent per year (from $1,8 million
in 1972 to $8.3 million (5.0 + 3.3) in 1977), this supported
by a sales growth of 14 percent per year. A similar
estimate for 1983 has been precluded by the lack of a
meaningful forecast of product growth.
Cost Per Unit Perspectives
Another measure by which to gauge the importance of the
costs in Table VIII-2 is to relate them to the sales price
of the products as is done in Table VTII-3. The average
range of water pollution control costs under BPCTCA was
estimated at 0.3 percent to 1.3 percent of current sales
prices. On average, the range of costs for applying BATEA
to existing plants was 0.6 to 3.3 percent of sales price.
The cost of BADT-NSPS was estimated at 0.5 percent of sales
price over the fifteen products. These cost impacts are
lower on average than those for the eighteen resin products
studied earlier primarily because the average price of these
polymers is higher,
Waste Water Treatment Cost Estimates
The average range of water pollution control costs (Table
VIII-4) under BPCTCA, BATEA, and BADT-NSPS technologies
respectively were $0.16 ($0.63), $0.40 ($1.52), and $0.17
($0.66) per cubic meter (per thousand gallons). Table VIII-
4 and its 30 associated tables portray the costs of major
195
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treatment steps required to achieve the recommended
technologies. Where municipal user charges are not
considered directly, the appropriate charge would be $0.39
or $0.63 per thousand gallons depending on the size
economies of the representative municipal system.
In each of the representative plant cost analyses, typical
plant situations were identified in terms of production
capacity, hydraulic load, and treatment plant size. Capital
costs have been assumed to be a constant percentage (8
percent) of fixed investment. Depreciation costs have been
calculated consistent with the faster write-off (financial
life) allowed for these facilities (10 percent per year)
over 10 years even though the physical life is longer.
Cost-effectiveness relationships are implicit in the
calculation of these costs together with the effluent levels
achieved by each treatment step in each major relevant
pollutant dimension. These effluent levels are indicated at
the bottom of each representative plant sheet.
Industrial Waste Treatment Model Data
In Tables VIII-5/1 to VIII-5/3 the total discharges for each
product subcategory are estimated for 1972 and 1977. The
quality of effluents remaining untreated in 1977 is
indicated as that consistent with the application of BPCTCA
technology. Finally, the current status of treatment in
each product group is estimated in terms of the proportion
utilizing primary treatment and that utilizing a form of
biological treatment, whether industrial or municipal.
Energy Cost Perspectives
Each of the representative plant analyses in the 30 tables
summarized by Table VIII-H includes an estimate of energy
costs (of control). The basis for these energy cost
estimates was explained in the earlier development document
for resins production. The most important assumption
therein was one of 1972 energy prices. That assumption has
been retained, for purposes of comparison, in this analysis
of polymers production.
Generally, the biological treatment systems employed by
industries and municipalities are not large consumers of
energy. By the cost models employed in this report, the
energy costs of BPCTCA and BADT-NSPS technologies in this
industry were estimated at about 2 percent of the total
annual waste water treatment costs in Table VIII-2. The
196
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add-on technologies for BATEA compliance, however, were
estimated to raise that proportion to 7 percent by 1983.
Non Water Quality Effects
The nonwater quality aspects of the treatment and control
technology found in the synthetics and plastics industry are
related to (1) the disposal of solids or slurries resulting
from waste water treatment and in-process plant control
methods, (2) the generation of a by-product of commercial
value, (3) disposal of off-specification and scrap products,
and (4) the creation of problems of air pollution and land
utilization. These effects were discussed in the
development document for resins production.
Other nonwater quality aspects of treatment and pollution
control are minimal in this industry and largely depend upon
the type of waste water treatment technology employed. In
general, noise levels from typical waste water treatment
plants are not excessive. If incineration of waste sludges
is employed, there is potential for air pollution,
principally particulates and possibly nitrogen oxides,
although the latter should be minimal because incineration
of sludges does not normally take place at temperature
levels where the greatest amounts of nitrogen oxide are
generated. There are no radioactive nuclides used within
the industry, other than in instrumentation, so that no
radiation problems will be encountered. Odors from the
waste water treatment plants may cause occasional problems
since waste waters are sometimes such that heavy, stable,
foams occur on aerated basins and septicity is present.
But, in general, odors are not expected to be a significant
problem when compared with odor emissions possible from
other plant sources.
The final part of this section reports on updated inputs for
EPA's Industrial Waste Treatment Model (Tables VIII-5/1 to
VIII-5/3). The estimated total volume of waste waters
discharged for product subcategories has been estimated for
1972-1977. Also, general estimates of the current level and
source of treatment in different industry segments have been
made.
Alternative Treatment Technologies
The range of components used or needed to effect best
practicable control technology currently available (BPCTCA),
best available technology economically achievable (BATEA) ,
and best available demonstrated technology for new source
performance standards (BADT-NSPS) in this portion of the
197
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plastics and synthetics industry have been combined into
eight alternative end-of-pipe treatment steps. These are as
follows:
A. Initial Treatment; For removal of suspended solids
and heavy metals. Includes equalization,
neutralization, chemical coagulation or
precipitation, API separators, and primary
clarification.
B. Biological Treatment: Primarily for removal of
BOD. Includes activated sludge (or aerated
stabilization basins), sludge disposal, and final
clarification.
c- Multi-stage Biological; For further removal of BOD
loadings. Either another biological treatment
system in series or a long-residence-time polishing
lagoon.
D. Granular Media Filtration; For further removal of
suspended solids (and heavy metals) from biological
treatment effluents. Includes some chemical
coagulation as well as granular media filtration.
E. Physical-Chemical Treatment; For further removal
of COD, primarily that attributable to refractory
organics, e.g., with activated carbon adsorption.
F- Liquid Waste Incineration; For complete treatment
of small volume wastes.
G. Municipal Treatment; Conventional municipal
treatment of industrial discharge into sewer
collection systems. Primary settling and secondary
biological stages assumed.
198
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TABLE VIII-1
PERSPECTIVES ON THE PRODUCTION OF SYNTHETIC POLYMERS
WATER USAGE
Guidelines Subcategory
Product
Number of
Company
Operations(1)
Percent of
Total 15 Product
Production(2)
Percent of
Water Used
by 15 Products
Percent of Growth
In Water Usage of
15 Products:
1972-1977
II
EVA Copolymers
Fluorocarbons
Polypropylene Fibers
Polyvinylidene Chloride
I
Acrylic Resins
Cellulose Derivatives
Subtotal - A&B
III
Alkyd and Unsaturated
Polyester Resins
Cellulose Nitrate
Polyamids
Polyesters (thermoplastic)
Polyvinyl Butyral
Polyvinyl Ethers
Sillcones
IV
Nitrile Barrier Resins
Spandex Fibers
Subtotal - C&D
Total - 15 Products
5
5
3
4
>4
_3
>24
2
3
3
2
2
4
3
_3
>36
>60
5.9
1.0
5.5
1.0
11.8
3.9
29.1
58.8
2.0
1.0
0.2
1.6
0.4
5.1
1.0
0.8
70.9
100.0
0.8
4.6
1.7
0.4
14.6
17.6
39.7
7.5
10.9
0.8
0.4
5.9
0.4
33.2
0.8
0.4
60.3
100.0
0.7
2.6
1.3
0
34.4
8.6
47.6
11.9
0
0.6
0.6
2.6
0.6
32.9
3.2
0
52.4
100.0
(1) Number of companies producing each of the products; the number of plants is greater because
of multiple sites for any one company.
(2) Estimated annual 15-product production in 1972-73 period: 1.15B kkg (2.55 B Ibs).
(3) Result of projected product growth at current representative hydraulic loads.
199
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TABLE VIII-2
PERSPECTIVES ON SYNTHETIC POLYMERS PRODUCTION
ANNUAL TREATMENT COSTS
Guidelines Subcategory
Total Annual Costs, $MM
I
n
in
IV
Product
EVA Copolyners
Fluorocarbona
Polypropylene Fibers
Polyvlnylidene Chloride
Acrylic Resins
Cellulose Derivatives
Alkyds and UnsaturaCed
Polyester Resins
Cellulose Nitrate
Polyamldes
Polyesters (thermoplastic)
Polyvlnyl Butyral
Polyvlnyl Ethers
Slllcones
Kltrlle Barrier Resins
Spandex Fibers
Exist in? Plants
1977
0.12
0.36
0.17
0.01
0.58
0.97
0.45
0.30
0.08
0.03
0.30
0.03
1.56
0.04
0.04
1983
0.37
0.36
0.17
0.04
0.64
2.84
0.59
0.51
0.22
0.07
0.92
0.07
5.21
0.08
0.08
New Plants
1983
0.10
0.13
0.08
0.00
0.86
0.34
0.45
Q.OO
0.04
0.03
0.09
0.03
1.13
0.12
0.00
Total
5.04
12.17
3.40
200
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TABLE VItl-3
PERSPECTIVES ON SYNTHETIC POLYMERS PRODUCTION
COST IMPACT
Control Cost Range as Z of Sales Price
Guideline Subcategory
Product
jt
11
III
IX
EVA Copolyners
Fluorocarbons
Polypropylene Fibers
Polyvlnylidene Chloride
Acrylic Resins
Cellulose Derivatives
Alkyd and Bnsaturated
Polyester Resins
Cellulose Nitrate
Folyamids
Polyesters (thermoplastic)
Polyvinyl Butyral
Polyvlnyl Ethers
Silicones
Nitrile Barrier Resins
Spandex Fibers
Price Level
c/lb
15
325
35
55
70
50
20
50
130
70
70
100
100
60
100
BPCTCA
X
1.0
0.1
0.7
0.1
0.1
1.1
0.4
0.8
0.1
0.1
0.4
0.2
0.6
0.1
0.1
- 2
- 0
- 1
- 0
- 0
- 2
- 1
- 1
- 0
- 2
- 2
- 0
- 1
- 0
- 0
.0
.6
.4
.2
.4
.0
.9
.7
.9
.9
.1
.7
.2
.6
.3
2.
0.
0.
0.
0.
3.
0.
1.
0.
0.
0.
0.
1.
0.
0.
BATEA
Z
3 -
1 -
7 -
1 -
1 -
3 -
4 -
0 -
2 -
3 -
4 -
2 -
7 -
1 -
1 -
6
0
1
0
0
5
3
3
2
6
.2
.6
.4
.7
.4
.7
.8
.6
.5
.4
10.7
1
3
1
0
.8
.5
.3
.5
BAM
X
1.
0.
0.
0.
0.
1.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0
1
7
1
1
2
8
9
2
2
8
3
7
3
2
Unweighted Average
0.4 - 1.3
0.7 - 3.3
0.5
201
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TABLE VIII-4
SUMMARY OF WATER EFFLUENT TREATMENT COSTS3
COST PER UNIT VOLUME BASIS
Guidelines Subcategory
BPCTCA COSTS
BATEA COSTS
BADT COSTS'
r ruuuci.
EVA Copolymers
Fluorocarbons
Polypropylene Fibers
Polyvinylidene Chloride
rc
Acrylic Resins
Cellulose Derivatives
III
Alkyd and Unsaturated
Polyester Resins
Cellulose Nitrate
Polyamids
Polyesters (thermoplastic)
Polyvinyl Butyral
Polyvinyl Ethers
Silicones
lY.
Nitrile Barrier Resins
Spandex Fibers
Average
$/cu m $/1000 gal
0.16
0.26
0.33
0.9 - 0.13
0.13
0.18
0.13 - 0.66
0.08 - 0.11
0.32
0.26
0.13 - 0.26
0.13 - 0.26
0.09 - 0.22
0.13 - 0.18
0.13 - 0.33
0.17
0/60
1.00
1.25
0.35 - 0.50
0.50
0.70
0.50 - 2.50
0.30 - 0.40
1.20
1.00
0.50 - 100
0.50 - 1.00
0.35 - 0.85
0.50 - 0.70
0.50 - 1.25
0.63
$/cu m $/1000 gal $/cu m $/1000 gal
0.49
0.26
0.33
0.13 - 0.53
0.15
0.54
0.13 - 1.32
0.11 - 0.22
0.87
0.59
0.13 - 1.32
0.13 - 0.66
0.26 - 0.66
0.13 - 0.40
0.13 - 0.66
0.40
1.85
1.00
1.25
0.50 - 2.00
0.55
2.05
0.50 - 5.00
0.40 - 0.85
3.30
2.25
0.50 - 5.00
0.50 - 2.50
1.00 - 2.50
0.50 - 1.50
0.50 - 2.50
1.52
0.16
0.26
0.33
0.12
0.13
0.21
0.20
0.11
0.32
0.26
0.18
0.24
0.18
0.18
0.33
0.17
0.60
1.00
1.25
0.45
0.50
0.80
0.75
0.40
1.20
1.00
0.70
0.90
0.70
0.70
1.25
0.66
Assume 330 day /year operation. Estimated proportions treated
municipal systems factored in at $0.50/1000 gal.
^Assume new plants are larger facilities with minimum flows. New
plant production assumed equivalent to growth between 1972 and
1977.
202
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TABLE VIII-4/1
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Ethylene Vinyl Acetate
Plant Description: Small Plant - Large Industrial Complex
Representative Plant Capacity
million kilograms (pounds) per year: 11.3
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb)
11.9
Treatment Plant Size
thousand cubic meters per day (MGD): 6.4
(25)
(1.3)
(1.7)'
Costs - $1000
Alternative Treatment Steps
Initial Investment
28
65
15
106
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs 5.4 15 3
Effluent Quality (expressed in terms of yearly averages)
2.2
2.8
0.3
0.1
5.2
6.5
3
0.3
1.2
1.5
0.3
—
8.5
10.6
15.9
4
39
B.O.D.
C.O.D.
Suspended Solids
Raw Waste Load
1
2
N/A
Resulting Effluent Levels
(units per 1000 units of product)
A 1 .2. I
0.1 - 0.08
1 - 0.7
0.3 - 0.05
*The EVA contribution is 0.4 thousand cubic meters per day (0.1 mgd). This
is approximately 6% of the total flow to be treated.
203
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TABLE VIII-4/2
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Ethylene Vinyl Acetate
Plant Description: Large Plant - Industrial Complex
Representative Plant Capacity
million kilograms (pounds) per year: 22.7 (50)
Hydraulic Load
cubic meters/metric ton of product: 11.9 (1*3)
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD): 6.8 (1.8)*
Costs - $1000 Alternative Treatment Steps
Initial Investment 53 124 29 204
Annual Costs:
Capital Costs (8%) 4.1 9.8 2.3 16
Depreciation (10%) 5.3 12.4 , 2.9 20
Operation and Maintenance 0.5 5.3 0.4 32
Energy and Power 0.1 0.5 - 8
Total Annual Costs 10 28 5.6 77
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
A JB I) E
B.O.D. 1 0.1 0.08
C.O.D. 2 - 1 - 0.7
Suspended Solids N/A 0.3 - 0.05
* The EVA contribution is 0.8 thousand cubic meters per day (0.2 mgd).
This is approximately 11% of the total flow to be treated.
204
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TABLE VIII-4/3
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Fluorocarbons
Plant Description: Small Plant - Free Standing
Representative Plant Capacity
million kilograms (pounds) per year: 1.4 (3)
Hydraulic Load
cubic meters/metric ton of product: 125 (15.0)
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD): 0.5 (0.14)
Costs - $1000 Alternative Treatment Steps
A
Initial Investment 44
Annual Costs:
Capital Costs (8%) 3.5
Depreciation (10%) 4.4
Operation and Maintenance 2.0
Energy and Power 0-1
Total Annual Costs 1°
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
A
B.O.D. 3 2
C.O.D. 20 20
Suspended Solids 5 5
205
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TABLE VIII-4/4
WATER EFFLUENT TKEATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Fluorocarbons
Plant Description: Small Plant - Municipal Discharge
Representative Plant Capacity
million kilograms (pounds) per year: 1.4 (3)
Hydraulic Load
cubic meters/metric ton of product: 125 (15.0)
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD): 0.5 (0.14)
Costs - $1000 Alternative Treatment Steps
P* M M
Initial Investment 102
Annual Costs:
Capital Costs (8%) 8
Depreciation (10%) 10
Operation and Maintenance 4 -
Energy and Power 1 -
Total Annual Costs 23 18 29
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
B.O.D. 3
C.O.D. 20 (municipal treatment)
Suspended Solids 5
* Neutralization of acids
MI is the municipal treatment charge associated with a 38 to 76 thousand cubic
meters per day (10-20 mgd) treatment plant. A charge of 39 per 1000 gallons
has been used.
M« is associated with a 4 to 12 thousand cubic meters per day (1-3 mgd) muni-
cipal plant. A charge of 63 per 1000 gallons has been used.
206
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TABLE VIII-4/5
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Fluorocarbons
Plant Description: Large Plant - Free Standing
Representative Plant Capacity
million kilograms (pounds) per year: 6.8
Hydraulic Load
cubic meters/metric ton of product: 125
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD): 2.6
(15)
(15.0)
(0.7)
Costs - $1000
Alternative Treatment Steps
A
Initial Investment
145
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
11.6
14.5
8.6
0.3
Total Annual Costs 35
Effluent Quality (expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw Waste Load
3
20
5
Resulting Effluent Levels
(units per 1000 units of product)
A
2
20
5
207
-------
TABLE VIII-4/6
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Fluorocarbons
Plant Description: Large Plant - Municipal Discharge
Representative Plant Capacity
million kilograms (pounds) per year: 6.8 (15)
Hydraulic Load
cubic meters/metric ton of product: 125 (15.0)
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD): 2.6 (0.7)
Costs - $1000 Alternative Treatment Steps
I* % M2
Initial Investment 285
Annual Costs:
Capital Costs (8%) 23 - -
Depreciation (10%) 29 - -
Operation and Maintenance 6 -
Energy and Power 1 -
Total Annual Costs 59 88 142
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
B.O.D. 3
C.O.D. 20 (Municipal treatment)
Suspended Solids 5
* Neutralization of Acids
208
-------
TABLE VIII-4/7
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Polypropylene Fibers
Plant Description: Free Standing Treatment Plant
Representative Plant Capacity
million kilograms (pounds) per year: 20.4 (45)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 8.3 (1.0)
Treatment Plant Size
thousand cubic meters per day (MGD): 0.5 (0.14)
Costs - $1000 Alternative Treatment Steps
A D E
Initial Investment 96 50 433
Annual Costs:
Capital Costs (8%) 8 4 35
Depreciation (10%) 10 5 43
Operation and Maintenance 2 2 115
Energy and Power 0.5 - 10
Total Annual Costs 20.5 11 203
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
All
B.O.D. 0.5 0.3 - 0.1
C.O.D. 1.5 1.3 - 0.2
Suspended Solids 1.0 0.5 0.1
209
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TABLE VIII-4/8
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Polypropylene Fibers
Plant Description: Municipal Discharge
Representative Plant Capacity
million kilograms (pounds) per year: 20.4 (45)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 8.3 (1.0)
Treatment Plant Size
thousand cubic meters per day (MGD): 0.5 (0.14)
Costs - $1000 Alternative Treatment Steps
P* MI M2
Initial Investment 89 -
Annual Costs:
Capital Costs (8%) 7
Depreciation (10%) 9
Operation and Maintenance 18 - -
Energy and Power i - -
Total Annual Costs 35 18 29
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
B.O.D. 0.5
C.O.D. 1.5 (Municipal Treatment)
Suspended Solids 1.0
*Air flotation for oil and grease removal.
210
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TABLE VIII-4/9
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Polyvinylidene Chloride
Plant Description: Small Plant - Industrial Complex
Representative Plant Capacity
million kilograms (pounds) per year: 2.3 (5)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 4.2 (0.5)
Treatment Plant Size
thousand cubic meters per day (MGD): 1.7 (0.45)*
Costs - $1000 Alternative Treatment Steps
Initial Investment 4 2 11
Annual Costs:
Capital Costs (8%) 0.3 0.2 0.9
Depreciation (10%) 0.4 0.2 1.1
Operation and Maintenance 0.06 0.1 1.8
Energy and Power 0.04 - 0.2
Total Annual Costs 0.8 0.5 4.0
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
B.O.D. 0
C.O.D. 8 (No specific guidelines)
Suspended Solids 0.2
*The PVC1 contribution is 0.03 thousand cubic meters per day (0.007 MGD);
this is approximately 1.5% of the total flow to be treated.
211
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TABLE VIII-4/10
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Polyvinylidene Chloride
Plant Description: Large Plant - Industrial Complex
Representative Plant Capacity
million kilograms (pounds) per year: 11.3 (25)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 4.2 (0.5)
Treatment Plant Size
thousand cubic meters per day (MGD): 1.7 (0.45)*
Costs - $1000 Alternative Treatment Steps
Initial Investment 21 11 55
Annual Costs:
Capital Costs (8%) 1.7 9 4.4
Depreciation (10%) 2.1 11 5.5
Operation and Maintenance 0.2 0.1 9.4
Energy and Power 0.1 - 1.5
Total Annual Costs 4 20.1 21
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
B.O.D. 0 (No specific guidelines)
C.O.D. 8
Suspended Solids 0.2
*The PVC1 contribution is 0.13 thousand cubic meters per day (0.035 MGD);
this is approximately 20% of the total flow to be treated.
212
-------
TABLE VIII-4/11
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Acrylic Resins
Plant Description: Small Plant - Industrial Complex
Representative Plant Capacity
million kilograms (pounds) per year: 9.1 (20)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 32 (3.8)
Treatment Plant Size
thousand cubic meters per day (MGD): 17.4 (4.6)*
Costs - $1000 Alternative Treatment Steps
A B D
Initial Investment 45 110 24
Annual Costs:
Capital Costs (8%) 4 9 1.9
Depreciation (10%) 5 11 2.4
Operation and Maintenance 0.4 6.5 0.2
Energy and Power 0.1 0.5
Total Annual Costs 9.5 27 4.5
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
B.O.D. 15
C.O.D. 30 (No specific guidelines)
Suspended Solids 7.5
*The acrylic resin contribution is 0.9 thousand cubic meters per day (0.23 MGD),
this is approximately 5% of the total flow to be treated.
213
-------
TABLE VIII-4/12
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Acrylic Resins
Plant Description: Large Plant - Industrial Complex
Representative Plant Capacity
million kilograms (pounds) per year: 54.4 (120)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 32 (3.8)
Treatment Plant Size
thousand cubic meters per day (MGD): 13.1 (3.46)*
Costs - $1000 Alternative Treatment Steps
A B D
Initial Investment 296 724 156
Annual Costs:
Capital Costs (8%) 24 58 12
Depreciation (10%) 30 72 16
Operation and Maintenance 3 36 1
Energy and Power 13-
Total Annual Costs 58 169 29
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
B.O.D. 15
C.O.D. 30 (No specific guidelines)
Suspended Solids 7.5
*The acrylic resin contribution is 5.2 thousand cubic meters per day
(1.38 MGD), this is approximately 40% of the total flow to be treated.
214
-------
TABLE VIII-4/13
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:
Plant Description:
Cellulose Derivates
Small Plant - Industrial Complex
Representative Plant Capacity
million kilograms (pounds) per year: 4.5
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 117
Treatment Plant Size
thousand cubic meters per day (MGD): 8
(10)
(14)
(2.1)*
Costs - $1000
Alternative Treatment Steps
A B D E
Initial Investment
104
256
56
334
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
8
10
3
0.5
20
26
18
8
4.5
5.6
0.6
-
27
33
33
8
21.5
72
10.7
Effluent Quality (expressed in terms of yearly averages)
101
B.O.D.
C.O.D.
Suspended Solids
Raw Waste Load
180
650
20
Resulting Effluent Levels
(units per 1000 units of product)
(No specific guidelines)
*The cellulose derivative contribution is 1.6 thousand cubic meters per day
(0.42 MGD); this is approximately 20% of the total flow to be treated.
215
-------
TABLE VIII-4/14
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:
Plant Description:
Cellulose Derivatives
Large Plant - Industrial Complex
Representative Plant Capacity
million kilograms (pounds) per year: 22.7
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 117
Treatment Plant Size
thousand cubic meters per day (MGD): 151
(50)
(14)
(40)*
Costs - $1000
Alternative Treatment Steps
A B D E
Initial Investment
154
376
220
636
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs 34 160 44
Effluent Quality (expressed in terms of yearly averages)
12
15
5
2
30
38
54
38
18
22
4
-
51
64
200
50
365
B.O.D.
C.O.D.
Suspended Solids
Raw Waste Load
180
650
20
Resulting Effluent Levels
(units per 1000 units of product)
(No specific guidelines)
*The cellulose derivatives contribution is 8.0 thousand cubic meters per day
(2.12 MGD); this is approximately 5% of the total flow to be treated.
216
-------
TABLE VIII-4/15
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Alkyds and Unsaturated Polyester Resins
Plant Description: Large Plant - Once-thru Scrubber - Free Standing
Representative Plant Capacity
million kilograms (pounds) per year: 15.9 (35)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 3.3 (0.4)
Treatment Plant Size
thousand cubic meters per day (MGD): 0.15 (0.04)
Costs - $1000 Alternative Treatment Steps
A B* C**
Initial Investment 30 84 84
Annual Costs:
Capital Costs (8%) 2.4 6.7 6.7
Depreciation (10%) 3.0 8.4 8.4
Operation and Maintenance 2.4 15.3 10.4
Energy and Power 0.2 0.6 0.5
Total Annual Costs 8 31 26
Effluent Quality (expressed in terms of yearly averages)
, Raw Waste Load Resulting Effluent Levels
','..,; :.,.-.- (units per 1000 units of product)
A B_ £
B.O.D. 10 - 0.2 0.0?
C.O.D. 25 - 1 0.3
Suspended Solids 1 0.1 - 0.02
*Two-stage biological treatment
**Two additional stages of biological treatment
217
-------
TABLE VIII-4/16
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Alkyds and Unsaturated Polyester Resins
Plant Description: Small Plant - Recirculating Scrubber -
Municipal Discharge
Representative Plant Capacity
million kilograms (pounds) per year: 2.3 (5)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 0.4 (0.05)
Treatment Plant Size
thousand cubic meters per day (MGD): 0.003 (0.001)
Costs - $1000 Alternative Treatment Steps
P* MI M2
Initial Investment 5.0
Annual Costs:
Capital Costs (8%) Q.4
Depreciation (10%) Q.5
Operation and Maintenance I.Q
Energy and Power _ _ _
Total Annual Costs 1,9 o.l 0.2
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
B.O.D. 10
C.O.D. 25 (Municipal Treatment)
Suspended Solids 1
*Pretreatment is Clarification or Filtration.
218
-------
TABLE VIII-4/17
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Alkyds and Unsaturated Polyester Resins
Plant Description: Large Plant - Recirculating Scrubber-
Free Standing
Representative Plant Capacity
million kilograms (pounds) per year:
15.9 (35)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 0.4 (0.05)
Treatment Plant Size
thousand cubic meters per day (MGD): 0.15 (0.04)*
Costs - $1000 Alternative Treatment Steps
A B** C***
Initial Investment 30 84 84
Annual Costs:
Capital Costs (8%) 2.4 6.7 6.7
Depreciation (10%) 3.0 8.4 8.4
Operation and Maintenance 2.4 15.3 10.4
Energy and Power 0.2 0.6 0.5
Total Annual Costs 8 31 26
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
A _B £
B.O.D. 10 - 0.2 0.07
C.O.D. 25 - 1 0.3
Suspended Solids 1 0.1 - 0.02
*Dilution of 7:1 for effective operation of the biological treatment has
been allowed.
**Two-stage biological treatment,
***Two additional stages of biological treatment.
219
-------
TABLE VIII-4/18
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Alkyds and Unsaturated Polyester Resins
Plant Description: Large Plant - Recirculating Scrubber ,-
Municipal Discharge
Representative Plant Capacity
million kilograms (pounds) per year: 15.9 (35)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 0.4 (0.05)
Treatment Plant Size
thousand cubic meters per day (MGD): 0.02 (0.005)
Costs - $1000 Alternative Treatment Steps
P_* MI M2
Initial Investment 10 -
Annual Costs:
Capital Costs (8%) 0.8 -
Depreciation (10%) 1.0
Operation and Maintenance 1.0 -
Energy and Power - -
Total Annual Costs 2.8 0.7 1.1
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
B.O.D. 10
C.O.D. 25 (Municipal Treatment)
Suspended Solids 1
*Pretreatment is clarification or filtration.
220
-------
TABLE VIII-4/19
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:
Plant Description:
Cellulose Nitrate
Plant in Industrial Complex
Representative Plant Capacity
million kilograms (pounds) per year: 18.1 (40)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 167
Treatment Plant Size
thousand cubic meters per day (MGD): 43.1
(20.0)
(11.4)*
Costs - $1000
Alternative Treatment Steps
A B D E
Initial Investment
334
779
179
968
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs ,-, ,„„ „,
Effluent Quality (expressed in terms of yearly averages)
27
33
6.4
0.6
62
78
43
9
14
18
2
-
77
97
79
22
275
B.O.D.
C.O.D.
Suspended Solids
Raw Waste Load
35
75
85
Resulting Effluent Levels
(units per 1000 units of product)
A JL P_ JL
7-2
23 - 14
4 - 1
*The cellulose nitrate contribution is 9.2 thousand cubic meters per day
(2.43 MGD); this is approximately 20% of the total flow to be treated.
221
-------
TABLE VIII-4/20
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Cellulose Nitrate
Plant Description: Plant with Municipal Discharge
Representative Plant Capacity
million kilograms (pounds) per year: 18.1 (40)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 167 (20.0)
Treatment Plant Size
thousand cubic meters per day (MGD): 9.1 (2.4)
Costs - $1000 Alternative Treatment Steps
P_ MI
Initial Investment 260
Annual Costs:
Capital Costs (8%) 21
Depreciation (10%) 26
Operation and Maintenance 5.5
Energy and Power 0.5
Total Annual Costs 53 309
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
B.O.D. 35
C.O.D. 75 (Municipal Treatment)
Suspended Solids 35
222
-------
TABLE VIII-4/21
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:
Plant Description:
Polyamides (Nylon 6/12)
Production in a Complex
Representative Plant Capacity
million kilograms (pounds) per year: 4.5
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 16.7
Treatment Plant Size
thousand cubic meters per day (MGD): 4.8
(10)
(2.0)
(1.26)*
Costs - $1000
Alternative Treatment Steps
ABODE
Initial Investment
18
42
42
10
60
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs 3.7 13 13 2
Effluent Quality (expressed in terms of yearly averages)
1.4
1.8
0.4
0.1
3.4
4.2
3.7
1.7
3.4
4.2
3.7
1.7
0.8
1.0
0.2
-
4.8
6.0
7.1
1.1
19
B.O.D.
C.O.D.
Suspended Solids
Raw Waste Load
N/A
N/A
N/A
Resulting Effluent Levels
(units per 1000 units of product)
A JL £ D. 1
- 0.3 - 0.1
3 - 1.2
0.2 - - 0.07
*The polyamide contribution is 0.23 thousand cubic meters per day
(0.06 MGD), this is approximately 5% of the total flow to be treated.
223
-------
TABLE VIII-4/22
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Thermoplastic Polyester Resins
Plant Description: Large Plant - Industrial Complex
Representative Plant Capacity
million kilograms (pounds) per year: 2.3
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 8.3
Treatment Plant Size
thousand cubic meters per day (MGD): 2.2
(5)
(1.0)
(0.58)*
Costs - $1000
Alternative Treatment Steps
A B C D E
Initial Investment
21
20
24
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs 1.6 6 5 0.8
Effluent Quality (expressed in terms of yearly averages)
0.7
0.8
0.1
0.03
1.7
2.1
2.0
0.2
1.6
2.0
1.2
0.2
0.3
0.4
0.1
-
1.9
2.4
3.4
0.3
B.O.D.
C.O.D.
Suspended Solids
Raw Waste Load
5
15
N/A
Resulting Effluent Levels
(units per 1000 units of product)
A B_ £ ID .E
- - 0.4 - 0.2
- 5 - 1
0.2 - - 0.08
*The thermoplastic resin contribution is 0.06 thousand cubic meters per day
(0.015 MGD); this is approximately 3% of the total flow to be treated.
224
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TABLE VIII-4/23
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Polyvinyl Butyral
Plant Description: Free Standing Treatment Plant
Representative Plant Capacity 9.1 (20)
million kilograms (pounds) per year:
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 96 (11.5)
Treatment Plant Size
thousand cubic meters per day (MGD): 2.6 (0.7)
Costs - $1000
Alternative Treatment Steps
A 1 D E
Initial Investment
285 725
135 1614
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
23 58 11 129
29 73 14 161
3 50 2 525
0.5 4 - 155
Total Annual Costs 55.5 185 27 970
Effluent Quality (expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw Waste Load
30
40
N/A
Resulting Effluent Levels
(units per 1000 units of product)
A B D E
0.9
9
0.5 -
225
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TABLE VIII-4/24
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Polyvinyl Ether
Plant Description: Plant in Industrial Complex
Representative Plant Capacity
million kilograms (pounds) per year: i.g (4)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 12.5 (1.5)
Treatment Plant Size
thousand cubic meters per day (MGD): 2.3 (0.6)*
Costs - $1000 Alternative Treatment Steps
A B D E
Initial Investment 8 21 4 25
Annual Costs:
Capital Costs (8%) 0.6 1.7 0.3 2.0
Depreciation (10%) 0.8 2.1 0.4 2.5
Operation and Maintenance 0.1 1.1 0.1 4.0
Energy and Power - 0.1 - 0.5
Total Annual Costs 1,5 5 0.8 9
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
B.O.D.
C-O.D. 25 (No specific guidelines)
Suspended Solids
*The polyvinyl ether contribution is 0.07 thousand cubic meters per day
(0.018 MGD); this is approximately 3% of the total flow to be treated.
226
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TABLE VIII-4/25
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Silicones
Plant Description: Fluids Only - Free Standing
Representative Plant Capacity
million kilograms (pounds) per year: 22.7 (50)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 54 (6.5)
Treatment Plant Size
thousand cubic meters per day (MGD): 3.8 (1.0)
Costs - $1000 Alternative Treatment Steps
A *L P. 1.
Initial Investment 305 745 232 1338
Annual Costs:
Capital Costs (8%) 24 60 19 107
Depreciation (10%) 31 75 23 134
Operation and Maintenance 6 40 2 228
Energy and Power 0.6 9 - 53
Total Annual Costs 61.6 184 44 522
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
A B_ D IS
B.O.D. N/A - 1.5 - 0.6
C.O.D. 15 - 7.5 - 4.0
Suspended Solids N/A 1.0 - 0.2
227
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TABLE VIII-4/26
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Silicones
Fluids Only - Industrial Complex
Plant Description:
Representative Plant Capacity
million kilograms (pounds) per year: 22.7 (50)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 54 (6.5)
Treatment Plant Size
thousand cubic meters per day (MGD) : 43.5 (11.5)*
Costs - $1000 Alternative Treatment Steps
A :B p_ E
Initial Investment 143 334 77 436
Annual Costs:
Capital Costs (8%) 11 27 6 35
Depreciation (10%) 14 33 8 44
Operation and Maintenance 3 18 1 36
Energy and Power 0.3 4 - 10
Total Annual Costs 28.3 82 15 125
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
A Bi D E_
B.O.D. N/A - 1.5 - 0.6
C.O.D. 15 _ 7.5 _ 4.0
Suspended Solids N/A 1.0 - 0.2
*The silicone contribution is 3.8 thousand cubic meters per day (1.0 MGD); this is
approximately 9% of the total flow to be treated.
228
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TABLE VIII-4/27
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Silicones
Multi-product - Free Standing
Plant Description:
Representative Plant Capacity
million kilograms (pounds) per year: 22.7 (50)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 142 (17.0)
Treatment Plant Size
thousand cubic meters per day (MGD): 17.2 (4.55)
Costs - $1000 Alternative Treatment Steps
A 1 R. Ji
Initial Investment 720 1760 441 3044
Annual Costs:
Capital Costs (8%) 53 141 35 244
Depreciation (10%) 72 176 44 304
Operation and Maintenance 15 74 4 646
Energy and Power 2 14 - 200
Total Annual Costs 147 405 83 1394
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
A _B £ E
B.O.D. 85 7 3
C.O.D. 115 - 35 - 18
Suspended Solids 50 5 - 1
229
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TABLE VIII-4/28
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:
Plant Description:
Silicones
Multi-product - Industrial Complex
Representative Plant Capacity
million kilograms (pounds) per year:
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD):
22.7
142
42.8
(50)
(17.0)
(11.3)*
Costs - $1000
Alternative Treatment Steps
Initial Investment
509 1187 289 2191
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
41
51
9
1
95
119
66
13
23
29
2
175
219
622
194
102
293
i>4 1210
Effluent Quality (expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw Waste Load
85
115
50
Resulting Effluent Levels
(units per 1000 units of product)
A B_ D E_
7-3
35 - 15
5 1 -
*The silicone contribution is thousand cubic meters per day
this is approximately 20% of the total flow to be treated.
230
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TABLE VIII-4/29
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Nitrile Barrier Resins
Plant Description: Plant in Industrial Complex
Representative Plant Capacity
million kilograms (pounds) per year: 4.5 (10)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 25 (3.0)
Treatment Plant Size
thousand cubic meters per day (MGD): 8.3 (2.2)*
Costs - $1000 Alternative Treatment Steps
Initial Investment 23 59 12 67
Annual Costs:
Capital Costs (8%) 25 15
Depreciation (10%) 2617
Operation and Maintenance 0.3 5 0.1 6
Energy and Power 0.1 1 - 1
Total Annual Costs 4.4 17 2.1 19
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
B.O.D. 10
C.O.D. 30 (No specific guidelines)
Suspended Solids 5
*The nitrile barrier resin contribution is 0.34 thousand cubic meters per day
(0.09 MGD); this is approximately 40% of the total flow to be treated.
23i
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TABLE VIII-4/30
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Spandex Fibers
Plant Description: Plant in Industrial Complex
Representative Plant Capacity
million kilograms (pounds) per year: 2.3 (5)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 8.3 (1.0)
Treatment Plant Size
thousand cubic meters per day (MGD): 3.4 (0.9)*
Costs - $1000 Alternative Treatment Steps
A B D E
Initial Investment 8 16 3 21
Annual Costs:
Capital Costs (8%) 0.6 1.3 0.2 1.7
Depreciation (10%) 0.8 1.6 0.3 2.1
Operation and Maintenance 0.2 1.4 0.1 3.7
Energy and Power - 0.2 - 0.5
Total Annual Costs 1.6 4.5 0.6 8
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
B.O.D. 20
C.O.D. 40 (No specific guidelines)
Suspended Solids N/A
*The Spandex contribution is 0.06 thousand cubic meters per day (0.015 MGD);
this is approximately 2% of the total flow to be treated.
232
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TABLE VIII-5/1
INDUSTRIAL WASTE TREATMENT MODEL DATA SYNTHETIC POLYMERS PRODUCTIOH
EVA Fluorocarbons Polypropylene Polyvinylidcne Acrylic
Copolymers Fibers Chloride Resins
Total Industry Discharge
1000 cubic meters/day
4
80
65
20
233
-------
TABLE VIII-5/2
INDUSTRIAL WASTE TREATMENT MODEL DATA - SYNTHETIC POLYMERS PRODUCTION
Cellulose
Derivatives
Total Industry Discharge
1000 cubic meters/day
(or million gallons/day)
1972 15.9(4.2)
1977 20.9(5.5)
Quality of Effluents in 1977
(Expressed in terms of yearly averages)
Parameters :
(in units/1000 units of product)
BODS NA
COD NA
Suspended Solids NA
Hydraulic Load: 1972-1977
(cu m/kkg (or gal/lb) NA
Numbers of Companies 3
Percent of Treatment in 1972
(in percent now treated)
A. Industrial Pretreatment 100
B. Industrial Biological 100
C. Municipal 0
Alkyds and
Unsaturated
Polyesters
6.8(1.8)
13.7(3.6)
0.4
2.0
0.1
3.2(0.4)
10
10
90
Cellulose Polyamides Polyesters
Nitrate Thermoplastic
9.8(2.6) 0.8(0.2) 0.4(0.1)
9.8(2.6) 1.2(0.3) 0.8(0.2)
5.0 0.3 0.35
25 3.0 5.3
4.2 0.2 0.24
142(17) 6.7(0.8) 2.2(0.95)
2 33
100 100 100
40 60 50
60 00
234
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TABLE VIII-5/3
INDUSTRIAL WASTE TREATMENT MODEL DATA - SYNTHETIC POLYMERS PRODUCTION
Total Industry Discharge
1000 cubic meters/day
(or million gallons/day)
1972
1977
Quality of Effluents in 1977
Polyvinyl
Butyral
5.3(1.4)
6.7(1.8)
(Expressed in terms of yearly averages)
Parameters :
(in units/1000 units of product)
BOD5 NA
COD NA
Suspended Solids NA
Hydraulic Load: 1972-1977
cu m/kkg (or gal/lb)
Numbers of Companies
Percent of Treatment in 1972
(in percent now treated)
A. Industrial
B. Industrial Biological
C. Municipal
NA
2
100
25
75
Polyvinyl Silicones Nitrile Spandex
Ethers Barrier Resins Fibers
0.4(0.1) 29.9(7.9) 0.8(0.2) 0.4(0.1)
0.6(0.2) 48.5(12.8) 2.7(0.7) 0.4(0.1)
NA 10.5 NA NA
NA 53 NA NA
NA 7.0 NA NA
NA 233(28) NA NA
24 33
70 100 100 100
0 20 70 60
30 0 30 10
235
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-------
SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
GUIDELINES AND LIMITATIONS
Definition of Best Practicable Control Technology
Currently Available (BPCTCA)
Based on the analysis of the information presented in
Sections IV to VIII, the basis for BPCTCA is defined herein.
Best practicable control technology currently available
(BPCTCA) for existing point sources is based on the
application of end-of-pipe technology such as biological
treatment for BODjj reduction as typified by activated
sludge, aerated lagoons, trickling filters, aerobic-
anaerobic lagoons, etc., with appropriate preliminary
treatment typified by equalization, to dampen shock
loadings, settling, clarification, and chemical treatment,
for removal of suspended solids, oils, other elements, and
pH control, and subsequent treatment typified by
clarification and polishing processes for additional BOD5
and suspended solids removal and dephenolizing units for the
removal of phenolic compounds. Application of in-plant
technology and changes which may be helpful in meeting
BPCTCA include segregation of contact process waste from
noncontact waste waters, elimination of once-through
barometric condensers, control of leaks, and good
housekeeping practices.
The best practicable control technology currently available
has been found to be capable of generally effecting removal
efficiencies of upwards to 85 percent in single-stage
biological systems. The design and operating parameters of
the biological treatment system may vary from essentially
those of a municipal sewage treatment plant to those
uniquely tailored to a specific plant waste. The
acceptability of many of the waste waters into municipal
sewage systems has been established and often proves to be
one of the best methods of waste water treatment where
suitable pretreatment can be effected and where the
synergistic effects of treating with sewage ocsur. The
applicability of biological systems has been proven
regardless of the age or size of the manufacturing plant.
Because of the relatively small number of single product
waste water treatment plants (much of the industry uses
either multi-plant waste water treatment or municipal
treatment) the amount of data on which effluent limitations
can be based is limited, and it has been necessary to rely
237
-------
on analogy and technology transfer for guidelines in some
instances. Because of the variabilities inherent in the
performance characteristics of industrial waste water
treatment plants, especially those affecting the growth of
microorganisms such as temperature and variable
concentrations, the guidelines have taken into consideration
demonstrated unique properties such as high concentrations
of COD that can exist in the treated waste waters. The
parameters of primary concern are BOD5, COD, and suspended
solids. Other parameters such as pH, metals, nitrogenous
compounds and specific chemicals such as phenolics are also
of concern to the industry.
In Table Vll-4 of Section VII the effluent loadings which
are currently being attained by the product subcategories
for BOD£, COD, and suspended solids are presented. In some
instances it was necessary to calculate effluent loadings
based on the hydraulic flows emanating from the production
plant and the concentrations of the particular parameters in
the effluents from a waste water treating plant handling
waste water streams from a number of other processes. This
procedure was adopted when it was known that a significant
fraction of the waste water treatment plant load came from
the process under consideration or where the treatability of
the waste waters could be expected to be analogous to those
of the major product, e.g., the similarity of ethylene-vinyl
acetate wastes to low density polyethylene wastes. Using
this approach, it was apparent from the results of this work
that practicable waste water treatment plants are in
operation and that their operational parameters are
comparable to those of the resins segment of this industry
as well as with biological treatment systems in other
industries. It is apparent, therefore, that the most
significant factors in establishing effluent limitations
guidelines on a basis of units of pollutants per unit of
production are (1) the waste water generation rates per unit
of production established for an exemplary plant and (2) the
concentration levels in the waste waters from the best
practicable waste water treatment techniques.
The Guidelines
The effluent limitations guidelines as kg of pollutant per
kkg of production (lb/1000 Ibs) are based on attainable
effluent concentrations and demonstrated waste water flows
for each product and process subcategory where a sufficient
number of similar products or processes could be identified.
238
-------
Attainable Effluent Concentrations
Based on the definition of BPCTCA, the following long-term
average BOD5. and suspended solids concentrations were used
as a basis for the guidelines.
BOD5 TSS...
mg/liter mg/liter
Major Subcategory Z 15 30
Major Subcategory II 20 30
Major Subcategory III 45 30
Major Subcategory IV 75 30
The BOD5 and total suspended solids concentrations are based
on observed or reported performance of water treatment
plants. In many subcategories of this segment of the
plastics and synthetics industry, the in-place waste water
technology and treatment levels are inadequate. By proper
design and application of the defined technologies, the
levels proposed are attainable as demonstrated by other
subcategories within this industry and other industries such
as organics and petroleum refining. The COD limitations
were included in the proposed regulation because COD is a
measure of the chemical by-product waste of the
manufacturing process and falls under the definition of
pollutant contained in the Act [5502(6) ]. All of the
proposed 1977 COD limitations were non-controlling as to
technology. That is, the COD limitations were such that
adequate removal of BOD5 will usually result in adequate
removal of COD. The proposed numbers were derived from data
showing the removal of COD which accompanies reduction of
BOD5 to the levels proposed in the effluent limitations for
each subcategory. A plant which is achieving the BOD5
removal required by the regulations need not use any
additional technology to meet the proposed COD levels for
BPCTCA. The presence of a COD limitation nonetheless
fulfills an important function by requiring adequate
handling and treatment of discarded (bad) batches of
reactants and products, so as to avoid shock or peak COD
loadings which would be inadequately treated but would not
be discovered by a BOD^ analysis. Also, the COD test is a
much quicker and more convenient test for the presence of
oxygen demanding pollutants than is the BOD5 test. However,
since the proposed BPCTCA (1977) COD limits are liberal and
would be easily attainable if the BOD5_ limits are met, they
are being dropped as a limitation parameter for BPCTCA
(1977).
The COD characteristics of the polymer segment of the
synthetics and plastics industry vary significantly from
239
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TABLE 1X-1
COD/BOD RATIOS
Raw
Acrylic Resins
Alkyd and Unsaturated
Polyester Resins
Cellulose Derivatives
Cellulose Nitrate
Ethylene-Vinyl Acetate/
Polyethylene
Polytetrafluoroethylene
Nitrile Barrier Resins
Polyesters (thermoplastic)
Polypropylene Fibers
Polyvinyl Butyral
Polyvinyl Ether
Polyvinylidene Chloride
Silicones
1.3 - 2.7
2 - 3.7
2.4 - 4.2
2.5 - 4.1
4.2
1.8
2.3 - 2.9
3.2 - 3.8
1 - 4.8
Treated
1.4 - 3.3
5.2
5.0
4.6 - 23
2.5
5.1
240
-------
product to product and within an individual plant over time.
The ratio of COD and BODJ5 in the raw waste water and treated
waste waters are shown in Table IX-1 and range from a low of
1.0 to a high of 23. There is a real need for more data in
all sections of the polymer segment of the plastics and
synthetics industry to provide a better understanding of the
waste water loads, the treatability of the waste waters and,
in particular, a better understanding of the nature of the
COD component and methods for its reduction. In order to
promote the collection of data on the oxygen demanding
parameters of BOD5, COD and TOC (total organic carbon), the
Agency is planning to require that a majority of the plants
in each subcategory monitor their raw waste loads and
treated effluents for BOD5, COD and TOC. This data will be
collected for a reasonable period at which time the Agency
will consider revising the limitations and standards.
In applying the BOD5_ limitation guidelines, if a plant can
show a direct relationship over a long period of time
between BOD5_, COD and TOC (total organic carbon), or TOD
(total oxygen demand), the parameter measurement of the COD,
TOC, or TOD could be substituted for BOD5 if the COD, TOC,
or TOD limitations are set such that the BOD5 limitation is
not exceeded.
Although guidelines are not established for phenolics in the
polymers segment of the industry, wherever phenolic
compounds are identified their removal should remain the
same as for the resins portion of the industry, i.e., an
attainable concentration level of 0.5 mg/liter monthly limit
as demonstrated by dephenolizing units (12) activated carbon
(13, 14, 35, 39) or biological degradation.
The removal of oil and grease is based on 30 mg/liter
monthly limit attainable concentrations as demonstrated by
various physical and chemical processes in other industries
(35).
The removal of fluorides is based on an attainable
concentration of 20 mg/liter by lime precipitation as used
in effluent guidelines for the iron and steel industry. It
should be noted that the fluoride level shown for the
polytetrafluoroethylene (PTFE) subcategory applies to the
fluoride content of the effluent from the water scrubber in
the TFE monomer process only, not to the total waste water
discharge from the overall PTFE process. The scrubber
effluent, a dilute HCl solution, is the only significant
source of fluoride discharge from the PTFE process. At all
present PTFE manufacturing operations, this scrubber
effluent is segregated from other waste waters and disposed
241
-------
of by various means, including deep well, ocean dumping, or
off-site contract methods. The waste water flow from the
scrubber amounts to 1/5 or less of the total waste water
generated by the process. The guideline for fluoride was
derived on the basis of 20 mg/1 attainable concentration and
a scrubber effluent flow of 3500 gal/1000 Ibs product.
Cyanides, mercury, and cadmium limitations should be
consistent with the limitations of toxic and hazardous
chemicals prepared in the Federal Register of December 27,
1973(38).
The removal of copper and lead is based on an attainable
concentration of 0.5 mg/liter as demonstrated by alkaline
chemical precipitation (35) .
The copper limitations for the silicone production
facilities were established in the following manner.
1. Precipitation of soluble copper by means of lime
treatment was selected as the most applicable
treatment technology. It has been shown to be
capable of achieving effluent copper concentrations
of less than 0.5 mg/liter.
2. It was assumed that no internal waste stream
segregation would be employed and that the total
volume of waste water emanating from the production
facilities would be subjected to the above lime
treatment.
3. The average waste flows in terms of gal/1000 Ibs
were used for the silicones plants by averaging the
values of the reported range of waste flows.
H. The maximum average for a 30-day period for BPCTCA
was then developed using the average waste flows
established in (3) in conjunction with the
demonstrated 0.5 mg/liter copper effluent using
lime treatment. The maximum average daily
limitations were taken as twice the average 30-day
limitations.
Since the lime treatment process theoretically removes
copper to a fixed solubility limit rather than removing a
certain percentage of the influent copper, the quantity of
copper in the raw waste water is of no consequence with
respect to the attainable effluent copper concentration.
Thus, the fact that different silicone production facilities
may produce waste waters with vastly varying quantities of
242
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copper is irrelevant with respect to the established
limitations. The net result is that the limitations on
copper, in pounds/1000 pounds of product, are dependent on
hydraulic load attainable. In one respect, the copper
limitations are actually conservative in favor of the
industry, because it was not presumed that copper-bearing
waste streams would be segregated from other waste streams
for treatment, a practice which would reduce the total
quantity of copper in the effluent,
Demonstrated Waste Water Flows
The waste water flow basis for BPCTCA is based on demon-
strated waste water flows found within the industry.
Because of the small number of manufacturing plants in most
categories, and/or the limited data base, the demonstrated
waste water flows shown in Table IX-2 were based on
engineering judgments taking into consideration reported
flows and other assessments such as the type of operation,
nature of housekeeping, and apparent operational attention
to good water conservation practices. The demonstrated
waste water flows are based (where possible) on direct
contact process water only and do not include boiler water
blowdown, water treatment regeneration wastes, cooling water
blowdown, and any other waters deriving from utilities and
supporting services. The resultant wastewater flows used
for calculating the limitation guidelines were reasonable
and representative of what most plants in each subcategory
are or should be achieving. It is essential to take into
consideration the fact that waste water flow is often an
integral part of the basic process design and operation of
the process and plant and, therefore, would be subject to
significant reduction only at considerable expense.
Although generally the unit hydraulic loads are larger for
older plants, the availability of water influences the
design as does the designer's philosophy and the company's
operating procedures. No simple formula has been found for
relating hydraulic load to plant age, size or location.
Statistical Variability of a Properly Designed and Operated
Waste Treatment Plant
The effluent from a properly designed and operated treatment
plant changes continually due to a variety of factors.
Changes in production mix, production rate, climatic
conditions, and reaction chemistry influence the composition
of raw waste load and, therefore, its treatability. Changes
in biological factors influence the efficiency of the
treatment process. A common indicator of the pollution
characteristics of the discharge from a plant is the long-
243
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TABLE IX-2
DEMONSTRATED WASTEWATER FLOWS
WASTEWATER FLOW RATES
Alkyd Molding Compounds and
Unsaturated Polyester Resins
cum/kkg
Greases, Emulsions,
Rubbers, and Resins
Coupling Agents
3.3
142
8.34
150
6.7
Cellulose Nitrate
Ethylene-Vinyl Acetate
Polytetrafluoroethylene
Polyamides (Nylon 6/12 only)
Polyester Resins (Thermoplastic) 7.9
Polypropylene Fibers 16.7
Silicones
Fluids
10.4
133
83.4
gal/1000 Ibs
400
17,000
1,000
18,000
800
950
2,000
1,250
16,000
10,000
244
-------
term average of the effluent load. The long-term (e.g.,
design or yearly) average is not a suitable parameter on
which to base an enforcement standard. However, using data
which show the variability in the effluent load, statistical
analyses can be used to compute short-term limits (monthly
or daily) which should not be exceeded, provided that the
plant is designed and run in the proper way to achieve the
desired long-term average load. It is these short-term
limits on which the effluent guidelines are based.
In order to reflect the variabilities associated with
properly designed and operated treatment plants for each of
the major subcategories as discussed above, a statistical
analysis was made of plants where sufficient data was
available to determine these variances for day-to-day and
month-to-month operations. The standard deviations for day-
to-day and month-to-month operations were calculated. For
the purpose of determining effluent limitation, a
variability factor was defined as follows:
Standard deviation = Q monthly, Q daily
Long-term average (yearly or design) = x
Variability factor = y monthly, y daily
y monthly = x * 2Q monthly
x
y daily = x + 3Q daily
The variability factor is multiplied by the long-term yearly
average to determine the effluent limitations guideline for
each product subcategory. The monthly effluent limitations
guideline is calculated by use of a variability factor based
on two standard deviations and is only exceeded 2 to 3
percent of the time for a plant that is attaining the long-
term average. The daily effluent limitations guideline is
calculated by the use of a variability factor based on three
standard deviations and is exceeded only 0.0-0.5 percent of
the time for a plant that is attaining the long term
average. Any plant designed to meet the monthly limits
should never exceed the daily limits. The data used for the
variability analysis came from plants under voluntary
operation. By the application of mandatory requirements,
the effluent limitations guidelines as discussed in this
paragraph should never be exceeded by a properly designed
and operated waste treatment facility.
The variability factors in Table IX-3 are based on the data
obtained in the synthetic resin segment (16) of the plastics
and synthetics industry.
245
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The variability factors for suspended solids removal are the
same as used in the resins segment of the industry, i.e., a
monthly variability of 2.2 and a daily variability of 4.0.
The variability factors recommended for total chromium,
phenolics, copper, lead, and oils and grease are based on
the monthly limits and a variability factor of 2.0 for the
daily maximum.
Based on the factors discussed in this section, the effluent
limitations guidelines for BPCTCA are presented in Tables
IX-* and IX-5.
246
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TABLE IX-3
VARIABILITY FACTORS FOR BODC
BOD5 Variability Factors
Monthly Daily
Major subcategory I 1.6 3.1
" " II 1.8 3.7
" " III 2.2 4.0
" " IV 2.2 4.0
247
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TABLE IX-4
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE EFFLUENT LIMITATIONS GUIDELINES
fkg/kkg (Ib/jOCO 1h) of production]
Foot-
note
No.
1
. 2
3
4
5
6
7
K5 8
*-
00 9
10
11
12
13
14
15
BODr
Subcategory Kaxinum Average of Maxixurc for Any
Daily Values for Any Ope !\*y
Period of Thirty
Consecutive Days
Etbylene-Vinyl Acetate Copolymera 0.20 0.39
Poly tatraf luoroethylens 3.6 7.0
Poljpropylene Fiber 0.40 0.73
Polyvl.-.yiiclene Chlorldts No numerical guidelines -see discussion
ir. footnote
Acrylic Resins " "
Cellulose Derivatives " "
Alkyds and Ur.aaturated folyester Reains 0.33 0.60
Cellulose Nitrate 14 26
?olya;3ide5 (Nylon 6/i2 only) O.&S 1.20
Polyester Resins (thermoplastic) 0.73 1.4
Polyvlnyl Butyral No numerical guidelines-see discussion
ia footnote
Polyyinyl Ethers " "
Sillcones
fl"1~" 1.0 1.9
Creases, Eiuilsions,
Rubber;), Kesins ,, » 2i
— j . *.
Coupling Agents 8.2 I5
.Kltrile Barrier E«cica Ko nuaerlcal ^uidtliac s-see dis-
cussion in footnote
Spandex Fibers " "
SUSPE.VJKD SO-iDS
Maximum ^VPr^gc of Kaxic.uzi for A-iy
Ji-ily Values for Any One Day
Period of Thirty
Coiisecutlve D.-.vs
0.53 1.0
9.9 18.0
1.1 2.0
Ko numerical guidelines-see discussion
in footnote
M . II
„
0.22 0.40
9.4 17
0.44 O.SO
0.52 0-95
No numerical guidelines-see discussion
in foctnote
"
0.69 1.25
8.8 I*
5.4 -0
No nuMricai guidelines-*** din-
cufisicn in footnote
ii «
-------
FOOTNOTES FOR TABLES IX-4 and IX-5
- 1. Zl.}iy_lexe^'inyl_At'.etate_ (EVA) Copolymer. Two of the five
knirwn producers verc contacted. All plants are located
at polyethylene production facilities. Water use and
vastewater characteristics for EVA are essentially iden-
tical to those for low density polyethylene. However,
en emulsion polymerization process is known and produces
e distinctly different waste load which is essentially
that of polyvinyl acetate csulsion polymerization
reported in EPA 440/1-73/010. Both multi-plant and
n.unicipal si-wage t r oat cent is used.
2 . Po]y_t_e_i r^J^l 11 o r^ic t: ViyJ JVTK^. Three of the s"ci tranuf acturlng
plants were viniti:d. A wide range uf products are produced.
The HOB t i nip or tcint is poly tetr.'if luarotthylenc (I'TFK) and
these guitlaLin^^ are recommended for PTFE granular and
fine powder grades only. The wostewater discharges differ
considerably depending upon the process recovery sclicir.cs
for hydrochloric acid ac.J the disposal o~ selected streams
by ctefp well, oce.-m (lunptnf; or off-site cm tract methods.
Ihe use of elhy 1 ent* glycol in G process csin b' gnif icantiy
affect the was tc loads. Fluoride concentrations in
untreated uvj.sLewaters sre generally below lev Is attain-
able by al'KAliiifi precipitation.
3. Fn 1 vT-to-.'YIt-1 c_F 1 rLftr_s. T-'o of the three proJucera were
cc'r t .11 ted. 1 in: vuiu i'k.'. r ic f leu zauyes per unit of p ro-
il >~t Ion vary widely depend i:ia upon the tvpc of cooling
tyt c oa ust J. "iiie was ce loads :ire for pi ant a where selec-
ted concentrated wastes are negragatcd and disposed of
l^i by landfilllng, etc. I*riisary treatment at one plant alto
VO *as observed while the other plant discharges to a
municipal sewage system.
*• P^Jyv- ".•'! *_d£ n_"^j-^A9^1J^' ^e two Kjjor tt'-inulacturers
veie contacted. Beth plant sites Bend wastcwaters to
xultt-plant treaincnt plants of which the polyvinylidena
chloride is a £.r:all port ion, Consequently, there was
insufficient data to develop reconar.ended guidelines.
'- A£ry!Jc Kc,sj"^.' ^-iree -°* tne four manufacturers were
contacted. Large numbers of product grades are produced
by b-.il.k, solution, suspension and emulsion polyneriza-
ticn. The widely varying hydraulic loads for the large
number of products in addition to treatment of the waste-
watnrs by cultt-pl.-tnt wastcvater trcatr.ent facilities
prohibited obtaining sufficient meaningful data to
zecozr^end effluent limitation guidelines.
^" £5JJL^°s- P?r-iy^_civcs^- Cellulose derlvatea investigated
Included ethyl cellulose, hydroxyethyl cellulose, tacthyl
cellulose and carboxyccthyl cellulose. Wide variations
in unit flow rates for two plants producing the same
produce, differences in nanufacturiag techniques and the
availability of data prevented recoixicncling guidelines.
The wastew^ters from the three manufacturers are being
treated in multi-plant waatewater treatment facllltiea
or will enter municipal ecwage aysterna.
7. Alkyds and t/ris.'tturated Po^'escer Kesins. Six carefully
selected plants were visited to provide a crosa-section
of the Industry for size of operation, type of manufac-
turing process and wastew.iter treatment methods. Hydrau-
lic loads vary widely depending upon the process designs.
Similarly, raw waste loadu vary widely because some
plants segragnte wastca foi disposal in other manners.
Generally, the industry dit?charges wastcwaters into
municipal sewage systems ard should continue. Also, the
type of air pollution control, e.g. combustion or scrub-
bing, has a significant effect on the wastewater loads.
The recommended guidelines are for plantd having their
own wastewater treatment system - a very infrequent
occurrence.
^* Cellulose Nicrajc. The two aajor manufacturers of the
four manufacturers were contacted. These wastes require
pH control and contain lar^e amounts of nitrates. One
plant discharges to a municipal sewage system while the
other goes into a multi-plant treatment complex,
9. Polywnl^es. Various polyamides are produced but only
Nylon 6/12 produces significant amounts of wastewater,
e.g. Nylon 11 UBOS no proceja water. Consequently, the
guidelines are restricted to Nylon 6/12 and were develop-
ed en the basis of similarity with waste loads from
Nylon 66 production.
10. Vol^vxtGT T\ i e r ri op1 a B t ic: R es i_n s. There ore three manu-
facturers, two of which produce poly(ethylene, terephtha—
late) in quantities leas than 22 of their total thermo-
plastic production. The guidelines are recommended for
poly(ethy 1 one teroptithalate) since the other product
poly(butylene tercplitlulate) is produced at only one
plant and the wastewater gees into a municipal sewage
system, so no data en performance could be obtained.
11, P_oI_vyijiy 1 Butv£aJ_. Of three production sites,two have
processes beginning with vinyl-acetate monomer which
generates much larger wastewater volumes than the pro-
cess beginning with polyvinyl alcohol. Since the manu-
facturing sites where production starts with a monomer
discharge into municipal sewage systems, there was no
data available. Consequently, there are no recommended
guideline* since they would b'e ' tantamount~ to establishing
a permit for the direct discharger production site.
Polyvinyl ethers. The three present planta use differ-
ent processes each of which produces several grades of
product. The different chemical compositions used In
both bulk and solution polyaerlzacion processes and the .
lack, of data on both raw and treated wastewatere pre-
vented establishing guidelines. The wautewaters are
presently sent to either cmXti-plant treatment faclllti*
or municipal a e wage ayateics.
, Slllconeg. Four companies manufacture silicones at f,
locations. Three plants vere visited and data were
obtained from all planes. The major processing steps
the five plants are chovn belov.
Major Processes nt Five Silicone Plants
Plant No. 32345
CH.C1 x xx
Chlorosilane prod. x x x x x
Hydrolysis x X x x x
Fluids, greases,
emulsions prod.
Resin production x x x
Elastomer production x x x x
Specialties prod.* x x x
Fumed silica prod. x
HC1 production x
* e.g. surfactants, tluorinated silicones* coupling
agents, and other materials.
Based on the msnufacturir.a process, the waste
watc-r flov-s a.id tVe rrv vaat.& loaiie, the plants
1, 2, 3 dn
-------
TABLE IX-5
BEST PRACTICABLE CONTROL TECHNOLOGY.CURRENTLY AVAILABLE EFFLUENT LIMITATIONS GUIDELINES
(Other Elements and Compounds)
Product
Parameter
kg/kkg (lbs/1000 Ibs of production)
Maximum average of daily Maximum
values for any period of For Any
thirty consecutive days One Day
CO
Ui
o
Alkyds and unsaturated
polyester resins
Mercury
Polytetrafluoroethylene Fluorides
Spandex fiber
Nitrile barrier resins
Polypropylene fibers
Silicones
Fluids
Cyanides
Cyanides
Oils & grease
Copper
Toxic and hazardous chemicals guidelines to apply
0.6 1.2
Toxic and hazardous chemicals guidelines to apply
0.5
0.005
1.0
0.010
Greases, Emulsions,
Rubbers and Resins Copper
Coupling Agents Copper
Polyester resins ...mi urn
(Thermopl ast.i c)
0.067 0.13
0.042 0.084
and hazardous chemic?.7 auidel
-------
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
Definition of Best Available Technology Economically
Achievable (BATEA1
Based on the analysis of the information presented in
Sections IV to VIII, the basis for BATEA is defined below.
Best available technology economically achievable (BATEA)
for existing point sources is based on the best in-plant
practices of the industry which minimize the volume of waste
generating water as typified by segregation of contact
process waters from noncontact waste water, maximum waste
water recycle and reuse, elimination of once-through
barometric condensers, control of leaks, good housekeeping
practices, etc., and end-of-pipe technology, for the further
removal of suspended solids and other elements typified by
granular media filtration, chemical treatment, etc., and
further COD removal as typified by the application of
adsorption processes such as activated carbon and adsorptive
floes, and incineration for the treatment of highly
concentrated small volume wastes and additional biological
treatment for further BOD5 removal when needed.
Best available technology economically achievable can be
expected to rely upon the usage of those technologies which
provide the greatest degree of pollutant control per unit
expenditure. Historically, this has been the approach to
the solution of any pollution problem — as typified by the
mechanical and biological treatment used for removal of
solids and biochemically active dissolved substances,
respectively. At the present stage of development, it is
technologically possible to achieve complete removal of
pollutants from waste water streams. The economic impact of
doing this must be assessed by computing cost benefits to
specific plants, entire industries, and the overall economy.
The application of best available technology will demand
that the economic achievability be determined, increasingly,
on the basis of considering water for its true economic
impact. Unlike best practicable technology, which is
readily applicable across the industry, the selection of
best available technology economically achievable becomes
uniquely specific to each process and in each plant.
Furthermore, the human factors associated with conscientious
operation and meticulous attention to detail become
increasingly important if best available technology is to
251
-------
achieve its potential for reducing the emission of
pollutants from industrial plants.
The Guidelines
Achievable Effluent Concentrations
Suspended Solids
The removal of suspended solids from waste water effluent is
based on well-understood technology developed in the
chemical process industries and water treatment practices.
Application of filtration to the effluents from waste water
treatment plants has not been applied often, although its
feasibility has been demonstrated in projects sponsored by
the Environmental Protection Agency. The operation of
filtration systems, such as the in-depth granular media
filter for waste waters, is not usually as straightforward
as it is in water treatment. This is due, especially, to
the biological activity still present in waste waters and
sometimes to the nature of the colloidal particles from the
process.
Long residence time lagoons with their low flow-through
rates are often effective means for the removal of suspended
solids, although the vagaries of climatic conditions, which
can cause resuspension of settled solids, and the occurrence
of algal growth can cause wide fluctuations in the
concentration of suspended solids in the effluent. Although
technology is available for reducing suspended solids in
effluents to very low levels (approaching a few mg/liter),
the capital and operating cost for this technology adds
significantly to waste water treatment costs. The
concentration basis for BATEA is 10 mg/liter for all product
and process subcategories (1, 15, 35). This concentration
is achievable by use of filtration techniques including
mixed media filtration. Mixed media filtration is a
pollution control technique which is well established and is
currently used with considerable success in a number of
treatment works - including municipal systems and waste
treatment systems used in the petroleum industry. The
wastes from biochemical treatment systems consists mostly of
microbial cells regardless of the original source of the raw
wastes. Microbial cells have similar solids removal
characteristics. While it has not been demonstrated in the
plastics and synthetics industry, the success shown in other
uses convinces the Agency that mixed media filtration is
fully adaptable to this industry and will achieve the
effluent concentration required, if necessary.
252
-------
Oxygen-Demanding Substances
Removal of biochemical-oxygen-demanding substances to
concentration levels less than the range proposed for
municipal sewage treatment plants will require the
utilization of physical-chemical processes. It is expected,
however, that the chemical-oxygen-demanding substances will
present a far greater removal problem than BOD5 because the
biochemically treated waste water will have proportionally
much higher ratios of COD to BOD5 than entered the waste
water treatment plant. In the case of a few polymer
products, the waste waters may contain substances giving a
significant COD concentration while being resistant to
biological degradation under the most optimum conditions.
To reduce the COD in a treated effluent, it will be
necessary either to alter processes so that nonbiodegradable
fractions are minimized or attempt to remove these
substances by some method of waste water treatment. Both of
these approaches may be difficult. Alteration of processes
so that they produce less refractory wastes may not be
possible within the constraints of the required chemical
reactions. However, reduction in the quantities of wastes
generated by spills, leaks, and poor housekeeping practices
can contribute significantly to reducing the total COD
discharges, especially where a large fraction of the
pollutants are refractory to biological degradation.
Consequently, one of the first steps in a program to reduce
emissions should be a thorough evaluation of the process
operation alternatives and techniques for preventing
pollutants from entering the waste water streams.
In other methods for removal of oxygen demanding substance,
adsorption by surface-active materials, especially activated
carbon, has gained preeminence. Although the effectiveness
of activated carbon adsorption has been well demonstrated
for removing BOD5 and COD from the effluents of conventional
municipal sewage treatment plants, its effectiveness for the
removal of the complex chemical species found in the waste
water of this industry can be expected to be highly
specific. Evidence of the low adsorption efficiency of
activated carbon for a number of different chemical species
is beginning to appear in the technical literature.
However, the only way to determine if activated carbon
adsorption is an effective method for removing COD is to
make direct determinations in the laboratory and in pilot
plants. In some instances, activated carbon adsorption may
be used to remove substances selectively (for example,
phenols) prior to treatment by other methods. Although
activated carbon adsorption is proving to be a powerful tool
for the removal of many chemical oxygen demanding and
253
-------
carbonaceous substances from waste water streams, it is not
a panacea. Its use must be evaluated in terms of the high
capital and operating costs, especially for charcoal
replacement and energy, and the benefits accrued.
Removal of carbonaceous and oxygen demanding substances can
sometimes be achieved through oxidation by chlorine, ozone,
permanganates, hypochlorites, etc. However, not only must
the cost benefits of these be assessed but certain ancillary
effects, such as (1) the production of chlorinated by-
products which may be more toxic than the substance being
treated, (2) the addition of inorganic salts, and (3) the
toxic effects of the oxidants themselves, must be taken into
account. Consequently, when chemical oxidation is employed
for removal of COD, it may be necessary to follow the
treatment with another step to remove the residuals of these
chemicals prior to discharge to receiving waters.
Degradation of oxygen demanding substances may take place
slowly in lagoons if sufficiently long residence time can be
provided. If space is available, this may be an economic
choice. Also, the use of land irrigation, or the "living
filter" approach to water purification, is receiving
selected attention. Ultra-filtration and reverse osmosis,
both of which are membrane techniques, have been shown to be
technically capable of removing high molecular species, but
they have not been shown to be operationally and
economically achievable. With these techniques, the
molecular distribution of the chemical species determines
the efficiency of the separation. They probably have
limited potential in the plastics and synthetics industry,
due to the particular spectrum of molecular weights
occurring in the waste waters.
The concentration basis for BATEA for COD is either 130
mg/liter as demonstrated in an activated carbon plant (4) in
the plastics and synthetics industry, or that concentration
documented by plants in Table VTI-3 as attainable in
biological treatment systems or retention lagoons. The BOD5
concentrations which are attainable by biological treatment
plants as expressed in the better waste water treatment
plants as presented in data from the synthetic resins
segment (16) of this industry, are 15 mg/liter for Major
Subcategory I and II products and 25 mg/liter for Major
Subcategory III and IV products. The removal of fluorides
is on the same basis as for BPCTCA as outlined in Section
IX. Similarly, the limitations on mercury, cadmium, and
cyanides should be those prescribed for toxic and hazardous
chemicals.
254
-------
The removal of oils and greases to a concentration of 10
mg/liter, copper to a concentration of 0.25 mg/liter, and
lead to 0.03 mg/liter is based on the concentrations
attainable (35) when filtration is used for solids removal.
Waste load Reduction Basis
The waste load recommendation for BATEA is based on overall
loading reduction through the use of the best achievable
concentrations and the reduction of waste water flows from
BPCTCA to a level between the BPCTCA waste water flows and
the verified BADT waste water flows as described in Section
XI. The wastewater flows are given in Table X-1. The
wastewater flows used for calculating BATEA are reasonable
estimates of reductions which industry should be able to
achieve by 1983, using the various methods of wastewater
flow reduction and recycle as outlined in sections VII and
IX.
255
-------
BATEA Waste Water
TABLE X-1
Flow Rates
cum/kkq gal/1000 Ibs
Alkyd Molding Compounds and
unsaturated Polyester Resins 1.83
Cellulose Nitrate 125
Ethylene-Vinyl Acetate 7.92
Polytetrafluoroethylene 91.7
Polyamides (Nylon 6/12 only) 6.67
Polyester Resins
(Thermoplastic) 7.92
Polypropylene Fibers 9.17
Silicones
fluid products 10.*
multi products 133
220
15,000
950
11,000
800
950
1,100
1,250
16,000
256
-------
Increased efficiency in the utilization of water combined
with closer operational control to prevent pollutants from
entering waste water streams have the greatest promise for
reducing the amounts of pollutants discharged from waste
water treatment plants. While the reduction of water usage
may directly reduce the total emission of certain
pollutants, it may mean that advanced waste water treatment
systems become more economically feasible.
Variability
The variability factor for BATEA guidelines is based on the
variability determined by data from BPCTCA. Both the
monthly and daily variabilities are based on two standard
deviations. As technology and plant operations improve, it
is expected that these variabilities will become more
stringent. The BOD5, COD, and TSS variabilities are
presented in Table X-2. The TSS factors are based on data
obtained from multi-media filters used in the petroleum
refining industry. The other parameters are based on the
achievable concentration for monthly maximum and a
variability factor of 2 to determine the daily maximum.
TABLE X-2
Variability Factors BATEA
BOD5 and COD
Monthly" Daily
TSS
Monthly Daily
Major Subcategory I 1.6
Major Subcategory II 1.8
Major Subcategory III 2.2
Major Subcategory IV 2.2
2.4
2.8
3.0
3.0
1.7
1.7
1.7
1.7
2.0
2.0
2.0
2.0
Based on the factors discussed in this section, the Effluent
Limitations Guidelines for Best Available Technology
Economically Achievable, BATEA, are presented in Tables X-3
and X-4.
257
-------
TABLE X-3
5LST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE EFFLUENT LIMITATIONS GUIDELINES
[kg/kkg (lb/1000 Ib) of production]
Subcategory
ZtV.ylt r.e-Vinvl Acetate Copoly/cers
Polytctrafluorocthylene
P_-;y;rc;,;er.e Fiber
rclyvU.ylidcne Chlcride
A ryl ic RCK ins
AiVvds and Unpaturated Polyester Resins
Cellulose Nitrate
££ polyjaiJes (Nylon 6/12 only)
00
Pollster fc <; * i n G (thi-naoplastic)
Polyv :;v I EuLyraL
?ciyv;;:vl Ethers
Sili.cor.es
Flu I A
Greases, Eculstons,
Rubbers, Keslna, end
Coupling Amenta
Ni-.rili: Barrier Xusins
BOD.
Kaximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive DOTS
0.19
2.2
0.22
No numerical guidelines-see
in footnote
0.10
6.9
0. 37
0.44
No numerical guidelines-see
In footnote
"
0.57
6.4
No numerical guidelines-see
0.29
3.3
0.33
discussion
0.14
9.4
0.50
0.59
discussion
"
0.28
8.8
discussion
COD
Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecut tve Davs
1.63'
4.0
0.40
No numerical
0.52
34
1.9
2. 3
No numerical
"
3
33.4
Kn niimp^'trAl
2.43
5.9
0.59
guide] inos-see discussion
in footnote
0. 74
47
2.6'
3.1
guldel ines-ste discussion
in footnote
"
4
45.5
fuiirfpl 1 nt>K— seo dl fidustii on
s.,_ -, c.. ....
?trii-d c: T'r.irty
0-1* 0.16
1.6 i . -'
0.16 C"f'
No nu-.:rical ^ui _< ! .::- - -^-v . •.---,
in : > v-l.'.' t v
0.03 C . C t
2.1 if
0.11 C.I.)
°'14 C..C
No r..UT.v*r ieal •t'J\.'.^- i ;•.>:--•-<-•
i.-i f,- t>.> u-
ii
0.21 0.1B
2.0 2.3
in footnote jn footnote
Spandtx Tibars " "
-------
FOOTNOTES FOR TABLES X-3 and X-4
*- Ethyl ere-Vinyl_^ jte_etate (EW\> Copolymcr. Two of the fiva
kp.t-Vii producers were contacted. All plants tre located
at polyethylene production facilities. Water use and
vsKtewater characteristics for EVA are essentially Iden-
tical to these for low density polyethylene. However,
en es'jlsion polycerization process is known and producer
a distinctly different waste load which is essentially
that of puly vinyl acetate emu Is ion polyrccr izat Ion
reported in EPA 440/1-73/010. Both multi-plant and
cur.iclpal suuoLg c treat, cent is used.
2. Po3 vtej_Tiiif'J_ti'jroe"!i_\'7enjp_. Three of the seven manufacturing
plrnts wc-ra visited. A wide ran^e of products are produced,
Tie rr.ost itnjior tr.nt is poly tetrof luoroatiiylene (PTFK) and
these guidelines are re contended for PTFE granular and
fire powder graces only. The wastewater discharges differ
considerably depending upon the process recovery schemes
for hydrochloric acid and the disposal of selected fitreams
by deep well, ocean dumping or off-site contract cr^thods.
The use of ethvlt;r.c glycol in ,-. process can significantly
effect the w.is :o loadr;. Fluoride ccr.cer.trations in
untreated wast.tracers are generally below lev Is attain-
able by a3kft.Vlnu precipitation.
3* Poj. v}>ro;->• I_gj,o^Fib £T_s . Two of the three producers were
c:--r.r..acted. Iht vtixiae'. r Ic flow ranges per unit of pro-
duction vary widely dtperidinx upon the tyoe of coolin?
system use-!. Tue waste loads are for plants where eelec-
! ted concentrated wastes are Bcgragated and disposed of
by lar. it 11 ling, etc. Primary treatment at one plant sittt
w;?s observed while the other plant discharges to a
Bun*cipsl sevage system.
two
manufacturers
*• Z.9- * y_X_' yy J- *Ae n_e . , - -Q1 !-. ° -r-AJ- ^
were contacted. Both plant sites send wastewaters to
cul ti-plr.nt treatment plants of which the polyvinylidene
chloride is a s~all portion. Consequently, there was
insufficient data to develop rec&ncr.ended guidelines.
5- Acj-y 11 c_ Ra s i_ns_ . Three of the four manufacturers were
contacted. Large numbers of product gr-ides are produced
by bulk, solution, suspension and emulsion polymeriza-
tion. The widely varying hydraulic loads for the large
number cf products In addition to treatment of the waste*
waters by multi-plant wastcwater treatment facilities
prohibited obtaining sufficient oeaningful data to
reccrcicnd effluent limitation guidelines.
^» Ce^ulosc Dcriya' ivcs. Cellulose derivates Invest 'r.^.ted
included ethyl cellulose, hydroxyethyl cellulose, nyl
cellulose anJ carboxynethyl cellulose. Wide variations
in unit flow rates for two plants producing the same
product, differences In manufacturing techniques and the
availability of data prevented recormcnding guide-1 '.
Hit vasteujters from the three manufacturers are beinft
treated in aultl-plant wastewater treatment ' liitlt-j
or viil enter municipal acwdge »y elects.
10.
11.
ftd^y^jatjir^ji^ Six carefully
selected plants were visited to provide a cxosa-cection
of the Industry for size of operation, type of manufac-
turing process and uastcw.itcr treatment method.-a. Hydrau-
lic loads vnry widely depending upon the process designs.
Similarly, raw waste lo;tdH vary widely because some
plants segragate wastes for' disposal In other manners.
Generally, the Industry dlechargcs wastewaters into
municipal sewage systems ar.d should continue. Also, the
type of air pollution conttol, e.g. combustion or scrub-
bing» lias a significant effect on the wastewater loads.
The recomracnded ftuldelines are for plants having their
own wastewater treatment system - a very infrequent
occurrence.
CcHulos_e^Nj.t1ra_te_. The two ni.ijor manufacturers of the
four manufacturcra wcri; contacted. The;;e wastes require
pH control and contuin lar^e amountc of nitrates. One
plant discharges to a municipal sewage system while the
other goes into a multi-plant treatment complex.
Polyami OPS. Various polyaraldeo are produced but only
Nylon 6/12 produces signifleant amounts of wastewater,
e.g. Nylon 11 tides no process water. Consequently, the
guidelines are restricted to Nylon 6/12 and wore develop—.
ed on the basis of aliuilnrity with waste loads from
Nylon 66 production.
Polyester Thermoplastic Pcslna* There are three manu-
facturers, two ot which produce poly(et.hylene, terephtha—
late) in quantities less than 2'? of their total thermo-
plastic production. The guidelines are recommended for
poly(ethylen<: terephtlialate) cince the other product
poiy(butyler.o tcrephth;ilate) Is produced ot only one
plant and thy waste-water fn>es into a njniclpal sewage
system, so no data on performance could be obtained.
Polvvir.yl Butyra_I. Of three production cites,two have
processes beginning with vinyl-acetate monomer which
generates much larger wastewater volumes than the pro-
cess beginning with polyvinyl alcohol* Since the manu-
facturing sites where production starts with a monomer
discharge into municipal sewage systcirs, there was no
data available. Consequently* there are no recotnended
guidelines aince they would be tantamount to establishing
a permit for the direct discharger production «ite.
12.
ethers. The throe
ent processes each of which
product. The different t.
both bulk and solution i .". -;\
lack of data on both raw -
vented establishing guide
presently sent to eithe ..
OL* municipal sewage ays ;
nt plants uae dlffer-
.ces several grades of
* compositions used in
nation processes and the .
v'tcd wactewaters pre-
The wastewaters are
:\ ant treatment facllitla
13. Slliconcs. Four ccncpanieti canufBctv.re sillcones at fivo
locations. Three plants were visited and data vera
obtained front all plants. The major processing steps a:
the five plants are stiovn below.
K.ijor Processes gt___Piy_c___Sj He one Plants
Plant No. 1 2 3 4 5
CH.C1 x xx
Chlorosilane prod. x x x x x
Hydrolysis x x x x x
Fluids, greases,
emulsions prod.
Resin production x x x
Elastomer production x x x x
Specialties prod,* x x x
Fuiatd silica prod. x
HC1 production x
* e.g. surfactants, fluorinatcd etlicones, coupling
agents, and other materials.
Based on the mnnufacturing process, the waste
water fU-w:; ji.tl th-i itw v;:stc loode, the plants
1, 2, 3 and 5 w«rt iiesl;-.'"-itfid as multi-product
plants while i was dt:BignRt^d EB « fluid
product [)lant.
Z4. Nlt_rUe Barrier
Com:erciAl scale
sale of these resins has not yet begun. The ce^p_nies
expected to Iiave production facilities were crr.tactc-,
and two provided estirMtts of raw waste lo-ds. Btcsase
of the lack of demcnstratcd flows and raw waste loaJs
It was impossible to establish effluer.t guiJclin*;
limitations.
Spntviex FJbo^s. Three c5r^;f acturcrs eje*h'p-foJuce* •
Spandex fibers by significantly different processes.
These are dry, wet and reaction spinning cethois. '
Because of United data on raw w^ste loid.v nra
because each plant operates a differoce process,
it waa iBp->G6ibZe to establish ceaningful guicelinaa.
-------
to
c*
o
TABLE X-4
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE EFFLUENT LIMITATIONS GUIDELINES
(Other Elements and Compounds)
Product
Greases, Fmulslons,
Rubbers, Resins and
Coupling Agents
Polyester resins
(thermoplastic)
Parameter
Alkyds and unsaturated
polyester resins
Mercury
Polytetrafluoroethylene Fluorides
Spandex fibers
Nitrile barrier resins
Polypropylene fibers
Silicones
Fluids
Cyanides
Cyanides
Oils and grease
Copper
Copper
kg/kkg (Ibs/lOOQ Ibs of Production)
Maximum average of daily
values for any period of
thirty consecutive days
Maximum
For Any
One Day
Toxic and hazardous chemicals guidelines to apply
0.6 1.2
Toxic and hazardous chemicals guidelines to apply
0.092
.0026
0.18
.0052
.029 .058
.. and hazardous chemicals gui -1?lines to ap^l
-------
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
BEST AVAILABLE DEMONSTRATED TECHNOLOGY
Definition of New Source Performance Standards Best
Available Demonstrated Technology JNSPS-BADT)
Based on the analysis of the information presented in
Sections IV to VIII, the basis for NSPS-BADT is defined
below.
Best available demonstrated technology (BADT) for new source
performance standards (NSPS) is based on BPCTCA, the maximum
possible reduction of process waste water generation along
with the application of solids removal operations such as
granular media filtration and chemical treatment for
additional suspended solids and other element removal as
well as additional biological treatment for further BOD£
removal as needed.
The Standards
Achievable Effluent Concentration
The concentration basis for NSPS-BADT is the same as that
for BATEA for BOD5, TSS, oil and grease, copper and
fluoride. The COD concentration basis for NSPS-BADT is
based on the concentrations which were attainable in
observed biological treatment plants or retention lagoons as
expressed in Table VII-3, or were rationally transferable
from similar type products. In cases where attainable
concentrations were not available as long term or
transferable data, COD is not required as a standard.
Waste Load Reduction Basis
The waste water flow basis for NSPS-BADT is based on the
lowest verified flows associated with each product. Use of
the lowest verified existing waste water flows for
calculation of new source standards is fully justified since
a new plant can be planned and designed for the lower flows
which are currently being demonstrated by plants within each
subcategory. The product specific waste water flows are
summarized in Table XI-1.
It is apparent that effluent limitations standards requiring
significant reductions over that attainable by best
practicable control technology currently available (BPCTCA)
261
-------
TABLE XI-1
LOWEST DEMONSTRATED WASTEWATER FLOWS
Product Subcategory cu meter/kkg gal/1000 Ibs
Alkyd molding compounds
and unsaturated polyester
resins 0.33 40
Cellulose nitrate 108 13,000
Ethylene-vinyl acetate 7.51 900
Polytetrafluoroethylene 33 4,000
Polyamides (Nylon 6/12 only) 6.7 800
Polyester resins - (thermoplastic) 7.9 950
Polypropylene fibers 1.67 200
Polyvinyl butyral 47 5,600
Silicones
Fluids 10.4 1,250
Greases, Emulsions,
Rubbers, Resins and
Coupling Agents 100 12,000
262
-------
requires considerable attention to both the process
generation of waterborne pollutants as well as the water use
practices of the plant.
Variability
The variability factors for BADT standards are based on the
variability factors determined for BPCTCA for BOD5 and COD.
The TSS variability factors are 1.7 monthly and 2.5 daily as
demonstrated by multi-media filtration data obtained from
the petroleum industry. The other parameters are based on
the achievable concentration for monthly maximum and a
variability factor of 2 to determine the daily maximum.
Alkyds gnd Unsaturated Polyesters
The new source standards for alkyds and unsaturated
polyesters are based on a process wastewater flow of 40
gal/1000 Ibs of production as demonstrated by several plants
within the subcategory. Since the flow basis for this
subcategory is substantially lower than for any other
subcategory in the plastics and synthetics industry, a brief
description of how it is currently being attained is
discussed below.
In the manufacture of alkyds and unsaturated polyesters,
there are three main sources of process-related waste water:
1. Water of reaction
2. Scrubber water
3. Reactor cleanout water
(Surface condensers are assumed to be used instead of
barometric type.)
Minimum discharge may be achieved by (1) reducing in-plant
water usage through good housekeeping and water conservation
practices, (2) recirculating scrubbing water until the
concentration of organic material in that water is
sufficiently high to allow for periodic incineration. If
the organics are sufficiently concentrated the combustion
may be self-supporting, (3) reusing reactor cleanout water
to the maximum permissible, then combining it with the water
of reaction, concentrating the blend by evaporation and
sending the resulting waste to contract disposal.
Based on the factors discussed in this section, the New
Source Performance Standards for Best Available Demonstrated
Technology (NSPS-BADT) are presented in Tables XI-2 and XI-
3.
263
-------
TABLE XI-2
BEST AVAILABLE DEMONSTRATED TECHNOLOGY NEW SOURCE PERFORMANCE STANDARDS
[kg/kkg (lb/1000 Ib) of production]
Foot-
note
No.
1
2
3
4
5
7
$10
6*
11
12
13
Subcategory
Ethylene-Vi.iyl Acetate Copolymcrs
Polytetraflucroethylene
Polypropylene Fiber
Polyvlnylider.e Chloride
Acrylic Resins
Al'^yds and Unsaturated Polyester Resioa
Pel yam Idee (Hyloa 6/12 only)
Polyester Resins (thermoplastic)
Pclyvinyl E^tyral
Polyvinyl Ethers
Sl'iccnen
Fluid
Rubbers, !>sins, and
BOD,
Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Days
0.1S
0.80
0.04
No numerical guidelines-see
in footnote
0.02
6.0
0.37
0.44
No numerical guidelines-see
In footnote
.57
5.5
0.35
1.60
0.08
discussion
0.0 3
11
0.67
0.80
discussion
1.0
10
COD
Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Days
1.8 3.5
1.4 2.9
0.07 0.14
No numerical guidelines-see discussion
in footnote
00.11 0.20
30 54
1.9 3-«
6.5 12
No numerical guidelines-see discussion
iu footnote
4.7 8.5
45 82
Suspended Solids
Maximum Average of
Daily Values for Any
Period of Thirty
Consecutive Days
0.13
0.57
0.03
No numerical guidelines-see
in footnote
0.0 06
0.11
0.14
No numerical guidelines-see
in footnote
0.18
1.7
Kaximiua fcr Any
One Dsy
0.19
0.83
0.04
discussion
0.008
0.17
0.20
discussion
0.26
2.5
14 Xitriie Sarrier Resins
15 Spandex Fibers
No ouaerical guide linen -see discussion
in footnote
Ho numerical guidelines-see discussion
In footnote
So numerical guidelines-see discussion
in footnote
-------
FOOTNOTES FOR TABLES XI-2 and XI-3
1* Ethyl en*-^Jnyl Acetate (EVA) Cepolymer. Two of the five
known producers were contacted. All plants are located
at polyethylene production facilities. Water use and
vasttvattr characteristics for EVA are essentially iden-
tical to these for low density polyethylene. However,
an exulsion polymerization process is known and produces
a distinctly dHfeicnt waste load which Is essentially
that of polyvinyl acetate emulsion polymerization
reported in EPA 440/1-73/010. Both multi-plant and
Kunlcipal sewage treatment is Used.
2. Poly.ticj.mfluoroethyjene^. Three of the seven manufacturing
plants were vioitied. A ult!c range of prctV-ets are produced.
The n?or. t iR!;nrti~rit is polytetraf luorouthyltine (1'TFfc) ond
these ^uitJelLnas Are recormended for ?TFE granular and
fire povder prccles only. The wastcwater discharges differ
considerably depending upon the process recovery schemes
for hydrochloric acid and the disposal of selected streams
by deep well, ocey_Ltlr ~^'^^Til ^u° °^ t'%e tn^ee producers were
Ci.rr.acled. "ilie v:ilu--i--'. r Ic flow ranges per unit of pro-
duction vary widely depending upon the type of coolin*
syitea U3ti. 'Ilie waste Joada are for plants where selec-
ted concentrated wastes are segregated and disposed of
by land!illing, etc. Primary treatment at one plant site
was observed vtiiT.c the other plant discharges to a
ttunlclpal sewage eystcra.
v^rc contacted. Sotti plant sites send wastewaters to
zuiti-plant treatment plants of which the polyvinyliden*
chloride is a snail portion. Consequently, there was
insufficient data to develop recoKr«nded guidelines.
5. AHIi.LLS_^~s!—* T'V'ree °* c^c four aanufacturers were
contacted, Lar^e r.osbers of product grades are produced
by bulk, solution, suspension and emulsion polyiaeriza-
ticn. Die vldfely vaiyJng hydraulic loads for the large
r:ur.btfr cf products in aJJlticn to treatment of the wasts*
waters by n.ulti-pl.ir.t wastewater treatment facilities
prchibitcj obtaining sufficient raeaningful data to
reccsszcnd effluent limitation guidslincs.
6, Cellulose Derivatives. Cellulose dcrlvates investigated
included ethyl cellulose, hytiroxyethyl cellulose* methyl
cellulose and carboxyaothyl cellulose. Wide variations
in unit flow rates for two plants producing the same
product, ciftercnces in manufacturing techniques and the
availability of, data prevented recortscadinjj guidulinea.
The vj£tevaters from the three manufacturers are being
treated in multi-plant wastewater treatment facilities
or vlll enter aunicipal sewage systems.
N>
Oi
11.
AlkydB and Unoaturatcd Polyester Rosins, Six carefully
selected plants were visited to provide a cross-section
of the industry for size of operation, type of manufac-
turing process and wastcw.itcr treatment methods. Hydrau-
lic loads vtry widely depending upon the process designs.
Similarly, rav waste loads vary widely because some
plants ecgragate wastes for disposal in other manners.
Generally, the Industry discharges wastewaters Into
municipal sewAge syntens ard should continue. Also, the
type of air pollution contzol, e.g. combustion or scrub-
bing, has a significant effect on the wastewater loads.
The recommended guidelines are for plants having their
own wastevater treatment system - a very infrequent
occurrence.
Cc 11 u lose N11 ra te_. The two major manufacturers of the
four rs.-mufacturers were contacted. These wastes require
pH control and contain larga amounts of nitrates. One
plant discharges to a municipal sewage system while the
other goes into a mulci-plant treatment complex.
Po^l^^f'i^pg. Various polyamideo are produced but only
ilylon 6/12 produces significant amounts of wascewater,
e.g. Nylon 11 USOB no process water. Consequently, the
guidelines are restricted to Nylon 6/12 and wore develop-
ej on the basis of similarity with waste loads from
Nylon 66 production.
Fgly^tgr The moping t i c Res ins. There are three manu-
facturers, two ot which produce poly(ethylanet tercphtha—
Ince) in quantities less than 2? oC their total thermo-
plastic production. The guidelines are recommended for
poly(ethylcii(; tetephthalatc) since the other product
poly(iiutylene tercplithalate) is produced at only one
plant aid the wasrtwater goes into a municipal sewage
system, sc no un'a en pertora.ince could be obtained.
Pqlyyinyl JJutvral. Of Llnoe or'oduction sites, two have
processes btgin.-i.ing with vinyl-acetate Dvonoiiie-r which
generates much larger Wiist^wsttr volumes than cite pro-
cess beginning with polyviuyl alcohol. SLnc'p £'ie manu-
facturing aitfis where producrion r>tatts with a wunomor
discharge into municipal sewage systems, there was no
data available. Consequently, there are no recon«tendcd
tuldelinev since they would be tantamount to eetablishlns
• permit for the direct discharger production site.
T;felyyinyl cthera* The three present plants use differ-
ent processes each of which produces jcv^ral gradus of
product. The different »:hetnical compositions used in
both bulk and solution polymerization processes and the
lack, of data on both raw and treated wastewaters pre-
vented establishing guidelines. The wastewaters are
presently sent to either cmltl-plant treatment facilitte
or municipal sewcge systems.
Sllicones. Four companies xumufacture siliconct at five
locations. Three plants were visited and data wera
obtained from all plants. The major processing steps at
Che five plants are shown belov.
Ka.lor Processes at..Five Siliccne Plants
Plant No. 1 2 3 4 5
Chlorosilane prod. z x x x x
Hydrolysis x x x x x.
Fluids t greases,
cnulsions prod,
Resin production ac x x
Elastomer production x x x x
Specialties prod.* x x x
Fumed silica prod. x
HC1 production x
* e.g. surfactants, fluorinatcd silicones, coupling
agents, and other materials.
Based on the manufacturing process, the waste
water flcvs at-d the r&u waote loads, the plants
1, 2, 3 and 5 ware desife^atcd as mlti-product
plants while A was dfislgnatad as a fluid
product plant.
Nitrile »arrier_Ref;ln&. Cocnscrcial scale rrojucticn anj
sale of these resins has not yet begun. The ccxpcr.ics
expected to have production facilities were contacted,
and two provided estimates of raw waste loads, because
of the lack of demonstrated flows ind raw waste loads,
it was impossible to establish efiltent guideline
lioitatlons.
-Spar.dax Fibers. Three manufacturers each produce-.
Spandex fibers by sl^nlficantly different processes.
These are dry, wet and reaction spinning methods.
Because of lintted data on rav waste loads- and
because each plant operates a different process,
it was impossible to establish meaningful guidelines.
-------
TABLE XI-3
BEST AVAILABLE DEMONSTRATED TECHNOLOGY - NEW SOURCE PERFORMANCE STANDARDS
(Other Elements r.nd Compounds)
Product
Parameter
kg/kkg (lbs/1000 Ibs of Production)
Maximum average of daily
values for any period of
thirty consecutive days
Maximum
For Any
One Day
Alkyds and unsaturated
polyester resins
1-leicury
PolvtetrafIuoroethylene Fluorides
Spandex fibers
Nitrile barrier resins
Polypropylene fibers
Silicones
Fluids
Greases, Emulsions,
Rubbers, Resins and
Coupling Agent0
Polyester resins
(thermop la.« tic)
Cyanides
Cyanides
Oils and grease
opper
;,.mium
Toxic and hazardous chemicals guidelines to c?.pply
0.6 1.2
Toxic and hazardous chemicals guidelines to apply
0.017
0.0026
0.034
0.0052
0.025 ^.050
T( .. . id hazardous chemicals s,u: Alines to ap
-------
SECTION XII
ACKNOWLEDGMENTS
The preparation of the initial draft report was accomplished
through a contract with Arthur D, Little, Inc., and the
efforts of their staff under the direction of Henry Haley,
with James I. Stevens and Terry Rothermel as the Principal
Investigators. Industry subcategory leaders were Robert
Eller, Charles Gozek, Edward Icteress, and Richard Tschirch.
J. E. Oberholtzer coordinated the sampling and analytical
work and Anne Witkos was Administrative Assistant.
David L. Becker, Project Officer, Effluent Guidelines
Division, through his assistance, leadership, advice, and
reviews has made an invaluable contribution to the overall
supervision of this study and the preparation of this
report.
Allen Cywin, Director, Effluent Guidelines Division, Ernst
Hall, Assistant Director, Effluent Guidelines Division, and
Walter J. Hunt, Chief, Effluent Guidelines Development
Branch, offered many helpful suggestions during the program.
The members of the working group/steering committee who
coordinated the internal EPA review are:
Walter J. Hunt - Effluent Guidelines Division (Chairman)
Allen Cywin - Effluent Guidelines Division
David Becker - Effluent Guidelines Division
(Project Officer)
William Frick - Office of Enforcement and
General counsel
Bruce Diamond - Office of Enforcement and
General Counsel
Judy Nelson - Office of Planning and Evaluation
Robert Wooten - Region IV
Walter Lee - Region III
Frank Mayhue - Office of Research and Monitoring (Ada)
Wayne Smith - National Field Investigation Center
(Denver)
David Garrett - Office of Categorical Programs
Paul Des Rosiers - Office of Research and Monitoring
Herbert Skovronek - Office of Research and Monitoring
Murray Strier - Office of Enforcement and
General Counsel
Acknowledgment and appreciation is also given to the
secretarial staffs of both the Effluent Guidelines Division
267
-------
and Arthur D. Little, Inc., for the administrative
coordination, typing of drafts, necessary revisions, and
final preparation of the effluent guidelines document. The
following individuals are acknowledged for their
contributions. Brenda Holmone, Kay Starr, and Nancy Zrubek
- Effluent Guidelines Division. Mary Jane Demarco and
Martha Hananian, Arthur D. Little, Inc.
Appreciation is extended to staff members from EPA's Regions
III and IV offices for their assistance and cooperation.
Appreciation is also extended to both the Manufacturing
Chemists Association and the Synthetic Organic Chemical
Manufacturers Association for the valuable assistance and
cooperation given to this program. Appreciation is also
extended to those companies which participated in this
study:
Air Products and Chemicals, Inc.
Allied Chemical corporation
Ameliotex
American Cyanamid
Aquitaine Societe Nationale des Petroles
Ashland Chemical Company
BASF Wyandotte
Celanese Chemical company
Chemplex Company
Cook Paint and Varnish company
Diamond - Shamrock
Dow Chemical company
Dow-Corning Company
E.I. duPont de Nemours and Co., Inc.
Durez
FMC Corporation
Freeman Chemical Corporation
GAF Corporation
General Electric Corporation
Globe Manufacturing Corporation
Goodyear Tire and Rubber Conpany
Hercules, Inc.
ICI American, Inc.
Koppers Company
Monsanto Company
Pennwalt Corporation
Phillips Fibers Company
Plastics Engineering company
Reichhold chemicals. Inc.
Rilsan Industrial, Inc.
Rohm and Haas Company
SCM-Glidden-Durkee
268
-------
SWS Silicones
Sherwin-Williams Company
Standard Oil Company
Swedlow, Inc.
Tennessee Eastman
3 M company
Union Carbide Corporation
U.S. Industrial Chemicals
U.S. Polymeric Company
W. R. Grace, Inc.
269
-------
-------
SECTION XIII
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273
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274
-------
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Chemical Processes, 6, 7-11 (1961).
50. "Wastewater Treatment Facilities for a Polyvinyl
Chloride Production Plant," EPA Water Pollution
Control Research Series Report No. 12020 DJI,
Washington, D.C. (June 1971),
51. "Water Quality Criteria 1972," National Academy of
Sciences and National Academy of Engineering for
the Environmental Protection Agency, Washington, D.C.
1972 (U.S. Govt. Printing Office Stock No. 5501-00520)
275
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SECTION XIV
GLOSSARY
Refers to that portion of a molecular structure which is
derived from acetic acid.
Addition Polvmerization
Polymerization without formation of a by-product (in
contrast to condensation polymerization.)
Aerobic
A living or active biological system in the presence of
free, dissolved oxygen.
Alkyl
A general term for monovalent aliphatic hydrocarbons,
Allophanate
A derivative of an acid, NH2CONHCOOH, which is only known in
derivative forms such as esters.
Alumina
The oxide of aluminum.
Amorphous
Without apparent crystalline form.
Anaerobic
Living or active in the absence of free oxygen.
Annealing
A process to reduce strains in a plastic by heating and
subsequent cooling.
Arvl
A general term denoting the presence of unsaturated ring
structures in the molecular structure of hydrocarbons.
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Atactic Polymer
A polymer in which the side chain groups are randomly
distributed on one side or the other of the polymer chain.
(An atactic polymer can be molded at much lower temperatures
and is more soluble in most solvents than the corresponding
isotactic polymer, g.q.).
Autoclave
An enclosed vessel where various conditions of temperature
and pressure can be controlled.
Azeotrope
A liquid mixture that is characterized by a constant minimum
or maximum boiling point which is lower or higher than that
of any of the components and that distills without change in
composition.
Bacteriostat
An agent which inhibits the growth of bacteria.
Slowdown
Removal of a portion of a circulating stream to prevent
buildup of dissolved solids, e.g., boiler and cooling tower
blowdown.
BODS
Biochemical Oxygen Demand (5 days as determined by
procedures in standard Methods) 19th Edition, Water
Pollution Control Federation, or EPA's Manual 16020-07/71,
Methods for Chemical Analysis of Water and Wastes.
Catalyst
A substance which initiates primary polymerization or
increases the rate of cure or crosslinking when added in
quantities which are minor as compared with the amount of
primary reactants.
Caustic Soda
A name for sodium hydroxide.
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Chain Terminator
An agent which, when added to the components of a
polymerization reaction, will stop the growth of a polymer
chain, thereby preventing the addition of MER units.
COD
Chemical Oxygen Demand (determined by methods explained in
the references given under BODS.)
copolvmer
The polymer obtained when two or more monomers are involved
in the polymerization reaction.
Cross-link
A comparatively short connecting unit (such as a chemical
bond or a chemically bonded atom or group) between
neighboring polymer chains.
Crystalline
Having regular arrangement of the atoms in a space lattice
— opposed to amorphous.
Delusterant
A compound (usually an inorganic mineral) added to reduce
gloss or surface reflectivity of plastic resins or fibers.
Dialysis
The separation of substances in solution by means of their
unequal diffusion through semipermeable membranes.
Diatomaceous Earth
A naturally occurring material containing the skeletal
structures of diatoms - often used as an aid to filtration.
Effluent
The flow of waste waters from a plant or waste water
treatment plant.
Emulsifier
An agent which promotes formation and stabilization of an
emulsion, usually a surface-active agent.
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Emulsion
A suspension of fine droplets of one liquid in another.
Facultative Lagoon or Pond
A combination of aerobic surface and anaerobic bottom
existing in a basin holding biologically active waste
waters.
Fatty Acids
An organic acid obtained by the hydrolysis (saponification)
of natural fats and oils, e.g., stearic and palmitic acids.
These acids are monobasic and may or may not contain some
double bonds. They usually contain sixteen or more carbon
atoms.
Filtration
The removal of particulates from liquids by membranes on in-
depth media.
Formalin
A solution of formaldehyde in water.
Free Radical
An atom or a group of atoms, such as triphenyl methyl
(C6H5>)3C», characterized by the presence of at least one
upaired electron. Free radicals are effective in initiating
many polymerizations.
Godet Roll
Glass or plastic rollers around which synthetic filaments
are passed under tension for stretching.
Gallons per day.
GPM
Gallons per minute.
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Halogen
The chemical group containing chlorine, fluorine, bromine,
iodine.
Isotactic Polymer
A polymer in which the side chain groups are all located ^n
one side of the polymer chain. See also "Atactic Polymer."
Lewis Acid
A substance capable of accepting from a base an unshared
pair of electrons which then form a covalent bond. Examples
are boron fluoride, aluminum chloride.
Homopolymer
A polymer containing only units of one single monomer.
Humectant
An agent which absorbs water. It is often added to resin
formulations in order to increase water absorption and
thereby minimize problems associated with electrostatic
charge.
Influent
The flow of waste waters into a treatment plant.
M
Thousands (e.g., thousands metric tons).
MM
Millions (e.g., million pounds).
Monomer
A relatively simple compound which can react to form a
polymer,
EH
A measure of the relative acidity or alkalinity of water on
a scale of 0-14. A pH of 7 indicates a neutral condition,
less than 7 an acid condition, greater than 7 an alkaline
condition.
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Phenol
Class of cyclic organic derivatives with the basic chemical
formula C6H5OH.
Plasticizer
A chemical added to polymers to impart flexibility,
workability or distensibility.
Polymer
A high molecular weight organic compound, natural or
synthetic, whose structure can be represented by a repeated
small unit (MER).
Polymeri zation
A chemical reaction in which the molecules of a monomer are
linked together to form large molecules whose molecular
weight is a multiple of that of the original substance.
When two or more monomers are involved, the process is
called copolymerization.
Pretreatment
Treatment of waste waters prior to discharge to a publicly-
owned waste water treatment plant.
Primary Treatment
First stage in sequential treatment of waste waters -
essentially limited to removal of readily settlable solids.
Quenching
Sudden cooling of a warm plastic, usually by air or water.
Reflux
Condensation of a vapor and return of the liquid to the zone
from which it was removed.
Resin
Any of a class of solid or semisolid organic products of
natural or synthetic origin, generally of high molecular
weight with no definite melting point. Most resins are
polymers.
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Scrubber
Equipment for removing condensable vapors and particulates
from gas streams by contacting with water or other liquid.
Secondary Treatment
Removal of biologically active soluble substances by the
growth of microorganisms.
Slurry
Solid particles dispersed in a liquid medium.
gpinnerette
A type of extrusion die consisting of a metal plate with
many small holes through which a molten plastic resin is
forced to make fibers and filaments.
Staple
Textile fibers of short length, usually one-half to three
inches.
Stoichiometric
Characterized by being a proportion of substances exactly
right for a specific chemical reaction with no excess of any
reactant or product.
TDS
Total dissolved solids - soluble substances as determined by
procedures given in reference under BOD5.
Thermoplastic
Having property of softening or fusing when heated and of
hardening to a rigid form again when cooled.
Thermosetting
Having the property of becoming permanently hard and rigid
when heated or cured.
TOG
Total Organic Carbon - a method for determining the organic
carbon content of waste waters.
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TOW
A large number of continuous filaments of long length. Tow
is the usual form of fibers after spinning and stretching
and prior to being chopped into short lengths of staple.
Transesterification
A reaction in which one ester is converted into another.
Vacuum
A condition where the pressure is less than atmospheric.
Ziegler-Natta Catalyst
A catalyst (such as a transition metal halide or an
organometallic compound) that promotes an ionic type of
polymerization of ethylene or other olefins at atmospheric
pressure with the resultant formation of a relatively high-
melting polyethylene or similar product.
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TABLE XIV-1
METRIC TABLE
CONVERSION TABLE
MULTIPLY (ENGLISH UNITS) by TO OBTAIN (METRIC UNITS)
ENGLISH UNIT ABBREVIATION CONVERSION ABBREVIATION METRIC UNIT
acre ac
acre - feet ac ft
British Thermal
Unit BTU
British Thermal
Unit/pound BTU/lb
cubic feet/minute cfm
cubic feet/second cfs
cubic feet cu ft
cubic feet cu ft
cubic inches cu in
degree Fahrenheit °F
feet ft
gallon gal
gallon/minute gpm
horsepower hp
inches in
inches of mercury in Hg
pounds Ib
million gallons/day mgd
mile mi
pound/square
inch (gauge) psig
square feet sq ft
square inches sq in
ton (short) ton
yard yd
* Actual conversion, not a multiplier
U.S. GOVERNMENT PRINTING OFFICE: 1975-582-420:233
0.405
1233.5
0.252
0.555
0.028
1.7
0.028
28.32
16.39
0.555(°F-32)*
0.3048
3.785
0.0631
0.7457
2.54
0.03342
0.454
3,785
1.609
(0.06805 psig +1)*
0.0929
6.452
0.907
0.9144
ha
cu m
kg cal
kg cal/kg
cu m/min
cu m/min
cu m
1
cu cm
°C
m
1
I/sec
kw
cm
atm
kg
cu m/day
km
atm
sq m
sq cm
kkg
m
hectares
cubic meters
kilogram - calories
kilogram calories/kilogram
cubic meters/minute
cubic meters/minute
cubic meters
liters
cubic centimeters
degree Centigrade
meters
liters
liters/second
killowatts
centimeters
atmospheres
kilograms
cubic meters/day
kilometer
atmospheres (absolute)
square meters
square centimeters
metric ton (1000 kilograms)
meter
285
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U.S. ENVIRONMENTAL PROTECTION AGENCY (A-107)
WASHINGTON, D.C. 20460
POSTAGE AND FEES PAID
ENVIRONMENTAL PROTECTION AGENCY
EPA-335
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