EPA 440/1-74/036
Development Document for
Proposed 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
SEPTEMBER 1974
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DEVELOPMENT DOCUMENT
for
PROPOSED 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
«*v
Allen Cywin
Director, Effluent Guidelines Division
David L. Becker
Project Officer
September, 1974
Effluent Guidelines Division
Office of Water and Hazardous Materials
U.S. Environmental Protection Agency
Washington, D.C. 20460
60604
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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
Fluorocarbons
Polypropylene Fiber
Alkyds and Unsaturated Polyester Resins
Cellulose Nitrate
Polyamides (Nylon 6/12)
Polyester Resins (thermoplastic)
Silicones
Multi-Product Plants
Fluid-Product Plants
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 degre;e 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
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TABLE OF CONTENTS
SECTION PAGE
I CONCLUSIONS 1
II RECOMMENDATIONS 3
III INTRODUCTION 13
PURPOSE AND AUTHORITY 13
METHODOLOGY 14
GENERAL DESCRIPTION OF THE INDUSTRY 15
PRODUCT AND PROCESS TECHNOLOGY 23
Acrylic Resins 25
Alkyd Molding Compounds 32
Cellulose Derivatives 33
Cellulose Nitrate 36
Chlorinated Polyethylene 39
Diallyl Phthalate Resins 42
Ethylene-Vinyl Acetate Copolymers 44
Fluorocarbon Polymers 47
Nitrile Barrier Resins 54
Parylene Polymers 58
Poly-Alpha-Methyl Styrene 62
Polyamides 64
Polyaryl Ether (Arylcn) 65
Polybenzimidozoles 69
Polybenzotheazoles 74
Polybutene 77
Polycarbonates 81
Polyester Resins (Thermoplastic) 86
Polyester Resins (Unsaturated) 89
Polyimides 94
Polymethyl Pentene 98
Polyphenylene Sulfide 100
Polypropylene Fibers 104
Polysulfone Resins 109
Polyvinyl Butyral 114
Polyvinyl Carbazole 118
Polyvinyl Ethers 120
Polyvinylidene Chlorides 125
Polyvinyl Pyrolidone 127
Silicones 130
Spandex Fibers 136
Urethane Prepolymers 142
IV INDUSTRY CATEGORIZATION 145
V WASTE CHARACTERIZATION 149
RAW WASTE LOADS 149
VI SELECTION OF POLLUTANT PARAMETERS 155
ill
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SELECTED PARAMETERS 155
OTHER POLLUTANT PARAMETERS 158
VII CONTROL AND TREATMENT TECHNOLOGY 165
PRESENTLY USED WASTE WATER TREATMENT
TECHNOLOGY 166
VIII COST, ENERGY, AND NONWATER QUALITY
ASPECTS 177
COST MODELS OF TREATMENT TECHNOLOGIES 178
COST EFFECTIVENESS PERSPECTIVES 178
ANNUAL COST PERSPECTIVES 178
COST PER UNIT PERSPECTIVES 179
WASTE WATER TREATMENT COST ESTIMATES 179
INDUSTRIAL WASTE TREATMENT MODEL DATA 179
ENERGY COST PERSPECTIVES 180
NON-WATER QUALITY EFFECTS 180
ALTERNATIVE TREATMENT TECHNOLOGIES 181
IV
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TABLE OF CONTENTS (CONT'D)
SECTION PAGE
IX CURRENTLY AVAILABLE GUIDELINES AND
LIMITATIONS 219
DEFINITION OF BEST PRACTICABLE CONTROL
TECHNOLOGY CURRENTLY AVAILABLE (BPCTCA) 219
THE GUIDELINES 220
ATTAINABLE EFFLUENT CONCENTRATIONS 220
DEMONSTRATED WASTE WATER FLOWS 225
STATISTICAL VARIABILITY OF A WELL-
DESIGNED AND OPERATED WASTE WATER
TREATMENT PLANT 225
X BEST AVAILABLE TECHNOLOGY ECONOMICALLY
ACHIEVABLE 233
DEFINITION OF BEST AVAILABLE TECHNOLOGY
ECONOMICALLY ACHIEVABLE (BATEA) 233
THE GUIDELINES - ACHIEVABLE EFFLUENT
CONCENTRATIONS 234
SUSPENDED SOLIDS 234
OXYGEN-DEMANDING SUBSTANCES 234
WASTE LOAD REDUCTION BASIS 236
VARIABILITY 238
XI NEW SOURCE PERFORMANCE STANDARDS - BEST
AVAILABLE DEMONSTRATED TECHNOLOGY 243
DEFINITION OF NEW SOURCE PERFORMANCE
STANDARDS - BEST AVAILABLE DEMONSTRATED
TECHNOLOGY (NSPS-BADT) 243
THE STANDARDS 243
ACHIEVABLE EFFLUENT CONCENTRATION 243
WASTE LOAD REDUCTION BASIS 243
VARIABILITY 243
ALKYDS AND UNSATURATED POLYESTERS 245
V
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TABLE OF CONTENTS (CONT«D)
SECTION PAGE
XII ACKNOWLEDGMENTS 249
XIII REFERENCES 251
XIV GICSSARY 255
VI
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LIST OF FIGURES
Figure No. Page
III-l Typical Reactions tc Form Poly(Methyl
Methacrylate) - Including Monomer
Manufacture 26
III-2 Acrylic Resin Production - Eulk Poly-
merization Process 27
III-3 Acrylic Resin Production - Emulsion
Polymerization Process 29
III-a Acrylic Resin Production - Suspension
Polymerization Process 30
III-5 Typical Reactions to Form Cellulose
Derivatives 34
III-6 Cellulose Ethers Production 35
III-7 Typical Reaction to Form Cellulose
Nitrate 37
III-8 Cellulose Nitrate Production 38
III-9 Typical Reaction to Form Chlorinated
Polyethylene 40
111-10 Chlorinated Polyethylene Production 41
IH-11 Typical Reactions to Form Diallyl
Phthalate 43
111-12 Ethylene-Vinyl Acetate Copolymer
Production 45
HI-13 Polytetraf luoroethylene (PTFE) Pro-
duction - TFE Monomer Process 49
111-14 Typical Reactions to Form Fluorocarbon
Polymers 50
111-15 Polytetrafluoroethylene (PTFE) Pro-
duction - PTFE Polymer Process 51
111-16 Nitrile Barrier Resin Production -
Emulsion Polymerization Process 57
Vll
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LIST OF FIGURES (CONT'D)
Figure No. Page
111-17 Typical Reactions -to Form Parylene
Polymers 59
111-18 Parylene Production 61
111-19 Typical Reaction to Form Alpha-Methyl
Styrene 63
111-20 Typical Reactions to Form Folyaryl Ether 66
111-21 Typical Reactions to Form Polybenzimi-
dazoles 70
111-22 Typical Reactions to Form Polybenzo-
thiazoles 75
III-23 Typical Structures Produced in the
Synthesis of Polybenzothiazoles 76
111-24 Typical Reaction to Form Polybutene 78
111-25 Polybutene Production - Huels Process 79
111-22 Typical Reaction to Form Polycarbonate 86
111-27 Polycarbonate Production - Semi-
continuous Process 84
111-28 Thermoplastic -Polyester Resin Production 88
I11-29 Typical Reaction and Raw Materials Used
to Form Unsaturated Polyester Resins 90
111-30 Typical Reactions to Form Polyimides 95
111-31 Typical Reactions to Form Polymethyl
Pentene 99
111-32 Typical Reaction to Form Polyphenylene
Sulfide 101
111-33 Polyphenylene Sulfide Production 103
Vlll
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LIST OF FIGURES (CONT • D)
Figure No. Page
111-34 Polypropylene Fiber Production 105
111-35 Polypropylene Monofilament Production 106
111-36 Typical Reactions to Form Polysulfone
Resins 110
111-37 Polysulfone Resins Production 112
111-38 Typical Reaction to Form Polyvinyl
Butyral 115
111-39 Polyvinyl Butyral Production - DuPont,
Inc. Process 116
111-40 Polyvinyl Butyral Production Monsanto,
Inc. Process 117
111-41 Typical Reaction to Form Polyvinyl
Carbazole 119
111-42 Typical Reactions to Form Polyvinyl
Ethers - Including Monomer Manufacture 121
111-43 Polyvinyl Ether Production - Solution
Polymerization Process 122
111-44 Polyvinyl Ether Production - Bulk Poly-
merization Process 123
111-45 Typical Reaction to Form Polyvinylidene
Chloride 126
111-46 Typical Reactions to Form Polyvinyl
Pyrrolidone 128
111-47 Production of Silane Monomers, Oligomers,
and Dimethyl Silicone Fluid 131
111-48 Production of Silicone Fluids, Greases,
Compounds Emulsions, Resins, and Rubber 132
111-43 Typical Reactions to Form Silicones 139
IX
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LIST OF FIGURES (CONT'D)
Figure No. Page
111-50 Typical Reactions to Form Spandex Fibers 137
111-51 Spandex Fiber Production - Dry Spinning
Process 138
III-52 Spandex Fiber Production - Wet Spinning
Process 139
111-53 Spandex Fiber Production - Reaction
Spinning Process 141
111-54 Typical Reactions to Form Urethane Pre-
polymers 143
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LIST OF TABLES
TABLE NUMBER 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
II-4 Best Available Technology Economically
Achievable Efflument Limitations Guide-
lines (Other Elements and Compounds) 9
11*5 Best Available Demonstrated Technology -
New Source Performance Standards 10
II-6 Best Available Demonstrated Technology -
New Source Performance Standards (Other
Elements and Compounds) 11
III-l Plastics and Synthetics Fcr Consideration 17
III-2 Products to be Considered for Development
of Effluent Guideline Limitations 20
III-3 Products Eliminated from Consideration for
Establishment of Effluent Guideline
Limitations 22
III-4 Manufacturers of Products to be Considered
for Development of Effluent Limitations
Guidelines 24
III-5 Commercial Fluorocarbon Polymers 53
III-6 Properties of Polyaryl Ethers 67
III-7 Acids Whose Derivatives are Used in
Polybenzimidazole Synthesis 71
IV-1 Industry Subcategorization 147
XI
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LIST OF TABLES (CONT'D)
TABLE NUMBER PAGE
V-l Waste Water Loading for Synthetic Polymers
Production 150
V-2 Synthetic Polymers Production Raw Waste
Loads 151
V-3 Other Elements, Compounds, and Parameters 153
VI-1 ether Elements and Compounds Specific to
the Resins Segment of Plastics and
Synthetic Industry 164
VII-1 Operational Parameters of Waste Water
Treatment Plants (Metric Units) 167-168
VII-2 Operational Parameters of Waste Water
Treatment Plants (English Units) 169-170
VII-3 Performance of Observed Waste Water
Treatment Plants 171
VII-4 Observed Treatment and Average Effluent
Loadings from Plant Inspections 172
VIII-1 Perspectives on the Production of Syn-
thetic Polymers - Water Usage 182
VIII-2 Perspectives on Synthetic Polymers
Production - Annual Treatment Costs 183
VIII-3 Perspectives on Synthetic Polymers
Production - Cost Impact 184
VIII-4 Summary of Water Effluent Treatment
Costs - Cost Per Unit Volume Basis 185
VIII-4/1 Water Effluent Treatment Costs: Ethylene
Vinyl Acetate (Small Plant - Large
Industrial Complex) 186
VIII-4/2 Water Effluent Treatment Costs: Ethylene
Vinyl Acetate (Large Plant - Industrial
Complex) 187
Xll
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LIST OF TABLES (CONT'D)
TABLE NUMBER PAGE
VIII-4/3 Water Effluent Treatment Costs:
Fluorocarbons (Small Plant - Free
Standing) 188
VIII-4/4 Water Effluent Treatment Costs:
Fluorocarbons (Small Plant - Municipal
Discharge) 189
VIII-4/5 WETC: Fluorocarbons (Large Plant -
Free Standing) 190
VIII-U/6 WETC: Fluorocarbons (Large Plant -
Municipal Discharge) 191
VIII-4/7 WETC: Polypropylene Fibers (Free
Standing Treatment Plant) 192
VIII-U/8 WETC: Polypropylene Fibers (Municipal
Discharge) 193
VTII-4/9 WETC: Polyvinylidene Chloride (Small
Plant - Industrial Complex) 194
VIII-4/10 WETC: Polyvinylidene Chloride (Large
Plant - Industrial Complex) 195
VIII-4/11 WETC: Acrylic Resins (Small Plant -
Industrial Complex) 196
VIII-4/12 WETC: Acrylic Resins (Large Plant -
Industrial Complex) 197
VIII-4/13 WETC: Cellulose Derivatives (Small
Plant - Industrial Complex) 198
VIII-4/14 WETC: Cellulose Derivatives (Large
Plant - Industrial Complex) 199
VIII-4/15 WETC: Alkyds and Unsaturated Polyester
Resins (Large Plant - Once-Through
Scrubber - Free Standing) 200
VIII-4/16 WETC: Alkyds and Unsaturated Polyester
Resins (Small Plant - Recirculating
Scrubber - Municipal Discharge) 201
Xlll
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LIST OF TABLES (CONT ' D)
TABLE NUMBER PAGE
VIII-4/17 WETC: Alkyds and Unsaturated Polyester
Resins (Large Plant - Recirculating
Scrubber - Free Standing) 202
VIII-4/18 WETC: Alkyds and Unsaturated Polyester
Resins (Large Plant - Recirculating
Scrubber - Municipal Discharge) 203
VIII-4/19 WETC: Cellulose Nitrate (Plant in
Industrial Complex) 204
VIII-4/20 WETC: Cellulose Nitrate (Plant with
Municipal Discharge) 205
VIII-4/21 WETC: Polyamides (Nylon 6/12) Pro-
duction in a Complex 206
VIII-4/22 WETC: Thermoplastic Polyester Resins
(Large Plant - Industrial Complex) 207
VIII-4/23 WETC: Polyvinyl Butyral (Free Standing
Treatment Plant) 208
VIII-4/24 WETC: Polyvinyl Ether (Plant in
Industrial Complex) 209
VIII-4/25 WETC: Silicones (Fluids Only - Free
Standing) 210
VIII-4/26 WETC: Silicones (Fluids Only - Indus-
trial Complex) 211
VIII-4/27 WETC: Silicones (Multi-product -
Free Standing) 212
VIII-4/28 WETC: Silicones (Multi-product -
Industrial Complex) 213
VIII-4/29 WETC: Nitrile Barrier Resins (Plant
in Industrial Complex) 214
VIII-4/30 WETC: Spandex Fibers (Plant in
Industrial Complex) 215
xiv
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LIST OF TABLES (CONT'D)
TABLE NUMBER PAGE
VIII-5/1 Industrial Waste Treatment Model Data
Synthetic Polymers Production 216
VIII-5/2 Industrial Waste Treatment Model Data
Synthetic Polymers Production 217
VIII-5/3 Industrial Waste Treatment Model Data
Synthetic Polymers Production 218
IX-1 COD/EOD5 Ratios 222
IX-2 COD/BOD5 Ratios Corresponding to
Individual Products 223
IX-3 Demonstrated Waste Water Flows 226
IX-4 Variability Factors for BOD5 228
IX-5 Best Practicable Control Technology
Currently Available Effluent Limita-
tions Guidelines 229-230
IX-6 Best Practicable Control Technology
Currently Available Effluent Limita-
tions Guidelines 231
X-1 BATEA Waste Water Flow Rates 237
X-2 Variability Factors EATEA 238
X-3 Best Available Technology Economically
Achievable Effluent Limitations Guide-
lines 239-240
X-4 Best Available Technology Economically
Achievable Effluent Limitations
Guidelines (Other Elements and Compounds) 241
XI-1 Lowest Demonstrated Waste Water Flows 246
XI-2 Best Available Demonstrated Technology
New Source Performance Standards 248
XI-3 Best Available Technology Economically
Achievable Effluent Limitations
Guidelines 249
XIV-1 Metric Units Conversion Table 267
xv
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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, fluorocarbons, 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 Sufccategory IV - high or low waste load,
high attainable BOD5 concentration (2 products:
nitrile barrier resins and spandex fibers).
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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), $0.40 ($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 sailes price. On
average, the range of costs for applying EATEA 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
RECOMMENDATIONS
BODJ5, COD, and total suspended solids and pH are recommended as
the critical parameters requiring effluent limitations guidelines
and standards. Guidelines and standards for total suspended
solids, pH, and fluorides only are recommended for the
fluorocarbons subcategory since the fluorocarbons subcategory
wastes are similar to those seen in the inorganic chemicals
industry and contain only minimal BCD5 and COD in the raw waste.
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.
Guidelines
Recommended
Alkyd compounds and
unsaturated polyester
resins
Fluorocarbons
Spandex fibers
Acrylic resins
Polypropylene fibers
Nitrile barrier resins
Polyamides
Cellulose derivatives
Cellulose nitrate
Silicones
x
x
Pollutant
Parameters
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 x
fluorides
Polyvinylidene chloride polychlorinated organics
Polyester resins
(thermoplastic)
cobalt
manganese
cadmium
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Effluent limitations guidelines and standards of performance are
proposed for those parameters noted above as based on analogy
with other industries, since there was 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 BODS reductions
(typified by the activated sludge process, trickling filters,
aerated lagoons, aerobic - anaerobic lagoons, and so on). These
biological systems are presumed tc 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
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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-U, II-5,
and 11-6}. 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-l
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE EFFLUENT LIMITATIONS GUIDELINE^
[kg/kkg (lb/]000 Ib) of production]
Foot-
note
No.
1
2
3
4
5
«
7
8
9
10
11
12
13
Subcategory
Ethylene-Vinyl Acetate Copolymers
Fluorocarbons
Polypropylene Fiber
Polyvfnylidene Chloride
Acrylic Resins
Allcyds and Unsaturated Polyester Reains
Cellulose Nitrate
Polyamldes (Nylon 6/12 only)
Polyester Resins (thermoplastic)
Polyvinyl fiutyral
Polyvinyl Ethers
Silicones
Multi-Product Plants
Fluid Product Plants
BODj
Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Days
0.07 0.14
3.6 7.0
0.40 0.78
No nunerical guidelines-see discussion
in footnote
0.33 0.60
14 26
0.66 1.20
0.78 1.4
tfo numerical guidelines-see discussion
In footnote
14 26
8.2 15
3.3 6.0
No numerical guidelines-see dis-
COD
Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Days
0. 35
6. 7
2.0
No numerical guidelines-see
in footnote
1. 7
46
3.3
12
No numerical guidelines-see
in footnote
0. 70
13
3.9
discussion
3.0
85
6.0
22
discussion
70 127
41 75
17 30
No numerical guidelines-see dis-
niHR^on fn footnote
SUSPENDED SOLIDS
Maximum Average of Kaximun for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Davs
0.19 0.35
9.9 18.0
1.1 2.0
No numerical guidelines-see discussion
in footnote
0.22 0.40
9.4 17
0.44 0.80
0.52 0.9'5
No numerical guidelines-see discussion
in footnote
9.1 17
5.4 10
2.2 4.0
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
Fluorocarbons
Spandex fiber
Nitrile barrier resins
Polypropylene fibers
Silicones
Multi-product
Al1ocati on for
Barometri c
Condensers
Fluid-product
Polyester resins
(Thermoplastic)
Mercury
Fluorides
Cyanides
Cyanides
Oils & grease
Copper
Copper
Coppe r
Cadrni um
Toxic and hazardous chemicals guidelines to apply
0.6 1.2
Toxic and hazardous chemicals guidelines to apply
0.5
0 .071
0.042
0.017
1.0
0 .1*
0.083
0.034
Toxic and hazardous chemicals guidelines
to apply
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TABLE II-3
AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE EFFLUENT LIMITATIONS GUIDELINES
[kg/kkg (lb/1000 Ib) of production]
Fe-.it- Subcategory
note
No.
1 Ll: , lene -Vin> 1 Acfct site Copo lycers
; Fiuorocarbors
3 Polyprcf. lene Fiber
3 A ryl Ic Resins
7 Aikvds and I'n saturated Polvester Resins
00 9 P^l.LiZUwts <\ Ion 0/12 only)
0 Pollster Resins ( theraoplast Ic)
11 Poly, in- 1 B Jt> ral
12 ?civv*.->i Ethurs
13 Silicones
fluid Pcodoct Plants
BOD,
Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Davs
0.06
2.2
0.22
No numerical guidelines-see
In footnote
0.10
6.9
0. 37
0.44
No numerical guidelines-see
in footnote
6.7
1.2
0.09
3.3
0.33
discussion
0.14
9.4
0.50
0.59
discussion
9.1
1.6
COD
Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Davs
0.19
4.0
0.40
No numerical
0.52
34
1 .9
2. 3
No numerical
35
6.3
0.29
5.9
0.59
guidelines-see discussion
in footnote
0. 74
47
2.6
3.1
guidelines-bee discussion
in footnote
47
8.5
Si .,. _D ,.,...
Kaxir.uT Average of N:LX;-.,- f : r ;
Daily V',:-jc? ft r A-.v G --c :..
Period til Ti i r ty
0.04 ', . ".
1.6
0.16
No nu.-c r i cal ^i. . -< . , • - —
0.03
2 .1
0.11
0. 14
No numerical gind> j , — (
la f, t , It
2.0 . -
0.37 , --
14 Jiitrile Barrier Resins No numerical guidelines-see di.cus.ion No numerical guidelines-see discussion Xo numerical g,J;d, ... o,-s
c J «. . in footnote in footnote in £o,.c;,-.t.
15 Spandex Fioers " "
-------
TABLE II-4
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE EFFLUENT LIMITATIONS GUIDELINES
(Other Elements and Compounds)
Product
Alkyds and unsaturated
polyester resins
Fluorocarbons
Spandex fibers
Nitrile barrier resins
Polypropylene fibers
Silicones
Multi-product
Fluid-product
Polyester resins
(thermoplastic)
Parameter
Mercury
Fluorides
Cyanides
Cyanides
Oils and grease
Copper
Copper
Cadmium
kg/kkg (lbs/1000 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
0.03
0.011
0. 18
0.06
0.0055
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]
BOD5
yoot_ Subcategory Maximum Average of Maximum for Any
notc Daily Values for Any One Day
Ho Period of Thirty
Consecutive Days
2 Fluorocarbons °-8° i'6°
3 Polypropylene Fiber °-04 °-08
4 Polyvinylldene Chloride No numerical guidelines-see discussion
in footnote
5 Acrylic Resins
6 Cellulose Derivatives
7 Alkyds and Unsaturated Polyester Resins 0.02 0.03
O 8 Cellulose Nitrate 6.0 11
• rolT««ides (Fylon 6/12 only) 0.37 0.67
10 Polyester Resins (thermoplastic) 0.44 0.80
11 Polyvinyl Butyral
12 Polyvinyl Ethers No numerical guidelines-see discussion
in footnote
13 Slllcones
Multi-Product Plants 5.5 • "
Fluid Product Plants 0.57 1.0
14 Bltrlle Barrier Resins »o numerical guidelines-see discussion
in footnote
15 Spandex Fibers
COD Suspended Solids
Maximum Average of Maximum for Any Maximum Average of Maximum for Any
Daily Values for Any One Day Dally Values for Any One Day
Period of Thirty Period of Thirty
Consecutive Days Consecutive Days
0.22 0.40 0.04 0.05
1.4 2.9 0.57 0.83
0.07 0.14 0.03 0.04
No numerical guidelines-see discussion No numerical guidelines-see discussion
in footnote ^ *"> footnote
" ] "
00.11 0.20 0.0 06 0.008
30 54 1.8 2'7
1-9 3.4 0.11 °-17
6.5 12 0.14 0.20
No numerical guidelines-see discussion No numerical guidellnea-see discussion
46 82 1.7 2.5
4.7 8.5 0.18 0-26
No numerical guidelines-see discussion No numerical guidelines-see discussion
in footnote In footnote
„
-------
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
Fluorocarbons
Spandex fibers
Nitrile barrier resins
Polypropylene fibers
Silicones
Multi-product
Fluid-product
Polyester resins
(thermoplastic)
Keicury
Fluorides
Cyanides
Cyanides
Oils and grease
Copper
Copper
Cadmium
Toxic and hazardous chemicals guidelines to apply
0.6 1.2
Toxic and hazardous chemicals guidelines to apply
0.017
0.025
0.0026
0.034
0.050
0.0052
Toxic and hazardous chemicals guidelines to apply
-------
FOOTNOTES FOR
II-l, II-3, II-5
| — '
^
Ethylene -Vinyl Acetate (EVA) Copolymer. Two of the five
known producers were contacted. All plants are located
at polyethylene production facilities. Water use and
vaste'Jater characteristics for EVA are essentially iden-
tical to those for low density polyethylene. However,
an emulsion polymerization process is known and produces
a distinctly different waste load which Is essentially
that of poly vinyl acetate emul sion polymerization
reported in EPA 440/1-73/010. Both multi-plant and
municipal sewage treatment is used.
Fluorocarbons . Three of the seven manufacturing plants
were visited. A wide range of products are produced.
The cost ixportant is polyt etraf luorethylene (PTFE) and
these gu id el In ss are recommended for PTFE granular and
f I ne powder grades only . The wastewater discharges
differ considerably depending upon the process recovery
echenes for h> dro chloric acid and the disposal of selec-
ted screams by deep well, ocean dumping or off-site
contract methods. The use of ethylene glycol in a pro-
cess can significantly affect the waste loads. Fluoride
concentrations in untreated wastewaters are generally
below levels attainable by alkaline precipitation,
Po_lypropy K'ne Fibers. Two of the three producers were
contacted. The volu.net.rlc flow ranges per unit of pro-
duction vary widely depending upon the type of coolinn
system used. The waste loads are for plants where selec-
ted concentrated wastes are » eg rag a ted and disposed of
by landfilling, etc. Primary treatment at one plant site
was obst-rved while the other plant discharges to a
municipal sewage system.
F o 1> v i ny 1 i J e ne Ch 1 o ride. The two major manufacturers
were contacted. Both plant sites send was tew.it era to
multi -plant treatment plants of which the polyvinylidene
chloride is a saall port Ion. Consequently, there was
Insufficient data to develop recommended guidelines .
Acrylic jtcsins. Three of the four manufacturers were
contacted. Large r.unbers of product grades are produced
by bulk, solution, suspension and emulsion polymeriza-
tion. The widely varying hydraulic loads for the large
nunber of products in addition to treatment of the waste-
waters by multi-plant wastewater treatment facilities
p roll ibi tea obtaining Sufficient meaningful data to
recommend ef fluent limitation guidelines.
Cellulose Derivatives. Cellulose derivates investigated
included eth>l cellulose, hydroxyethyl cellulose, methyl
cellulose and carboxymetbyl cellulose. Wide variations
in unit flow rates for two plants producing the same
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. Alkyde and Unsaturated Polyester Resin^. Six carefully
selected plants were visited to provide a crosa-section
of the industry for size of operation, type of manufac-
turing process and wastewater treatment methods. Hydrau-
lic loads vary widely duperdtng upon the process designs
Similarly, raw waste loads vary widely because some
plants segragate wastes foi disposal in other manners.
Generally, the industry discharges wastewatera into
municipal sewaye sy^teras aid should continue. Also, tht
type of air pollution control, e.g. combustion or scrub-
bing, has a significant effect on the wastewater loada.
The recommended guidelines are for plants having their
own wastewater treatment system - a very infrequent
occurrence.
8. Cellulose Nttra_te_. 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-piant treatment complex.
9. j'ojjamities. 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.
10. Polyester Thermoplastic Resins. There are three manu-
facturers, two of which produce polyCethylene, terephtha-
late) in quantities less than 21 of their total thermo-
plastic production. The guidelines are recommended for
poly(ethylenc terephthalate) since the other product
polyCbutylene t erephth,-ilate) is produced at only one
plant and the waste waiter g^es into a municipal sewage
system, so no data on perfonnance could be obtained.
11. Folyvinyl Butyral. Of three production sites,two have
processes beginning with vinyl acetate monomer wnich
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 Iiito municipal sewage systems, there was no
data available. Consequently, the recommended guide-
lines are only for NSl'S-BADT when starling witli poly-
vinyl alcohol since any other guidelines would be
tantamount to establishing a permit for the production
sice.
12. Polyvinyl ethers. The three present planto use differ-
ent processes each of which produces several grades of
product. The different chemical compositions used in
both bulk and solution polymerization processes and the
lack of data on. both raw and treated wastewatera pre-
vented establishing guidelines. The wastewatera are
presently sent to either multi-plant treatment facilltla
or municipal sewage systems.
13. Silicones. Four companies manufacture sillconea at five
locations. Three plants were visited and data were
obtained from all plants. The major processing steps at
the five plants are shown below.
Major Processes at Five Silicone plants
Plant No. 12345
CH.C1 x xx
Chlorosilane prod. x x x x x
Hydrolysis x x x x x
Fluids, greases, x x x x x
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, fluorinated
agents, and other materials.
i Hi cone s, coupling
Eased on the manufacturing process, the wastewater flows
and the raw waste loads, the plants 1, 2, 3 vere desig-
nated as multi-product plants while 4 and 5 vere desl.,-
nated as fluid product plants. Guideline quantities
based on production rates that were e&cicated
from sales volumes for BPT.
1A- Nitrlle Barrie_r_Restns. Commercial scale production aid
Bale of these resins has not yet begun. The co— >nies
expected to have production facilities were contacted
and two provided estimates of raw waste loads. Because
of the lack of demonstrated flows and raw waste loads
It was impossible to establish effluent guideline
llmitat ions.
i*. Spandex Fibers. Three manufacturers eacTh produce
Epandex fibers by significantly different processes.
These are dry, wet and reaction spinning methods.
Because of limited data on raw waste lends ara
because each plant operates a different process
it was impossible to establish meaningful guidelines.
-------
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 point 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
30a (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 304 (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 regu-
lations establishing Federal standards of performances for new
sources within such categories. The 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.
13
-------
Methodolocfi
The effluent limitations guidelines and standards of performance
proposed herein were developed in the following manner for a
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 pcunds per year. The products were examined
for categorization 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 subcategory 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 technologies which are
existent or capable of being engineered for each subcategory. It
also includes an identificaticn 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 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 economiccilly achievable
(BATEA) ," and the "best available demonstrated control
technology, processes, operating methods, or other alternatives."
14
-------
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 techno-
logies 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, a survey of waste water treatment practices
by the Manufacturing Chemists Association, 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 440/1-
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.
General DescriptionnOf 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 a toy, synthetic fiber, packaging film,
adhesive, and so on. The development document for the first
group of plastics and synthetics (EPA 440/1-73/0lOa) 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.
15
-------
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), such as chlorinated polyethers, methyl
pentene, phenoxy resins, parylene phosphonitrilic resins,
polyaryl ether, polybenzothiazoles, polyethylene amines, poly-
benzimidazoles, polyimides, polymethylpentene, 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, poly-
vinyl butyral, diallyl phthalates, fluorocarbons, silicones,
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.
16
-------
TABLE III-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
Polymethylaerylate
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
17
-------
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.
Directgryr gf Chemical_Producers , 1973, USA,
Chemical Information Services, S.R.K.
Modern_Plastics_Encyclopj5dia, 1972-1973,
Suppliers-Resins and Molding Compounds.
Elasticsjtorld, 1972-1973, Directory of the Plastics
Industry.
Chemical_Hor izons_Fj.leJL_Predica^t , including
updates to July 1973 (this includes references
to journals such as Chemical_week) .
Qhemical_Marketing_Regorter, "Chemical Profile"
SectlonT 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
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:
18
-------
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 cf compounds or further 5
generic groupings
3. Insufficient nurrber 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
Ajnine_rej3ins - not a meaningful designation for
a specific or generic group of products.
- not an article of commerce -
probably meant to apply to cellulose acetate
butyrate.
£2li2!§£hacrylcnitrile_res_inis - combined with the
more general category of nitrile barrier resins.
M.§thy.l_p.entene - another name for polymethyl
pentene.
(2) Families of compounds or further generic
groupings.
The product category "cellulose derivatives" was created by
combining methyl cellulose, ethyl cellulose, cellulose
propionate, cellulose acetate prcpionate, and cellulose acetate.
19
-------
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
Fluorocarbons
Nitrile barrier resins
Polyamides (other than Nylon 6 and 66)
Polyester resins (thermoplastic)
Polyester resins (unsaturated)
Polypropylene fibers
Polyvinyl butyral
Polyvinyl ethers
Polyvinylidene chloride and copolymers
Silicones
Spandex fibers
20
-------
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.
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)
Sohio'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.
21
-------
TABLE III-3
PRODUCTS ELIMINATED FRCW CONSIDERATION
FOR ESTABLISHMENT OF EFFLUENT GUIDELINE LIMITATIONS
Produc^
Chlorinated Polyethers
Chlorinated Polyethylene
Diallyl Phthalate Compounds
lonomers
Parylene
Phenoxy Resins
Phosphonitrilic Resins
Polyallomer
Poly-alpha-Methyl Styrene
Polyaryl Ethers
Polybenzimidazoles
Polybenzothiazoles
Polybutylene (called polybutene
in Table I)
Polycarbonate s
Polyethylene Imine
Polymethyl Pentene
Polyphenylene Oxides
Polysulfone
Polyvinyl Carbazole
Polyvinyl Pyrrolidone
Urethane Prepolymers
22
-------
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 where-
as 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 guide-
lines are shown in Table III-4.
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.
23
-------
TABLE III-4
MANUFACTURERS OF PRODUCTS TO BE CONSIDERED FOR DEVELOPMENT OF EFFLUENT LIMITATION GUIDELINES
&
o
CJ
01
n
X «|
O) ™
P. <"
g g
Cellulose Nitrate
Nitrile Barrier Resins
Fluorocarbon Polymers
Ethylene-Vlnyl Acetate
Polypropylene Fibers
Polyvlnyl Butyral
Polyvinyl Ethers
Polyvinylidene Chloride
Alkyd Molding Compounds
Polyester Resins (Unsat.)
Polyester Resins (Thermoplastic)
Acrylic Resins
Silicones
Polyamides (Except Nylpn 6 and 66)
Cellulose Derivatives
Spandex Fibers
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-------
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 aerylate 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 compounds 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, transportation,
appliances, and merchandizing. Because of excellent suspending,
rheological, and durability characteristics, 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 concentration
(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 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
25
-------
(1)
(CH3)2C(OH)(CN) + H2SO4 CH2 = C(CH2)CONH2 • H2S04
CH2 =C(CH2)CONH2 • H2SO4 + CH2OH — CH2 = C(CH2)COOCH3 + NH4HS04
(2) n
CH2 = C COOCH3
CH3
COOCH3
. CH2 - C
CH3
(where n is 500 to 3000)
FIGURE 111-1 TYPICAL REACTIONS TO FORM POLY (METHYL METHACRYLATE)
INCLUDING MONOMER MANUFACTURE
26
-------
REUSED MOLDS
to
-j
MONOMER
CATALYST
ADDITIVES
PARTING
AGENT
MIXING
i
MOLD
FILLING
POLYMERIZATION
BATH OR
OVEN
t
i
PARTING
\
t
I
MOLD
CLEANING
1
AIR OR
WATER
(CONTROLLED
TEMPERATURE)
CAST
SHEET
PRODUCT
WASTE
WATER
FIGURE 111-2 ACRYLIC RESIN PRODUCTION - BULK POLYMERIZATION PROCESS
-------
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-4) 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.
Waste Water Generation - The primary waste water streams are
obvious from inspection cf 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 soire 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 con-
centration 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).
28
-------
VENT
MONOMER
HOLD
TANK
MIX
TANK
AIR POLLUTION
DEVICES
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
•RIVER
INITIATOR,
GRANULATING AGENT,-
MISC. ADDITIVES
WATER
WATER
WATER
POLYMERIZATION
•DEMIN. WATER
RECYCLE
COOLING WATER* STEAM
TO EXTRUDERS
RIVER
CENTRIFUGE
DEMIN WATER
DRYING
•COOLING WATER'
-DRIVER
-^-ACRYLIC BEAD POLYMER
EXTRUSION
'WATER
ACRYLIC MOLDING POWDER
"* NON-CONTACT WATER
FIGURE 111-4 ACRYLIC RESIN PRODUCTION - SUSPENSION
POLYMERISATION PROCESS
30
-------
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.
31
-------
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 sindlar 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 (41).
32
-------
Cellulose Derivatives
This group of materials includes ethyl cellulose, methyl
cellulose, carboxymethyl cellulose, and hydroxyethyl cellulose.
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. Carboxymethyl
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.
33
-------
(1) (C6H1005)n + CH3CI + NaOH -methyl cellulose + NaCI + H2 O
(2) (C6Hi005)n + C2HSCI + NaOH ethyl cellulose + NaCI +H20
(3) (C6H1005)n + CIC2H302Na+NaOH «-carboxymethyl cellulose + NaCI + H2O
(4) (C6H10Os)n + H2C-CH2 hydroxyethyl cellulose
\ /
0
FIGURE III-5 TYPICAL REACTIONS TO FORM CELLULOSE DERIVATIVES
34
-------
CELLUOSE ALKALI
REACTION
FRESH
SOLVENT
REACTANT
(ETHYL CHLORIDE,
-METHYL CHLORIDE,
CHLORACETIC ACID,
ETHYLENE OXIDE)
PURIFICATION
•*-WASTE
I
SOLVENT
RECOVERY
DRYING
.WASTE
WASTE
PACKING
FIGURE 111-6 CELLULOSE ETHERS PRODUCTION
35
-------
Cellulose Nitrate
Cellulose nitrate is produced ty 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 14.1 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 commercially
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.
4. 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 manu-
facture of nitrocellulose constitute primarily acids (both nitric
and sulfuric) 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
36
-------
(C6H1005)n + 3HN03 + H2S04^=^:(C6H702 (N03)3)n + H20 + H2S04
FIGURE 111-7 TYPICAL REACTION TO FORM CELLULOSE NITRATE
37
-------
NITRICACID - AC|D M|X
TANKS *
OLEUM >
f
SPENT <-
ACID
WATTI7 ^^^^— _
T T fl M -
t
SPENT
ALCOHOL
RECOVERY
STILLS "*
1
1
WASTE
WATER
DRYFR
1
NITRATING
POTS
I
rFNTRlFllftF
i r
BOILING TUBS
(STABILIZATION)
\
DIGESTER
(VISCOSITY
CONTROL)
1
BLENDING
\
i
DEHYDRATING
PRESS
I
PACKAGING
(ALCOHOL
WET)
^.WASTE
WATER
FIGURE 111-8 CELLULOSE NITRATE PRODUCTION
38
-------
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 (122-149°F) are used, and a
suitable catalyst is necessary to establish economic reaction
rates at atmospheric pressure. Artificial light of wavelength
below 4785 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 iirpact strength and processibility of poly-
vinylchloride, 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 ty-product of the reaction.
Waste Generation - The primary waste generated is the by-product
hydrogen chloride. Recovery or ether 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 (5, 10,
11, 40, 44, 45).
39
-------
CH2 — CH2-h + CI2—--(- CHCI— CH2 -b + HC1
FIGURE 111-9 TYPICAL REACTION TO FORM CHLORINATED POLYETHYLENE
40
-------
POLYOLEFIN
SOLUTION
CHLORINE
SEPARATOR
PRODUCT
SOLUTION
CONDENSER
FEED MATERIALS
POLYETHYLENE
CHLORINE
kg/1000 kg PRODUCT
450
1140
SOURCE; us. PATENT 2,954,509 BYD.M.HURT (TODUPONT)
(DECEMBER 13, 1960).
FIGURE 111-10 CHLORINATED POLYETHYLENE PRODUCTION
41
-------
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 orthophthalic
anhydride to produce diallyl orthophthalate (trademark Dapon 35,
FMC Corp.) or with the isophthalate acid. The isophthalate ester
is identified as Dapon M, FMC Corporation.
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 polyester 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 1<49°C or
300°F) favors the use of diallyl phthalate over styrene,
particularly for larger parts. This low volaitility permits
aHylic 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 prepolymers 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.
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).
42
-------
(1)
CH, = CH - CH2 - OH
(2)
-COOCH2 CH = CH2
- COO CH2 CH = CH2
FIGURE 111-11 TYPICAL REACTIONS TO FORM DIALLYL PHTHALATE
43
-------
Ethylene-Vinyl Acetate Copolymers
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 shewn 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 cf a waxy residue that is incinerated
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 aidditives 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 polymerization
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 polyvinyl 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
44
-------
PEROXIDE
INITIATOR
VINYL
ACETATE.
ETHYLENE-
COMPRESSOR
I
I
VINYL ACETATE
RECYCLE
ETHYLENE
RECYCLE
AUTOCLAVE
SEPARATOR
OIL LEAKAGE AND
SPILLS TO
PROCESS SEWER
Ul
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 by Wt.)
MAKE-UP WATER
REFRIGERATION
COOLING
PURGE TO PROCESS SEWER
(VINYL ACETATE AND
POLYMER FINES
CONTAMINATION)
FIGURE 111-12 ETHYLENE-VINYL ACETATE COPOLYMER PRODUCTION
-------
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 compressors
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).
46
-------
Fluorocarbon Polymers
The term "fluorocarbon 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 fluorocarbcn 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 descriptions 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 tech-
nology is considered highly confidential. The process
descriptions that follow, therefore, are necessarily general in
nature.
A. Polytetrafluoroethylene (PTFE)
1. TFE Monomer Process
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
47
-------
reaction involved is shown at the top of Figure III-1U. Various
other fluorinated side products may also be forrr^d in minor
amounts.
The process stream from the reaction furnace is scrubbed first
with water, then with dilute caustic solution to remove by-
product HCl 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 peroxydisulfates 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 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
48
-------
ALTERNATIVE
DRYING
METHODS
GLYCOL LOSS
AQUEOUS WASTE
DISTILLATION
PURE
TFE
FIGURE 111-13 POLYTETRAFLUOROETHYLENE (PTFE) PRODUCTION - TFE MONOMER PROCESS
-------
Feedstock
Monomer
Polymers
2CHF2CI >-2HCI
heat
(chlorodifluoromethane)
CF2 =CF2
(TFE)
+ CH2 =CH2
(ethylene)
CF3
CF2 = CF
(HFP)
CF2CI-CH3 «
heat
(chlorodifluoroethane)
HCI
CF2CI-CFCI2
Metal Cat.
(trichlorotrifluoroethane)
CF2 = CH2
(VDF)
+ CF2 = CFCI
(CTFE)
CH2 =CH2
(ethylene)
(PTFE)
~(CH2-CH2-CFj-CF2-)-n
(ETFE)
CF3
-fCF2-CF2-CF2-CF-)-n
(FEP)
CF3
H-CF2-CH2-CF2-CF-)-n
(VDF-HFP)
-fCF2 -CHj-)-n
(PVDF)
—fCF2-CH2-CF2-CFCI-^
(CTFE-VDF)
-tCF2-CFCIt-n
(PCTFE)
-4CH2-CH2-CF2-CFCI4-n
(ECTFE)
HC = CH + HF —
(acetylene) (hydrogen
fluoride)
CH2 = CHF
VF
-f-CH2-CHF-hn
(PVF)
Source: Chemical Economics Handbook, Stanford Research Institute.
FIGURE 111-14 TYPICAL REACTIONS TO FORM FLUOROCARBON POLYMERS
50
-------
WATER
INITIATORS
STABILIZERS
TFE
BATCH
POLYMERIZATION
SURFACTANT-
POLYMER
RECOVERY/WASH
I
WASH
WATER
DISPERSION
GRADE
AQUEOUS WASTE
(SUPERNATE LIQUOR)
GRANULE
EXTRUSION/
PELLETIZING
T
CHILL WATER
FINE
POWDER
FIGURE 111-15 POLYTETRAFLUOROETHYLENE (PTFE) PRODUCTION -
PTFE POLYMER PROCESS
-------
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 Fluorocarbon 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 111-14.
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 arid 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 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 seme of the polymer processes (6, 29, 30).
52
-------
TABLE III-5
COMMERCIAL FLUORCCARBON 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
53
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Nitrile Barrier Resins
This class of resins has assumed importance primarily because
nitrile tarrier 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 vias 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 proprietary
by the resin manufacturers. The general structure however may be
viewed as a butadiene backbone to which acrylonitrile/
methylacrylate 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 preferred method. The
final composition may result from a two-step polymerization
scheme in which a copolymer (such as acrylonitrile/acrylate) is
polymerized by eirulsion 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 (48).
54
-------
Typi cal^Late x^Recipe Parts
Acrylonitrile 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 shewn below is taken from EPA.
Development Document No. 440/1-73/010 (16) along with a
generalized flowsheet shown as Figure 111-16.
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
55
-------
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 w.ater
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 rronomer 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.
56
-------
Ul
EMULSIFIER
PROCESS
WATER
CATALYST
L"DOLING
WATER
MONOMERS'
WASH WATER
BATCH
REACTOR
CYCLE
COAGULATION
AGENT
SOLID
WASTE
COAGULATION
TANK
WASTE
WATER
DRY
PRODUC1
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 dichlorodi-
p-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 284°C (543°F) and a density
of 1.22 g/cm3. Dichlorodi-p-xylylene has a melting point of 140-
160°C (28U-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 recrys-
tallization from xylene. Dichlorodi-p-xylylene is a mixture of
isomers as prepared by chlcrination 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).
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 formation
of stable species (Figure 111-17, Equation 2) in which n is 1, 2,
58
-------
(1)
CH,
CH,
CH2
•*• 2CH,
CH7
CH2
X = H
or
X = Cl
r\CH,_CH,/n
CH2' + CH,
(2)
CH,
CH2-|— CH2.
n
CH,
FIGURE 111-17 TYPICAL REACTIONS TO FORM PARYLENE POLYMERS
59
-------
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
-40°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 cf 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 111-18). 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 seme derivatives, it is heated as high as
160°C (320°F) to permit deposition of polymer over a fairly broad
area.
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).
60
-------
Dl-P-XYLYLENE
VAPORIZER
PYROLYSIS
DEPOSITION
CHAMBER
COLD TRAP
FIGURE 111-18 PARYLENE PRODUCTION
61
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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 141.8°F), and thus depolymerization can
occur easily during fabrication. In addition, the hcinopolymer 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 polymerization
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) .
62
-------
CfiHc C ~ CH?
CH2
C6HS
C
FIGURE 111-19 TYPICAL REACTION TO FORM ALPHA-WIETHYL STYRENE
63
-------
Polyamides
Materials considered to fall in this category include nylons
other than Nylon 66 or 6, which were covered in EPA Development
Document No. EPA 440/1-73/010 (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 produced
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 (41).
64
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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 III-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 +190°C (-27<4°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-4-
bromophenol in aqueous potassium hydroxide is reacted with
potassium-ferricyanide, producing poly-2,6-dimethyl-l,4-phenylene
ether.
One manufacturer produces poly-2,6-dimethyl-l,4-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.
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-dimethyl 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.
65
-------
(1)
-fArO-R-04-n
(2)
02, R3N
Cu+
(3)
O =
= O
FIGURE 111-20 TYPICAL REACTIONS TO FORM POLYARYL ETHER
66
-------
TABLE III-6
PROPERTIES OF POLYARYL ETHERS
Density 1.06 1.06
Tensile strength, psi 111,000 9,600
kg/sq cm 7UO 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
264 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
67
-------
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-dimethyl-l,4-phenylene ether, 159 mass units of
water per 1000 mass units of polymer product (23).
68
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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 III-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 111-21.
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, dimethyl-
formamide, dimethylsulfoxide, N-methylpyrrolidone, phenol, and
cresol were used. Polyphosphoric acid has been investigated
because the oxidation sensitivity of the tetraamines could be
circumvented by use of the tetrahydrochloride salt. Upon heating
in an inert atmosphere, hydrogen chloride is evolved at about
140-150°C (28U-302°F), giving a solution of tetraamine and
polyphosphoric acid.
69
-------
(Equation 1)
N
H
benzimidazole
NH,
NH2
HCO2H
HNOCH
H20 (Equation 2)
o-Phenylenediamine Formic acid
NH2
Amide intermediate Water
HNOCH
.NH2
Amide intermediate
NH
+ H20
Benzimidazole Water
H, N
Generalized Synthesis of Polybenzimidazole
H2N NH2
3,3'-Diaminobenzidine
Diphenyl isophthalate
Polybenzimidazole
(Equation 3)
-00H
Phenol
FIGURE 111-21 TYPICAL REACTIONS TO FORM POLYBENZIMIDAZOLES
70
-------
0
II
HOC
COM
Isophthalic Acid
Terephthalic Acid
TABLE 111-7 ACIDS WHOSE DERIVATIVES ARE USED IN POLYBENZIMIDAZOLE SYNTHESIS
71
-------
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 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.
72
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Waste Water Generation - Process wastes will include the water
and the phenol evclved 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).
73
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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 111-22 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 (320-482°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).
74
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(1)
SH
Polybenzothiazole
HCI • H2N
(2)
NH2 • HCI + CIOC
HS SH
3,3'-Dimercaptobenzidine dihydrochloride
-HCI
--HIM
NH OC
I n
FIGURE 111-22 TYPICAL REACTIONS TO FORM POLYBENZOTHIAZOLES
75
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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 HO2C-
HS SH
3,3'-Dimercaptobenzidine
O
p-Oxydibenzoic acid
C02H
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
76
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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-4 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.
There are several important differences between the Mobil and
Huels 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-4 cut, which requires purification prior to
polymerization. The Mobil process does not produce atactic
77
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n QcHs CH2 - CH = CH^j-
CH—CH2--
CH2
I
CH3
FIGURE 111-24 TYPICAL REACTION TO FORM POLYBUTENE
78
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DISTILLATION
COLUMNS t LIGHT-
ENDS
EXTRACTION EXTRACTOR
SOLVENT AGENT
WATER
FRESH BUTENE
(C4 CUT)
POLYMERIZATION REACTORS
ATACTIC
POLYBUTYLENE
BAGGING
PRODUCT POLYBUTENE
FIGURE 111-25 POLYBUTENE PRODUCTION - HUELS PROCESS
-------
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-U washing are likely (25).
80
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Polycarbonate s
Polycarbonates are a special variety of linear thermoplastic
polyesters in which a derivative of carbonic acid is substituted
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 te 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 transesterificaticn, 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 111-26.
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 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,
81
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(1)
C5 Hs N + (CH3)2 + C(C6H4OH)2 + COCI2
Solvent
Pyridine BisphenolA Phosgene
C5H5N + -K>C6H4C(CH3)j C6H40
-------
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 hydrochloride
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
"antisolvent" 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, 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
83
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HYDROCHLORIC
ACID
POLYCONDENSATION
WATER
PYRIDINE
RECOVERY
I
SODIUM
CHLORIDE
SOLUTION
SEPARATION
ORGANIC PHASE
PRECIPITATION
PRECIPITANT
FILTRATION
I
DRYING
I
PELLETIZING
FIGURE 111-27 POLYCARBONATE PRODUCTION - SEMI-CONTINUOUS PROCESS
84
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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).
85
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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 requirements
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 infor-
mation. They are, however, known to include acetates of cobalt,
manganese, and cadmium.
Manufacture - Many plants still use the batch polymerization
process. A typica^. continuous polymerization process based on
DMT consists of a DMT melter, ester exchange vessel, and a poly-
merization reactor (s). This process is shown schematically in
Figure III-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
86
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shipping. The figure shows polyester resin production from
ethylene glycol or fcutanediol.
Waste Water Generation - Liquid wastes result from the conden-
sation 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) .
87
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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
oo
00
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)
Unsaturated 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 III-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 reinforced 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 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.
89
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HYDROCARBON STARTING MATERIALS
I II
HC^ CH
H
ACIDS
Benzene
COOH
COOH-
Ortho-phthalic Acid Iso Phthalic Acid (IPA)
Toluene
Ortho-xylene
CH3
Meta-xylene
HC - COOH HC - COOH
II II
HC - COOH HOOC -CH
Maleic Acid Fumaric Acid (FA)
CO
Phthalic Anhydride (PA)
GLYCOLS
HOCH (CH3)CH2 OH
Propylene Glycol (PG)
REACTIVE SOLVENT
CH =CH2
Styrene (S)
POLYESTERS
HOOC - R-COOH + HO - R' - OH •
HCCO
II >
HCCO
Maleic Anhydride (MA)
HOCH2 C(CH3)2 CH2 OH
Neopentyl Glycol (NPG)
(- OOC - R - COOR' -)n + 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
90
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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
order to reduce the concentration of entrained 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
91
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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
a]so 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
which originates from the long chain, unsaturated fatty acids
used in the alkyd recipe. The presence of this material 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 esterification 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.
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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 (41).
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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 mole-
cular 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 rrolecular 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 poly-
imides 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 pcly-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 formation of a polyamic acid according to Equation 5 of
Figure II1-30. 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
94
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(1)
CO. CO
CO
\N-R'-
/
(2)
CO CO
(3)
HOOC /^. COOH
sl-(CH2)m-NH2-
CH3OOC
HOOC
COONH3-(CH2)m-NH2
A
CH3OOC ^ COOCH3
x. s^ ,CO.
-N <
\
>N-(CH2]
CO ^ ,C
(4)
). CO. ~~|
\R/ \IM-R'- ,whereR' =
X NCOX J n
(5)
/
.co
^^^
0 <( >R<( ^>0 +H2N-R'-NH2
HOOC^ ^ CO-NH-R'-
-NH-CO^
(6)
COOH
.2nH2Q
CO CO
FIGURE 111-30 TYPICAL REACTIONS TO FORM POLYIMIDES
95
-------
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 (-4-158°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 (140 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 stepwise increase of
temperature. Thermal treatment at high temperatures (above 2CO°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.
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 (482°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
96
-------
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 pclyimides 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 water per mole of
imide linkages. If R and R1 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) .
97
-------
Polymethyl Pentene
Methyl pentene (or U-methyl-1-pentene) is made by the alkali
metal catalyzed dimerizaticn of propylene as shown in Equation 1
of Figure 111-31. The polymerization of 4-methyl-l-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 hcmopolymerized 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 U-
methyl-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 washing step may
use water or, in some cases, hydrocarbon or alcohol. Conse-
quently, the wash liquids may contain dissolved mertals. 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).
98
-------
(1) CH2 = CH - CH3 •- CH3 - CH - CH2 - HC = CH2
CH3
(2) n CH3 -CH -CH2 - CH = CH2
CH3
--CH-CH2- —
I n
'CH2
I
CH
A
CH3 CH3
FIGURE 111-31 TYPICAL REACTIONS TO FORM POLYMETHYL PENTENE
99
-------
Polyphenylene Sulfide
Polyphenylene sulfide polymers possess recurring units of sulfur
which provide linkage for aromatic compounds. Polyphenylene
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 pyrrclidone 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 (266-347°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 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 compound 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
100
-------
Cl
+ Na2S
C5H9NO
-+2NaCI
FIGURE 111-32 TYPICAL REACTION TO FORM POLYPHENYLENE SULFIDE
101
-------
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 (374°F) 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.
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).
102
-------
N-METHYL
PYRROLIDONE
LLf
P-DICHLORO-
BENZENE
RECOVERY
SEPARATION
WATER
AQUEOUS
WASTES
FIGURE 111-33 POLYPHENYLENE SULFIDE PRODUCTION
103
-------
Polypropylene Fibers
Manufacture - The polymerization of polypropylene was described
previously in EPA Development Document No. EPA 440/1-73/010 ±161.
Polypropylene fibers are made by melt spinning. The general
process, shown in Figure III-34, consists of coloring polypro-
pylene 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 sub-
sequently 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 filamemts. 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 mono-
filament 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 tc> 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 that used
for nylon and polyester fibers. After extruding the
filaments downward and quenching by air under carefully
controlled conditions, the new 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
104
-------
DRY PIGMENT OR
"COLOR MASTERBATCH
QUENCH
WASTE
SKIMMED
SOLID
WASTE
PELLETIZE
COLORED
PELLET
STORAGE
i
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 MONOFILAMENT PRODUCTION
-------
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 crystalline
structure. This highly-oriented film is then fibrillated by
applying various kinds of forces perpendicular to the machine
direction. The fibrillation 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.
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 cf 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
107
-------
the plants (41). Phosphate can be present in the wastes due to
phosphate containing surfactants.
108
-------
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,U«-dichloro-
diphenyl 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 fourd 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'-hydroxydiphenvl
sulfone (Figure 111-36, Equation 3).
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. Conse-
quently, it becomes in-possible 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 for-
109
-------
HO
CH3
C
I
CH3
OH + 2NaOH
(1)
NaO
CH
CH3
ONa + 2H20
NaO
CH3
I
C-
I
CH3
o-m
ONa + Cl
(2)
CH
.+2NaCI
(3) Cl Ca H* S02 C6 H4 CI + 2 NaOH—Cl C6 H4 S02 C6 H40 Na + NaCI + H2O
CH3
CH
(4)
S02 +OH"
CH
HO
O
S02
FIGURE 111-36 TYPICAL REACTIONS TO FORM POLYSULFONE RESINS
110
-------
nation of two phenoxides, as shown in Figure 111-36, 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 dichlcrodiphenyl sulfone expands the list
considerably.
Manufacture - A typical process scheme is shown in Figure 111-37.
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 stoichicmetrically 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
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.
Ill
-------
BISPHENOL A
SODIUM
HYDROXIDE
(50%)
DIMETHYL
SULFOXIDE
DICHLORO
DIPHENYL
SULFONE
TERMINATORS
COAGULANTS
TO
RECOVERY
REACTION
DISODIUM
SALT
POLYMERIZATION
I
FILTRATION
I
COAGULATION
SEPARATION
SOLIDS
DRYING
i
PELLETIZING
WATER
I
FIGURE 111-37 POLYSULFONE RESINS PRODUCTION
112
-------
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 azeo-
tropic 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).
113
-------
Polyvinyl Butyral
Polyvinyl butyral is formed by condensation of polyvinyl alcohol
with butyraldehyde in the presence of an acid catalyst (Figure
111-38) .
Manufacture - Two processes, shown in Figures 111-39 and III-UO,
are used for production of polyvinyl butyral.
The process shown in Figure 111-39, which is used, by E. I.
DuPont de Nemours and Company, Inc., Fayetteville, N.C., starts
with powdered polyvinyl alcohol. The alcohol is dissolved 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), 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 111-40 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 111-39. 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-UO,
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, Ul).
114
-------
x
[CH2CHOHCH2CHOH]n + C3H7C ^ [CH2CH CH2CH] n + H20
H
0 O
\ /
c
/ \
7 H
FIGURE 111-38 TYPICAL REACTION TO FORM POLYVINYL BUTYRAL
115
-------
DEMIN WATER & STREAM
PVA
1
CATALYST
BUTYRALDEHYDE
DEMIN. WATER
PLASTICIZER
I
POLY VINYL
ALCOHOL (PVA)
DISSOLVING
BIOTREATMENT
EXTRUSION
SHEETING
FINISHED
PRODUCT
5% BOD 30% OF BOD
(MISC. SOURCES)
POWDERED ROLLS
I
REFRIGERATED ROLLS
I
TINTED ROLLS
DEMIN. WATER
FIGURE 111-39 POLYVINYL BUTYRAL PRODUCTION - DU PONT INC. PROCESS
-------
VINYL
ACETATE-
SUSPENDING AGENT
i WATER
CATALYST
LIME _
SLURRY
POLYMERIZATION
ETHYL
ALCOHOL
MINERAL
CATALYST
ETHYL
ALCOHOL
I
CENTRIFUGE
DISSOLVING
PV
ACETATE
HYDROLYSIS
PV
ALCOHOL
CENTRIFUGE
WASTE WATER TREATMENT
NEUTRALIZING
FACILITY
0.9% FLOW
WATER-
OTHER
• PLANT
WASTE
STORAGE
30.6% FLOW
MISC.
DRYING
68.5% FLOW
CENTRIFUGE
STEAM
WATER
SOLVENT
RECOVERY
SYSTEM
BUTYRALDEHYDE
WATER
r
WASHING
WATER
PRECIPITATION
BUTYRALDEHYDE
ACETAL
REACTION
FILTRATION
PV BUTYRAL
FIGURE 111-40 POLYVINYL BUTYRAL PRODUCTION - MONSANTO INC. PROCESS
117
-------
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, resenrbling 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-
41.
Substitution of other solvents such as toluene, carbon tetra-
chloride, 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).
118
-------
FIGURE 111-41 TYPICAL REACTION TO FORM POLYVINYL CARBAZOLE
119
-------
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 irineral acids) , producing acetalydehyde, as
shown in Figure III-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 reaictivity of
monomer. Long chain alkyl ethers are generally less reactive
than the short chain hcmologs. 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, iraleic anhydride, acryloni-
trile, 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 111-43 and III-4U. In the
solution polymerization process, when a solvent-free product is
desired, it is dried by heating 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
120
-------
H+ H+
(1) CH2=CHOR + H20 [CH2 = CHOH] CH3CHO
(2)
VW-CH2-CH
I
O
I
R
=CH-OR-
H H
I I
-AVCH2-C-CH2-C
I I
O 0
II I
R R
FIGURE 111-42 TYPICAL REACTIONS TO FORM POLYVINYL ETHERS
INCLUDING MONOMER MANUFACTURE
121
-------
COOLING WATER
OR REFRIGERATED
BRINE (INDIRECT)
STEAM
COOLING WATER
(INDIRECT)
NJ
to
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
POLYMERIZER
ORGANIC
OR AQUEOUS
SOLVENT
FINAL
REACTOR
STEAM
EJECTOR
BAROMETRIC
CONDENSER
DILUTION
ADJUSTMENT
.COOLING
WATER
WASTE
WATER
PRODUCT TO
PACKAGING
FIGURE 111-44 POLYVINYL ETHER PRODUCTION - BULK POLYMERIZATION PROCESS
-------
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 polyalkyl
vinyl ethers (25) .
124
-------
Polyvinylidene Chlorides
Polyyinylidene 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) .
125
-------
CCJI]
-*(CH2-CCI2)n
FIGURE 111-45 TYPICAL REACTION TO FORM POLYVINYLIDENE CHLORIDE
126
-------
Polyvinyl Fyrrolidone
Polyvinyl pyrrolidone is a water soluble polymer characterized by
unusual ccmplexing 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
III-46, 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 (253.4°F) at 114 mm. It is completely miscible
with water and most organic solvents. The monomer is
manufactured by the vinylation of 2-pyrrolidone with acetylene in
the presence of alkali metal salts of pyrrolidone.
The polymerization to the product polymer (shown in Figure III-
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 successfully
accomplished with a number of co-monomers. Among these are
ethylene glycol monovinyl ether, ethylene, laurylacrylamide, CJJ!
to CJJ3 methacrylate, divinyl carbonate, cinnamic acid, and
crotonaldehyde. A typical process utilizes solvents such as
alcohol or benzene, a 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. Pharmaceutical
127
-------
(1)
Monomer
N-Vinyl-2-Pyrrolidone
CH2 - CH2
I I
CH2 C = 0
CH = CH2
(2) Polymer
Cii2 ~~~ •"
1
CH2
\NX
1
PM
CH2
C = 0
PH«
—I n
NH4OH
H202 "2HO-
HO- + CH2= CH—^HO-CH2-C-
I I
H
HO-CH2~C- + nCH2=CH-
(3)
HO-CH2- C — (CH2 - CH) , -CH2- CH-
I I I
FIGURE 111-46 TYPICAL REACTIONS TO FORM POLYVINYL PYRROLIDONE
128
-------
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).
129
-------
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-U7 and 111-48 are simplified flowsheets which suggest
the complexity of silicones plants. Figure III-U7 shows
processes used for production of several different chlorosilanes
and hydrolysis of dimethyl dichlorosilane to dimethyl silicone
fluid. Figure III-48 shows transformation of the dimethyl
silicone fluid to finished fluids, greases, emulsions, rubber,
and resins. These figures dc 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 111-49, 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 purchcised.
2. Chlorosilane production. For the methyl fluids, methyl
chlorosilanes are produced by the reaction shown in
Figure 111-49, 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. Chlorosilanes may
also be made by a Grignard process, represented by Equations
3 and 4 in Figure III-U9. 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
130
-------
V
£
(j
. Transistor-grade silicon
Benzene,
olefms,
acetylene, and
other reagents
T
Fluids,
rubber
FIGURE 111-47 PRODUCTION OF SI LANE MONOMERS, OLIGOMERS AND
DIMETHYL SILICONE FLUID
-------
Co
NJ
Dimethyl silicone fluid
Hexamethyldisiloxane
from Me3SiCI
n
i
Depolymerizef
Phenyl oligomers
Vinyl oligomers*
Fluoropropyl oligomers*
Catalyze
and use
Blends of
chlorosilanes
s
| Water
'+ y
"7
Catalysts
,
i /
/
~~ /
Hydrolysis
kettle "
Bodying
' kettle
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 -CH3MgCI
C1
i
(4) 2CH3MgCI + SiCI4 -2MgCI2 + CH3-Si-CH3
i
Cl
(5) (CH3)2SiCI2 + H20 -~(CH3)2 Si(OH)2 + 2 HCI
(6) (CH3)2Si(OH)2 -(CH3)2 Si-0-Si(CH3)2
I i
0 0
(CH3)2 Si-0-Si(CH3)2
and HO [Si (CH3)2 0]nH
FIGURE 111-49 TYPICAL REACTIONS TO FORM SILICONES
133
-------
chlorosilanes, olefins or acetylene may be reacted with
appropriate silane ironomers.
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 silane;s 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.
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
134
-------
glass-silane-resin. The resin may be epoxy, polyester,
melamine, or ether. 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.
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 recycled, for example in
the production of irethyl 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,
Multi-Product Plants
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 49. 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.
F luid Pr oduc t.,Plant s
By virtue of being both newer plants and because of the
inherently more controllable process from the viewpoint of water
recycling and less product variation, the fluid product plants
have been able to achieve considerably lower levels of unit water
use.
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 f luorosilicones are being manufactured.
135
-------
Spandex Fibers
Spandex fibers are made from conventional polyurethane ingre-
dients. Textile Organon (43) defines spandex fibers as being
composed of "at least 85 percent by weight of a segmented
polyurethane." In ccmmon with ether 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 III-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 111-51.
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 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
136
-------
(1)
H(OROCO CH2 CH2 CH2 CH2 CO)nOROH
(2)
H [0(CH2)3CH]nOH
(3)
H [0(CH2)5CO]nOROH
(4)
H3C (( )} NCO
NCO
(5)
OCN-< >— CH2-( )>— NCO
-0-IM-C-
(6) OCN-0-CH2 -0-N-C-OCH2CH20
H
,L
-(CH2)4C-OCH2CH2O -C -N -0-CH2 -0IMCO
H
(7) OCN- R -
Prepolymer
H2NCH2CH2NH2
0 O
C-N-R-N-C-N-CH2-CH2 - N - -
H H H H
FIGURE 111-50 TYPICAL REACTIONS TO FORM SPANDEX FIBERS
137
-------
00
00
MAKE UP
DIISOCYANATE
DIAMINE
POLYMER-
IZATION
VESSEL
BLOW-DOWN
RECYCLE
SOLVENT
PURIFICATION
(N- DtMETHYLFORMAMIDE)
SOLVENTS
WASTE SOLUTION
TO INCINERATION
WASTE TO INCINERATION
SOLVENT +
HOT AIR
SPINNING
SPINNING WASTE
TO INCINERATION
HOT AIR
LUBRICANT
o
SOURCE: BASED ON DISCUSSION
WITH DUPONT.
\
HOUSEKEEPING WASTE WATER
TO BIOLOGICAL TREATMENT
FIGURE 111-51 SPANDEX FIBER PRODUCTION - DRY SPINNING PROCESS
-------
U)
VD
TOLUENE
DlISOCYANATE
POLYTETRAMETHYLENE
GLYCOL
LUBRICANT
COOLING
WATER FROM
CITY
POLYMER-
Z AT I ON
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
-------
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 discussions and
communications with Globe is shown in Figure III-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.
4. 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 producers' 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 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, 43).
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 frcm the presence of ethylene diamine.
140
-------
POLYESTER
MDI
•ISOCYANATE
RECYCLE-
TOLUENE
I
DIAMINE
COOLING
WATER "
POLYMER-
IZATION
VESSEL
DECANTED
WASTE
H20
STREAM
DRUMMED AND
HAULED TO DUMP
_^.WASTE WATER TO
MUNICIPAL
FIGURE 111-53 SPANDEX FIBER PRODUCTION - REACTION SPINNING PROCESS
-------
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 III-5U, 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 intentional 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 111-54, Equation 2). Another
isocyanate group can then react with the amine to produce a
fciuret linkage. Additional -NCO groups can also react with a
hydrogen of the urethane linkage (Equation 1, Figure 111-54) 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 polyurethane
resin. A prepolymer in the ccmmcn 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 III-
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 technique
rather than the one-shot approach in which the isocyanate,
polyol, and other components of a formulation are simply mixed
together and allowed to react. The prepolymer approach often
provides tetter central 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 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
142
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0
II
(1) R-OH + R'-NCO -R-0-C-N-R'
I
H
(2) R'-NCO + H20—-R'-NH2 + C02
(3) 3R (NCO)2 + HO R'-OH -
OCN - R (NHCOO - R' - OCO NHR)2 NCO
FIGURE 111-54 TYPICAL REACTIONS TO FORM URETHANE PREPOLYMERS
143
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it is the most economical method to make polyurethanes.
Prepolymers are generally used where smaller volumes and more
specialized applications of pclyurethanes 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 prepclymer 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 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 wat€;r 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 ndscible 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 - Lew raw waste load (less than 10
units/1000 units of product); attainable low BODS
concentration (less than 20 ing/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 BODS raw waste loads are
less than 10 units/1000 units of product and where hydraulic
flows ranged from 0.4 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 BODS concentrations. Hydraulic flows varied from 14.2
to 116 cu m/kkg (1700 to 14,000 gal./lOOO Ibs). Influent
concentrations of froir 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 Sufccategory III plants are characterized by high raw waste
loads and observed flows from 0 to 170 cu m/kkg (0 to 20,400
gal./lOCO 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 abcut 97 percent in a four-stage aeration basin
indicating that ir.ediurr 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 subcategories
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 ssummarized
in Table IV-1.
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
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TABLE IV-1
INDUSTRY SUBCATEGORIZATION
Major
Subcategory I
Major Major Major
Subcategory II Subcategory III Subcategory IV
Ethylene-vinyl
acetate
copolymers
Fluorocarbons
Polypropylene
fibers
Polyvinylidene
chloride
Acrylic resins
Cellulose
derivatives
Alkyds and un- Nitrile barrier
saturated poly- resins
ester resins Spandex fibers
Cellulose nitrate
Polyamids
(Nylon 6/12)
Polyesters (therm-
plastic)
Polyvinyl-
butyral
Silicones
147
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water treating facilities. The age of the plants in this
industry are determined largely ty 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 BOD5, 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 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.
Note also that in some instances, insufficient operating data on
raw wastes and treatment were available to establish
variabilities; as a result those chemical products that employ
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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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G
M
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
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
E = Estimated
NA «• Not available
BODC
COD
SS
2 - 30
9-25
140 - 220
55 - 110(E)
0.44 - 4.4(E)
3-55
15 - 80
340 - 950
75 - 275(E)
0.2 - 54(E)
5-10
1-2
1-42
35(E)
0 - 4.1
0 - 6.6(E) 4.4 - 44(E) 2.2 - 6.6(E)
5 - 10(E)
NA
0-10
0.4 - l.l(E)
30 - 200
NA
0(E)
5 - 110
20(E)
10 - 30(E)
NA
1-30
3 - 10(E)
NA
NA
1.8 - 2.6(E) 0.2 - 2.2(E)
40 - 400
10(E) - 40(E)
8(E)
15 - 200
40(E)
NA
NA
0.2(E)
50(E)
NA
-------
primary -treatment only for treatment of plant wastes may show raw
waste loads lower than guideline limits; it was announced that
their variabilities were the same as those of other products in
the same major sutcategory.
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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 sufccategories 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 sufccategory 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 irake them 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
155
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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 lacfc 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
sulfa-te) . 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.
The slow accumulation of refractory (resistant to biological
decomposition) compounds in watercourses has caused concern among
various environmentalists and regulatory agencies. However,
until these compounds are identified, analytical procedures
developed to quantify them, and their effects on aquatic plants
and animals are documented, it may be premature (as well as
economically questionable) to require their removal from waste
water sources.
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 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
156
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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 mechanisir, 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. J
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 damacrina
things, including blanketing the stream or lake bed and thereby
destroying the living spaces for those benthic organisms that
"2"™ otherwise °ccupy 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 I
substitute method of quickly estimating the total suspended
solids when the concentration is relatively low.
P.H, 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
AtK?faJ ' aClds' a"d the salts <»« strong acids and weak bases!
Alkalinity is caused by strong bases and the salts of strong
alkalies and weak acids. y
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 neutraU
£lE?l3Valuesj;ndicatf acidity while higher values indicate
alkalinity. The relationship between pH and acidity or
alkalinity is not necessarily linear or direct.
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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,gollutant_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
parameters which may have to be considered in the National
Pollution Discharge Elimination System permits.
Phenolic ggmpounds
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.
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Phenols also reduce the utility of water for certain industrial
uses, notatly food and beverage processing, where it creates
unpleasant tastes and odors in the product.
N i tr ogenou s_ConjEg unds
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 fcrm 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 (N03) 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.
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 (NO3-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
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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 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, thermoplastic 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
associated with a condition of accelerated eutrophication or
160
-------
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, 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 silicones, polypropylene!
and spandex fibers may require that oil and grease be considered
a parameter.
°*i anf Crease exhibit an oxygen demand, oil emulsions may
adhere to the gills of fish cr 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.
161
-------
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 guidelines 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
Fluorocarbons
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 4000 mg/1 of total
salts are generally considered unfit for human use, although in
hot climates such higher salt concentrations can be tolerated
whereas they could not be in temperate climates. Waters
containing 5000 mg/1 or mere are reported to be bitter and act as
bladder and intestinal irritants. It is generally agreed that
the salt concentration of good, palatable water should riot exceed
500 mg/1.
Limiting concentrations of dissolved solids for freshwater fish
may range from 5,000 to 10,000 mg/1, according to species and
prior acclimatization. Some fish are adapted to living in more
saline waters, and a few species of freshwater forms have been
found in natural waters with a salt concentration of 15,000 to
20,000 mg/1. Fish can slowly become acclimatized to higher
salinities, but fish in waters of low salinity cannot survive
sudden exposure to high salinities, such as those resulting from
discharges of oil-well hrines. Dissolved solids may influence
the toxicity of heavy metals and organic compounds to fish and
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
162
-------
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, consequently, 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 cr 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.
163
-------
TABLE VI-1
OTHER ELEMENTS AND COMPOUNDS SPECIFIC TO THE
RESINS SEGMENT OF PLASTICS AND SYNTHETICS INDUSTRY
Alkyd Compounds and
Ester Resins
Fluorocarbons
Spandex Fiters
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
Polychlor inated
Organics
Copper
Fluorides
Polychlorinated
Organics
Cobalt
Manganese
Cadmium
164
-------
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
specifxc 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
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 frcm 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.
As indicated earlier, the survey found no waste water treatment
technologies unique to this segment of the plastics and syn-
thetics 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
165
-------
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 VII-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 fluorocarbon 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 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 weiste 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
166
-------
TABLE VII-1
OPERATIONAL PARAMETERS OF WASTEHATEB TREATMENT PLANTS
(Metric Units)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Type of Plant
Type of Treatment
Hydraulic Load (cu m/day) 1]
Residence Time (hours) '
BODe (kg removed/ day / cu m)
COD ( kg removed/day/cu n)
Power (HP/cu m)
Suspended solids (mg/liter)
Clarifier overflow (m/day)
Biomass (mg/liter)
BODj (kg removed/day/ kg MLSS)
Typical Values NH,-N out (ag/liter)
Typical Values T1QI out (lag/liter)
BOD5 in (mg/llter)
BOD out (mg/liter)
COD BOD5 In
COD in (mg/liter)
COD out (mg/llter)
COD/BOD5 out
Eff. BODj Removal
Eff. COD Removal
Methyl*
Methacrylate
equalize,
cool, nutrient,
bio ox, clarify,
sludge aeration
& centrifuging
1,000(6800 actual)
19+
0.85+
-
0.106+
50+
24.5
3000+
-
-
-
800+
120+
-
-
-
-
85+
-
Polyvinyl Thermoplastic*
Butyral P/E
lagoon coag aer lagoons
add, clarif
1,135 43,906
34 120(2904)
0.36 0.009
0.46
0.06 0.018
135
7.7
2991
0.17
14.6
14.8
543 1,476
39.7 422
1.5
839
179
4.5
92.7+ 71+
79+
Acrylic*
(30-70% of wastes
due to acrylic
rafg) equal, 2
trickling filters
parallel or series
clarif 4 polish
lagoons (57 acres)
3,936
41.5(424)
0.109
-
-
42
24.4 & 57.0
-
-
1.89
8.33
1,946
11
-
-
16
1.45
99.4
-
Vinyl Acetate
EVA
ill* 42*
Skin, oil sep Skim, filter, Skim, oil sep
equal, bio-aer burn recovered clar, anaerob
clarif w/chem oil, recycle bio
add, bio-anaer-recovered
obic polymer
(primary only)
409 4,807 30,280
36
1.03
0.5?
0.007
28
0.20
1200-1800
-
-
-
1,562
17
0.6(TOC/BOD)
904 (TOC)
37 (TOC)
2.2(TOC/BOD)
99+
96+(TOC)
0.3 8760
(API type skimmer)
_ _
40.7
23
51
_
_ _
.1 to 1.5
— _
(154) +
13
(4.2) +
20, 000 (TOC)
47 800 (TOC)
3.6
-
96 (TOC)
Polypropylene Polyvinylldene*
Chloride
Skim before Aerated lagoon
discharge settling basin
(primary only)
1,890 4,650
_
_
„ „
_ _
33 35
_
_ _
_
_
_ _
59
22
13
776
27 251
11.4
63+
68+
Comments:
+ Design Values
Submerged aerators
horsepower
calculated from
size of blowers.
* Indicates wastewater plant serves a chemical manufacturing
First value is residence time in aerobic biological syste
Values In ( ) is residence time in total system.
-------
Type of Plant
1 Type of Treatment <»•«'•>
" municipal
treatment
2 Hydraulic Load (cu tc/day) '•'
3 Residence Time (hours)
4 BOD, (/removed/day/ cu m) *
5 COD (fremoved/day/cu m)
6 Power (HP/cu m)
7 Suspended solids (mg/liter)
8 Ciarifier overflow (a/day)
9 Blomass (mg/liter)
10 'BOD, (kg removed/day/kg MLSS)
11 Typical Values NHj-N out (mg/liter)
12 Typical Values TKS out (mg/liter)
13 BODj indag/liter)
14 BOD, outtmg/llter)
15 COD BODj in
16 COD in (mg/liter)
17 COD out (mg/liter)
18 COD/BOD, out
:>
19 Eff. BODj Removal
in vff rnn Vc**™ral -
OPERATIONAL
Alkyd/Polyester Resins
Settling, bio- Municipal
aerobic (4 treatment
stage)clarify (neut) &
hold lagoon
1 in 1
170 *
252
0.28
0.36
0.034
64
12.7
4,000
0.7
(Nutrient* added) -
2,960
•\Q ..
£.0
1.36
3,890
146
5.2
99+
96.2+
TABLE VI1-1
(Continued)
PARAMETERS OF WASTEWATER TREATMENT PLANTS
(Metri: Units)
Silicones
Neut screen Neut . clarify Bio-aerobic,
sedimentation sludge dewater clarify
screen, , skim, basin
filtration
(primary only) (primary only) secondary)
1,022 25,740 25,740
1.3 3+
(Ciarifier)
20 100
43.2 24.4
6500+
0.04
1.12
276+
24 - 38+
688
13.9 - 205+
0.58 - 5-4+
86.2+
70.2+
Cellulose* Polyvinyl Ether Spandex
Nitrate
tl* »2*
Neut. sediment Equal, neut. Settle S, neut Biological Municipal
spray oxidation process wastes coagulation, treatment
chlorinate city centrifug-
wastes act . ation
aludge clarify
2.0 «.«20 34,440
8.4 - '-5 plant
^ city
•- 0.93
0.66
0.02 - -
40.6 60 208 120
- - 52.3
_
- - ~ ~
- 156 - -
16 - -
219 - 776 2,200 3,
30 1,100 104 225
3.05 2.1
2,370 4,440
123.4 1,800 640 li**0
4.1+ 1.6 6-2 6.4
or t 73 -
86 - 86-6 "
_ 73 65-70+
Conenu:
•fDesign Values
Submerged aerators
horsepower
calculated from
size of blowers.
* Indicates waatewater plant serves a
chemical manufacturing complex,
(1) First value is residence time in
aerobic biological system.
Values io ( ) ifl residence tiae in
total syeten.
Includes lagoon
separator -
skimmer, sump
& pU controller.
-------
TABLE VII-2
OPERATIONAL PARAMETERS OF WASTEWATER TREATMENT PLANTS
(English Units)
1
2
3
4
5.
6
7
8
9
10
11
\~>
CTi ,2
kD 1-!
13
14
15
16
17
18
19
20
Type of Plant
Type of Treatment
Hydraulic Load (MGD)
Residence Time (hours) '
BOD5 (Cremoved/day/lOOO ft3)
COD (Jreaoved/day/1000 ft3)
Power (HP/1000 ft3)
Suspended solids (mg/liter)
Clarifier overflow (GPD/ft )
Blonass (mg/liter)
BOD5 (f removed/day/*MLSS)
Typical Values NH -s out (mg/liter)
Typical Values TKN out (me/liter)
EODj in (mg/liter)
BODj out (mg/liter)
COD/BOD5 in
COD in (mg/liter)
COD out (ing/liter)
COD/BOD out
Eff. BCD, 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 & aeut, (30-707. of wastes
aer lagoons due to acrylic
fflfg) equal, 2
tricking filters
parallel or series
clarif 4 polishing
lagoonR (57 acres)
11.6 1.04
120(2904) 41.5(424)
0.54 6.8
_
0.5
42
600 & 1400
-
-
1.89
8.33
1,476 1,946
422 11
-
-
16
1.45
71+ 99.4
_
Vinyl Acetate EVA
#1 112
Skim, oil sep Skim, filter, Skim, oil sep
equal, bio-aer burn recoverd clar, anaerob
clarif w/chem oil, recycle bio
obic polymer
(primary only)
0.108 1.27 8
36 °-3 8,760
64 (API type skimmer)
36 (TOO
0.2
28 23
5 - 1,257
1200-1800
-
.1 to 1.5
-
(154)+
17 13
0.6(TOC/BOD) - (4.2)+
904 (TOC) - 20,000(TOC)
37(TOC) 47 800(TOC)
2.2(TOC/BOD) 3.6
Q04- _ _
96+(TOC) - 96 (TOC)
Polypropylene Poly% inylidene*
Chloride
Skim before Aerated lagoon
discharge settling basin
(prijaary only)
0.5 1.23 MGD
-
-
-
33 35
-
-
-
-
-
59
22
13
776
27 251
11.4
63+
68+
Comments:r
Notes;
+ 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.
-------
T
1
2
3
4
5
6
7
8
9
10
11
i2
"
14
15
-Lo
17
18
19
20
ype of Plant
Type of Treatment (Neut.)
Hydraulic Load(MGD) 0.0015
Residence Time (hours)'1^
BOD (t removed/day/ 1000 cu ft)
COD (fraaoved/day/1000 cu ft)
Po'.er (HPAOOO cu ft)
Suspended solids (mg/liter) -
Clarifler overflow (m/day)
Biomass (mg/llter)
EOD5 ( t removed/day/ * MLSS)
Typical Values KU^-N out (mg/liter)
Typical Values TOf out (mg/llter)
BOD5 in (mg/liter)
BOD, out (mg/liter)
COD BOD in
C03 in teg/liter)
COO out (mg/liter)
COD/BOD5 out
Eff. BOD Removal
Eff. COD Removal
OPERATIONAL
Alkyd/Polyester Resins
Settling, Municipal
aerobic (4 treatment
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+
TABLE VII-2
(Continued)
PARAMETERS OF WASTEWATER TREATMENT PLANTS
(English Units)
Silicones
Neut screen Neut. clarify Bio-aerobic,
sedimentation sludge dewater clarify
screen, skim, basin
(proposed
(prijoary only) (primary only) secondary)
0.27 6.6 6.8
1.3 3+
(clarifier)
-
-
20 100
1,060 600+
6,500+
0.04
-
1.12
276+
24 - 38+
2.5
688
13.9 - 205+
0.58 - 5.4+
86.2+
70.2+
Cellulose* Polyvinyl Spanie*
Nitrate Ether
H 12
chlorinate city centrifuga-
sludge clarify
2.0 1.3 9.1
8.4 - 7.5 plant
2 city
- 58 -
41 - -
0.6 - - -
40.6 60 208 120
1,283
.
-
- 156 - - -
- 16 - -
219 - 776 2,200 3,900
30 1,100 104 225
3.05 2.1
2,170 4,400
123.4 1,800 640 1,440
4.1+ 1.6 6.2 6.4
86 - 86.6 90+
- - 73 65-70+
^Design Values
Submerged aerators
horsepower
calculated irom
size of blowers.
•Indicates wastewater plane serves a chemical
manufacturing complex.
(1) First value is residence time in aerobic
biological system.
Values 10 ( > is residence time in total
system.
Includes lagoon
separator -
skimmer, sump
& pH controller.
-------
TABLE VI I-3
PERFORMANCE OF OBSERVED WASTEWATER TREATMENT PLANTS
BODr
COD
Suspended Solids
Inlet Outlet
mg/liter mg/liter
Inlet Outlet Inlet Outlet
Eg/liter mg/liter mg/llter 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***
Silicones**
Major Subcategory IV
Nitrile Barrier Resins
Spandex*
59
630
666
543
1476
776
276
10
22
17
66
40
2960 28
251 34
422
104
38
20,000(TOC) SOO(TOC)
48
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 °f a multi-plant wastewater treatment facility : Polyester operations contribute app. 14Z of the
** Design values - facility not operable at time of visit
*** Combined industrial municipal treatment facility
171
-------
TABLE VII-4
OBSERVED TREATMENT AND AVERAGE EFFLUENT LOADINGS FROM HASTE WATER TREATMENT PLANT INSPECTIONS
Piodjct
Control and Treat-
ment Technology
Currently in Use
Acrylic Resine
Equalization,
Trickling Filters
Polishing Lagoons
Acrylic Resins
Neutralization,
- Equalization
Bio-oxidation
(design)
Alkyds and
Unsatucated
Polveeter
Settling. Four-
Stages of Bio-
oxidation
Cellulose
Nitrate*
Neutralization,
Sedimentation
Spray Oxidation
Ethylene-
Vinyl Acetate*
Skimming
B io-ox id a t ion
Polypropylene
Fibers
Skimming
Only
Polyvinyl
Butyral
Sludge
(Multi-Product)
Bio-oxidation
(design)
Siliconea
(Fluid Product)
£ds£««:
Observed or Reported Effluent Loading
Ug/kkg'(lb«/1000)
of Product]
BOD5
£OD
"Suspended Solids
o.io
3.1
30.8
0.09
0.47
0.21
0.07
0.25
0.15
0.24
0.78
0.98
*Multi-plant vai
cillty
-------
for these waste waters; however, when significant amounts of oils
or solvents do occur, the use of oil separators, skimmers, and
settling basins or lagcons 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).
Cop.p_er
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.
173
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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 fcr 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 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.
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.
174
-------
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
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.
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.
175
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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.
176
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SECTION VIII
COST, ENEKGY, 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 multiprcduct 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 14 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 product-
specific analyses are presented in Tables VIII-4/1 to VIII-4/30.
£°st_Modeis_of_Treatment_Technolo2ies
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
177
-------
in which they are located. Many times the main production in
these multi-product plants includes the resins covered earlier.
Consequently, the tasic 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 74 percent weighted average removal of BOD5 was
calculated for these synthetic polymers in 1972. This is
substantially higher than the 42 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 municipal or industrial system.
Similarly, by 1983, the estimated costs (Table VII1-2) for
existing plants using best available technology were $12.0
million. It is noted that these costs were associated with end-
of-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
178
-------
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 VIII-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_Persp.ectives
Another measure by which to gauge the importance of the costs in
Table VIII-2 is to relate them tc the sales price of the products
as is done in Table VIII-3. The average range of water pollution
control costs under EPCTCA was estimated at 0.3 percent to 1.3
percent of current sales prices. On average, the range of costs
for applying EATEA 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_Cgst_jEstimates
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 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.
l£^ustrial_Waste_Treatment_Model_Data
In Tables VIII-5/1 to VIII-5/3 the total discharges for each
product sufccategory are estimated for 1972 and 1977. The quality
of effluents remaining untreated in 1977 is indicated as that
179
-------
consistent with the application of EPCTCA 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.
Each of the representative plant analyses in the 30 tables
summarized by Table VIII-4 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 c± 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 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.
180
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The final part of this section reports on updated inputs for
EPA's Industrial Waste Treatment Model (Tables Vlll-5/1 to VIII-
5/3). The estimated total volume of waste waters discharged for
product sutcategories 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_Technoloigies
The range of components used or needed to effect best practicable
control technology currently available (EPCTCA) , best available
technology economically achievable (BATEA), and best available
demonstrated technology for new source performance standards
(BADT-NSPS) in this portion of the plastics and synthetics
industry have been combined into eight alternative end-of-pipe
treatment steps. These are as follows:
A« l2it.ial_Treatmenti For removal of suspended solids and
heavy metals. Includes equalization, neutralization,
chemical coagulation or precipitation, API separators,
and primary clarification.
B« Ii2l2aical_Treatment:. Primarily for removal of BOD.
Includes activated sludge (or aerated stabilization
basins), sludge disposal, and final clarification.
c- Mai^iz§taa§_iiolocticali 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- 5jhysical-Chemical_Treatmentj. For further removal of
COD, primarily that attributable to refractory organics,
e.g., with activated carbon adsorption.
F- £iauid_Waste_Incinerationi For complete treatment of
small volume wastes.
G. Municj.2al_Treatmentj. Conventional municipal treatment
of industrial discharge into sewer collection systems.
Primary settling and secondary biological stages
assumed.
181
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TABLE VIII-1
PERSPECTIVES ON THE PRODUCTION OF SYNTHETIC POLYMERS
WATER USAGE
Guidelines Subcategory
Product
I
EVA Copolymers
Fluorocarbons
Polypropylene Fibers
Polyvinylidene Chloride
II
Acrylic Resins
Cellulose Derivatives
Subtotal - A&B
III
Alkyd and Unsaturated
Polyester Resins
Cellulose Nitrate
Polyamids
Polyesters (thermoplastic)
Polyvinyl Butyral
Polyvinyl Ethers
Silicones
IV
Nitrile Barrier Resins
Spandex Fibers
Subtotal - C&D
Total - 15 Products
Number of
Company
Operations (1)
5
5
3
4
>4
_3
>24
>14
2
3
3
2
2
4
3
_J.
>36
>60
Percent of
Total 15 Product
Production(2)
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
Percent of
Water Used
by 15 Products
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
Percent of Growth
In Water Usage of
15 Products:
1972-1977
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.
182
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TABLE VIII-2
PERSPECTIVES ON SYNTHETIC POLYMERS PRODUCTION
ANNUAL TREATMENT COSTS
Guidelines Subcategory
III
IV
Alkyds and Unsaturated
Polyester Resins
Cellulose Nitrate
Polyamides
Polyesters (thermoplastic)
Polyvinyl Butyral
Polyvinyl Ethers
Silicones
Nitrile Barrier Resins
Spandex Fibers
Total
Total Annual Costs, $MM
Product
I.
EVA Copolymers
Fluorocarbons
Polypropylene Fibers
Polyvinylidene Chloride
Acrylic Resins
Cellulose Derivatives
Existing Plants
1977
0.04
0.36
0.17
0,01
0.58
0.97
1983
0.12
0.36
0.17
0.04
0.64
2.84
New Plants
1983
0.02
0.13
0.08
0.00
0.86
0.34
0.45
0.59
0.45
0.30
0.08
0.03
0.30
0.03
1.56
0.04
0.04
0.51
0.22
0.07
0.92
0.07
5.21
0.08
0.08
0.00
0.04
0.03
0.09
0.03
1.13
0.12
0.00
4.96
11.92
3.32
183
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TABLE VIII-3
PERSPECTIVES ON SYNTHETIC POLYMERS PRODUCTION
COST1 HIP ACT
Control Cost Range as % of Sales Price
Guideline Subcategory
Product
EVA Copolymers
Fluor ocarbons
Polypropylene Fibers
Polyvinylidene Chloride
Acrylic Resins
Cellulose Derivatives
III
Alkyd and Unsaturated
Polyester Resins
Cellulose Nitrate
Polyamids
Polyesters (thermoplastic)
Polyvinyl Butyral
Polyvinyl Ethers
Silicones
II
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
0.2
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
- 0.6
- 1.4
- 0.2
- 0.4
- 2.0
- 1.9
- 1.7
- 0.9
- 2.9
- 2.1
- 0.7
- 1.2
- 0.6
- 0.3
BATEA
0.4
0.1
0.7
0.1
0.1
3.3
0.4
1.0
0.2
0.3
0.4
0.2
1.7
0.1
0.1
- 6.2
- 0.6
- 1.4
- 0.7
- 0.4
- 5.7
- 3.8
- 3.6
- 2.5
- 6.4
-10.7
- 1.8
- 3.5
- 1.3
- 0.5
BADT
0.2
0.1
0.7
0.1
0.1
1.2
0.8
0.9
0.2
0.2
0.8
0.3
0.7
0.3
0.2
Unweighted Average
0.3- 1-3
0.6 - 3.3
0.5
-'-Low end of cost range generally based on large plants with standard water
usage or municipal treatment charges. High end of range based on small
plants with high water usage. BADT costs based on mininum water usage
by larger plants.
184
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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'
EVA Copolymers
Fluorocarbons
Polypropylene Fibers
Polyvinylidene Chloride
II
Acrylic Resins
Cellulose Derivatives
III
Alkyd and Unsaturated
Polyester Resins
Cellulose Nitrate
Polyamids
Polyesters (thermoplastic)
Polyvinyl Butyral
Polyvinyl Ethers
Sillcones
IV
Nitrile Barrier Resins
Spandex Fibers
Average
$/cu m S/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 S/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
185
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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 (25)
Hydraulic Load
cubic meters/metric ton of product: <••? (.
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD): 6.4 (1.7)*
Costs - $1000 Alternative Treatment Steps
Initial Investment 7.6 18 3 24
Annual Costs:
Capital Costs (8%) 0.6 1.4 0.3 2.0
Depreciation (10%) 0.8 1.8 0.3 2.4
Operation and Maintenance 0.1 0.8 0.1 3.7
Energy and Power 0.1 0.1 - 1
Total Annual Costs 1.6 4.1 0.7 9.1
Effluent Quality (expressed in terms ot yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
A B_ J) !
B.O.D. 1 - °-03 - 0.03
C.O.D. 2 0.2 0.1
Suspended Solids N/A 0.1 - 0.02
*The EVA contribution is thousand cubic meters per day ( mgd). This
is approximately i.g% of the total flow to be treated.
186
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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
Hydraulic Load
cubic meters/metric ton of product: 2.9
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD): 6.8
(50)
(0.35).
(1.8)*
Costs - $1000
Alternative Treatment Steps
Initial Investment
14
33
47
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs 2.7 7.6 1.3
Effluent Quality (expressed in terms of yearly averages)
1.1
1.4
0.1
0.1
2.7
3.3
1.4
0.2
0.5
0.7
0.1
3.8
4.7
7.4
1.8
17.7
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 E L> E
0.03 - 0.03
0.2 - o.l
0.1 - 0.02
* The EVA contribution is thousand cubic meters per day.
This is approximately 3% of the total flow to be treated.
187
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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'^
Operation and Maintenance 2-0
Energy and Power ".1
Total Annual Costs ^
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
Suspended Solids
188
-------
TABLE VIII-4/4
WATER EFFLUENT TREATMENT 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
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
tt^ 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.
M2 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.
189
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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
Total Annual Costs
11.6
14.5
8.6
0.3
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
190
-------
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
-* -1 ^2
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
191
-------
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)
A P. 1
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
192
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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* Mj 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 13 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-°-D. 1-5 (Municipal Treatment)
Suspended Solids 1.0
*Air flotation for oil and grease removal.
193
-------
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
D
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.
194
-------
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.
195
-------
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 3.9
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.
196
-------
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 Q20)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb) 32 (3i8)
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.
19?
-------
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 (10)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD):
117
(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.
198
-------
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.
199
-------
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 <°'4>
Treatment Plant Size
thousand cubic meters per day (MGD): 0.15 (0.04,1
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. c_
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
200
-------
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* MJL M2
Initial Investment 5.0
Annual Costs:
Capital Costs (8%) 04-
Depreciation (10%) 0'5
Operation and Maintenance 10-
Energy and Power
Total Annual Costs i^ Q.I Q 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-°-D- 25 (Municipal Treatment)
Suspended Solids 1
*Pretreatment is Clarification or Filtration.
201
-------
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 15** £***
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. C_
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.
202
-------
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%) Q.8
Depreciation (10%) i.o
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.
203
-------
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
27
33
6.4
0.6
62
78
43
9
14
18
2
-
77
97
79
22
67
192
34
Effluent Quality (expressed in terms of yearly averages)
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 B D E
7
23
2
14
*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.
204
-------
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
205
-------
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
A B C D E
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 IB £ I) E
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.
206
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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_ C_ D_ E_
0.4 - (D.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.
207
-------
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 S teps
A 1 D E
Initial Investment 285 725 135 1614
Annual Costs:
Capital Costs (8%) 23 58 11 129
Depreciation (10%) 29 73 14 161
Operation and Maintenance 3 50 2 525
Energy and Power 0.5 4 - 155
Total Annual Costs 55.5 185 27 970
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
A 1 D E
B.O.D. 30 - 0.9 -
C.O.D. 40 9
Suspended Solids N/A - - 0.5 -
208
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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: 1.8 (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.
209
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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 B D E
Initial Investment
305 745
232 1338
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs 61.6 184 44 522
Effluent Quality (expressed in terms of yearly averages)
24
31
6
0.6
60
75
40
9
19
23
2
-
107
134
228
53
B.O.D.
C.O.D.
Suspended Solids
Raw Waste Load
N/A
15
N/A
Resulting Effluent Levels
(units per 1000 units of product)
A B_ D E_
1.5 - 0.6
7.5 - 4.0
1.0 - 0.2
210
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TABLE VII1-4/26
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 Jl P_ E.
Initial Investment 143 334 77 435
Annual Costs:
Capital Costs (8%) n 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 I 5. I
B-°'D- N/A - 1.5 - 0.6
C'°-D- 15 - 7.5 - 4.0
Suspended Solids jj/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.
211
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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 & Ji
Initial Investment 720 1760 441 3044
Annual Costs:
Capital Costs (8%) 58 141 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 I 2. _E
B.O.D. 85 _ 7 - 3
C.O.D. 115 - 35 - 18
Suspended Solids 50 5 - 1 -
212
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TABLE VIII-4/28
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Silicones
Plant Description: Multi-product - Industrial Complex
Representative Plant Capacity
million kilograms (pounds) per year: 22.7 (50)
Hydraulic Load
cubic meters/metric ton of product:
(gal/lb)
142
Treatment Plant Size
thousand cubic meters per day (MGD): /~ i
(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
102
95 23 175
119 29 219
66 2 622
13 194
293
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
~ 1 ~ ~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.
213
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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%) 26 17
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.
214
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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-°'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.
215
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TABLE VIII-5/1
INDUSTRIAL WASTE TREATMENT MODEL DATA SYNTHETIC POLYMERS PRODUCTION
EVA Fluorocarbons Polypropylene Polyvinylidene Acrylic
Copolymers Fibers Chloride. Resins
Total Industry Discharge
1000 cubic meters/day
(or million gallons/day)
1972 0.6(0.2) 4.2(1.1) 1.5(0.4) 0.4(0.1) 13.2(3.5)
1977 1.1(0.3) 5.7(1.5) 2.3(0.6) 0.4(0.1) 33.1(8.7)
Quality of Effluents in 1977
(Expressed in terms of yearly averages)
Parameters:
(in units/1000 units of product)
BOD
COD
Suspended Solids
Hydraulic Load: 1972-1977
cu m/kkg (or gal/lb) 8.3(1.0) 92 (18) 16.7(2.0) NA NA
Numbers of Companies 5 53 4 >4
Percent of Treatment in 1972
(in percent now treated)
A. Industrial Pretreatment 100 100 0 100 80
B. Industrial Biological 60 0 0 50 65
C. Municipal 0 100 100 0 20
0.13
1.3
0.25
2.3
23
4.5
0.25
1.25
0.50
NA
NA
NA
NA
NA
NA
216
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TABLE VIII-5/2
INDUSTRIAL WASTE TREATMENT MODEL DATA - SYNTHETIC POLYMERS PRODUCTION
Cellulose
Derivatives
Alkyds and
Unsaturated
Polyesters
Total Industry Discharge
1000 cubic meters/day
(or million gallons/day)
1972
1977
15.9(4.2)
20.9(5.5)
Quality of Effluents in 1977
(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) 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
0.4
2.0
0.1
Cellulose Polyamides Polyesters
Nitrate Thermoplastic
6.8(1.8) 9.8(2.6)
13.7(3.6) 9.8(2.6)
5.0
25
4.2
3.2(0.4) 142(17)
L4 2
0.8(0.2)
1.2(0.3)
10
10
90
100
40
60
0.3
3.0
0.2
6.7(0.8)
3
100
60
0
0.4(0.1)
0.8(0.2)
0.35
5.3
0.24
2.2(0.95)
3
100
50
0
217
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TABLE VIII-5/3
INDUSTRIAL WASTE TREATMENT MODEL DAT£ - SYNTHETIC POLYMERS PRODUCTION
Polyvinyl
Butyral
Total Industry Discharge
1000 cubic meters/day
(or million gallons/day)
1972 5.3(1.4)
1977 6.7(1.8)
Quality of Effluents in 1977
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)
(Expressed in terms of yearly averages)
Parameters:
(in units/1000 units of product)
BOD
COD
Suspended Solids
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
NA
NA
NA
2
100
25
75
NA
NA
NA
NA
2
70
0
30
10.5
53
7.0
233(28)
4
100
20
0
NA
NA
NA
NA
3
100
70
30
NA
NA
NA
NA
3
100
60
10
218
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SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
GUIDELINES AND LIMITATIONS
Definition of Best Practicable^ Control Technology Currently
Available_JBPCTCAl
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 BOD5 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 occur. 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 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,
219
-------
metals, nitrogenous compounds and specific chemicals such as
phenolics are also of concern to the industry.
In Table VII- 4 of Section VII the effluent loadings which are
currently being attained by the product subcategories for BOD5,
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 plaint 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.
Attainable Ef f luent_Cgncentrations
Based on the definition of BPCTCA, the following long-term
average BOD5 and suspended solids concentrations were used as a
basis for the guidelines.
SS
mg/liter mg/liter
Major Subcategory I 15 30
Major Subcategory II 20 30
Major Subcategory III 45 30
Major Subcategory IV 75 30
The BOD5 and suspended solids concentrations are based on
observed or reported performance of water treatment plants. In
many sufccategories of this segment of the plastics and synthetics
220
-------
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 characteristics of the polymer segment of the synthetics
and plastics industry vary significantly from product to product
and within an individual plant over time. The ratio of COD and
BOD5 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. The COD
limits for BPCTCA guidelines are based on these values as well as
by analogy with the bases used in establishing guidelines for the
resins segment of the industry. They are expressed as ratios to
the BOD5 limit for upper limits of the ratio of COC/BOD5 of 5,
10, and 15. Table IX-2 records the ratios corresponding to the
individual products. where reasonable to do so, actual COC/BOD5
ratios that were observed were used.
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 the interim, the purpose of the proposed BPCTCA guidelines is
simply to reflect the removal of COD to be expected along with
best practicable removal of those pollutants measured by the BODS
" " —
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
. ^mg/1iter monthlv limit as demonstrated by deohenolizing
(13' ^' ^ 39> or 'biological
^1 H? 0±1 and greaS6 iS based on 30 mg/liter monthly
attainable concentrations as demonstrated by various
pnysical 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
th^eihne%n °r-,the ir°n and Steel i^ustry. it should be noted
that the fluoride level shewn for the f luorocarbons (PTFE)
?h?2^!°ry a^ll€? t0 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 HC1 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 of by various
^ahSA an^udin dee? 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
221
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TABLE IX-1
COD/BOD RATIOS
Raw
Acrylic Resins
Alkyd and Unsaturated
Polyester Resins
Cellulose Derivatives
Cellulose Nitrate
Ethylene-Vinyl Acetate/
Polyethylene
Fluorocarbons
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
222
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TABLE IX-2
COD/BOD5 RATIOS CORRESPONDING TO INDIVIDUAL PRODUCTS
(TREATED WASTEWATER)
Product COD/BOD
Alkyds and unsaturated polyesters, 5
cellulose nitrate, polyamides
Ethylene-vinyl acetate, polypropylene
fibers, silicones, fluorocarbons
Polyesters (Thermoplastic) 15
223
-------
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 cf toxic and hazardous chemicals prepared in
the Federal Register of December 27, 1973(38).
The removal of copper and lead is based on an eittainable
concentration of 0.5 mg/liter as demonstrated by alkaline
chemical precipitation (35).
The copper limitations for both multi-product silicone and fluid-
product 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
calculated for the fluid-product plants by averaging the
values of the reported range of waste flows. For the
multi-product plants an average was taken of the waste
flows of the two plants having the more reliable data.
In the case of the multi-product plants, estimates of
product quantities were estimated from actual sales
quantities.
U. 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 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
224
-------
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 EPCTCA is based on demonstrated
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-3 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
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.
as laboratories and so on. 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_Prop_erlv_Desi2ned 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-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
22f
-------
TABLE IX-3
DEMONSTRATED WASTEWATER FLOWS
Alkyd Molding Compounds and
Unsaturated Polyester Resins
Cellulose Nitrate
Ethylene-Vinyl Acetate
Fluorocarbons
Polyamides (Nylon 6/12 only)
WASTEWATER FLOW RATES
cum/kkg ^al/1000 Ibs
3.3
142
2.9
150
6.7
Polyester Resins (Thermoplastic) 7.9
Polypropylene Fibers
Polyvinyl Butyral
Silicones
Multi-products
Fluid Products
16.7
_*
233
33
400
17,000
1,000
18,000
800
950
2,000
_*
28,000
4,000
*See footnoote page 232b
226
-------
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_+_22_monthly,
x
y daily = x_+_3Q_daily_
x
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-4 are based on the data
obtained in the synthetic resin segment (16) of the plastics and
synthetics industry.
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-5
and IX-6.
227
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TABLE LX-4
VARIABILITY FACTORS FOR BODr
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
228
-------
TABLE IX-5
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE EFFLUENT LIMITATIONS GUIDELINE"
[kg/kkg (lb/]000 lb) of production]
Foot-
note
So.
1
. 2
3
4
S
6
7
S
NJ »
NJ
VO 1C
u
13
14
15
Subcategory
Ethylene-Vinyl Ac-Cate Copolymari.
Fli-orocarbons
Polypropylene Fiber
PflyvinyllJene Chloride
Ar.yllc e.iins
Cellulose Derivatives
A->yds ann Unsaturated Polyester tasln*
O'.lulosc Nitrat/
Polyanidc* (Syloi 6/12 oi,ly)
Prlyeste,. Resins (then»"^laatic)
Pflyvlnyi Butyral
Pclyvlnyi Ethem
Slllconeo
Multi-Product Plants
Allucatlo.i for
Fluid Product Plants
Spandex Fibers
B*jQr
Maximum Average of Maximum for Any
Dally Values for Any One Day
Period of Thirty
Consecutive Days
0.07 0.14
3.6 7.0
0.40 0.78
Ho numerical guldellnea-aee discussion
in footnote
n tt
" M
0.33 0.60
14 26
0.66 1.20
0.78 1.4
Ho numerical guidelines-see discussion
in footnote
14 26
8.2 15
3.3 6.0
No numerical guidelines-see dis-
cussion ln footnot.
1* n
COD
Maximum Average of Maximum for Any
Dally Values for Any One Day
Period of Thirty
0.35 0.70
6.7 13
2.0 3.9
No numerical guidelines-see discussion
in footnote
n n
1.7 3.0
46 85
3.3 6.0
12 22
No numerical guidelines -see discussion
in footnote
« ii
70 127
41 75
17 30
No numerical guidelines-see dis-
cussion in footnote
n n
— SUSPrKE'D SOLIDS '
Maximun Average of Maxis'ir for \r.v
Dally Values for Any One r..y
Period of Thirty
Consecutive D-t-s
0.19 0.35
9.9 13.0
1.1 2.0
No numerical guidelines-see discussion
in footnote
» n
0.22 0.40
9.4 17
0.44 O.SO
0.52 0.95
No numerical guidelines-see discussion
In footnote
9.1 17
5.4 10
2.2 4.0
No numerical guidelines-see dl&-
-------
FOOTNOTES FOR TABLES Ix~5
1. Ethylene-Vinyl Ac«tsts (EVA) Copolfner. Two of the flw
known producers were contacted.All plants sre located
at polyethylene production facilities. Hater 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 polyvlnyl acetate emulsion polymerization
reported in EPA 440/1-73/010. Both multi-plant and
municipal sewage treatment is used.
2, Fluorocarbons. Three of the seven manufacturing plants
were visited. A wide range of products are produced.
The most Important la polytetrafluorethylene (PTFE) and
these guidelines are recommended for PTFE granular and
fine povder grades only. The wastewater discharges
differ considerably depending upon the process recovery
schemes for hydrochloric acid and the disposal of selec-
ted streams bv deep well, ocean dumping or off-site
contract methods. The use of ethylene glycol In a pro-
cess can significantly affect the waste loads. Fluoride
concentrations In untreated wastewaters are generally
below levels attainable by alkaline precipitation.
3. Polypropylene Fibers. Two 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 aelec-
ted concentrated wastes are segregated and disposed of
by landfllllng, etc. Primary treatment at one plant slt«
was observed while the other plant discharges to a
Municipal sewage system.
4. folyvinylidene Chloride, the two major manufacturers
were contacted. Both plant sites send wastewaters to
multi-plant treatment plants of which the polyvlnylidena
chloride is a snail portion. Consequently, there was
insufficient data to develop reconnended guidelines.
5. Acrylic Resins. 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
recommend effluent limitation guidelines.
6. Cellulose Derivatives. Cellulose derlvates investigated
Included ethyl cellulose, hydroxyethyl cellulose, methyl
cellulose and carboxymethyl cellulose. Wide' variations
In unit flow rates for two plants producing the same
product, differences in manufacturing techniques and th»
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, AlkyJs and Unsaturated Polyester Resins. Six carefully
selected 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 for disposal in other manners.
Generally, the Industry discharges wastewaters into
municipal sewage systems and 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 plants having their
own vastewater treatment system - a very infrequent
occurrence.
8. 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.
9. Polyaaides. 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.
10, Polyester Thermoplastic Resins. There are three manu-
facturers, two of which produce polyfethylene, terephtha-
late) In quantities less than 21 of their total thermo-
plastic production. The guidelines are recommended for
poly(ethylene terephthalate) since the other product
poly(butylene terephthalate) Is produced at only one
plant and the wastewater goes Into a municipal sewage
syst 'm, so no data on performance could be obtained.
11, Polyvlnyl Sutyral. 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, the recommended guide-
lines are only for NSPS-BADT when starting with poly-
vinyl alcohol since any other guidelines would be
tantamount to establishing a permit for the production
site.
12. Polyvlnyl ethers. The three present plants use differ-
ent processes each of which produces several grades of
product. The different ctieaical conpaoUiuns used in
both bulk and solution polymerization processes and the •
lack of data on both raw and treated wastewaters pre-
vented establishing guidelines. The wastewatera are
presently sent to either multi-plant treatment faclliti*
or municipal sewage systems.
13. Silicones. Pour companies manufacture silicones at five
locations. Three plants vere visited and data were
obtained from all plants. The major processing steps at
the five plants are shown below.
Ha'or Processes st Five Stlicone Plants
Plant No. 12345*
CH.C1 x * »
Chlorosilane prod. x x x x x
Hydrolysis x x x x x
Fluids, greases, x x x x x
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, fluorinated silicones, coupling
agents, and other materials.
Based on the manufacturing process, the wastewater flows
and the raw waste loads, the plants 1, 2, 3 were desig-
nated as multir-product plants while 4 and 5 were desig-
nated as fluid product plants. Guideline quantities
based on production rates that were estimated
from sales volumes for BPT.
14. Nitrlle Barrier Resins. Commercial scale production and
sale of these resins has not yet begun. The companies
expected to have production facilities were contacted,
and two provided estimates of raw waste loads. Because
of the lack of demonstrated flows and raw waste loads,
It was impossible to establish effluent guideline
limitations.
15. Spandex Fibers. Three manufacturers each produce '
Spandex fibers by significantly different processes.
These are dry, wet and reaction spinning methods. '
Because of lij&ited data on raw waste loads and
because each plant operates a different process,
it was impossible to establiah meaningful guidelines.
-------
TABLE IX-6
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE EFFLUENT LIMITATIONS GUIDELINES
(Other Elements and Compounds)
Product
Parameter
kg/kkg (Ibs/lOQQ Ibs of production)
Maximum average of daily Maximum
values for any period of For Any
thirty consecutive days One Day
Alkyds and unsaturated
polyester resins
Lead
0.0017
0.0034
U)
Fluorocarbons
Spandex fiber
Nitrile barrier resins
Polypropylene fibers
Silicones
Multi-product
Fluid-product
Barometric
allocation
Polyester resins
(Thermoplastic)
Fluorides
Cyanides
Cyanides
Oils & grease
Copper
Copper
Copper
Cadmium
0.6 1.2
Toxic and hazardous chemicals guidelines to apply
0.5
.071
0.017
.042
1.0
.14
0.034
.083
Toxic and hazardous chemicals guidelines
to apply
-------
-------
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
Te chnolog2__EconomicallY__Achievable
n + he *nalysjs of the information presented in Sections IV
, 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
as" t±fSiS "h1^ I"inimiZe the V°1Ume °f -Degenerating "ter
as typified by segregation of contact process waters from
noncontact waste water, maximum waste water recycle and reuse
!iaks ano, °h 0nfe-thrOUgh b*^tric condensers, cltroTof
leaks good housekeeping practices, etc., and end-of-pipe
elemenisgY'tvnifiS "T^ ^T*1 °f susPend^ solids and o?ner
elements typified by granular media filtration, chemical
treatment, etc., and further COD removal as typified by the
adsorSivenflof adS°Jpti°n Processes such as activated carSn and
adsorptive floes, and incineration for the treatment of highly
concentrated small volume wastes and additional biological
treatment for further BOD5 removal when needed. io-Logica±
Best available technology economically achievable can be expected
areaS/T ^ ^ °f th°Se ^^^±e5 which provSf the
Historical fgrJ.' °H P°llutant ^ntrol per unit expenditure?
oollSSon S'H? een the aPProach to ^e solution of any
??ii££ ? Frobiem,- as typified by the mechanical and biological
treatment used for removal of solids and biochemically activ-
dissolved substances, respectively. At the present stage of
development, it is technologically possible to achieve complete
imnaS °ff P°lluta"ts from wa^e water streams. The economic
impact of doing this mist be assessed by computing cost benefits
to specific plants, entire industries, and the overall economy
The application of best available technology will demand Sat Se
economic achievability be determined, increasingly, on the basis
of considering water for its true economic impact/ Snlikl best
practicable technology, which is readily applicable across tSe
industry the selection of best available technology economically
achievable becomes uniquely specific to each proceS and ?n each
plant. Furthermore, the human factors associated wiS
conscientious operation and meticulous attention to detai! become
technology is to acMeve
froS
233
-------
The_Guidelines
Achievable_Effluent_Concentrations
Susp_ended_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
ing/liter for all product and process subcategories (1, 15, 35).
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 BODS because the biochemically treated waste water
will have proportionally much higher ratios of COD to BOD| than
entered the waste water treatment plant. In the case of a tew
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 ncnbiodegradable 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.
234
-------
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. -tiutdnxb
sorno m^h°ds ,for re*oval of oxygen demanding substance,
adsorption by surface-active materials, especially activated
carbon, has gained preeminence. Although the effectiveness of
activated carbon adsorption has teen 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
?^h T^-f I"1Cal sPecies is Beginning to appear in the
^nija^ ^erature. 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
prior tr° JTr S^tances ^lectively (for example, Pphenolsf
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 carbonaceous substances from
evSf»SSer- StrfamS' 1VS not a Panacea. Its use must be
H™ ?? ^ !rmS °f the high caPital a^ operating costs,
especially for charcoal replacement and energy, and the benefit
C carb?nace°us and oxygen demanding substances can
sometimes be achieved through oxidation by chlorine, ozone
ATChl?riteS' etC' H°Weve*' not °n" must the
bf S be assessed but certain ancillary effects,
n » ,i y e
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 Sxidan?s
crr8'-/^ be taken int° acc^t. Consequnt, wen
chemical oxidation is employed for removal of COD, it may be
SSuS ^£f0Jnr thVreaTnt Wlth an°ther SteP to ««^e tSe
wafers? chemicals prior to discharge to receiving
Degradation of oxygen demanding substances may take place slowly
If sn^°nS lf.fu"icie»tly long residence time can be provided!
»L P? f X^ 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. 01?ra-f StrSiSn
Spnre^rSe 0!rno^is' bcth of ^ich are membrane techniques, SvS
species bSt tL hteChniCailY Capable °f rem°ving high molecular
species, but they have not been shown to be operationally and
disSibuSon7 ofCtieVahle' ,With theSe techniquL, the moIecuSr
distribution of the chemical species determines the efficiency of
the separation. They probably have limited potential in the
of ^S , M SYn^hetics industry, due to the particular spectrum
of molecular weights occurring in the waste waters
235
-------
The concentration basis for BATEA for COD is either 130 mg/liter
as demonstrated in an activated carbon plant (U) or that
concentration documented by plants in Table VII-3. The BODJ
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.
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_Reduct ion_ 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 EPCTCA waste water flows and the verified
BADT waste water flows as described in Section XI. These flows
are given in Table X-1.
236
-------
BATEA_Waste_Water
TABLE X-1
Flow gates
Alkyd Molding Compounds and
Unsaturated Polyester Resins
Cellulose Nitrate
Ethylene-Vinyl Acetate
Fluorocarbons
Polyamides (Nylon 6/12 only)
Polyester Eesins
(Thermoplastic)
Polypropylene Fibers
Polyvinyl Butyral
Silicones
multi-products
fluid products
*See footnote page 212a
121
21.9
1.83
125
2.50
91.7
6.67
7.92
9.17
220
15,000
300
11,000
800
950
1,100
14,500
2,625
237
-------
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
the petroleum refining industry. The other parameters are
in
based on the achievable- concentration for monthly maximum
variability factor of 2 to determine the daily maximum.
TABLE X-2
and
Variability Factors BATEA
BOD5 and COB
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.
238
-------
TABLE X-3
BiST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE EFFLUENT LIMITATIONS GUIDELINES
[kg/kkg (lb/1000 Ib) of production]
Fo;:-
r.^;e
Nj.
1
2
3
5
6
7
5
NO
$ 9
10
11
u
14
15
Subcategory
Ethylene -Vinyl Acetate Copolyseca
f luorocarbons
Po:>Trcf>lcne fiber
Pol>vinylldene Chloride
Acrylic Resins
Cellulose Derivatives
Alkyds and Unsaturated Polyester Realm
Cellulose Nitrate
?ol..aaiJ«s (Nylon 6/12 only)
Polyester Resins (theraoplastlc)
Polyvln; 1 Ejtyral
PclvvJi'yl Ethers
Sili.cor.ee
fluid Product Plants
N'itrile Barrier Kesins
Spandex Fibers
Maximum Average of Maximum for Any
Dally Values for Any One Day
Period of Thirty
Consecutive B...
0.06
2.2
0.22
Mo numerical guidelines-see
In footnote
..
0.10
6.9
0.37
0.44
Mo numerical guidelines-see
In footnote
6.7
1.2
No numerical guidelines-see
in footnote
0.09
3.3
0.33
dlacusaion
„
0.14
9.4
0.50
0.59
disrusslon
9.1
1.6
diacusaion
COD
Maximum Average of Maximum for Any
Dally Values for Any One Day
Period of Thirty
Consecutive Davs
0.19 0.29
4.0 5.9
0.40 0.59
No numerical guidelines-see discussion
In footnote
ti „
0.52 0.7«
34 47
1.9 2.6
2.3 3.1
In footnote
35 , *'
6.3 8.5
Mo numerical guidelines-see discussion
in footnote
S!T_: I £3' SCU35
Kaxir.uT Avcr.-.ge of Kaxi-ui fcr Av.
Daily V-.'.utf for Any G.i* 3iv
Period c: Tdirty
0.04 C.C5
1-6 :.S
0.16 ;';-
So numerical juiii-1 ;n< '-c«i li-."-. . .-
in frot.iclv
0.03 :. :
2.1 ; .
0.11 c.:;
0.14
,..,
in fo tr,ul<
2.0 2.4
0.37 ;.„
No nuaerical guidelinc5-%»,* iisr i\t ;-:.
In fCuCnoc*?
-------
FOOTNOTES FOR TABLES X-3
NJ
£»
O
1. Ethvlene -Vinyl Acetate (EVA) CopolTner. Two of the five
known producers were contacted. All plants are located
at polyethylene production facilities. Water use and
wastewater characteristics for EVA are essentially Iden-
tical to those for low density polyethylene. However,
an e'mulsion 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 cewage treatment is used.
2. Tluorocaibons . Three o{ the seven manufacturing plants
were visited. A wide range of products are produced.
The most important la polytetraf luorethylene (PTFE) and
these guide] Ines are recommended for PTTE granular and
fine powder grades only. The wastewater discharges
differ considerably depending upon the process recovery
schenes for hydrochloric acid and the disposal of selec-
ted streacs by deep well, ocean dumping or off-site
contract methods. The use of ethylene glycol in a pro-
cess can significantly affect the waste loads. Fluoride
concentrations In untreated wastewaters are generally
below levels attainable by alkaline precipitation.
3. Polypropylene Fibers. Two 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 segragated and disposed of
by landfllling, etc. Primary treatment at one plant site
was observed while the other plant discharges to a
lounicipal sewage system.
*. PolyvinyHdene Chloride. The two major manufacturers
were contacted. Both plant sites send wastewaters to
multi-plant treatment plants of which the polyvinylidene
chloride is a small portion. Consequently, there was
Insufficient data to develop recommended guidelines.
5. Acrylic Resins. Three of the four manufacturers were
contacted. Large numbers of product grades are produced
by bulk, solution, suspension and emulsion polymeriza-
tion. Ihe widely varying hydraulic loads for the large
number of products in addition to treatment of the waste-
waters by nulti-plant wastewater treatment facilities
prohibited obtaining sufficient meaningful data to
recommend effluent limitation guidelines.
7. Alkyds and Unsaturated Polyester Resins. Six carefully
selected 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 for disposal in other manners.
Generally, the industry discharges wastewaters into
municipal sewage systems and should continue. Also, the
type of air pollution control, e.g. combustion or scrub-
bing, has a significant effect on the wastewater load's.
The recommended guidelines are for plants having their
own wastewater treatment system - a very Infrequent
occurrence.
g. 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.
6. Cellulose Derivatives. Cellulose derlvates investigated
Included ethyl cellulose, hydroxyethyl cellulose, methyl
cellulose and carboxynethyl cellulose. Wide' variations
in unit flow rates for two plants producing the same
product, differences in nanufacturlng techniques and th«
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.
9, Polyamides. 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.
10. Polyester Thermoplastic Resins. There are three manu-
facturers, two of which produce poly(ethylene, terephtha—
late) in quantities less than 2Z of their total thermo-
plastic production. The guidelines are recommended for
poly(ethylene terephthalate) since the other product
polyibutylene terephthdlate) is produced at only one
plant and the wastewater goes into a municipal sewage
system, so no data on performance could be obtained.
11. Polyvlnyl 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 systesrs, there was no
data available. Consequently, the recommended guide-
lines are only for NSPS-BADT when starting with poly-
vinyl alcohol since any other guidelines would be
tantamount to establishing a permit for the production
site.
12. Polyvlnyl ethers. The three present plants use differ-
ent processes each of which produces several grades of
product. The different chemical compositions used In
both bulk and solution polymerization processes and th«
lack of data on both raw and treated wastewaters pre-
vented establishing guidelines. The wastewaters ate
presently sent to either multi-plant treatment facllitle
or municipal sewage systems.
13. Silicones. lour companies manufacture sillcones at five
locations. Three planta were visited and data were
obtained from all planta. The major processing steps at
the five plants are shown below.
Ma^or Processes at Five Sllicone Plants
Plant No. 12345'
CH-C1 * x *
Chlorosilane prod. x X x x X
Hydrolysis x x x x x
«uid., greases, x x x x x
emulsions prod.
Resin production x x x
Elastomer production x x x x
Specialties prod.* x x x
Fumed silica prod. x
BC1 production x
* e.g. surfactants, fluorinated sillcones, coupling
agents, and other materials.
Based on the manufacturing process, the wastewater flows
and the raw waste loads, the plants 1, 2, 3 were desig-
nated as multi-product plants while 4 and 5 were desig-
nated as fluid product plants. Guideline quantities
based on production rates that were estlcated
from sales vol
fo
BPT.
14. Hltrlle Barrier Resins. Commercial scale production and
sale of these resins has not yet begun. The companies
expected to have production facilities were contacted,
and two provided estimates of raw waste loads. Because
of the lack of demonstrated flows and raw waste loads,
it was Impossible to establish effluent guideline
limitations.
IS. Spandex Fibers. Three manufacturers each produce
Spandex fibers by significantly different processes.
These are dry, wet and reaction spinning methods.
Because of limited data on raw waste loads ana
because each plant operates a different process,
it was impossible to establish meaningful guidelines.
-------
NJ
*>.
TABLE X-4
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE EFFLUENT LIMITATIONS GUIDELINES
(Other Elements and Compounds)
Product
Alkyds and unsaturated
polyester resins
Fluorocarbons
Spandex fibers
Nitrile barrier resins
Polypropylene fibers
Silicones
Multi-product
Fluid-product
Polyester resins
(thermoplastic)
Parameter
Lead
Mercury
Fluorides
Cyanides
Cyanides
Oils and grease
Copper
Copper
Cadmium
kg/kkg (lbs/1000 Ibs of Production)
Maximum average of daily
values for any period of
thirty consecutive days
Maximum
For Any
One Day
0.000055 0.00011
Toxic and hazardous chemicals guidelines to apply
0.6 1.2
Toxic and hazardous chemicals guidelines to apply
0.092
0.03
0.011
0.18
0.06
0.0055
Toxic and hazardous chemicals guidelines to apply
-------
SECTION XI
NEVv SOURCE PERFORMANCE STANDARDS
BEST AVAILABLE DEMONSTRATED TECHNOLOGY
Definition of New Source Performance^Standards Best Available
Demonstrated TechnologY^iNSPS-EADTj ~~
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 as defined
in BATEA along with the application of granular media filtration
and chemical treatment for additional suspended solids and other
element removal as well as additional biological treatment for
further BOE5 removal as needed.
The_Standards
Achievable Effluent Concentration
The concentration basis for NSPS-BADT is the same as that for
BATEA for all parameters except COD. The COD concentration basis
for NSPS-BADT is based on the concentrations which were
attainable in observed plants as expressed in Table VII-3. In
cases where attainable concentrations were not available as long
term data, the BPCTCA ratios of COD/BOD5 were used for
determining COD. To determine limitations, the variability
factors determined from BPCTCA are applied to the COD
concentration basis. By the application of these factors, the
COD limitations are liberal, do not determine the technology
required, but in effect require that COD wastes be treated along
with the BOD_5 wastes.
Waste Load Reduction Basig
The waste water flow basis for NSPS-EADT is based on the lowest
verified flows associated with each product. The waste water
basis ranges from 0 to 50 percent of the BPCTCA basis and is
product specific. 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 (EPCTCA) 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 BODS and COD. The
243
-------
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 2.09 250
Fluorocarbons 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
Multi-products 100 12,000
Fluid products 10.4 1,250
244
-------
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 iraximum.
nd Unsaturated_Poly_esters
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 cleancut 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 maximuir 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.
245
-------
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
.6
j ?
a>
9
10
11
12
13
14
15
Subcategory
Ethylene-Vinyl Acetate Copolymers
Fluorocarbons
Polypropylene fiber
Polyvinylidene Chloride
Acrylic Resins
Cellulose Derivatives
Alky da and Unsatursted Polyester Resins
Cellulose Nitrate
Jolyamides (Hylon 6/1? only)
Polyester Resins (thermoplastic)
Polyvinyl Butyral
Polyvinyl Ethers
Slllcones
Multi-Product Plants
Fluid Product Plant*
Hitrlls Barrier Resin*
Spandex Fibers
__ _
Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Days
0.05 0.10
0.80 1.60
0.04 0.08
No numerical guidelines-see discussion
in footnote.
n n
« ii
0.02 0.03
6.0 11
0.37 0.67
Q. 44 0.80
No numerical guidelines-sea discussion
in footnote
5.5 -0
0.57 1.0
Ho numerical guidelines-see discussion
in footnote.
n "
COD
Maximum Average of Manlmimi for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Days
0.22 0.40
1.4 2.9
0.07 0.14
Ho numerical guidelinea-sae discussion
in footnote
„
00.11 0.20
30 54
1.9 3'*
6.5 12
Ho numerical guidelines-see discussion
in footnote
46 82
4.7 6.5
Ho numerical guidelines-see discussion
In footnote.
Suspended Solids
Maximum Average of Mayimina for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Days
0.04
0.57
0.03
Ho numerical guidelines-see
In footnote
"
0.0 06
1.8
0.11
0.14
No numerical guidelines-see
in footnote
1.7
0.18
Ho numerical guidelines-see
In footnote
0.05
0.83
0.04
discussion
"
0.008
2.7
0.17
0.20
discussion
2.5
0.26
discussion
-------
FOOTNOTES FOR TABLE XI-2
Ethylene-Vlnyl Acetate (EVA) Copolymer. Two of the fiv« 7.
known producers were contacted. All plants are located
at polyethylene production facilities. Water use and
wastewater characteristics for EVA are essentially Iden-
tical to those for low density polyethylene. However,
an emulsion polymerization process is known and produces
a distinctly different waste load which is essentially
that of polyvlnyl acetate emulsion polymerization
reported in EPA WO/1-73/010. Both multi-plant and
municipal sewage treatment is used.
Fluorocarbons. Three of the seven manufacturing plants
were visited. A wide range of products are produced.
Tile most important is polytetrafluorethylene (PTFE) and
these guidelines are recommended for PTFE granular and
fine powder grades only. The wastewater discharges
differ considerably depending upon the process recovery
scheaes for hydrochloric acid and the disposal of selec-
ted streams by deep well, ocean dumping or off-site
contract methods. The use of ethylene glycol in a pro-
cess can significantly affect the waste loads. Fluoride
concentrations in untreated wastewaters are generally
below levels attainable by alkaline precipitation.
Polypropylene Fibers. Two 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 landfllling, etc. Primary treatment at one plant sita
was observed while the other plant discharges to a
municipal sewage system.
Pplyvlnylidene Chloride. The two major manufacturers
were contacted. Both plant sites send uastewjters to
multi-plant treatment plants of which the polyvlnylldene
chloride Is a snail portion. Consequently, there was
insufficient data to develop recommended guidelines.
Acrylic Resins. 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 nulti-plant wastewater treatment facilities
prohibited obtaining sufficient meaningful data to
reccnzzend effluent limitation guidelines.
Cellulose Derivatives. Cellulose derlvates investigated
Included ethyl cellulose, hydroxyethyl cellulose, methyl 12.
cellulose and carboxymethyl cellulose. Wide variations
in unit flow rates for two plants producing the same
product, differences in manufacturing techniques and the
availability of data prevented recommending guidelines.
The vastewjters from the three manufacturers are being
treated in multi-plant wastewater treatment facilities
or will enter municipal sewage systems.
8.
9.
10.
11,
Alkyda and Unsaturated Polyester Resins. Six carefully
selected plants were visited to provide a cross-section
of the Industry for size oi operation, type of manufac-
turing process and vastewjter 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 di£ charges wastewaters Into
municipal sewage systems at-d 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 plants having their
own wastewater treatment system - a very Infrequent
occurrence.
Cellulose Nitrate. The two major manufacturers of the
four manufacturers were cortacted. 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.
Folyaroldes. Various polyamides are produced but only
Nylon 6/12 produces significant amounts of uastewater,
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.
Polyester Thermoplastic Resins. There are three manu-
facturers, two of which produce poly(ethylene, terephtha-
late) in quantities less than 2T of their total thermo-
plastic production. The guidelines are recommended for
poly(ethylene 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.
Polyvlnyl 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 was no
data available. Consequently, the recommended guide-
lines are only for NSPS-BADT when starting with poly-
vinyl alcohol since any other guidelines would be
tantamount to establishing a permit for the production
site.
Polyvinyl ethers. The three present plants use differ-
ent processes each of which produces several grades of
product. The different chemical compositions used in
both bulk and solution polymerization processes and the .
lack of data on both raw and treated vastewaters pre-
vented establishing guidelines. The vastewaters are
presently sent to either multi-plant treatment facilltie
or municipal sewage systems.
13. Slllconea. Four companies manufacture sillcones at five
locations. Three plants were visited and data were
obtained from all plants. The major processing steps at
the five plants are shown below.
Major Processes at Five Slllcone Plants
Plant No. 12345
CH3C1 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, fluorlnated sllicones, coupling
agents, and other materials.
Based on the manufacturing process, the wastewater flows
and the raw waste loads, the plants 1, 2, 3 were desig-
nated as multi-product plants while 4 and 5 were desig-
nated as fluid product plants.' Guideline quantities
based on production rates that were esc in.-, re d
from sales volumes for BPT.
l** Nltrlle Barrier Resins. Commercial scale production and
sale of these resins has not yet begun. The companies
expected to have production facilities were contacted,
and two provided estimates of raw waste loads. Because
of the lack of demonstrated flows and raw waste loads,
It was impossible to establish effluent guideline
limitations.
t»V-Spandex Fibers. Three maciufacturers each'produc.*-
Spandex fibers by significantly different processes.
These are dry, wet and reaction spinning methods. '
Because of limited data on raw 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 and Compounds)
Product
Parameter
kg/kkg (lbs/1000 Ibs of Production)
K)
£*
00
Alkyds and unsaturated
polyester resins
Fluorocarbons
Spandex fibers
Nitrile barrier resins
Polypropylene fibers
Silicones
Multi-product
Fluid-product
Polyester resins
(thermoplastic)
Ke.rcury
Fluorides
Cyanides
Cyanides
Oils and grease
Copper
Copper
Cadmium
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
0.017
0.025
0.0026
0.034
0.050
0.0052
Toxic and hazardous chemicals guidelines to apply
-------
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.
t* Decker, 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. Y
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 General Counsel
Judy Nelson - Office of Planning and Evaluation
Robert Wooten - Region IV
Walter Lee - Region III
Frank Mayhue - Office cf 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
Acknowledgment and appreciation is also given to the secretarial
staffs of both the Effluent Guidelines Division 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 Jan4
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
249
-------
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 Fetroles
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-Gl'idden-Durkee
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.
250
-------
SECTION XIII
REFERENCES
1. "Advanced Wastewater Treatment as Practiced at South
Tahoe," EPA Water Pollution Control Research
Series Report No. 17010 ELP, Washington, D.C.
(August 1971).
2. "An Act to Amend the Federal Water Pollution Control
Act," Public Law 92-500, Ninety-Second Congress,
S.2770 (October 18, 1972).
3. Arthur D. Little, Inc., "Technical Proposal: Effluent
Limitations Guidelines for the Plastics and
Synthetics Industry to the Environmental Protec-
tion Agency," Cambridge, Massachusetts
(November 16, 1S72).
4. Black and Veatch, "Process Design Manual for Phosphorus
Removal," Environmental Protection Agency
Contract 14-12-936, October 1971.
5. Boardman, Harold, "Penton (Chloroethers),« from
Manufacture_of_PlasticsJ_yolJ._lx edited by
W. Mayo Smith, Reinhold Publishing Corporation,
New York, 535-7, 550 (1964).
6. Qhe2}ic|l_lcongmics_HandbooJs, Stanford Research Institute,
Menlo Park, California (1971) .
7. Cgemicai_Engineerina_Flowsheets, Prepared by the editors
of Chemical and Metallurgical Engineering, McGraw-
Hill, New York (1940).
8. Chgmical_Horizgns_File, Predicasts, Cleveland,
Ohio.
9. £hemical_Marketinci ReEorterx "Chemical Profile" Section
from June 26, 1972^throu^h July 23, 1973. Action,
10. Chopey, N. P., ed., "Chlorinated Polyether," Chemical
ISSineerisa 68 (2), 112-115 (January 23, 196lf7
11. Connelly, F. j., "case History of a Polymer Process
Development," Chemical_En3ineerinq Progress
Sinip.osium_Series 60 (49) , 49-57 (1964)".
12. Contract for Development of Data and Recommendations
for Industrial Effluent Limitations Guidelines
and Standards of Performance for the Plastics
and Synthetics Industry, No. 68-01-1500, Issued
Member ' InC" Cambrid9e< Massachusetts
251
-------
13. Conway, R. A., et al. , "Conclusions from Analyzing
Report ' Treatability of Wastewater from Organic
Chemical and Plastics Manufacturing - Experience •
and Concepts'," Unpublished document (January
1973) .
14. Conway, R. A., J. C. Hovious, D. C. Macauley, R. E.
Riemer, A. H. Cheely, K. S. Price, C. T. Lawson,
"Treatability of Wastewater from Organic
Chemical and Plastics Manufacturing - Experience
and Concepts," Prepared by Union Carbide
Corporation, South Charleston, W. Virginia
(February 1973} .
15. Culp, Gordon L. and Robert W. Gulp, Advanced_Wa§te
Treatment , Van Nostrand Reinhold Company,
New York, New York (1971)
1 6 . peveloFment^Documentf or nProppsed_Ef fluent Limitations
Guidglines and New source Performance Standards;
for~the Synthetic^Resins SggmentLof the Plastics
and Synthetic Materials Manufacturing Point
gource_Cat egor y , Report No. EPA~"440/l-73/010 ,
Effluent Guidelines Division, Office of Air and
Water Programs, U.S. EPA, Washington, D.C.
(September 1973) .
T7. Si££££P£Y_2£_£h§]I!i£§i_E£2ducers, Chemical Information
Services, Stanford Research Institute, Menlo
Park, California (1973) .
18. "Directory of the Plastics Industry, 1972-1973,"
special edition of Plastics World 3_0 (11)
(August 1972) .
1 9 . Feder al_Wat er_Pol lut ion_Cont rol_Act_AmejQdments_;of __1 9 T_2 ,
House of Representatives, Report No. 92-1U65,
U.S. Government Printing Office, Washington, D.C.
(September 28, 1972).
20. Forbath, T. P., ed., "For Host of Silicones: One
Versatile Process," Chemical_Enc[ineerinc[ 6U
(12), 228-231 (1957).
21. Galanti, A. V. and Mantell, C. L. , Propropylene _Fibers
and_Films, Plenum Press, New York, New York (1965) .
22. "Integration of Chemical Plant Facilities," Chemical_and
Metallurgical Engineering 52 (9), 129~141
7septeiiiber 1945J".
23. Johnson, R. N. , A. G. Farnham, R. A. Clendinning, W. F.
Hale, C. N. Merriair,, "Poly (aryl Ethers) by
Nucleophilic Aromatic Substitution. I. Synthesis
252
-------
P^rt_Azl (5), 2375-2398 (1967).
24. Jones, R. Vernon, "Newest Thermoplastic - PPS,"
2idrocarbon_Processina 51 (11) , 89-91 (November
1972) .
25. Kirk-Othmer, eds. , EncYclo£edia_of_che_inical_Technoloqy,
2nd Ed., Interscience Division of John Wiley and
Sons, New York, New York (1963-1971).
26. Labine, R. A., ed.r "Flexible Process Makes Silicone
Rubber," Chenucal_Ensineerina 67 (14), 102-105
(1960) .
27. Lee, H., D. Stoffey, K. Neville, New Linear Polymers.
NcGraw-Hill, New York (1967) . --
28. "Making Polycarbonates: A First Look," Chemical
Enaineering 67 (23) , 174-177 (1960) .
29. Mark, H., ed. , Ency.clo£edia_of_Poly.mer_Science and
Technol02Y, Interscience Division of John Wiley
and Sons, New York, New York (1964-1972) .
30. Modern_Plastics_EncycloEedia, McGraw-Hill, New York
New York (1973-1974) .
31. Monsanto Flow Sheet, Chemical Engineering, 346-349
(February 1954) . ----
32. Mudrack, Klaus, "Nitro-Cellulose Industrial Waste,"
P£2Ci_of_the_21st_lndustrial_Waste_Conference
^a^-^A_lx_§nd_5i_ 19 6 6 , Engineer ing~Extension
Series No. 121, Purdue University, Lafayette,
Indiana.
33. "National Pollutant Discharge Elimination System, Proposed
Forms and Guidelines for Acquisition of Information
From Owners and Operators of Point Sources »
|ed§£|l_Re3ister 37 (234) , 25898-25906 (December
->, 1 972) .
34. "Parylene Conformal Coatings," brochure prepared by
Union Carbide Corporation, New York, New York.
35. Paterson, James W. and Roger A. Minear, Wastewater Treat-
ment .Technology, 2nd Ed., January 1973, fo7~thi --------
State of Illinois Institute for Environmental
Quality.
36. "Polycarbonates - General Electric Company," Hydro-
car bon_Proc ess ing , p. 262 (November 1965) . ----
37" "^°cedures/ Actions and Rationale for Establishing
Effluent Levels and Compiling Effluent Limitation
253
-------
Guidance for the Plastic Materials and Synthetics
Industries," Unpublished report of the Environmental
Protection Agency and the Manufacturing Chemists
Association, Washington, B.C. (November 1972).
38. "Proposed Environmental Protection Agency Regulations
on Toxic Pollutant Standards," 38 FR 35388,
Federal^Register, December 27, 1973.
39. shumaker, T. P., "Granular Carbon Process Removes 99.0
to 99.2% Phenols," Chemical Processing (May 1973) .
40. Sittig, M . , Or g an i c_C hemic al_Pr oc e s s_Ency.c lop.edi a ,
2nd Edition, Noyes Development Corp., Park
Ridge, New Jersey (1969) .
41. supplement to this report, Detailed Record of Data Base.
42. "Supplement B - Detailed Record of Data Base," Develop-
ment J^ument_f^_Pr£^seJ_EfJluent_I^itay^n£
^idelajies_and_Ne\^Source_Performance_Standards
______
Ind_i£nthetic Materials_Manufacturing_Point
Source_Catigory,, Report No. EPA 440/1-73/010,
Effluent Guidelines Division, Office of Air and
Water Programs, U.S. EPA, Washington, D.C.
(September 1973) .
43. Textile Organ, Textile Economics Bureau, Inc., New
YorkT New York.
44. U.S. Patent 2,964,509 (December 13, 1960), D. M. Hurt
(to DuPont) .
45. U.S. Patent 2,994,668 (August 1, 1961), Eugene D. Klug
(to Hercules Powder Company) .
46. U.S. Patent 3,144,432 (August 11, 1964), Daniel W.
Fox (to General Electric Company) .
47. U.S. Patent 3,354,129 (November 21, 1967), James T.
Edmonds, Jr., and Harold Wayne Hill, Jr. (to
Phillips Petroleum Company) .
48. U.S. Patent 3,426,102 (February 4, 1969), T. A. Solak
and J. T. Duke (to Standard Oil Company) .
49. Weaver, D. Gray, ed. , and O'Connors, Ralph J., "Manu-
facture of Basic Silicone Products," Modern
Chemical_Processe§, 6, 7-11 (1961) .
254
-------
SECTION XIV
GLOSSARY
Refers to that portion of a molecular structure which is derived
from acetic acid.
Additign_Polyjneri z at ion
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.
Alky.1
A general term for monovalent aliphatic hydrocarbons.
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.
Annealincj
A • process to reduce strains in a plastic by heating and
subsequent cooling.
AryJ.
A general term denoting the presence of unsaturated ring
structures in the molecular structure of hydrocarbons.
A polymer in which the side chain groups are randomly distributed
en one side or the other of the polymer chain. (An atactic
polymer can be molded at much lower temperatures and is more
255
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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.
Azeotrpjoe
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.
Backer io_st at
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.
BOD5
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 Viater 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.
Chain Terminator
An agent which, when added to the ccirponents 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 EOD5.)
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The polymer obtained when two or more monomers are involved in
the polymerization reaction.
Crggs-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.
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 dzffusion through semipermeable membranes.
2i§t=.2!2.§c
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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 fcr stretching.
GPD
Gallons per day.
GPM
Gallons per minute.
Halogen
The chemical group containing chlorine, fluorine, bromine,
iodine.
Isotactic_Politner
A polymer in which the side chain groups are all located on 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.
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
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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.
El
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.
Phenol
Class of cyclic organic derivatives with the basic chemical
formula C6H50H.
A chemical added to polymers tc impart flexibility, workability
or distensibility.
Poly_mer
A high molecular weight organic compound, natural or synthetic,
whose structure can be represented by a repeated small unit
(MER) .
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.
Quenchincj
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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.
Scrubber
Equipment for removing condensable vapors and particulates from
gas streams by contacting with water or other liquid.
Second ary,_Treatment
Removal of biologically active soluble substances by the growth
of microorganisms.
Slurry
Solid particles dispersed in a liquid medium.
Spj.nnerette
A type of extrusion die consisting of a metal plate with many
small holes through which a mclten plastic resin is forced to
make fibers and filaments.
Stable
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
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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.
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 cf staple.
JJIa n sester if icati on
A reaction in which one ester is converted into another.
Vacuum
A condition where the pressure is less than atmospheric.
Ziealer-Natta_Catal^st
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.
261
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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 lb
million gallons/day mgd
mile mi
pound/square
inch (gauge) psig
square feet sq ft
square inches sq in
ton (short) ton
yard yd
0.405
1233.5
0.252
ha
cu m
kg cal
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
,785
1.609
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
(0.06805 psig +1)* atm
0.0929 sq m
6.452 sq cm
0.907 kkg
0.9144 m
hectares
cubic meters
kilogram - calories
kilogram calories/kilogra
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 kilograt
meter
* Actual conversion, not a multiplier
262
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Protection Agency
TT C TT1— •«• n -d /•> n TTT '! ' L (i J- •*• A -
U . O .
st'eet, Boom 16*0
60604
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