EPA
Development Document for Effluent Limitations Guidelines
and New Source Performance Standards for the
SYNTHETIC RESINS
Segment of the Plastics and
Synthetic Materials Manufacturing
Point Source Category
MARCH 1974
$ f\ ro U.S. ENVIRONMENTAL PROTECTION AGENCY
^ _ ^^ ^ ^ j _ X
Washingto.1, D.C. 20460
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DEVELOPMENT DOCUMENT
for
EFFLUENT LIMITATIONS GUIDELINES
and
NEW SOURCE PERFORMANCE STANDARDS
for the
SYNTHETIC RESINS SEGMENT OF THE
PLASTICS AND SYNTHETIC MATERIALS MANUFACTURING
POINT SOURCE CATEGORY
Russell E. Train
Administrator
Roger Strelow
Acting Assistant Administrator for Air & Water Programs
Allen Cywin
Director, Effluent Guidelines Division
David L. Becker
Project Officer
March, 1974
tffluent Guidelines Division
Office of Air and Water Programs
U.S. Environmental Protection Agency
Washington, D.C. 20460
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ABSTRACT
This development document presents the findings of an extensive
study of the synthetic resin segment of the Plastics and
Synthetics Industry for the purposes of developing effluent
limitation 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:
ABS/SAN Nylon 66
Acrylics Polyester
Cellophane Polypropylene
Cellulose Acetate Polystyrene
High-Density Polyethylene Polyvinyl Acetate
Low-Density Polyethylene Polyvinyl Chloride
Nylon 6 Rayon
Effluent limitation guidelines contained herein set forth the
degree of reduction of pollutants in effluents that is attainable
through the application of best practicable control technology
currently available (BPCTCA), and the degree of reduction
attainable through the application of best available technology
economically achievable (BATEA) by existing point sources for
July 1, 1977, and July 1, 1983, respectively. Standards of
performance for new sources are based on the application of best
available demonstrated technology (BADT).
Annual costs for this segment of the plastics and synthetics
industry for achieving BPCTCA control by 1977 are estimated at
$66,000,000, and costs for attaining BATEA control by 1983 are
estimated at $192,000,000. The cost for BADT for new sources is
estimated at $35,000,000.
Supporting data and rationale for the development of proposed
effluent limitation guidelines and standards of performance are
contained in this development document.
111
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CONTENTS
Section Page
I Conclusions 1
II Recommendations 3
III Introduction 11
Purpose and Authority 11
Methodology 12
General Decription of the Industry 13
Plastics 13
Synthetic Fibers 16
Cellophane 18
Product and Process Technology 18
Typical Polymerization Products 18
Emulsion and Suspension Polymerization 18
Atmospheric or Low-Pressure Mass 22
Polymerization
High-Pressure Mass Polymerization-Low 25
Density Polyethylene
Polyolefins - Solution Polymerization 27
Polyolefins - Ziegler Process 29
Polyolefins - Particle Form Process 29
Polyacetal Resins 31
Cellophane 33
Rayon 34
Pol ester Resin and Fiber 39
Nylon 66 Resin and Fibers 44
Cellulose Acetate Resin 46
Cellulose Acetate Fibers 48
Cellulose Triacetate Fibers bO
Epoxy Resins 50
Phenolic Resins 54
Ami no Resins - Urea and Mel amine 63
Acrylic Fibers 70
Nylon 6 Resins and Hbers 72
IV Industry Categorization 79
V Waste Characterization 83
Raw Waste Loads 83
VI Selection of Pollutant Parameters 87
Selection Criteria 87
Selected Parameters 87
BOD5 87
COD 88
Total Suspended Solids 86
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pH Acidity, and Alkalinity 8.9
Zinc 90
Phenols 91
Chromium 92
Nitrogeneous Compounds 92
Dissolved Solids 93
Toxi and Hazardous Chemicals 94
Iron, Alluminum, Nickel, Vanadium, 95
Titanium, and Molybdenum
Uil and Grease, Color, Turbidity, 95
Phosphates, Sulfides, Copper,
Cadmium, Manganese, Magnesium, Antimony
VII Control and Treatment Technology 97
Presently Used Wastewater Treatment 97
Treatment Potentially Usable Wastewater 110
Technology
Adsorption 112
Suspended Solids Removal 118
Chemical Precipitation 118
Anaerobic Process 119
Air Stripping 119
Chemical Oxidation 120
Foam Separation 120
Algae Systems 120
Incineration 121
Liquid-Liquid Extraction 121
Ion Exchange 122
Reverse Osmosis 122
Freeze Thaw 122
Evaporation 123
Electrodialysis 123
In-Plant Control of Waterborne Pollutants 123
Operational Philosophy 127
Organization 127
Specific Measures 127
Procedures and Operating Methods for 129
Elimination or Reduction of Pollutants
VIII Cost, Energy and Non-Water Quality Aspects 133
Alternative Treatment Technologies 132
Costs of Treatment Technology Now in 13r
Practice
Cost of advanced Treatment Technologies 139
Non-Water Quality Aspects of Alternate 143
Treatment Technologies
Disposal of Solids and Slurries 143
Generation of Comrnerlcally-Valuable 147
By-Products
Disposal of Off-Specification and 152
Scrap Products
Other Non-Water Quality Pollution Problems 152
Industry Cost Perspectives 152
Water Effluent Treatment Costs 154
vi
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Industrial Waste Treatment Model Data 157
IX Best Practicable Control Technology Cur-
rently Available Guidelines and Limitations
Definition of Best Practicable Contol 199
Technology Currently Available (BPCTCA)
The Guidelines 200
Attainable Effluent Concentrations 200
Demonstrated Wastewater Flows 202
Statitcal Variability of a Properly 203
Designed and Operated Waste Treatment
Plant
X Best Available Technology Economically 209
Achievable
Definition of Best Available Technology 209
Economically Achievable (BATEA)
The Guidelines 2iC
Achievable Effluent Concentrations 210
Suspended Solids 210
Oxygen Demanding Substances 210
Waste Load Reduction Basis 212
Variability 212
XI New Source Performance Standards - Best 215
Available Demonstrated Technology
Definition of New Source Performance 215
Standards - Best Available Demonstrated 215
Technology (NSPS-BADT)
The Standards
Achievable Effluent Concentrations 215
Waste Load Reduction Basis 215
Variability 215
XII Acknowledgments 225
XIII References 227
XIV Glossary 233
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FIGURES
Number Title Page
1 Typical Polymerization Reactions for
Polyethylene, Polypropylene, Polyvinyl acetate, 19
Polyvinyl chloride, Polyslyrene
2 Typical Polymerization Reactions for 20
Polyacrylonitrite and Polybutadiene
3 Typical Polymerization Reaction for Polyacetol 21
Resins
4 Emulsion Polymerization 23
5 Mass Polymerization 24
6 Low-Density Polyethylene Production - High 26
Pressure Process
7 Polyolefin Production - Solution Process 28
8 Polyolefin Production - Ziegler Process 30
9 Polyolefin Production - Particle Form Process 32
10 Cellophane Production 35
11 Viscose Rayon Production 37
12 Typical Polymerization Reaction for Polyester 41
Resins and Fiber
13 Polyester Fiber and Resin Production 43
14 Typical Polymerization Reaction for Nylon 66 45
Resins and Fiber
15 Nylon 66 Production 47
16 Cellulose Acetate Resin Production 49
17 Cellulose Acetate Fiber Production 51
18 Reactions Between Epichlorohydrin and Bisphenol 53
Bisphenol A
19 Liquid Epoxy Resin Production 55
20 Solid Epoxy Resin Production . 56
IX
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Number Title Page
21 Typical Reaction to Form One-Step Resins or 58
Resols
22 Typical Reaction to Form Novolak Resin 60
23 Phenolic Resin Production 61
24 Typical Polymerization Reaction for Urea and 64
Formaldehyde
25 Typical Polymerization Reactions for Melamine 67
and Formaldehyde
26 Amino Formaldehyde Resin Production 69
27 Acrylic Fiber Production - Wet Spinning 72
28 Acrylic Fiber Production - Dry Spinning 75
29 Typical Polymerization Reactions to Form 76
Nylon 6 Resin and Fiber
30 Nylon 6 Production 77
31 BOD Removal as Function of Total System 101
Residence Time
32 COD Removal as Function of Total System 103
Residence Time
33 Biological Treatment in Plastics and 137
Synthetics Industry - Capital Costs
34 Biological Treatment in the Plastics 133
and Synthetics Industry - Operating Costs
35 Biological Treatment in the Plastics and
Synthetics Industry - Energy Requirements -
Initial Treatment
36 Biological Treatment in the Plastics and
Synthetics Industry - Energy Requirements -
Aeration and Sludge Handling Equipment
37 Granular Media Filtration for the Plastics 142
and Synthetics Industry - Capital Investment
38 Activated Carbon Adsorption for the Plastics
and Synthetics Industry - Capital Investment
39 Activated Carbon Adsorption for the Plastics
and Synthetics Industry - Operating Costs
40 Net Cost of Recovering Dilute Wash Solutions
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Number Title Page
1 Best Practicable Control Technology Currently 5
Available Effluent Limitation Guidelines
2 Best Practicable Control Technology Currently 6
Available Effluent Guidelines for Other Elements
3 Best Available Technology Economically 7
Achievable Effluent Limitation Guidelines
4 Best Available Technology Economically g
Achievable Effluent Guidelines for Other Elements
or Compounds
5 Best Available Demonstrated Technology for New 9
Sources Performance Standards
6 Best Available Demonstrated Technology for New 10
Source Performance Standards for Other Elements
or Compounds
7 1972 Consumption of Plastics and Synthetics 15
8 Major Resin Producers 16
9 Synthetic Fiber Producers 17
10 Capacity 17
11 Markets for Amino Resins 66
12 Performance of Observed Waste Water Treatment gr
Plants
82
13 Industry Subcategorization
14 Wastewater Loading for the Plastics and fi4
Synthetics Industry
15 Plastics and Synthetics Industry Raw Waste Loads or-
CS D
16 Other Elements, Compounds and Parameters 86
17 Other Elements and Compounds Specific to Plastics 96
and Synthetics Products
18 Performance of Observed Waste Water Treatment 99
Plants
19 Operational Parameters of Wastewater Treatment 105
Plants (Metric Units)
XI
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Number Title Page
20 Operational Parameters of Wastewater Treatment 106
Plants (English Units)
21 Observed Treatment and Average Effluent ill
Loading From Plant Inspections
22 Summary of Industrial Sources Using Granular 113
Activated Carbon Systems
22a Summary of EPA Research Development and Demon- 114-117
stration projects utilizing Activated Carbon
Technology
23 Matrix for Evaluating Liquid Handling Facilities 125
24 Perspectives on the Plastics and Synthetics 134
Industry - Water Usage
25 Typical Stream Compositions 150
26 By-Product Credit Value for Break-Even Stream 150
27 Operating Cost Per 1000 Ibs (4536 kg) H20 151
Recycled
28 Perspectives on the Plastics and Synthetics 155
Industry - Treatment Costs
29 Perspectives on the Plastics an.d Synthetics 156
Industry - Cost Impact
30 Summary of Water Effluent Treatment Costs for 158-159
Representative Plants in the Plastics and
Synthetics Industry
30-1 Water Effluent Treatment Cost - Plastics 160
and Synthetics Industry - Expoxies (small)
30-2 Water Effluent Treatment Costs - Plastics 161
and Synthetics Industry - Epoxies (large)
30-3 Water Effluent Treatment Costs - Plastics 162
and Synthetics Industry - Melamine (Small)
30-4 Water Effluent Treatment Costs - Plastics 163
and Synthetics Industry - Melamine (large)
30-5 Water Effluent Treatment Costs - Plastics 164
and Synthetics Industry - Urea (small)
30-6 Water Effluent Treatment Costs Plastics 165
and Synthetics Industry - Urea (large)
30-7 Water Effluent Treatment costs - Plastics 166
and Synthetics Industry - Phenolics (small)
xii
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Number Title Page
30-8 Water Effluent Treatment Costs - Plastics 167
and Synthetics Industry - Phenolics (large)
30-9 Water Effluent Treatment Costs - Plastics 163
and Synthetics Industry - Polyvinyl Chloride
(small)
30-10 Water Effluent Treatment Costs - Plastics 169
and Synthetics Industry - Polyvinyl Chloride
(large)
30-11 Water Effluent Treatment Costs - Plastics 170
and Synthetics Industry - ABS/SAN (small)
30-12 Water Effluent Treatment Costs - Plastics 171
and Synthetics Industry - ABS/SAN (large)
30-13 Water Effluent Treatment Costs - Plastics 172
and Synthetics Industry - Polystyrene (small)
30-14 Water Effluent Treatment Costs - Plastics 173
and Synthetics Industry - Polystyrene (large)
30-15 Water Effluent Treatment Costs - Plastics 174
and Synthetics Industry - Polyvinyl Acetate
(large)
30-16 Water Effluent Treatment Costs - Plastics 175
and Synthetics Industry - Polyvinyl Acetate
(large)
30-17 Water Effluent Treatment Costs - Plastics 176
and Synthetics Industry - Low Density
Polyethylene (small)
30-18 Water Effluent Treatment Costs - Plastics 177
and Synthetics Industry - Low Density Poly-
ethylene (large)
30-19 Water Effluent Treatment Costs - Plastics
and Synthetics Industry - High Density
Polyethylene (small)
30-20 Water Effluent Treatment Costs - Plastics
and Synthetics Industry - High Density
Polyethylene (large)
30-21 Water Effluent Treatment Costs - Plastics
and Synthetics Industry - Polypropylene (small)
30-22 Water Effluent Treatment Costs - Plastics lgl
and Synthetics Industry - Polypropylene (.large)
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Number Title Page
30-23 Water Effluent Treatment Costs - Plastics 182
and Synthetics Industry - Acrylics (small)
30-24 Water Effluent Treatment Costs - Plastics 183
and Synthetics Industry - Acrylics (medium)
30-25 Water Effluent Treatment Costs - Plastics 184
and Synthetics Industry - Acrylics (large)
30-26 Water Effluent Treatment Costs - Plastics
and Synthetics Industry - Polyester (small)
30-27 Water Effluent Treatment Costs - Plastics 186
and Synthetics Industry - Polyester (large)
30-28 Water Effluent Treatment Costs - Plastics 187
and Synthetics Industry - Nylon 6 (small)
30-29 Water Effluent Treatment Costs - Plastics 188
and Synthetics Industry - Nylon 6 (large)
30-30 Water Effluent Treatment Costs - Plastics I8g
and Synthetics Industry - Nylon 66 (small)
30-31 Water Effluent Treatment Costs - Plastics
and Synthetics Industry - Nylon 66 (large)
30-32 Water Effluent Treatment Costs - Plastics
and Synthetics Industry - Cellophane
30-33 Water Effluent Treatment Costs - Plastics -JQ2
and Synthetics Industry - Cellulose Acetate
30-34 Water Effluent Treatment Costs - Plastics
and Synthetics Industry - Rayon
31 Industrial Waste Treatment Model Data - ,_.
Plastics and Synthetics Industry (Product
Group #1)
32 Industrial Waste Treatment Model Data - ,qc.
Plastics and Synthetics Industry (Product
Group #2)
33 Industrial Waste Treatment Model Data - nq_
Plastics and Synthetics Industry (Product
Group #3)
34 Industrial Waste Treatment Model Data -
Plastics and Synthetics Industry (Product
Group #4)
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Number Ti tle Page
35 Industrial Waste Treatment Model Data - 198
Plastics and Synthetics Industry (Product
Group #5)
36 COD/BOD Ratios in Effluent Streams 2Q1
37 COD/BOD Guidelines Basis 202
38 Demonstrated Wastewater Flows 204
39 Demonstrated Variability 20>5
40 Variability Factor 20(6
40A Suspended Solids Removal 207
40B Variability Factors BATEA 212
40C Lowest Demonstrated Wastewater Flows 216
41 Best Practicable Control Technology 218
Currently Available Effluent Limitation
Guidelines
42 Best Practicable Control Technology Currently 219
Available Effluent Guidelines for other
Elements
43 Best Available Technology Economically "220
Achievable Effluent Limitation Guidelines
44 Best Available Technology Economically 221
Achievable Effluent Guidelines for Other
Elements or Compounds
45 Best Available Demonstrated Technology for 222
New Source Performance Standards
46 Best Available Demonstrated Technology for 223
New Source Performance Standards for Other
Elements or Compounds
47 Metric Units Conversion Table 238
xv
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SECTION I
CONCLUSIONS
In this survey of the plastics and synthetics industry,
approximately 280 company operations are involved in the
seventeen larger-volume product subcategories. The 1972
production for these products was estimated at 12 million kkg (26
billion pounds) per year. The 1972 water usage was estimated to
be 1035 thousand cubic meters per day (275 MGD). Water usage (at
current hydraulic loads) was projected to increase at 6.7 percent
per year through 1977, while production was projected to increase
at 10 percent per year 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 BODj> 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/1 (low attainable BOD5
concentration), from 30 to 75 mg/1 (medium attainable BOD5
concentration), and over 75 mg/1 (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 (5 products: polyvinyl chloride,
polyvinyl acetate, polystyrene, polyethylene, and
polypropylene) .
Majog Subcategory II - high waste load, low attainable BOD5
concentration (3 products: ABS/SAN, cellophane,
and rayon) .
Major Subcategory III - high waste load, medium attainable BOD5
concentration treatability (H products: polyesters.
Nylon 66, Nylon 6 and cellulose acetates.
Malor Subcategory IV - high waste load, low treatability (1
product: acrylics) .
Additional subcategorization within the above four 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 limitation guidelines and standards of performance
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by providing clear and unambiguous direction as to the proper
standard applicable to that product. The substantial advantage
of clarity appears to outweigh any technical advantages of
product grouping. Hence, for these reasons the individual
product subcategories are used for the application of effluent
limitation guidelines and standards of performance in this
category.
Annual costs of treatment for this segment of the plastics and
synthetics industry in 1972 were roughly estimated at $25
million. By 1977, under BPCTCA guidelines, these same plants in
seventeen product subcategories were estimated to expect annual
costs for pollution control of $66 million - an increase of 21
percent per year. By 1983, under BATEA guidelines, existing
plants would be expected to have annual costs for pollution
control of $192 million - an increase of 19 percent per year
between 1977 and 1983. By 1977, under BADT-NSPS and estimated
product growth, the annual costs for new plants is estimated at
$35 million. The estimated average costs of treatment over the
industry for BPCTCA, BATEA, and BADT-NSPS technologies
respectively were: $0.19 ($0.73), $0.56 ($2.11), and $0.27
($1.02) per cubic meter (per thousand gallons).
On average for BPCTCA the costs for the smaller plants with
higher water usage were 3.5 times higher than the larger plant in
each subcategory. The average range for the smaller plants was
0.7 percent to 2.8 percent of sales price. On average for BATEA
the costs for the smaller plants with higher water usage were 3.9
times higher than the larger plants in the industry. The average
range of costs for applying BATEA to existing plants was 2.1 to
8.1 percent of sales price. The cost of NSPS was estimated at
0.9 percent of sales price over the broad industry.
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SECTION II
RECOMMENDATIONS
BOD5, COD and suspended solids are the critical constituents
requiring guidelines and standards. Other constituents are even
more specific to the product subcategory, and are sumarized
below.
Subcategory Other Element or Compound
ABS/SAN Iron
Aluminum
Nickel
Total Chromium
Organic Nitrogen
POLYSTYRENE Iron
Aluminum
Nickel
Total Chromium
POLYPROPYLENE Vanadium
Titanium
Aluminum
HI-DENSITY POLYETHYLENE Titanium
Aluminum
Vanadium
Molybdenum
Total Chromium
CELLOPHANE Dissolved Solids
RAYON Zinc
Dissolved Solids
NYLON 6 and 66 Organic Nitrogen
ACRYLICS Phenolic Compounds
Effluent limitations guidelines and standards of performance are
proposed for total chromium, phenolic compounds, and zinc for the
specified product. The additional pollutant parameters of
dissolved solids, organic nitrogen, iron, nickel, aluminum,
vanadium, titanium and molybedenum were selected because they are
known to be used in the processes or to occur in the waste waters
of specific product subcategories. However, insufficient data
was available on raw waste loads or treated waste waters to
permit proposing guidelines and standards at this time. In most
cases where metals are used, biological treatment systems reduce
or remove them to low concentration levels. Receiving water
quality standards should determine if limitations are necessary.
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 BOD 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 sub-
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sequent treatment typified by clarification and polishing
processes for additional BOD and suspended solids removal and
dephenolizing units for phenolic compound removal when needed.
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.
Best available technology economically achievable (BATEA) for
existing point sources is based on the best in-plant practices of
the industry which minimize the volume of waste generating water
as typified by segregation of contact process waters from
noncontact waste water, maximum waste water recycle and reuse,
elimination of once through barometric condensers, control of
leaks, good housekeeping practices, and end-of-pipe technology,
for the further removal of suspended solids and other elements
typified by media filtration, chemical treatment, etc., and
further COD removal as typified by the application of adsorption
processes such as activated carbon and adsorptive floes, and
incineration for the treatment of highly concentrated small
volume wastes and additional biological treatment for further
BOD5 removal when needed.
Best available demonstrated technology (BADT) for new source
performance standards (NSPS) are based on BPCTCA and the maximum
possible reduction of process waste water generation and the
application of media filtration and chemical treatment for
additional suspended solids and other element removal and
additional biological treatment for further BODj> removal as
needed.
The levels of technology defined above as BPCTCA, BATEA, and
BADT-NSPS are correlated to effluent limitation guidelines and
standards of performance in the following tables. The tables are
based on attainable effluent concentration by the application of
BPCTCA, BATEA and BADT as defined above, demonstrated process
waste water flowrates, and consideration for the normal
variations which occur in properly designed and operated
treatment facilities.
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TABLE NO. 1
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
EFFLUENT LIMITATIONS GUIDELINES
Subcategory
kg/kkg (lb/1000 Ib of production)
BOD_5
Maximum Average Maximum
of daily values for any
for any period one day
of thirty
consecutive days
Polyvinyl chloride
Suspension
Emulsion
Bulk
Polyvinyl Acetate
Polystyrene
Suspension
Bulk
Polypropylene
Polyethylene
Low Density
High Density Solvent
High Density Polyform
Cellophane
Rayon
ABS/SAN
Polyester
Resin
Fiber
Resin and Fiber Continuous
Resin and Fiber Batch
Nylon 66
Resin
Fiber
Resin and Fiber
Nylon 6
Resin
Fiber
Resin and Fiber
Cellulose Acetate
Resin
Fiber
Resin and Fiber
Acrylics
0.36
0.13
0.06
0.20
0.22
0.04
0.42
0.20
0.30
0.052
8.7
4.8
0.63
0.78
0.78
0.78
1.56
0.66
0.58
1.24
3.71
1.90
5.61
4.13
4.13
8.26
2.75
.70
.26
.12
.39
.43
.08
.81
.39
.53
.10
17.8
10
1.30
1.4
1.4
1.4
2.8
1.20
1.1
2.3
6.8
3.5
10.3
7.5
7.5
15.0
5.00
COD
Maximum Average Maximum
of daily values for any
for any period one day
of thirty
consecutive days
3.6
1.3
0.60
2.0
2.2
0.40
2.1
2.0
3.0
0.52
87
72
6.3
11.7
11.7
11.7
23.4
3.3
3.0
6.2
37.1
19
56.1
41.
41.
7.0
2.6
1.2
3.9
4.30
.80
4.10
3.9
5.8
1.0
178
150
13.0
21.5
21.5
21.5
43.00
6.0
5.3
11.3
68.
35.
82.6
13.8
103.1
75.1
75,1
150.1
25.0
SS
Maximum Average Maximum
of daily values for any
for any period one day
of thirty
consecutive days
0.99 1.8
0.36 .65
0.16 .29
0.55 1.00
0.61 1.1
0.11 .20
1.16 2.11
0.55
0.83
0.14
16
8.8
1.16
0.52
0.52
0.52
1.04
0.44
0.39
0.83
1.00
1.51
.25
29.10
16.0
2.1
.95
.95
.95
1.90
.80
. <70
1.52
2.48 4.51
1.27 2.31
3.75 6.81
2.75 5.0
2.75 5.0
5.5 10.0
1.1 2.0
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TABLE NO.2
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
EFFLUENT LIMITATIONS GUIDELINES
kg/kkg (lb/1000 Ib of production)
Product
Parameter
Polystyrene suspension
High Density Polyethylene Solvent
ABS/SAN
Rayon
Acrylics
Total Chromium
Total Chromium
Total Chromium
Zinc
Phenolic Cmpds
Maximum Average
of daily values
for any period
of thirty
consecutive days
0.0023
0.0031
0.0044
0.534
0.0083
Maximum
for any
one day
0.0046
0.0062
0.0088
0.91
0.017
vo
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Subcategory
TABLE NO. 3
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
EFFLUENT LIMITATION GUIDELINES
kg/kkg (lb/1000 Ib of production)
BOD5_
Maximum Average Maximum
of daily values for any
for any period one day
of thirty
consecutive days
Polyvinyl chloride
Suspension 0.28
Emulsion 0.13
Bulk 0.06
Polyvinyl Acetate 0.19
Polystyrene
Suspension 0,22
Bulk 0.040
Polypropylene 0.32
Polyethylene
Low Density 0.19
High Density Solvent 0.30
High Density Polyform 0.052
Cellophane 5.1
Rayon 2.8
ABS/SAN .45
Polyester
Resin .44
Fiber .44
Resin and Fiber Continuous .34
Resin and Fiber Batch .87
Nylon 66
Resin .37
Fiber .32
Resin and Fiber .69
Nylon 6
Resin 1.8
Fiber .92
Resin and Fiber 2.7
Cellulose Acetate
Resin 1.7
Fiber 1.7
Resin and Fiber 3.4
Acrylics .§9
0.41
0.20
0.09
0.29
0.33
0.06
0.48
0.29
0.45
0.078
7.9
4.4
.70
.59
.59
.47
1.20
.5
.44
.94
2.45
1.25
3.7
2.35
2.35
4.7
1.2
COD
Maximum Average
of daily values
for any period
of thirty
consecutive days
1.28
0.61
0.28
0.89
1.03
0.19
2.14
1.65
1.60
0.28
43.9
24.4
3.3
2.3
2.3
1.8
4.5
1.9
1.7
3.6
9.3
4.8
14.1
8.9
17.8
4.7
Maximum
for any
one day
1.92
0.92
0.42
1.33
1.55
0.29
3.21
2.48
2.40
0.42
68.3
37.9
5.1
3.1
3.1
2.4
6.2
2.6
2.3
4.9
12
6
19
12.2
12.2
24.4
6.3
SS
Maximum Average Maximum
of daily values for any
for any period one day
of thirty
consecutive days
0.19 0.23
0.092 0.11
0.042 O.p5
0.14 0.16
0.16 0.18
0.028 0.033
0.23 0.27
0.14 0.16
0.21 0.25
0.037 0.043
3.19 3.75
1.77 2.08
0.28 0.33
0.13 0.16
0.13 0.16
0.11 0.13
0.27 0.32
0.11 0.13
0.10 0.12
0.21 0.25
0.55 0.65
0.28 0.33
0.84 0.98
0.53 0.63
0.53 0.63
1.06 1.26
0.27 0.33
-------
TABLE NO. 4
BEST AVAILABLE TECHNON06Y ECONOMICALLY ACHIEVABLE
EFFLUENT LIMITATIONS GUIDELINES
kg/kkg (lb/1000 Ib of production)
Product
Parameter
Polystyrene suspension Total Chromium
High Density Polyethylene Solvent Total Chromium
ABS/SAN Total Chromium
Rayon Zinc
Acrylics Phenolic Cmpds
Maximum Average
of daily values
for any period
of thirty
consecutive days
0.0023
0.0031
0.0042
0.105
0.0016
Maximum
for any
one day
0.0046
0.0062
0.0084
0.210
0.0032
00
-------
TABLE NO. 5
BEST AVAILABLE DEMONSTRATED TECHNOLOGY FOR
NEW SOURCE PERFORMANCE STANDARDS
kg/kkg (lb/1000 Ib of production)
BODS
Subcategory
Polyvinyl chloride
Suspension
Emulsion
Bulk
Polyvinyl Acetate
Polystyrene
Suspension
Bulk
Polypropylene
Polyethylene
Low Density
High Density Solvent
High Density Polyfoxm
Cellophane
Rayon
ABS/SAN
Polyester
Resin
Fiber
Resin and Fiber Continous
Resin and Fiber Batch
Nylon 66
Resin
Fiber
Resin and Fiber
Nylon 6
Resin
Fiber
Resin and Fiber
Cellulose Acetate
Resin
Fiber
Resin and Fiber
Acrylics
MnTlnnnn Average
of daily values
for any period
of thirty
consecutive days
0.19
0.13
0.06
0.18
0.22
0.04
0.22
0.18
0.30
0.054
3.6
2.02
.43
.44
.44
.25
.87
.37
.32
.69
1.51
.78
2.29
1.15
1.15
2.29
»Maximum
for any
one day
0.37
0.26
0.12
0.35
0.43
0.08
0.43
0.35
0.58
0.10
.41
.17
.88
7.
4.
.79
.79
.46
1.58
.67
.58
1.25
75
42
4.17
2.08
2.08
4.17
1.58
COD
Maximum Average Maximum
of daily values for any
for any period one day
of thirty
consecutive days
0.89 1.70
0.61 1.20
0.28 .54
0.84 1.60
1.03 2.00
0.19 0.37
1.47 2.9
1.80 3.47
1.60 3.10
0.28 .54
48 98
47 97
3.1 6.5
4.0 7.3
4.0 7.3
2.32 4.2
8.0 14.6
2.6 4.8
2.3 4.2
4.95 9.0
15.7 28.6
8.1 14.7
23.9 43.4
11 20
11 20
22 40
16.7 30.4
SS
Maximum Average
of daily values
for any period
of thirty
consecutive days
0.13
0.092
0.042
0.13
0.16
0.028
0.16
0.13
0.21
0.036
27
28
0.27
0.13
0.13
0.078
0.27
0.11
0.10
0.21
0.47
0.24
0.71
0.35
0.35
0.71
0.27
Maximum
for any
one day
.19
.14
.06
.19
.24
.04
.24
.19
.31
.05
3.3
1.92
.40
.19
.19
.12
0.40
.16
.15
.31
.69
.35
1.1
.51
1.1
0.40
-------
TABLE NO. 6
BEST AVAILABLE DEMONSTRATED TECHNOLOGY FOR
NEW SOURCE PERFORMANCE STANDARDS
Product
Parameter
Polystyrene suspension
High Density Polyethylene Solvent
ABS/SAN
Rayon
Acrylics
Total Chromium
Total Chromium
Total Chromium
Zinc
Phenolic Cmpds
kg/kkg (lb/1000 Ib of production)
Maximum Average
of daily values
for any period
of thirty
consecutive days
0.0023
0.0031
0.0040
0.075
0.0016
Maximum
for any
one day
0.0046
0.0062
0.0080
0.150
0.0032
o
•H
-------
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
304(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) to 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 largest volume products of the plastic
and synthetic materials manufacturing source category.
Section 306 of the Act requires the Administrator, within one
year after a category of sources is included in a list published
pursuant to Section 306 (b) (1) (A) of the Act, to propose
regulations establishing Federal standards of performances for
new sources within such categories. The Administrator published
in the Federal Register of 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.
11
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Methodology
The effluent limitations guidelines and standards of performance
proposed herein were developed in the following manner. The
plastics and synthetics industry was first categorized for the
purpose of determining whether separate limitations and standards
are appropriate for its different segments. considerations in
the industry subcategorization process included raw materials,
products, manufacturing processes, raw waste characteristics and
raw waste treatability and attainable effluent concentrations.
The raw waste characteristics for each subcategory were
identified through analyses of (1) the sources and volumes of
water and waste waters and (2) the constituents (including
thermal) of all waste waters including toxic or hazardous
constituents and other constituents which result in taste, odor,
color, or are toxic to aquatic organisms. The constituents of
waste waters which should be subject to effluent limitations
guidelines and standards of performance were identified.
The full range of control and treatment technologies existing
within the industry was identified. This included an
identification of each distinct control and treatment technology,
including both in-plant and end-of-process technologies, which
are existent or capable of being designed for each subcategory.
It also included an identification, in terms of the amount of
constituents (including thermal) and the chemical, physical, and
biological characteristics of pollutants, of the effluent level
resulting from the application of each of the treatment and
control technologies. The problems, limitations, and reliability
of each treatment and control technology and the required
implementation time were also identified. In addition, the non-
water quality environmental impact, such as the effects of the
application of such technologies upon other pollution problems,
including air, solid waste, noise, and radiation were identified.
The energy requirements of each of the control and treatment
technologies were identified as well as the cost of the
application of such technologies.
The information, as outlined above, was then evaluated in order
to determine what levels of technology constituted the "best
practicable control technology currently available," "best
available technology economically achievable," and the "best
available demonstrated control technology, processes, operating
methods, or other alternatives." In identifying such
technologies, various factors were considered. These included
the total cost of application of technology in relation to the
effluent reduction benefits to be achieved from such application,
the age of equipment and facilities involved, the process
employed, the engineering aspects of the application of various
types of control techniques process changes, non-water quality
environmental impact (including energy requirements), the
treatability of the wastes, water use practices, and other
factors.
12
-------
The data for identification and analyses was derived from a
number of sources. These sources included EPA research
information, EPA permit applications, records of selected state
agencies, published literature, previous EPA technical guidance
for plastics and synthetics manufacture, a survey of waste water
treatment practice by the Manufacturing Chemists Association,
qualified technical consultation, and oh-site visits and
interviews at plastics and synthetics manufacturing facilities
practicing exemplary waste water treatment in plants within the
United States. Samples for analyses were obtained from selected
plants in order to establish the reliability of the data
obtained. All references used in developing the guidelines for
effluent limitations and standards of performance or new sources
reported herein are listed in Section XIII of this document.
General Description of the Industry
The plastics and synthetics industry is composed of three
separate segments: the manufacture of the raw material or
monomer; the conversion of this monomer into a resin or plastic
material; and the conversion of the plastic resin into a plastic
item such as a toy, synthetic fiber, packaging film, adhesive,
paint, etc. This analysis is concerned primarily with the
manufacture of the basic plastic or synthetic resin (SIC 2821).
We are also including within this study the production of
synthetic fibers such as nylon (SIC 2824), man-made fibers such
as rayon (SIC 2823), and cellulose film, namely, cellophane (SIC
3079) .
The present report segment deals with 16 of the major resins, all
of the major synthetic fibers, all of the cellulosic fibers, and
cellophane film, and covers over 90 percent of the total
consumption of the plastics and synthetics industry.
Plastics
The synthetic plastics industry for this segment, accounts for
approximately 12 million kkg (26 billion Ibs) of material having
a dollar value of about $5 billion. This is an increase over the
1962 consumption of 3.18 million kkg (7 billion Ibs) for an
average growth rate over the last decade of just over 13 percent.
The industry supplies a secondary converting industry with annual
sales of $21 billion and supports a raw material industry by
purchasing $3 billion of materials. This larger industry is
composed of some 300 producers operating over 400 plants. Of
these 300 producers, there are about 35 major corporations having
individual sales of over $500 million. These are primarily the
major oil companies, which have integrated from oil and monomer
raw material production to the manufacture of the resins and
chemical companies, some of whom have integrated back to raw
materials and forward to end-products. Perhaps one-third of all
the final plastic items are fabricated by the basic resin
producers. A large number of the basic resin producers are
integrated to raw material production. In many cases, a given
installation will produce both monomer, polymer, and the end-use
13
-------
items, and it is difficult to isolate the source of pollution
between the three separate segments. At the small end of the
scale, the plastics industry includes many companies having sales
of less than $1 million per year, often producing one resin in
small quantities for a specific customer. Such companies might
average no more than twenty employees.
The major plastic materials considered in this report with their
annual consumption are shown in Table 7, along with the number of
producers.
The industry considered is expected to grow at a rate of
approximately 10 percent per year over the next five years. Its
major outlets are:
1. The building and construction industries, i.e.,
paint, flooring, wall covering and siding.
2. The packaging industry, notably polyethylene
films, rigid plastic containers and bottles.
3. The automotive industry, including trim,
steering wheels, outside grill, etc.
These three industries account for somewhat over 50 percent of
the total production of plastic materials.
The type of plant constructed depends primarily on the specific
resins being produced. The large volume commodity resins,
polyvinyl chloride, polystyrene and the polyolefins are generally
produced in plants ranging in size from 45,500 kkg (100 million
Ibs) to 226,700 kkg (500 million Ibs) per year. They are usually
part of a petrochemical complex, which includes the production of
monomer, such as ethylene, and the production of end products,
such as film.
14
-------
TABLE 7
1972 CONSUMPTION OF PLASTICS AND SYNTHETICS
Consumption Number of
Products .10£0_kkc[ Producing nUnits
Urea and Melamine** 411 11
Polyvinyl Acetate 198 26
Low Density Polyethylene 2,372 12
High Density Polyethylene 1,026 13
Polypropylene 767 9
Polystyrene 1,196 19
ABS/SAN 431 8
Polyvinyl Chloride 1,975 23
Phenolic** 652 81
Acrylic Resins 208 5
Polyester Resins 30 4
Nylon Resins 110 6
Acrylic Fibers 286 6
Polyester Fibers 1,040 15
Nylon Fibers 896 14
Cellulose Acetates* 257 7
Cellophane 145 4
Rayon 430 7
Total 12,508 278
*Includes fibers and resins.
**These products will be covered in greater detail in the
Development Document for the Synthetic Polymers Segment of the
Plastics and Synthetics Industry.
Because of their dependence on petroleum and gas feedstocks,
these plants are usually located on the Gulf Coast, operations
are generally continuous in nature, and the product is shipped in
hopper cars to distribution points throughout the United States
where fabrication is carried out. Fabricating operations are
often located near population centers. There are four main
centers of converting operations: New England, Middle Atlantic
States, Mid-West and Far West. A second segment of the industry
consists of the manufacture of resins by batch processes for
particular end uses. These plants are generally smaller, i.e.,
under 45,500 kkg (100 MM Ibs), and are likely to be oriented
toward markets rather than raw materials since the raw materials
can be readily shipped from producing points. Thus a manu-
15
-------
facturer of phenol formaldehyde resin for grinding wheels may
locate a plant in upper New York State and buy his raw materials
from petrochemical plants located elsewhere in the country. Such
products are produced in relatively small quantities and often
discharge their waste water to municipal systems. A list of
major producers of resins is shown in Table 8.
TABLE 8
MAJOR RESIN PRODUCERS
Allied Chemical Hercules
American Cyanamid Koppers
Ashland Oil Mobay (Bayer)
Borden Monsanto
Borg-Warner (Marbon) National Distillers
Celanese Occidental Petroleum (Hooker)
Dart Industries Phillips Petroleum
Diamond Shamrock Reichhold
Dow Rohm 6 Haas
DuPont Shell
Eastman Standard Oil (Indiana)
Ethyl Standard Oil (New JErsey)
Foster Grant Standard oil (Ohio)
General Electric Stauffer Chemical
B.F. Goodrich Tenneco
w.R. Grace Union Carbide
Gulf Uniroyal
Synthetic Fibers
The synthetic fiber industry is composed of both synthetic
materials based on nylon, polyester and acrylic resins, and man-
made fibers based on cellulose acetate, cellulose triacetate and
rayon. The synthetic fibers which generally produce relatively
minor quantities of pollutants when compared with celluloses
account for 2,280,000 kkg (5 billion Ibs), whereas the cellulose
fibers account for about 685,000 kkg (1.5 billion Ibs). There
are 6 producers of acrylic fibers, 15 producers of polyester
fibers, and 11 producers of nylon fibers. There are 5 producers
of cellulose acetate fibers and 7 producers of rayon. In many
cases there is overlap since a given producer of fibers may
produce as many as four types.
16
-------
The
below:
table showing the producers of synthetic fibers is found
Table 9
SYNTHETIC FIBER PRODUCERS
Allied Chemical
American Cyanamid
American Enka
Celanese
Courtaids
Dow Badische
DuPont
Eastman
Beaunit
Midland
Firestone
Goodyear
Hystron
Monsanto
Phillips Fibers
Rohm 6 Haas
Union Carbide
Nylon
x
x
X
X
X
X
X
X
X
X
X
Polyester
x
X
X
X
X
X
X
X
X
X
X
Acrylic
X
X
X
As can be seen, this industry is dominated by major corporations.
In general synthetic fibers have been growing in importance
whereas the cellulose acetate and rayon fibers have been
declining in importance over the years.
Capacity by producer for the cellulosic based fibers is shown
below:
Table 10
CAPACITY
1000 kkg/Year (MM Ibs/Year)
Company
American Cyanamid
Akzona
(American Enka)
Celanese
Courtaulds
DuPont
Eastman
El Paso (Beaunit)
FMC
Rayon
Filament
Rayon
Acetate
33
45
(73)
(100)
11
41
(24)
(90)
45 (100)
88.5 (195) 120 (265)
88.5 (195)
22.8 (50)
41 (90)
210 (460)
17
-------
Growth for these materials is limited, and major new capacity
additions are not expected. The profitability of the cellulose
and rayon fiber industry depends on its pricing policy in
relation to cotton and synthetic fibers. Many of the plants are
quite old and may not have modern waste water treating
facilities.
Cellophane
Cellophane, which was originally produced in 1912, reached its
peak of consumption in 1960 with sales of 200,000 kkg (440
million Ibs). Due to competition from polyethylene in the baked
goods business, polyvinyl chloride in the meat and produce wrap
business, and the introduction of new competing clear films, such
as polypropylene, polyester and polybutylene, consumption of
cellophane has dropped uninterruptedly since 1964, reaching a
level of 145,000 kkg (320 million Ibs) in 1971. Continued
decline is expected with consumption reaching as low as 123,000
kkg (270 million Ibs) by 1975. Further inroads from other
synthetic films as well as a shift to the use of thinner gauges
of cellophane, possible in combination with other packaging
films, can be expected to further reduce demand. Cellophane
production is carried out by three companies (Olin, FMC
Corporation, and Du Pont) in relatively old plants.
Product and Process Technology
Typical Polymerization. Products
Polymers are characterized by vinyl polymerizations. The common
reaction is the "opening" of a carbon-to-carbon double bond to
permit growth of a polymer chain by attachment to the carbons.
Substitute groups on the carbons may be all hydrogen (ethylene)
or one or more other radicals (e.g. methyl for propylene, and
phenyl for styrene). Polymerization proceeds until propagation
is stopped by the attachment of a saturated group. In the
formulae shown in Fig. 1 hydrogen is written as this "chain-
stopper." ABS (acrylonitrile, butadiene, styrene) plastics are
co-polymers of two or three of the monomers named. Polystyrene
has been diagrammed in Fig. 1. Polyacrylonitrile and
polybutadiene are shown in Fig. 2. Polybutadiene forms the
rubbery backbone of ABS polymers, and is modified by the
substitution of styrene and/or acrylonitrile elements. The
presence of the double-bond in the polybutadiene introduces both
sterospecificity and the opportunity for cross-linking.
Polyacetal resins are condensation polymers of formaldehyde and
may be synthesized in a one or two step process. This is shown
in Fig. 3.
Emulsion and Suspension Polymerization
A large number of polymers are manufactured by processes in which
the monomer is dispersed in an aqueous, continuous phase during
the course of the reaction. There are technical differences
between emulsion and suspension systems which pertain to the
18
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Polyethylene
Polypropylene
Polyvinyl Acetate
Polyvinyl Chloride
Polystyrene
FIGURE 1 TYPICAL POLYMERIZATION REACTIONS FOR POLYETHYLENE,
POLYPROPYLENE, POLYVINYL ACETATE, POLYVINYL CHLORIDE,
POLYSTYRENE
19
-------
Polyacrylonitrile
Polybutadiene
FIGURE 2 TYPICAL POLYMERIZATION REACTIONS
FOR POLYACRYLONITRILE AND POLYBUTADIENE
20
-------
OR
n/3
0 - C
I
H
- O - C - 0
u — u—i
"I
trioxane
FIGURE 3 TYPICAL POLYMERIZATION REACTION FOR POLYACETAL RESINS
21
-------
polymerization reaction itself, but these do not have a bearing
on the potential aqueous pollution problem. Therefore both
methods will be covered by this discussion.
Products of this process include:
Polystyrene (PS)
Acrylonitrile, butadiene, styrene (ABS)
Styrene, acrylonitrile (SAN)
Polyvinyl chloride (PVC)
Polyvinyl acetate (PVA)
A batch process, as shown in Fig. 4, is commonly used. Typical
reactor size is 5,000 to 30,000 gal (18.9 to 113.5 cu m). 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 coolingtower 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.
A number of products, polyvinyl acetate for example, are marketed
in this latex form with no further processing required. Thus,
although water is a process material, there is no aqueous waste
inherent. When the product is isolated and sold in solid form,
the screened latex is pumped to another reactor. A small
quantity of a flocculating agent is added which destroys the
emulsion and permits subsequent separation of the polymer.
Atmospheric or Low-Pressure Mass Polymerization
A number of important plastics are manufactured by mass
polymerization, a system in which the purified monomer is allowed
to polymerize under controlled conditions of temperature and
reaction rate. This process is shown in Fig. 5. Catalysts and
modifiers are used to initiate the reaction, control its rate,
and influence the final molecular weight. These materials are
used in very small amounts, and their residue remains in the
product. Removal of the heat of reaction is a difficult problem
in this process and limits the type of equipment which can be
used.
Products of this process include:
Polystyrene (PS)
22
-------
INITIATOR
EMULSIFIER
PROCESS
WATER
V 1
COOLING
WATER
VINYL ACETATE
MONOMER
WASH WATER
LATEX PRODUCTS
SHIPMENT
FIGURE 4
EMULSION POLYMERIZATION
-------
MONOMER
INHIBITOR
WASTE
CONDENSER
VACUUM
SYSTEM
LIGHT
ENDS
DECANTER
OLIGIMER
BY-PRODUCT
WATER
POLYMER
PRODUCT
FIGURE 5
MASS POLYMERIZATION
-------
Acrylonitrile, butadiene, styrene (ABS)
Styrene, acrylcnitrile (SAN)
Polyvinyl chloride (PVC).
It is usually necessary to protect the purified monomers from
autopolymerization in storage. The inhibitor used for this
purpose is removed by distillation or washing. This frequently
results in an aqueous waste. The reaction system is usually
continuous, or multi-stage, and the first step is to bring the
monomer to reaction temperature by indirect heating. A heat-
transfer oil or fluid such as Dowtherm, circulated from a fired
heater, is used. Once reaction begins the heat is removed by
transfer to a cooling oil circulated through coils or in a
jacket. The circulated oil is cooled by water in conventional
heat-exchange equipment.
On leaving the reactor, the polymer contains unreacted monomer
and small amounts of contaminants and by-products. These
materials are removed by vacuum stripping.
Vapors from this unit pass through an oil-cooled tar condenser.
The vent from this ccndenser is connected to a steam jet ejector,
and steam and volatile hydrocarbons condense in a water-cooled
surface condenser. Insoluble oils are decanted and recovered,
and contaminated condensate goes to the process sewer.
Pure polymer from the bottom of the stripper is forced through
multiple orifice extruders to make strands of polymer, which are
cooled in a water bath before pelletizing for storage and
shipment.
High Pressure Mass Polymerization - Low Density Polyethylene
The high pressure process for low density polyethylene is a very
simple one, as illustrated in Fig. 6. Ethylene gas is mixed with
a very small quantity of air or oxygenated organic compounds as a
catalyst, and with recycled ethylene, and raised to high pressure
in reciprocating compressors. The operating pressure is
considered to be confidential information, but the trend in the
industry has been to the highest practical pressures, and
literature references to design ratings of 40,000 psi (2722 atm)
and up are common. At the operating pressure and at an
appropriate temperature, polymerization is carried out in
jacketed tubular reactors. The heat of reaction is removed to
hot water in the jacket, which circulates through a waste heat
boiler for the generation of steam. On completion of the
reaction, the pressure is reduced and specification polymer
separated in flash drums. This molten material is pumped through
a multiple orifice extruder to an underwater chiller and chopper
to produce polyethylene pellets. The water is separated on a
screen and pumped through a cooler for recycling. A purge stream
of this water is removed and replaced with high-quality, clean
water. The purge is at a rate sufficient to remove polymer fines
generated in chipping. The quantity of fines depends on the
25
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ETHYLENE
FEED
CATALYST
ETHYLENE RECYCLE
REACTOR
PROCESS WATER
DRYER
EXTRUDER
CHILLER,
CHOPPER
SCREEN
WASTE WATER
PRODUCT POLYETHYLENE
FIGURE 6
LOW-DENSITY POLYETHYLENE PRODUCTION - HIGH PRESSURE PROCESS
26
-------
grade of polymer produced and with some grades is negligible.
Wet polymer from the screen is dried and stored in silos.
Polyolefins - Solution Polymerization
In the solution process for polyolefins shown in Fig. 7, the
polymer is dissolved in the reaction solvent as it is formed, and
the catalyst is present as a separate solid phase. The catalyst
system is activated chromium oxide deposited on a carrier such as
alumina. This process is one of two for polyolefins which first
came into prominence in the late 1950's; the other is the Ziegler
process, in which the polymer precipitates as it is formed.
Products of the solution system include high density polyethylene
and a limited number of co-polymers.
As the concentration of polymer, or the molecular weight of the
polymer in solution, increases, the viscosity of the solution
also increases markedly. This phenomenon places severe
limitations on the processability of the reaction mass.
Temperature control is accomplished by indirect cooling with
refrigerated water, and the viscosity must not be allowed to
exceed a reasonable limit for efficient heat transfer.
Viscosity is also an important limitation in the next step, which
is the removal of the catalyst by filtration or centrifugation.
From the filter, the catalyst, wet with solvent, is mixed with
hot water and the solvent removed by steam stripping. Solvent-
free catalyst slurry is processed in a skimmer and solid catalyst
removed to land fill.
The aqueous phase is recycled to the steam stripper. Vapor from
the steam stripper is combined with other recovered solvent for
purification.
The catalyst-free polymer solution is processed in a system which
concentrates and precipitates the polymer, and then removes the
last traces of solvent by steam stripping, leaving the polymer as
a slurry in water. The slurry is filtered or centrifuged, and
the filtrate recycled to the stripper.
Solvent recovered in the concentrator and vapors from the steam
strippers are processed by distillation in the solvent recovery
section. All process water used in the catalyst and polymer
separation area appears as an aqueous waste stream from this
distillation unit. It contains small quantities of dissolved
hydrocarbons, but in at least one plant it is used as boiler feed
water.
Dry polymer crumb or flake is blended, melted, extruded and
pelletized. This pelletizing operation is carried out under
water, with cooling and transport accomplished with recirculated,
clean, softened water. A purge stream amounting to a few percent
of the circulation rate is withdrawn to waste. This system is
the same as already described for the low-density polyethylene
process.
27
-------
OLEFIN
SOLVENT
00
SOLVENT
DISTILLATION
AQUEOUS
WASTE
PRIMARY CATALYST
FILTRATION
POLYMER
SOLUTION
STEAM-
SOLVENT
STRIPPER
AND
POLYMER
PRECIPITATION
•PRODUCT
FIGURE 7
POLYOLEFIN PRODUCTION - SOLUTION PROCESS
-------
Polyolefins - Ziegler Process
This process depends on a catalyst system discovered and patented
by Dr. Karl Ziegler. There have been a number of improvements by
companies using the t,asic principle, and the name in fact applies
to the catalyst system. Each user has had to design his own
plant. It is convenient, however, to group under this name all
polyolefin processes which employ a reaction solvent in which the
polymer precipitates as it is formed. Fig. 8 details this type
of polyolefin production. The catalyst is a relatively complex
alkyl, or alkyl halide, of metals such as titanium and aluminum.
Products of this process include:
High Density Polyethylene
Polypr opy1ene
Polybutene
Copolymers.
Catalyst preparation, monomer addition, and reaction proceed as
already described for the solution process. Temperatures and
pressures are lower; and, because the polymer does not dissolve,
problems caused by excessive viscosity do not arise.
The next step is the removal of the catalyst, which historically
has been the most troublesome part of the system. The residual
catalyst content of the final polymer must be very low, and for
this reason a system is employed which allows transfer of
catalyst to a separate liquid phase. Aqueous alcohol is used for
this purpose and the catalyst is removed in solution, leaving the
polymer slurried in the hydrocarbon solvent.
The aqueous alcohol phase is treated to precipitate the catalyst
as the oxides (e.g., titanium, aluminum), and these materials
eventually appear as finely-divided suspended solids in the
aqueous waste. They will settle sufficiently to permit discharge
of a clarified effluent, but consolidation of the sludge left
behind has been a problem. Alcohol is recovered for reuse by
distillation. The aqueous phase remaining is the principal waste
product of the plant. This water contains a finite amount of
dissolved alcohol, and this chemical constitutes the largest raw
waste load on the treatment facilities.
The polymer slurry is processed by steam stripping, filtration,
drying, extruding and pelletizing as is done for the solution
process, and the hydrocarbon solvent is purified by distillation.
A small quantity of aqueous waste is recycled to the alcohol
unit.
Polyolefin - Particle Form Process
The problems of the solution process for polyolefins described
above have to a large degree been overcome in a newer version
called the particle form process, and the method has a growing
29
-------
UJ
o
OLEFIN
SOLVENT
CATALYST
>
REACTOR
-1,
AQUEOUS ALCOHOL
POLYMER
SLURRY
STEAM
RECYCLE
SOLVENT
SOLVENT
DISTILLATION
*• PRODUCT
FIGURE 8
POLYOLEFIN PRODUCTION - ZIEGLER PROCESS
-------
commercial acceptance. Fig. 9 details this method of production.
There have been three major changes:
1. The catalyst system has been modified and
its activity increased to the point that
special measures for catalyst removal are
unnecessary for many grades of polymer.
2. The solvent system has been modified so that
the polymer is obtained as a slurry rather
than a solution in the diluent.
3. Special design loop-reactors have been
developed which allow the polymerization
system to operate under good control of
reaction conditions and at satisfactory rate.
In practicing this method, catalyst and olefin feed are added to
the reaction mass which is circulated continuously through the
loop reactors. A stream is also withdrawn continuously from the
reactor to a flash drum. Polymer is removed from the bottom of
the flash drum, dried, and processed through an extruder
pelletizer as with the other methods.
The vapor stream from the flash drum is scrubbed to remove
polymer fines. This step produces a small quantity of waste
water. Both unreacted olefin, and recovered diluent are then
separated from the overhead stream and recycled to the reaction
step.
Polyacetal Resins
These resins are polymerization products of formaldehyde. At
present they are manufactured at two U.S. plants, operated by
different companies and by quite different processes. Polyacetal
resins might have been eliminated from the scope of this report
on the basis of unique process considerations. This was not done
because of the growing commercial importance of the material, and
because of the large dependence on aqueous processing which its
manufacture involves.
The specific discussion of process details, and the presentation
of a process flow sheet is, however, inappropriate and this has
not been included.
As stated above, formaldehyde is the raw material, other process
materials required include caustic soda, benzene, methanol,
formic acid, and intermediate condensation products such as
trioxane, dioxalene, dioxane, and tetroxane.
Process operations include the polymerization reaction steps,
solvent extraction using aqueous wash solutions, and
distillation.
31
-------
OLEFIN RECYCLE
KJ
OLEFIN
FEED
CATALYST
1
CATALYST
PREPARATION
t
t
1
t
AQUEOUS
WASTE
SLURRY
WATER
FIGURE 9
POLYOLEFIN PRODUCTION - PARTICLE FORM PROCESS
POLYMER
PRODUCT
-------
Cellophane
Cellophane is produced in a wide variety of grades. However,
these variations primarily represent differences in film
thickness, plasticizer content, and coatings applied. Waste
loads are essentially independent of product mix.
Process Description - Cellophane manufacture is divided into
three major process operations: viscose preparation, film
casting, and coating. A schematic diagram of the manufacturing
operations is shown in Fig. 10. The basic reactions involved are
represented by the following:
Steeping
R (cell) OH + NaOH —>• R(cell) ONa + H20
cellulose alkali cell.
Xanthation
R(cell) ONa + CS2 —*- R(cell) OCSSNa
cell. xanthate
Coagulation and_Regeneratign
R(cell) OCSSNa + H2SO4 >• R (cell) OH + CS2 + Na2 SOJi
cellophane
Viscose Preparation - Viscose, a solution of sodium cellulose
xanthate in dilute aqueous caustic, is prepared by a series of
multiple-batch type operations.
Dissolving grade wood pulp, received in baled sheet form, is
slurried in caustic solution to form alkali cellulose. Most of
the caustic is then squeezed from the fiber on perforated roll
presses. Part of the caustic solution is reused for steeping,
the remainder is used in subsequent xanthate dissolving or other
steps. There is no caustic purification (dialysis) system as in
rayon manufacture since the requirements for cellophane are less
stringent. Impurities (mainly hemicelluloses) extracted from the
pulp by the caustic solution are maintained at a controlled level
in the system by the purging effect of using a portion of the
caustic steeping liquor in subsequent process steps such as to
dissolve the xanthate.
The alkali crumbs from the roll presses are aged in the presence
of air in cans in a controlled temperature environment to a
specified degree of depolymerization of the cellulose. They are
then reacted in churns with carbon disulfide to form xanthate.
The xanthate is dissolved by the addition of dilute aqueous
caustic to form viscose. The viscose is aged in tanks, filtered
in plate and frame filter presses, deaerated, and pumped to the
casting machines.
33
-------
Film Casting - Film casting and processing is a continuous
operation. Viscose is metered by pump through a slit die into a
primary spin bath containing an aqueous solution of sulfuric acid
and sodium sulfate. Cellophane is formed in this bath. The film
subsequently passes through a series of processing baths as
indicated in Fig. 10. These include dilute acid wash,, warm
water wash, cool water bath to cool film prior to bleach, bleach
bath, water rinse, and plasticizer bath. An "anchoring" resin
which serves as a tie-coat for subsequent coatings is usually
applied in this bath. For colored film (a minor portion of
total) a dye bath is included in the wet processing sequence.
After the plasticizer bath, the film is dried, wound into rolls,
and sent to coating.
Film coating - Most of the cellophane production is coated.
Coatings are generally applied from organic solvent solutions.
The solvents are recovered by an activated carbon recovery
system. Water usage related to solvent recovery is cooling water
and steam for stripping solvent from the carbon beds.
Water/solvent mixtures condensed from the carbon beds are
separated by decanting and/or distillation.
Spin Bath Reclaim - Water and sodium sulfate are generated in the
primary spin bath by the reaction between viscose and sulfuric
acid. To maintain proper bath composition and recover chemicals,
the spin bath liquor is recycled through a reclaim operation.
The effluents from the dilute acid backwash and countercurrent
water wash processes are also sent to the reclaim plant. In the
reclaim plant, one portion of the spent baths is passed through
double-effect evaporators to remove water. The other portion is
passed through crystallizers where sodium sulfate is separated
out, subsequently converted to the anhydrous form, and sold as a
by-product. The liquors from the evaporators and crystallizers
are adjusted in concentration as required, and recycled to film
processing. The yield from the sodium sulfate recovery operation
is estimated at about 80 percent of the total generated in the
process.
Rayon
Rayon is a generic term covering regenerated cellulose fibers in
which not more than 15 percent of the hydrogens of the hydroxyl
groups have been substituted. Rayon fibers are produced in a
wide variety of cross-sectional shapes, sizes, and performance
characteristics by modification in the viscose process and
spinning condition. The major product types may be classified
as:
High tenacity continuous filament (tire and
industrial type yarn)
Regular tenacity continuous filament (textile
yarn)
Regular tenacity staple
34
-------
NaOH Make-up
Viscose Preparation
Carbon Disulfkte
Pulp
1 1 NaOH Solution
Alkali Steep
Press
Alkali
Crumbs
Aging
Aged
Crumbs ""
|
Churn-Mixers
Viscose ^_
Aging Tanks
Viscose
Deaeration
Viscose
Filter
1
Wastes: Equipment Wash-ups
Oil. Caustic/Viscose
Floor Drains
Cone. Viscose to Landfill
HjSO,
Na,SO.
CS2
HjS
Spills
Wash-ups
Entrainment
Still Bottoms
Minor Solvent Content
Filter Cloth Laundry
Notes: For dyed film, spent dye bath to dye bath pit.
Cooling Water Boiler Discharges not shown.
FIGURE 10
CELLOPHANE PRODUCTION
-------
High performance (e.g., high wet modulus) staple.
The types of fiber produced at any one rayon plant vary from
plant to plant.
Process Description - Rayon manufacture is divided into two major
process operations: viscose preparation and fiber spinning.
Viscose, a solution of sodium cellulose xanthate in dilute
aqueous caustic, is prepared by a series of multiple-batch-type
operations. In the spinning operation, fibers are produced by
continuously metering the viscose through spinnerettes into
coagulation and regeneration baths. The fibers are then
processed through a series of water-based purification steps
prior to drying. These operations are described further below.
The basic reactions involved are represented by the following:
Steeping
R(cell) OH + NaOH—** R(cell) ONa + H20
cellulose alkali cell.
Xanthation
R(cell) ONa + CS2 »-R(cell) OCSSNa
cell, xanthate
Coagulation and Regeneration
R(cell) OCSSNa + H2SO4 +• R(cell) OH + CS2 + Na2 SOJJ viscose
rayon
Viscose Preparation - A schematic flow diagram of the viscose
process is shown in Fig. 11. Dissolving grade wood pulp is
received in baled sheet form. The sheets are steeped in about
111 percent NaOH solution in steeping presses. After the
specified time, the presses close to squeeze out caustic solution
to a controlled alkali/cellulose ratio. The initial, relatively
free draining caustic solution is recycled. The final, and much
smaller, portion pressed from the sheets contains hemicelluloses
and other impurities which cannot be tolerated in the process.
This press liquor is sent to dialysis units to recover purified
caustic solution and purge the hemicelluloses.
The alkali cellulose sheets are shredded to crumb form and aged
in containers in the presence of air at controlled temperature to
a specified degree of polymerization. The aged crumbs are
charged to churns and reacted with carbon disulfide to form
cellulose xanthate. The xanthate is then dissolved in relatively
dilute aqueous caustic to form viscose. Special additives or
modifiers may be added to the viscose at this stage.
36
-------
NaOH Make-up
Spent Spin Bath
Cont. Staple Spinning
[
o Sewer
Shredding
<
Crumb Aging
Aq.NaOH ,
Additives
Cloth
Laundry
T
Churn
~»
Mixer
Aging (Ripening)
I
Deaeration
1
Fi
ter
CS3
Viscose
-« r
-* r
t f
-« f
\
•\
•\
^
Spin Bath
Wet Processing Dry
J *
Bath Discharges
Cont. Yarn Spinning
Spin Bath
Wet Processing Dry
J I
Bath Discharges
Pot Spinning
Cake Wash Machines
Spin Bath
^ Wet Processina
-J 1
Bath Discharges
Spool Spinning
Spool Wash Machines
Spin Bath
^ Wet Processing
J J
Bath Discharges
Fiber Spinning and Processing
Waste Sources: Wet Process Be
1»- Stapl
*_Cont
^ Drv
» Dry
th Discharges
H2S04_
ZnS04
Make-up
Return to Spin Bath
. Spool Yarn
Anhydrous
Na2SO4 By product
Acid Reclaim
Waste Sources: Equipment Wash-ups
Floor Drains
Entrapment (if barometric condensers)
H2SO4
Na2 SO4
ZnSO4
Viscose Preparation
Waste Sources: Dialyzer Purge
Equipment Wash-ups
Floor Drains
Nature: Caustic
Hemicelluloses
Dilute Viscose (cone, viscose to landfill)
Equipment Wash-ups
Floor Drains
Nature: H2SO3 Surfactants
Na3SO.4 Yarn Lubricants
ZnSO, Hemicelluloses
Sulfides Proprietary Additives
Polysulf ides Possibly: MgSO4
Thiosulfate CH,O
FIGURE 11
VISCOSE RAYON PRODUCTION
-------
From the dissolver the viscose is usually pumped to a blending or
receiving tank where a number of batches are blended to minimize
possible batch-to-batch variations. From the blend tank the
viscose is pumped through plate and frame filter presses to
remove contaminants and undissolved cellulosic material. The
filtered viscose is aged in ripening tanks at controlled
temperature until it reaches the proper condition for spinning.
The ripened viscose is deaerated under vacuum, usually filtered a
second time, and pumped to the spinning machines. Details of
viscose preparation are tailored to the performance
characteristics required in the fiber to be spun.
Spinning Operations - Rayon fibers are produced in spinning
operations by pumping the viscose through spinnerettes into a
primary spin bath containing sulfuric acid, sodium sulfate, and,
in most cases, zinc sulfate. The specific composition of the
bath depends primarily on the type of rayon being spun, but will
vary with the process from plant to plant. Modifiers or spinning
aids (proprietary) may also be present in minor quantities.
Coagulation and regeneration of the cellulose occurs in this
bath. In some instances, regeneration may be completed in a
secondary, dilute acid bath. The bundle of fibers produced is
stretched during the regeneration process to produce the desired
degree of orientation within the fibers.
The fibers from the spin bath are in an acid condition, contain
salts and occluded sulfur, and must be purified to prevent
degradation. This is accomplished by a series of wet process
washes which include extensive water washes, and, depending on
application requirements, some combination of treatment in
aqueous desulfurizing, bleaching, and pH adjustment baths, and
application of fiber lubricating oil. The manner in which the
treatments are carried out varies with the spinning method.
After these purification treatments, the fibers are dried and
converted by dry mechanical processes to final product forms.
A number of different spinning methods are employed in the
production of rayon fibers. Briefly, these are as follows:
1. Continuous Staple Machines
On continuous staple production machines, fibers
are spun in the form of a relatively large bundle
of untwisted, continuous filaments called tow.
After the regeneration step, the tow is wet-cut
in rotary cutters to the desired staple length.
The staple is sluiced with water onto some form
of porous conveyor belt to form a "blanket."
Subsequent wet purification steps are carried
out by shower application of treating liquors
as the staple is carried along the washing line.
2. Pot or Box Spinning
In pot spinning, the bundle of continuous fila-
38
-------
ments from the spin bath, after stretching, is
fed through a tube down into a pot rotating at
high speed which imparts a controlled twist to
form yarn. The yarn builds up on the walls of
the pot to form a cylindrical package or "cake."
Water is sprayed into the pot to wash out some of
the salt to prevent crystal formation and con-
sequent fiber damage. This "pot spray" spins
out through holes in the side of the pot.
The cakes are transferred from the pots to cake
washing machines where the wet process purifi-
cation treatments are completed.
3. Spool Spinning
Spool spinning is similar to pot spinning except
that the bundle of filaments is wound on a
revolving spool. The spools are mounted in
spool washing machines for the final purifica-
tion washings.
4. Continuous Yarn Spinning
In continuous yarn spinning, the bundle of
regenerated filaments travels over thread
advancing rolls where the washes are applied
to individual yarns on a continuous basis to
complete the purification treatments before
the yarn is wound into a package.
Spin Bath Reclaim - In the spin bath, water and sodium sulfate
are generated by the reaction between the alkaline viscose and
sulfuric acid. To maintain proper spin bath compositions and
conserve chemicals, the spin bath liquors are continuously
circulated through a reclaim operation. One portion of the spent
liquors is sent to evaporators to strip off water; another
portion is sent to crystallizers to remove excess sodium sulfate.
The mother liquors are recombined, corrected in composition as
required, and returned to the spin baths. Spin bath liquors of
different composition are kept segregated through the reclaim
operation.
Sodium sulfate recovered from the crystallizers is purified by
washing, converted to the anhydrous form, and sold as a by-
product. Implications of this reclaim operation with respect to
further reducing dissolved solids discharge from rayon
manufacturing are discussed in Section VIII.
Polyester Resin and Fiber
A polyester fiber is defined by the FTC as a manufactured fiber
in which the fiber forming substance is any long-chain synthetic
polymer composed of at least 85 percent by weight ester of a
dihydric alcohol (usually ethylene glycol) and terephthalic acid.
39
-------
The most common polyester is derived from the linear polymer
poly(ethylene terephthalate). The only other homopolymer to
achieve commercial significance is manufactured by Eastman Kodak.
In this polymer, the dihydric alcohol is 1,4-
cyclohexanedimethanol rather than ethylene glycol.
Molecular weights in the region of 15,000 are required for useful
textile fiber properties. Most products contain a delusterant,
typically titanium dioxide, added in quantities up to 2 percent.
The term polyester resin as used in this report refers to the
saturated polyester polymers based on poly (ethylene
terephthalate) or poly (1,4 cyclohexanedimethylene terephalate).
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 reactions involved in polymerizing
saturated polyesters are shown in figure 12.
The saturated polyester resins referred to in this report
represent about 10 percent of total polyester fiber manufacture,
and are used primarily in film form (i.e., Mylar, Celenar). 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. Since the polymerization
process, raw materials and waste loads are, with some exceptions,
identical, polyester resin and fiber are treated as a single
subcategory.
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 as a waste stream in addition to ethylene glycol, whereas
the TPA based polymerization process generates only ethylene
glycol.
Titanium dioxide is used in polyester fibers as a delusterant.
Optical brighteners are often used. These are applied either
topically (by the textile finisher) or via addition of
fluorescent dyes to the molten polymer prior to melt spinning.
40
-------
(1) Via dimethyl terephthalate (DMT) route:
a - Alcoholysis with ethylene glycol
OCH3 \=/ OCH3
DMT
2CH2OH-CH2OH
ethylene glycol
^C\ Vc'
HOH4C2O=/DC2 H4OH
"monomer"
b — Polymerization of "monomer"
260-300° F^
"Monomer" Vacuum H0
+2CH3OH
I
COOJ
polyethylene terephthalate (PET)
JT_ HOC2H4OH I
2
ethylene glycol distilled off
(2) Via terephthalic acid (TPA) route:
°%
C
HOX
+ 2CH2OH-CH2OH »• PET
+ H20 I
OH
terephthalic acid
ethylene glycol
FIGURE 12 TYPICAL POLYMERIZATION REACTION
FOR POLYESTER RESINS AND FIBER
41
-------
The exact nature of the catalysts used in the polymerization
process varies somewhat and is regarded as proprietary
information. They are, however, known to include acetates of
cobalt, manganese, and cadmium.
Many different finish formulations are used and their exact
compositions are regarded as proprietary, but they are known to
contain long chain fatty acids, emulsifiers, bacteriostats, and
humectants.
The end product from a polyester fiber plant is in the form of
staple (usually shipped in bale form), continuous industrial yarn
or textile filaments. Shipment is in the form of either spools
or bales. Polyester resin is shipped in the form of solid chips.
Process Description - Although many plants still use the batch
polymerization process, continuous polymerization and direct
spinning combinations are more common for new facilities.
A typical continuous polymerization process based on DMT consists
of a DMT melter, ester exchange column, two polymerization
reactors (low- and high-molecular weights) , and a molten polymer
manifold system feeding several banks of spinning heads. 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 operations and broken up into chip form for
shipping. Fig. 13 shows polyester resin and fiber production.
The spinning operation involves forcing the molten polymer (at
about 290°C) through a sand bed filter to a steel spinnerette
containing cylindrical holes. The extruded filaments cool by air
convection in a carefully controlled environment free from
turbulence. Solidification of the filaments occurs within two
feet below the spinnerette. The spinning threadline is conveyed
below this point and passed over a spin finish application. In
the case of staple production, several threadlines, each
containing 250 to 1000 filaments, can be brought together, passed
over capstans and through an air ejector, and coiled in a large
can for subsequent drawing. For continuous filament yarns, the
spun threadline comprising 15 to 50 filaments is either wound on
bobbins for subsequent draw twisting or drawn directly at high
speed and wound on the final package.
In order to produce the oriented crystalline structure that gives
the fiber its characteristic strength, stiffness and abrasion
resistance, . the spun filaments are drawn to about four times
their original length.
For staple manufacture, large tows made by plying several ends of
spun yarn are drawn on a draw frame at temperatures above 80°C.
Heat is supplied by steam, hot water, heated rolls or infrared
42
-------
TPA
ETHYLENE
GLYCOL
H20
GLYCO
PRIMARY
ESTERIFIER
PRESSURE
RECTIFICATION
L GLYCOL WASTE STREAM
SEPARATION
rivrni GLYCOL TO ULYCOL 10
GLYCOL GLYCOL RECYCLE GLYCOL RECYCLE
UL.IOUL. ^^^^^ nrrn\trny _^__...ta. __^ rrrrnurnY *-
RECYCLE ^^^^ rlLOUVLUI •"•"" ~~ "^ ~™~^ KLCrUVLKT ^^^^^*"
(STEAM EJECTOR) (STEAM EJECTOR)
kf vJT" POLYMERIZATION J— POLYMERIZATION ^^
XS/ VA\ _ VS JT / \
I V^ r V*X. _/ BAND \ RESIf
1 T ... (OPTIONAL?) \CASTINGy ^H(P"
\ Kl
1
POLYMER POLYMER
MELT MELT
V
POLYESTER
TO BALER STAPLE
DR^ER
CY
CRIMPER
V
TOW
DRAWING
SPRAY
FINISH
POLYESTER
FILAMENT
FIGURE 13
fOLYESTER FIBER AND RESIN PRODUCTION
-------
heat. The drawn tow is then crimped using a stuffer box crimper,
dried and heat set. It is either packaged as tow or cut into
staple (lengths range from 1.5 to 6 in. or 3.8 to 15.2 cm) and
baled.
Continuous filament yarn is made by stretching between two rolls
running at a speed ratio of 3.5/1. The drawn yarn is wound at
speeds up to 4000 fpm (1200 meters per min) in a cylindrical
tube.
After the initial finish application, just after the spinnerette,
subsequent applications are made prior to filament drawing or tow
drawing. The filament drawing finish is more concentrated and is
usually applied as a light coating to individual filaments by
means of a spin-finish wheel. In drawing tow, however, the
entire tow bundle is passed through a bath. The quantities of
waste spin finish from tow operations are significantly higher
than from textile yarns and contribute significantly higher BOD
loads to the waste stream. Air conditioning plays a significant
role in the production process, thereby necessitating cooling
towers. In the large cooling towers often associated with the
air conditioning system, chromium salts and various algacides are
used; consequently the blowdown from the cooling towers is
usually treated separately from other waste water streams.
Nylon 66 Resin and Fibers
Nylon 66 is a condensation polymer produced by reacting
hexamethylene diamine with adipic acid to form nylon salt
(hexamethylene diammonium adipate). Polymerization involves a
condensation reaction of this nylon salt.
In addition to hexamethylene diamine and adipic acid, other raw
materials involved in nylon production are acetic acid (used as a
chain terminating agent) , titanium dioxide (Tio.2) , and spin
finishes. The latter two are used only in fiber production. The
reactions involved in polymerizing nylon 66 resins are shown in
figure 14.
The major difference between nylon resins used for plastics and
those used for fibers is that the plastics resins have a higher
molecular weight and viscosity. As a result, both resin and
fibers are often produced in a common polymerization facility
from the same raw materials but with slightly different process
conditions. For the purposes of this study, we have included
nylon 66 resins and fibers in the same subcategory.
The end products from nylon plants are similar to those described
aobve for polyester. Fiber is in the form of staple bales,
continous yarn, or textile filaments. Resin is in the form of
chip or pellets.
Process Description - The hexamethylene diammonium adipate is
made by neutralizing the adipic acid with the diamine. This is
followed by an activated carbon decolorization step which results
44
-------
(a) Formation of nylon "salt"
HOOC-(CH2)4 - COOH + H2 N (CH2 )6 NH2 H3N(CH2)6 NH3OOC(CH2)4 COO
HMDA,
hexamethylene
diammonium adipate or
nylon salt
(b) Polymerization of salt
HMDA ~2H2°> HN (CH2 )6 NHOC (CH2 )4 CO
FIGURE 14 TYPICAL POLYMERIZATION REACTIONS
FOR NYLON 66 RESINS AND FIBER
45
-------
in a liquid waste stream containing spent carbon, diatomaceous
earth, and some nylon salt (the backwash from the carbon
filtration), and a subsequent solids disposal problem. Some
plants start with a concentrated nylon salt solution as the raw
material rather than diamine and diacid. Such facilities also
carry out a decolorization step as described above.
The nylon 66 polymerization process consists of mixing nylon salt
with water and small quantities of acetic acid. This solution is
then passed to a steam-heated evaporator. The vapor from the
evaporator is composed of water mixed with a small percentage of
hexamethylene diamine (HMDA). This stream is passed through a
condenser and the condensate is then passed to the waste
treatment plant. (Condensate contains up to 1 percent HMDA and
is one of the primary sources of BOD in the waste stream.)
The concentrated salt from the evaporator is then passed to a
Dowtherm heated autoclave. Titanium dioxide (delusterant) is
added at this point. The polymerization proceeds in the
autoclave under the appropriate temperature, pressure and time
conditions to produce the desired molecular weight product.
Water is evolved in the polycondensation reaction and is
discharged overhead as a vapor (containing some HMDA) during
venting from the autoclave. This stream is passed to a water
scrubber system. The exit stream from the scrubber then joins
the exit stream from the condenser previously described, and the
combined stream is routed to the waste treatment plant. Some
waste heat is recovered. This process is shown in Fig. 15.
Cellulose Acetate Resin
Process Description - Cellulose acetate resin (flake) is produced
by a batch type operation shown schematically in Fig. 16.
Purchased, dissolving grade wood pulp is defiberized in attrition
mills, pretreated with acetic acid to activate the cellulose, and
charged to acetylaticn reactors where it is reacted with acetic
anhydride in the presence of glacial acetic acid. Sulfuric acid
is added as a catalyst. The acetic acid/anhydride mixture is
pre-chilled by refrigeration to aid in removing heat of reaction.
The reaction is carried to nearly complete acetylation of the
cellulose.
The clear, viscous solution is then transferred to a hydrolysis
reactor where dilute aqueous acetic acid is added, and the
acetate hydrolized back to the specified acetyl content. Some
magnesium acetate may be added to adjust the concentration of
sulfuric acid which also serves as a catalyst for the hydrolysis.
The hydrolysis step is necessary to remove sulfate ester groups
and to provide close control of the final acetyl content. At the
desired point, the reaction is stopped by adding magnesium
acetate to neutralize remaining sulfuric acid.
The overall reactions involved in the production of cellulose
acetate and triacetate may be represented as follows:
46
-------
50% NYLON
SALT SLURRY
CONDENSER
ACETIC ACID
I EVAPORATOR I
o
o
o
STEAM
HEATED
HEAT
EXCHANGER
POLYMER SKIN
FORMS HERE -
REMOVE WITH
ACETIC ACID WASH
ONCE-THRU
COOLING H20
•ATMOS.
TO WASTE TREATMENT
(CONTAINS UP TO 1%HMDA)
BAND CASTING COOLING H20 TO
COOLING TOWER MAKEUP (LIMITED
ONLY BY COOLING TOWER DEMAND)
BAND CASTING H20
CHIPPER
BATCH
BLENDING
DOWTHERM
HEATED
FIGURE 15
NYLON 66 PRODUCTION
FILAMENT
OUTPUT
RESIN OUTPUT
AS CHIPS
SPIN FINISH
TAKEUP
-------
Acetylation
R(cell) (OH) 3 + 3(CH3CO)2 0 —-*-
R(cell) (OCCCH3)3 + 3 CH3COOH
cell, triacetate""
Hydrolysis
R(cell) (OCOCH3)3 * XH20 —*• R(cell) (OCOCH3) (OH) x + XCH3COOH
~3-x
cell, triacetate cell, acetate
Cellulose acetate flake is recovered from the reaction solution
on a continuous precipitator by precipitation with weak acetic
acid solution from the counter current wash step that follows.
In the flake washing process, fresh water enters the second stage
washer, and flows counter-current to the flake through the
secondand first-stage washers. As noted above, the water from
the firststage washer is used for the flake precipitation step.
This water, which is separated from the flake on the vibrating
screens, is sent to acid recovery. Entrained fines are collected
in filters and recycled to the process.
Process waste waters from acetate resin production are treated in
an acid recovery plant to recover acetic acid. A recovery plant
flowsheet is shown in Fig. 16. The process waste streams are
filtered and held in a filtered acid tank. Miscellaneous streams
with sufficient acid value may also be collected in this tank.
Acetic acid is separated from the process water by solvent
extraction and distillation. Glacial acetic acid is recovered
from the bottom of the still. Reportedly about 99,8 percent of
the acetic acid in the collected process water is recovered in
this operation for reuse. A portion of the acid is converted by
a catalytic pyrolysis process to anhydride for the acetylation
reaction.
The solvent and water mixture from the top of the acid recovery
stills is sent to effluent stills where the solvent is recovered
and recycled to the extraction column. The water removed from
the bottom of the effluent stills flows to waste treatment. This
stream represents the major source of dissolved solids (magnesium
sulfate) in the plant discharge.
Cellulose Acetate Fibers
Process Description - Cellulose acetate fiber is produced by a
dry spinning process as indicated by the flowsheet in Fig.17.
Cellulose acetate flake is dissolved in acetone, filtered, and
deaerated. Fibers are produced by pumping the solution through
spinnerettes down through a hot air atmosphere in enclosed
cabinets where fibers are formed by evaporation of solvent. The
bundle of filaments from each spinnerette is drawn over a series
48
-------
Chilled Acetic Acid
Acetic Anhydride Aq. Acetic Magnesium
Acetic Acid H2SO4 Catalyst Acid Acetate
1111
Acet lation
ization
Drying Oven
Flake
Storage
Liquor To
Acid Recovery
Rnin Manufacture
Process Water (See effluent still bottoms)
Equipment Wash-ups
Spills
Vent Scrubber Water
Acetic Acid
Soluble Forms Cellulose
Cellulose Fines
MgSO4
AcM Recovery
Contaminants:
S Still
Process Water - effluent still bonoms
Equipment Clean-ups
Spills
Acetic Acid
MgSO4 /
Trace Solvents Major and Most Concentrated
Soluble Cellulose Acetate MgSO4 Stream
MgSO,
Trace Solvents
Soluble Cellulose Acetate
FIGURE 16
CELLULOSE ACETATE RESIN PRODUCTION
-------
of wheels to orient the fibers before being wound on a bobbin.
The filaments pass over a small roll applicator in this process
where a fiber lubricant is applied. There is no significant
waste discharge from this lubricating bath. The yarn is
subsequently converted by various dry mechanical processes to
final product form.
The acetone-laden air from the spinning cabinets is continuously
transported through ducts to an activated carbon solvent recovery
system. The acetone/air mixture is cooled and passed through
carbon beds, where the acetone is absorbed. When the beds become
saturated, the acetone is stripped out with steam and the vapors
condensed. The solvent is recovered by distillation. Direct
stream injection is employed in these stills. The water stream
which comes off the bottom of the stills is discharged to waste
treatment.
Cellulose Triacetate Fibers
Process Description - Cellulose triacetate fiber spinning and
associated solvent recovery operations are the same as those
described for cellulcse acetate fibers except that the solvent
employed for triacetate in a mixture of methanol and methylene
chloride.
Epoxy Resins*
Epoxy resins are characterized by the presence of the epoxy group
within their structure. Rather than an end resin in itself, the
epoxy family should be regarded as intermediates. They all
require further reaction with a second component, or curing agent
as the second material is often termed, in order to yield the
final thermoset material.
Almost all of the commercially-produced epoxy resins are made by
the reaction between epichlorohydrin and bisphenol A. Small
volumes, however, are produced from polyols other than bisphenol
A, such as aliphatic glycols and novolak resins formed from
phenol and formaldehyde. It is also possible to produce epoxy
resins by introducing the epoxy group after polymer has been
formed. An example of this is the epoxidation of a polybutadiene
material. The double bond present in these materials forms the
site for the epoxy linkage. The following discussion, however,
is limited to the materials produced from epichlorohydrin and
bisphenol A.
Epichlorohydrin is a liquid with a boiling point of 117°C. Bis-
phenol A is a solid which melts at 152°C. Bisphenol A is
insoluble in water, dissolving to the extent of 0.3 percent at
85°C, whereas epichlorohydrin is somewhat more soluble (in the
order of 5 percent).
The reaction between the two raw materials takes place under
alkaline conditions as shown by the equations in Fig. 18.
50
-------
Flake
Acetone
Make-up
Acetate Flake
Storage
pissolving
Acetone
Storage
Condensate Steam Steam
Distillation
Still Bottoms
Process Waste Water
Trace Acetone
Filtration and
Dope Storage
Extrusion
(Spinning)
Steam Condensate
Steam
Condensation
5
Absorption
Cooling Towers
Slowdown
Cooling
Acetate Yarn to
Mechanical Finishing
Acetone
Laden
Air
FIGURE 17
CELLULOSE ACETATE FIBER PRODUCTION
-------
The first step, shown by reaction 1, is the condensation of the
epichlorohydrin with the bisphenol A to form the chlorohydrin
compound. This compound is dehydrohalogenated with caustic soda
to form epoxy linkages yielding diglycidyl ether of bisphenol A,
as shown by Eq. 2. Sodium chloride and water of reaction are
also formed as by-products with the ether. Further reaction
between the ether and additional bisphenol A results in growth in
the chain length, as shown by Eq. 3.
Operating conditions and type of catalyst are selected to
minimize the formation of side chains and to prevent phenolic
termination of the chain. The final resin properties are
enhanced when the chain is terminated with epoxy groups, as shown
in Eq. 3, and when the chain is linear with a minimum of
branching. The possibility of branching exists since
epichlorohydrin could react with the hydroxyl group to start a
side chain.
The product epoxy resins fall into two broad categories, the low
molecular weight liquids and the high molecular weight solids.
In the liquids, n, the number of repeating units in the final
chain as designated in Eq. 3, is low, ranging in commercial
materials from 0.1 to 0.6 as the average value. For solid
materials, n ranges from 1.8 to 16. Control over chain length is
exercised primarily by the ratio of the two reactants charged to
the system. To produce the low molecular weight liquids, a large
excess of epichlorohydrin is used so that n is close to 0 in the
final product. In order to produce the high molecular weight
solid resins, the ratio of epichlorohydrin per mole of bisphenol
A is usually less than 2.
There are two general approaches to carrying out the synthesis of
epoxy resins. In the one-step process all of the reactions shown
earlier proceed at the same time. These are usually carried out
in the presence of sodium or potassium hydroxide. In the two-
step process, reaction 1 is carried out by itself in the presence
of a catalyst. Sodium or potassium hydroxide is then added to
carry out the dehydrohalogenation and further condensation or
polymerization as a second stage. Regardless of which of these
two approaches is used, the overall chemistry remains the same.
The product resins are utilized by the customer in conjunction
with a curing agent to provide the cross-linking necessary to
form a thermo-set material. The curing agents used cover a broad
variety of materials such as amines, polyamides, acids, acid
anhydrides, resins such as phenolic, urea or melamine
formaldehyde combinations; any of which are capable of reacting
with either the epoxy groups or the hydroxyl groups present in
the resin. The specific material picked depends upon the
properties desired in the end resin.
There is substantial production of the so-called modified
epoxies. Most of these are manufactured by reacting some
material such as a fatty acid, tall oil or the like to form an
ester with some of the epoxy groups present in the resin. The
52
-------
(1)
pH > 7
2CH2-CHCH2CI
O
Epichlorohydrin
OCH2CHCH2
' I
HO Cl
(2)
(3)
CH2CHCH20
Cl OH
CH2CHCH20
\t
OCH2CHCH2
I I
OH Cl
OCH2CHCH2
\ /
CH3
Diglycidyl Ether of Bisphenol A
-OCH2CHCH2
\/
O
_ < HO
2NaOH
2NaCI + 2H20
CH
CH3
OH
CH2CHCH2
\l
O
CH,
CH}
OH
CH3
/^?A\
CH
\/
0
FIGURE 18 REACTIONS BETWEEN EPICHLOROHYDRIN AND BISPHENOL A
53
-------
degree of esterification carried out depends upon the properties
desired in the final material. Most of these modified epoxies
find their way into coatings markets.
Process Description - The low molecular weight liquid resins can
be manufactured by either batch or continuous processes. Most of
the larger producers utilize a continuous process for this
material. Fig. 19, a schematic flowsheet of a typical continuous
process, is based upon using the two-step technique in order to
minimize the molecular weight of the epoxy resin produced.
Bisphenol A, with a large mole excess of epichlorohydrin, is
introduced into the polymerizer where, under the influence of the
catalyst and caustic conditions, the first step of the reaction
takes place. The excess epichlorohydrin is then vaporized from
the material and recycled.
A solvent, usually a ketone such as methylisobutyl ketone, is
then added together with additional caustic and water. The
epoxidaticn of the resin takes place with the formation of salt.
A solution of resin in the ketone solvent is water-washed to
remove the final traces of salt, the water decanted is sent to
waste, and the solvent is removed by vaporization. The liquid
epoxy resin product is then sent to storage.
The solid resins, which have a high molecular weight, are usually
produced by batch techniques in resin kettles. In producing
these materials where the repeating part of the epoxy chain is a
high number ranging from 1.8 to 16, the mole ratio of
epichlorohydrin to bisphenol A charged to the kettle is less than
2. No excess epichlorohydrin is used in this case. The process
is shown schematically in Fig. 20. Aqueous sodium or potassium
hydroxide is added to serve both as a catalytic agent and as one
of the reactants to form the epoxy links during the
polymerization reaction. Upon completion of the polymerization
reaction, the water-containing salt and a very small amount of
excess caustic is decanted to the process waste line.
A solvent such as methylisobutyl ketone is then added to dissolve
the resin, and the solution is washed with water to remove the
remaining amounts of sodium chloride and other salts which may be
present. This water is decanted to the process waste lines, and
then the methylisobutyl ketone is vaporized from the resin. The
solid resins have melting points ranging from about 70°C to
150°C, and the final temperature is such that the resin is
molten. It is then drained and cooled to form a solid mass which
is crushed to provide the final granular solid product.
Phenolic Resins*
The family of phenolic resins includes our oldest synthetic
polymers. The term is used to describe a broad variety of
materials, all of which are based upon the reaction between
phenol, or a substituted phenol such as creosol or resorcinol,
and an aldehyde such as formaldehyde or acetaldehyde. Nearly all
54
-------
CATALYST
i
BISPHENOL A— *•
CHLOROHYDRIN »•
©
50%NaOH *•
©
(4)
fYL ISOBUTYL **
KETONE
STORAGE
STORAGE
TANKS
STORAGE
TANKS
_*i
^
STORAGE
TANKS
^^•M*
1st. STEP
POLYMERIZATION
i
r
EPICHLOROHYDRIN
REMOVAL
i
2nd STEP
POLYMERIZATION
,
WASHING
1
SOLVENT
REMOVAL
WASH
WATER
©
LIQUID EPOXY
RESIN
(T
©
(3)
BISPHENOL A
EPICHLOROHYDRIN
50% CAUSTIC
NaOH
H20
WASH WATER
LIQUID RESIN
(6) WASTE WATER
H20
NaCL
lbs/1000lbs
PRODUCT
690.4
512.7
443.4
221.7
221.7
2218.0
1000.0
2859.0
2535.0
324.0
= o.2
FIGURE 19
LIQUID EPOXY RESIN PRODUCTION
55
-------
(1)
POLYMERIZATION
1
EPICHLOROHYDRIN— »• TANKS r*1
WASHING
<
•n«v Mnnn - STORAGE
©
METHYL ISOBUTYL * ^1™.™L *
lbs/1000lbs
PRODUCT
©BISPHENOL A 777.6
(D EPICHLOROHYDRIN 367.6
©50% CAUSTIC 318.0
NaOH 159.0
H20 159.0
0 WASH WATER 2218.0
§ SOLID RESIN 1000.0
WASTE WATER 2681.0
H20 2449.0
NaCl 232.0
DECANTING
•i
SOLVENT
RECOVERY
i
f
RESIN
SOLIDIFICATION
\
i
RESIN
GRINDING
I
SOLID
RESIN
PRODUCT
(D
n=5
i
WASTE
WATER
FIGURE 20
SOLID EPOXY RESIN PRODUCTION
56
-------
industriallysignificant resins, however, are based upon the
reaction of phenol with formaldehyde.
Phenol, commonly known as carbolic acid, is a solid at room
temperature but melts at between 42 and 43°C. It is usually
shipped and handled as a liquid by keeping it above its melting
point. Formaldehyde is normally a gas. It is handled
commercially in the form of formalin, which is a 37 percent by
weight solution of formaldehyde and water.
There are two broad types of resins produced by this industry for
subsequent utilization by their customers. In the first category
are the one-step resins, sometimes termed resols. These are
characterized by being formed from a mixture of phenol and
formaldehyde which contains more than one mole of formaldehyde
per mole of phenol. Often the mole ratio is about 1.5 to 1. An
alkali Buch as sodium hydroxide is used to catalyze the
polymerization which takes place at a pH of between 8 and 11.
The reaction is shown in Fig. 21.
The reacting mixture contains sufficient formaldehyde so that, if
allowed to proceed to completion, a cross-linked thermo-set resin
would be formed. The reaction, however, is stopped short of
completion at an average molecular weight of the polymer
appropriate for the end use of the material. The product may be
in the form of an aqueous syrup, or the water may be removed so
that a solid product is obtained. For other uses, such as many
coating applications, the material may be dissolved in alcohol
before it is shipped to the customer.
The material already contains sufficient formaldehyde to
completely cross-link the ultimate product so that it can be
thermally set into an infusable material by the application of
heat at the customer's facilities. Since cooling the mixture in
its partially polymerized form does not completely stop further
polymerization but merely retards it, these materials have a
somewhat limited shelf life (in the order of 60 days for many
types) .
The second category of resins is the novolaks. These are formed
from a reacting mixture which contains less than one mole of
formaldehyde per mole of phenol. The normal commercial range for
this mole ratio is between 0.75 and 0.90. To produce this
material, polymerization is carried out in an acid medium, using
a catalyst such as sulfuric acid. The pH of the reaction usually
ranges from 0.5 to 1.5. For special uses where a high c/rtho
linkage is desired, the polymerization may be carried out at a pH
of from 4 to 7, but this is not typical. The reaction is shown
in Fig. 22. Since the reacting mixture contains a deficiency of
formaldehyde, essentially all of the formaldehyde is consumed
during polymerization. Thus, no further polymerization can take
place, and the product is a low molecular weight, stable
material. The water which enters with the formaldehyde plus the
water reaction is removed at the end of the reaction, and a solid
meltable material results.
57
-------
OH
Alkaline
Catalyst
6HCHO
OH
HO-CH2 S ^ CH
HO-CH2
OH
i
r^ 1] +- 3H20
^
CH2OH
FIGURE 21 TYPICAL REACTION TO FORM ONE-STEP RESINS OR RESOLS
58
-------
In order to complete the polymerization, the user must add
additional formaldehyde. Sometimes this is done by using
paraformaldehyde, a solid polymer of formaldehyde, but the
extremely irritating nature of this material has limited its use.
Most users complete the reaction by using hexamethylenetetramine.
With this material ammonia is evolved from the reacting mass,
leaving the same types of methylene linkages as can be obtained
by using additional formaldehyde.
The basic resins described above are sometimes modified by the
use of materials such as drying oils or epoxy compounds in the
final stages of polymerization. These modified phenolics find
many specialty uses but do not affect the basic manufacturing
processes to any significant degree.
Manufacturing Processes for Typical Resins - Although continuous
processes for the production of phenolic resins have been
developed, they are seldom used. The production of these
continuous units must be high, and the industry calls for such a
wide variety of materials that it is seldom possible to have a
large enough run on a single grade of polymer to justify their
use.
The standard producing unit of the industry is typically a batch
resin kettle arrangement, such as is shown in Fig. 23. The heart
of the process, the resin kettle, varies in size from 2,000 to
10,000 gal. (7.6 to 38 cu m) These are jacketed, and in the
larger sizes internal cooling coils are used in order to provide
sufficient surface-to-volume ratio to remove the considerable
amount of heat generated during polymerization. The kettles are
agitated and can operate under either pressure or vacuum
conditions.
The feed system generally consists of two weigh tanks which weigh
in the required amounts of phenol and 37 percent formaldehyde
solution. The kettle is equipped with a water-cooled condenser,
which is also joined to a vacuum system.
In a typical cycle for a one-step resin, the phenol is charged in
a molten form to the kettle followed by formaldehyde, which
washes any residual phenol out of the lines leading to the
kettle. A sodium hydroxide catalyst solution is then added, and
the kettle is heated to bring the mixture to a temperature of
about 60°C. During this period the condensation reaction starts,
and the reaction becomes highly exothermic so that a change is
made from supplying steam to the coils to cooling water. The
mixture is held at a temperature ranging from 60°C to about 80°C
for a period of three to five hours. During this period
temperature is controlled by circulating cooling water through
the coils as well as by using total reflux returning from the
water-cooled condenser mounted above the kettle. When the
polymerization has reached the desired state, as shown by
laboratory tests, the mixture is cooled to about 35°C to
essentially stop further reaction. At this point the caustic is
59
-------
OH
-j- 4HCHO
Acid Catalyst
4H20
FIGURE 22 TYPICAL REACTION TO FORM NOVOLAK RESIN
60
-------
CATALYST
50% NOOM\
H2S04 /
PHENOL
FORMALDEHYDE
37% SOLN
COOLING
WATER
COOLING
WATER
(OR STEAM)
SEWER
PRODUCT RESIN
MOLTEN SOLID TO COOLING & GRINDING
SURUPS OR SOLUTIONS TO STORAGE
FIGURE 23
ONE-STEP
(ADHESIVE)
PRODUCT RESIN LBS
CATALYST LBS
PHENOL LBS
37% FORMALDEHYDE LBS
WASTE WATER LBS
GAL
1000.0
25.8
656.2
840.4
533.2
63.9
NOVOLAK
1000.0
NA
929.8
681.7
580.6
69.6
PHENOLIC RESIN PRODUCTION
-------
neutralized by the addition of sulfuric acid, which brings the
mixture to a pH of about 7.
The mixture is then heated by admitting steam to the coil, and
the resin is dehydrated to the desired water content at its
boiling point, about 98°C. The water which has been removed
contains some unreacted monomer and is collected in the receiver.
This water is waste water from the process. When the desired
amount of water has been removed, the mixture is cooled and
discharged for packaging and shipment. The total cycle takes
about 12 hours.
If a resin is desired which contains a very small amount of water
such that it cannot be dehydrated at a temperature low enough to
prevent further polymerization, a vacuum is applied during the
latter part of the dehydration cycle. This technique can be used
to produce an essentially anhydrous melt of a single-step resin.
The resin must be quickly discharged from the bottom of the
kettle through cooling plates for a quick quench in order to
prevent the mass from setting up into an insoluble, infusible
material. The cast material, when solidified, can be broken up
and crushed for shipment as a powder.
The manufacture of novolak resins is entirely analogous except
that an acid catalyst, such as sulfuric acid, is added at the
start of the batch. With strongly acid catalysts it is necessary
to utilize a vacuum reflux in order to maintain temperatures at
85 to 90°C, a slightly higher temperature range than that used
for the one-step reaction. Under milder reaction conditions,
atmospheric reflux is adequate to control the temperature.
At the end of the reflux period, three to six hours after
initiating the reaction, the condensate is switched to the
receiver and water is removed from the batch. When the
temperature reaches the order of 120 to 150°C, the vacuum is
applied to aid in removing the final traces of water and part of
any unreacted phenol. Final temperatures may rise to about 160°C
under a vacuum of 25 to 27 in. (63.5 to 68.5 cm) of mercury.
These higher temperatures are possible since the reaction
proceeds to completion and, therefore, no further polymerization
can be carried out until additional formaldehyde is added. The
completed batch is dumped in the molten form onto cooling pans
where it solidifies, or onto a flaker. If the product is needed
in solution form, solvent is added at the end of the batch as it
cools in the kettle and the solution discharged from the kettle
to storage tanks for drumming.
The finished products may be shipped to customers as such or may
be compounded with additives at the resin-producing point. The
solid resins may be ground, and wood fillers, pigmenting
materials and hexamethylenetetramine added to form a finished
molding compound. These processes all involve solids-handling
and do not give rise to waste water generation.
62
-------
Amino Resins - Urea and Melamine*
The term "amino resins" is used to describe a broad group of
polymers formed from formaldehyde and various nitrogen-containing
organic chemicals. The nitrogen group is in the form of the NH£.
Although called amino resins, in the case of most of the
compounds used they are more in the nature of amides than true
amines. The resins are characterized as being thermo-setting,
amorphous materials which are insoluble in most solvents.
Although many amino compounds are used in the formation of amino
resins, the two of primary commercial significance are urea and
melamine. Specialty materials are formed from other amino
compounds such as thiourea, acrylomide or aniline. These,
however, are produced only in small volumes and have little
significance in the total amino resin market.
Formaldehyde, the common raw material in all types of amino
resins, is normally a gas but is handled industrially as an
aqueous solution. It is infinitely miscible with water. Urea, a
solid under normal conditions, is highly soluble in water.
Melamine could be described as sparingly soluble and is also a
solid under the usual conditions, melting at the high temperature
of 355°C.
Another characteristic of the group of amino resins is that the
polymerization reaction proceeds in two distinct stages. In the
first of these, as indicated, for urea and formaldehyde in Eqs. 1
and 2 of Fig. 24, formaldehyde reacts with urea (depending upon
the mole ratio of the reactants) to form materials such as
monomethylol urea and dimethylol urea which are the reactive
monomers involved in the final polymer. As indicated in Eq. 3,
these materials may react among themselves to form dimers.
Although the structure of just one dimer is shown, a
consideration of the active hydrogen groups involved shows that
many other dimers containing both methylene and ether linkages
are possible. The initial reaction is an addition reaction with
no water formed as a result of the combination. The condensation
reaction, as indicated by Eq. 3, involves the formation of one
mole of water for each linkage formed.
As shown in Fig. 25, the reactions in the case of melamine and
formaldehyde are entirely analogous to those shown for urea
formaldehyde. It should be noted, however, that since melamine
contains three NH2 groups, as contrasted with the two present in
urea, the combinations and permutations are much greater than is
the case for urea. Again, the first two reactions indicate the
initial step of the polymerization. This consists of the
formation of reactive monomers between melamine and formaldehyde.
The further reactions, as indicated schematically by Eq. 3, can
involve the reaction of an additional mole of melamine with one
of the monomers, shown in this case as trimethylol melamine, to
form condensation compounds which involve the elimination of
water of reaction. Although not shown, it can be readily
visualized that a mole of trimethylolamine could react with an
additional mole of trimethylolamine to eliminate water and form
63
-------
o o
II II
(1) H2N-C-NH2 + CH20 —»• H2N-C-NH-CH2OH
Urea Formaldehyde Monomethylolurea
0 0
II II
(2) H2N-C-NH2 + 2CH20 ^HOCH2-NH-C-NH-CH2OH
Dimethylolurea
0 0
(3) H2N-C-NH-CH2OH + HOCH2-NH-6-NH-CH2OH
HOCH2 Q
0 N-C-NH-CH2OH +H20
H2N-C-NH-CH2
FIGURE 24 TYPICAL POLYMERIZATION FOR UREA
AND FORMALDEHYDE
64
-------
an ether linkage as contrasted to the methylene linkage formed
between the trimethylolamine and another molecule of melamine.
These reactions are catalyzed by hydrogen ions and, in general,
are moderated or slowed down by hydroxyl ions. Thus, the proper
pH selection is an important consideration in determining the
structure of the ultimate polymer formed.
The basic amino resin manufacturing process is generally stopped
with the formation of a predetermined amount of monomers, dimers
and trimers depending upon the specifications desired for the
ultimate resin. This mixture of materials is then utilized by
the customer to form the final thermal-set resin which is an
insoluble, heat resistant material. This is contrasted with the
mixture of very low irolecular weight materials produced by the
basic manufacturer which are usually a water soluble, very heat
sensitive material.
Consideration of the equations presented above will show there
are numerous possibilities for cross-linking the various
monomers, dimers and trimers which would be involved in the
initial stages of the reaction. The ultimate customer forms
these cross-links between the molecules by the application of
heat and pressure, sometimes with the aid of a catalyst depending
upon the nature of his application.
The ultimate markets for the amino resins are approximately as
shown in the table below.
65
-------
Table 11
Markets for Amino Resins
Percentage of
Applications Aming Resins^
Adhesives 36%
Textile and Paper Treating and Coating 22%
Laminating and Protective Coatings 18%
Moulding Compounds and All
Other Applications 24%
100%
66
-------
NH,
NHCH2OH
Xx
N N
(1)
H2N
NH2
3 CH20
N N
NOH2CHN C C — NHCH2OH
XN /
Trimethylol Melamine
HOCHj
CH2OH
NH2
(2)
6 CH20
H2N
NH2
/cs
N N
CH2OH
HOH2C
HOH2C CH2OH
Hexamethylol Melamine
NH2
N N
(3)
NH2
NHCH2OH
Cv
X
/C\N^\
NH
CH2OH
NHCH2OH
NH,
NHCH,OH
NH
NH2
H20
NHCHjOH
FIGURE 25 TYPICAL POLYMERIZATION REACTIONS FOR MELAMINE AND FORMALDEHYDE
67
-------
For most of these applications the resin is used in the form of
either an aqueous solution or a mixture of an aqueous and alcohol
solution, ethanol being the usual alcohol. For moulding
compounds and some of the others, a solid material is utilized.
In nearly all of these applications, the melamine part of the
amino resin family has superior properties. Because of its
higher cost, however, it is utilized principally where these
superior properties are necessary. In other instances the urea
formaldehyde resins, which are lower cost, are equally
applicable.
Since, as mentioned above, the reactive monomers, polymers,
trimers and low molecular weight material formed by the basic
resin manufacturer contain all of the reactive groups necessary
to further crosslink, the solution materials have a limited shelf
life, in the order of 60 days. Thus, the users who have a large
volume requirement for solution forms, such as paper m^lls,
textile mills and the like, may purchase material made in
solution form by the manufacturer since they will utilize it
quickly and not have a residual inventory. Other users, where
the shelf life of the product is of considerable importance, will
purchase the material in an anhydrous solid form which has a
relatively indefinite shelf life. Often, before the final use,
the solid may be re-dissolved in either water or alcohol or
mixtures thereof if a solution form is utilized in the
application.
Process Description - Since amino resins are produced in many
specialty grades with each run being a relatively modest volume,
continuous processes are not in general use in the industry. The
typical process is a standard batch polymer kettle arrangement.
As shown in Fig. 26, the normal arrangement consists of a
jacketed polymer kettle ranging in size from about 2,000 up to
10,000 gallons. The larger sizes contain internal coils for
additional heating and cooling surface in order to provide a
reasonable surface-to-volume ratio. The kettles are agitated and
can operate under either pressure or vacuum condition.
The kettle is equipped with a water-cooled condenser and tied
into a vacuum system so that the operating temperature can be
controlled through the use of both reflux and cooling or heating
in the jacket and coils of the kettle. The feed system consists
generally of weigh tanks for the batch operation of the kettle.
The techniques used are very similar for both melamine or urea
types of formaldehyde amino resins. As a typical example, the
production of a plywood adhesive grade urea formaldehyde resin is
as follows. Formaldehyde as a 30 percent solution is added to
the kettle and the pH adjusted to about 7 to 7.8. Boric acid,
the catalyst, is then added, and then urea in the form of a solid
is fed into the reaction vessel. The pH of the mixture is again
brought back to approximately neutral and the mixture heated to
100°C under atmospheric reflux conditions. During this initial
heating period the pH drops to about U as the reaction between
68
-------
FORMALDEHYDE
30% SOLN
BORIC ACID
SODIUM
HYDROXIDE
UREA
(ORMELAMINE)
COOLING
WATER
Y Y Y
A A X
\/
COOLING
WATER
(OR STEAM)
© RESIN PRODUCT (52.5% SOLIDS) 1000.0 LBS
SOLIDS 525.7 LBS
WATER 474.3 LBS
UREA
FORMALDEHYDE (30%)
BORIC ACID
SODIUM HYDROXIDE--
WASTE WATER
— 273.0 LBS
•- 908.7 LBS
— 45.4 LBS
-SMALL LBS
- 227.0 LBS
27.2 GALS
I
COOLING
WATER
(OR CONDENSATE)
RESIN SYRUP
TO STORAGE
OR DRYING
FIGURE 26
AMINO FORMALDEHYDE RESIN PRODUCTION
-------
urea and formaldehyde takes place to form di- and trimethylol
urea. Atmospheric reflux is maintained for a period of about two
hours. Then the vacuum is applied, and the system temperature
drops to approximately 40°C. It is maintained at this level for
approximately five hours. During this period of time there is a
limited amount of condensation reaction taking place between the
various monomers formed earlier. Simultaneous with this further
reaction water is removed from the system so that the final water
content, in the case of this particular adhesive formulation, is
about 50 percent. The water in the system derives from two
sources: that introduced with the 30 percent formaldehyde
solution used as a raw material, and that produced by the
reaction between the monomers, which eliminates a mole of water
for each pair of monomers or trimers reacting.
At the end of the vacuum reflux period, the system is put on
total reflux and the pH adjusted to slightly alkaline conditions.
The reactor is then returned to atmospheric pressure, and the
product is ready to be removed. The total cycle time is about 10
hours.
The mixture, at this point in the form of a thick syrup, is
drained to storage where quality checks are made to determine the
exact condition of the polymers. The material may be shipped in
this form for further polymerization by the customer or it may be
dried to be shipped as a solid which, as mentioned earlier, has a
much longer shelf life. If the material is to be dried, it is
fed to either a belt drier or a spray drier where the remaining
water is removed at low temperature in order to prevent further
polymerization. As mentioned earlier, the final adjustment of
the pH also helps prevent further condensation reaction and
polymerization of the monomers. The water removed during these
final drying operations is vented to the atmosphere.
Depending upon the end-use requirements, the final solid product
may be milled with pigments, dyes and fillers to provide a
moulding compound suitable for the particular end use desired.
The equipment used for the production of the first-step amino
resins is often used for other materials, such as phenolics.
Between these different uses, and indeed between production
batches of melamine and urea resins or between batches of
significantly different resins, it is customary to clean the
equipment by utilizing a hot dilute caustic solution. This
material is drained as process waste.
Acrylic Fibers
The term acrylic fibers refers to the general category of fibers
based on polyacrylenitrile. The modacrylic variation of the
basic fiber, which accounts for a minor proportion of total
acrylic fiber production, is based on the use of comonomers such
as vinylidene chloride or vinyl chloride. (The Federal Trade
commission defines a modacrylic as a man-made fiber in which the
fiber forming substance is any long chain synthetic polymer
70
-------
composed of less than 85 percent but at least 35 percent by
weight acrylonitrile units.) Other monomers such as the vinyl
halogens or acrylates may be included in the polymerization
mixture when fire retardance or specific property modification is
desired.
Solvent is used to dissolve the polymer. This can be dimethyl
formamide, dimethyl acetomide, tetramethylene cyclic sulfone, or
acetone. In-organic salts such as lithium bromide or sodium
sulfocyanide are also known to be solvents, although these are
not used in conventional U. S. practice. The wet spinning solvent
is not a raw material in the conventional sense since its
recovery is necessary for economical operation. Small solvent
losses, however, are a significant factor in wet spinning waste
loads. Other raw materials involved in the production process
include polymerization catalysts and finishing oils. The end
product of the production process is a white, unpigmented
synthetic fiber in staple, tow, or continuous filament form.
Process Description - Both wet and dry spinning are used in
acrylic fiber production. The wet spinning process is
predominant. This process consists of mixing acrylonitrile
monomer, water, catalyst and activator in a continuous
polymerization reactor where polymerization is carried to
approximately 65 percent conversion. The polymer slurry, after
passing through a holding tank, is then passed through a
centrifugal filter and drying bed. The product at this point is
a fine white powder. The polymerization reaction can be
represented as
H
1 (CH2 - CHCN) n
H2C = C - C = N —*•
acrylonitrile polyacrylonitrile
Polymer and solvent are then mixed to form a spinning dope which
is forced through spinnerettes into a coagulating bath (solvent +
E2O) to form the fiber. This is followed by washing baths, steam
stretching operations and a finish bath in which a spin finish
(fatty acids, ethylene glycol) is applied. After leaving the
spin finish bath, the product is then crimped, set (by passing
through a heated oven) and either cut or baled as staple.
In the dry spinning process the spinning dope is forced through
the spinnerette into a heated air chamber rather than a
coagulation bath.
Fig. 27 shows a typical large-scale acrylic fiber production
facility which includes both polymerization and fiber spinning.
Fig. 28 shows acrylonitrile polymerization and dry spinning of
acrylic fibers.
Nylon 6 Resins and Fibers
71
-------
POLYMER RECOVERED SOLVENT
DOPE
DOPE
FILTRATION
ZEOLITE TREATED
CITY WATER
MONOMER EVAPORATION
LOSS TO SCRUBBER
POLYMER
STORAGE
(DRY
POWDER)
RECOVERED MONOMER
MONOMER
RECOVERY
LOW MOL. WT POLYMER
j-
1400qpnn
RAW
MATERIALS
PRODUCT
(ACRYLIC FIBER
OR STAPLE)
WASH WATER
DEIONIZED
H20
DEIONIZED
H20
WASH H20
WASH I
FILTER SOLIDS WASTE TO LANDFILL
FIGURE 27
ACRYLIC FIBER PRODUCTION - WET SPINNING PROCESS
-------
Of the many commercially available polyamides, nylon 6 ranks
second in importance to nylon 66. Nylon 6 resin and fibers are
made from caprolactam. Other raw materials include a catalyst
and acetic acid (chain terminator) . As with other fibers, TiO.2
is added in the polymerization step as a delusterant, spin
finishes are used in processing and thermal stabilizers are
added. End products from the nylon 6 polymerization process are
either resin chips or fiber in the form of staple or continuous
filament.
Process Description - The polycaproamide polymerization process
involves three steps. In the first step (initiation and
addition) caprolactam adds a molecule of H20 to form aminocaproic
acid. Caprolactam successively adds to this growing chain. The
second step involves condensation polymerization of the short
chains formed in the first stage. In the third step the chain
stopping agent (usually a monofunctional acid, such as acetic
acid, or occasionally a monofunctional amine) terminates the
growing chains. The reactions for nylon 6 polymerization are
shown in figure 29.
Numerous processes for both batch and continuous polymerization
are in use. The current economic situation favors the continuous
process, particularly for facilities integrated to fiber
production.
The Lurgi process for continuous polymerization is shown in Fig.
30.
After melting, the molten caprolactam is mixed with catalyst,
acetic acid (chain stopper) and TiO2 delusterant and then passed
to a continuous polymerization tube. Molten polymer from the
polymerization tube is then passed to an extruder which forms the
resin into continuous strands which are solidified by cooling in
a water bath. The strands are continuously cut into chips which
must be subsequently washed by continuous, counter-current
exposure to water in order to extract residual caprolactam.
After extraction, the polymer chips are dried with hot nitrogen
and spun into filament.
The monomer recovery process consists of concentrating the 5
percent caprolactam solution, from the extractor, by a two-stage
distillation to 70 percent caprolactam. This stream is then
exposed to KMnO^ to oxidize impurities and purified by batch
distillation to pure caprolactam which is recycled to the
process.
The Vickers-zimmer process, which is also frequently used for
continuous nylon 6 polymerization, is similar to the Lurgi
process with the important exception that following
polymerization the residual monomer is extracted under vacuum
from nylon 6 polymer in the molten state rather than from solid
chips. It is then possible to avoid chip production, water
extraction, vacuum drying, chip conveying and renewed melting.
73
-------
The Vickers-zimmer process is thus based on two main units: the
polymerization reactor column and a thin-film evaporator.
*Revisions and updating of the process descriptions for the
epoxy resins, phenolic resins, urea and melamine resins will
be incorporated into the Development Document for the
Synthetic Polymers Segment of the Plastics and Synthetics Industry.
74
-------
RECOVERE MONOMER
HOPPER
DEHYDRATION
AND CATALYST
RECOVERY
RECOVERED
WATER AND
CATALYST
AQUEOUS-SUSPENSION ACRYUONITRILE POLYMERIZATION
PUMP
POLYACRYLONITRILE
SOLVENT
SPINNERET STRETCH|NG
HEATED
WALL
/EVAPORATION
/ CHAMBER
HEATED
CHAMBER
i
-------
(a) Initiation and addition to form aminocaproic acid
HN (CH2)S C=0 + H20—*-H2 N (CH2)5 COOH
caprolactam e — aminocaproic acid
(b) Polycondensation
r I' n
H2 N (CH2)5 COOH -*- H 4- N - (CH2)S - C 4- OH + (n-1) H2O
*~ U J M
0
N
Nylon 6
FIGURE 29 TYPICAL POLYMERIZATION REACTIONS TO FORM
NYLON 6 RESIN AND FIBER
76
-------
MELTED
CAPROLACTAM
FROM MELTER
POLYMER
CHIPS
5% SOLUTION OF
CAPROLACTAM TO
RECOVERY SYSTEM
CONCENTRATOR
CONCENTRATOR
17- 20%
CAPROLACTAM
WASTE TO
SEWER
70% CAPROLACTAM
SOLID WASTE TO
LANDFILL
• 70%
CAPROLACTAM
SOLUTION
CONTINUOUS
POLYMERIZATION
TUBE
WASTE TO
SEWER
DRY HOT
NITROGEN
BATCH
DISTILLATION
RECOVERED
CAPROLACTAM
RECYCLED TO
PROCESS
MOLTEN
POLYMER
STILL BOTTOMS
SOLID OLIGOMERS
+ HIGH BOILING
LIQUIDS TO
LANDFILL
(-2% OF
CAPROLACTAM
MONSMER)
DRY NYLON &
CHIPS TO
SPINNING
DOWTHERM
HEATED
JACKET
WATER TO
SEWER
FIGURE 30
NYLON 6 PRODUCTION
-------
-------
SECTION IV
INDUSTRY CATEGORIZATION
The most effective means of categorizing the plastics industry
for setting effluent guidelines is based on the characteristics
of the waste water. In particular, the two most relevant
characteristics are (a) raw waste load, expressed in kg of
pollutant/kkg of product, and (b) attainable BOD5 concentrations
as demonstrated by plastics and synthetics plants using
technologies which are defined as the basis for BPCTCA. The data
on treated wastewater characteristics obtained from the exemplary
plants visited in this program are summarized in Table 12. They
are grouped in four malor subcategories representing combinations
of the waste characteristics discussed above.
Manor Subcategory I - A low raw waste load; raw waste
load less than 10 units/1000 units of product;
attainable low BOD5 concentrations - less than 20
mg/liter. ~"
Major Subcategory II - High raw waste load; raw waste
load greater than 10 kg/tonne product; attainable low
BOD5 concentrations.
Malor Subcateqorv III - High raw waste load; attainable
medium BOD5 concentrations - in the 30-75 mg/liter
range.
Major Subcategory IV - High raw waste load; attainable
high BOD_5 concentrations over 75 mg/liter.
The attainable BOD.5 concentration in the effluent is influenced
by the treatability and, for a specific plant, by the variations
in the influent concentrations. In malor Subcategory I where raw
waste loads are less than 10 units/1000 units of product and
where hydraulic flows ranged from 8.3 to 29.2 cu m/kkg (1000 to
3500 gal/1000 Ib), the influent concentrations ranged from 33 to
530 mg/liter. Disregarding the low influent concentration of the
high density polyethylene plant, the influent concentrations
varied over nearly a five-fold range while the effluents varied
over a two-fold range. This indicates that practicable waste
water treatment plants should be capable of attaining effluent
BOD5 average concentrations in the vicinity of 15 mg/liter when
using properly designed and well operated biological systems.
The plants in major Subcategory II are characterized by high raw
waste loads but with waste waters that can be treated to low
attainable BOD5 concentrations. Raw and effluent loads are a
factor of 10 higher than for the major Subcategory I plants,
largely because of the high water usage for Rayon and Cellophane
and the high BOD5 influent concentration for ABS/SAN resins.
Ma-jor subcategory III plants are characterized by high raw waste
loads and moderate observed flows, which lead to high influent
concentrations. The waste treatment plants achieve BOD5 removals
ranging from 96.5 to 99.3 percent, which are high efficiencies by
79
-------
general standards of industrial waste treatment. Even with these
high removal efficiencies, effluent concentrations are moderate
due to the high concentration of the raw wastes. Major
subcategory IV plants have relatively high raw waste loads and
the observed attainable BOD5 concentrations were found to be
high. The design bases and operational modes of these plants are
such as to indicate that practicable waste water treatment
technology (e.g., two-stage biological treatment) might reduce
the effluent concentrations by a factor of nearly two which would
make them comparable to the plants appearing in major subcategory
III. However, attainable BOD5 concentrations below these levels
has not been documented.
Additional subcategorization within the above four major
subcategories was necessary to account for the wastewaster
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 limitation guidelines and standards of performance
by providing clear and unambiguous direction as to the proper
standard applicable to that product. The substantial advantage
of clairity appears to outweigh any technical advantage of
product grouping. The resulting major subcategories and product
and process subcategories are summarized in table 13.
Several other methods of subcategorization of the industry were
considered. These included plant size, plant age, raw materials
and products, and air pollution and solid waste generation. The
rate of higher unit treatment costs on smaller plants or their
potential for utilizing municipal systems was examined in the
economic analysis but: was not sufficient to warrant
categorization. The age of the plants in this industry are
determined by obsolescence due to size or process changes and not
physical age. Similar raw materials are often used to make
dissimilar products. The impact of air pollution control and
solid waste disposal are not sufficient to warrant segmentation.
For those reasons, none of the above-mentioned factors had
sufficient impact on categorization of the industry to be
considered further.
80
-------
TABLE 12
PERFORMANCE OF OBSERVED WASTE WATER TREATMENT PLANTS
BOD
COD
Cateogry A
Polyvinyl Chloride
Polyvinyl Acetate
Polystyrene
Polypropylene
Low Density Polyethylene
High Density Polyethylene
Inlet
(mg/liter)
380
167
110
517
530
33
Outlet Inlet Outlet
'mg/liter) (mg/liter) (mg/liter)
_TSS
Inlet Outlet
(mg/liter) (mg/liter)
9
10
10
19
16
6
1590
1499
70
72
72
149
80
1312
40
50
35
11
20
32
32
25
•-• Category B
Cellophane
Rayon
ABS/SAN
91
160
1605
20
24
11
288
550
2077
197
350
109
960
400
70
16
Category C
Polyester
Nylon 66
Nylon 6
Cellulose Acetate
Epoxy
Phenolics
Urea
Melamine
4412
1267
545
1200
29
44
65
41
5790
2076
231
183
265
240
382
20
45
58
32
48
Category D
Acrylics
990
140
1735
647
75
-------
TABLE 13
INDUSTRY SUBCATEGORIZATION
Major
Subcategory I
Polyvinyl chloride
Suspension
Emulsion
Bulk
Polyvinyl Acetate
Polystyrene
Suspension
Bulk
Polypropylene
Polyethylene
High Density
Solvent
Polyform
Low Density
Major
Subcategory II
Cellophane
Rayon
ABS/SAN
Major
Subcategory III
Major
Subcategory IV
Polyester Acrylics
Resin
Fiber
Resin & Fiber
Continuous
Resin & Fiber
Batch
Nylon 66
Resin
Fiber
Resin & Fiber
Nylon 6
Resin & Fiber
Resin
Fiber
Cellulose Acetate
Resin
Fiber
Resin & Fiber
82
-------
SECTION V
WASTE CHARACTERIZATION
The general process flow diagrams in Section III have indicated
some of the waste water generation points for individual
processes where information was readily available; however, flow
rates and analyses fcr process waste water streams at points of
origin were not obtainable since the companies surveyed have been
concerned principally with the combined waste water streams.
Analyses of these streams have been performed only because of the
necesssity to establish basis for design of waste water treatment
plants or to provide effluent data under present permits from
state regulatory bodies. As previously discussed, waste water
may emanate from within the process where it was required for the
process operating conditions; it may be formed during the course
of chemical reactions; or it may be used in washdown of process
vessels, area housekeeping, utility blowdowns and other sources
such as laboratories, etc.
R aw Wast e Lo a ds
The Industrial Waste Study of the Plastics and Synthetics
Industry by celanese Research Company (EPA Contract No. 68-01-
0030) (8) the Manufacturing Chemists Association survey of the
industry and plant visits by EPA and their representatives
provided ranges of pollutants occurring in the different product
subcategories of the industry. The reported ranges of raw waste
loads vary all the way from 0 to 135 units per 1000 units of
product for BOD5, from 0 to 334 for COD, and from 0 to 70 for
suspended solids.
Data from the above sources are recorded in Tables 14 and 15 for
waste water flows, BOD5, COD and T.S.S. for each of the product
subcategories. Other elements, compounds, and parameters which
are reported in the wastes from the industry are summarized in
Table 16. Information on raw waste loads for these parameters
was not available from the industry with the exception of zinc
from rayon manufacture. This range is reported in Table 15.
83
-------
TABLE NO. 14
WASTEWATER LOADING FOR THE PLASTICS AND SYNTHETICS INDUSTRY
Wastewater Loading
(gal/lOOO#)
Observed Reported
Flow Range
Uastewater Loading
(cu m/kkg)
Observed Reported
Flow Range
Product
Polyvinyl Chloride—Suspension
Polyvinyl Choride--Emulsioh
Polyvinyl Choride—Bulk
ABS/SAN
Polyvinyl Acetate
Polys tyrene—Suspensi on
Polystyrene—Bulk
Polypropylene
Lo Density Polyethylene
Hi Density Polyethylene--Solvent
Hi Density Polyethylene--Polyform
Cellophance
Rayon
Polyester Resin
Polyester Resin and Fiber
Nylon 66 Resin
Nylon 66 Resin and Fiber
Cellulose Acetate Resin
Cellulose Acetate Fiber
Epoxy
Phenolics
Urea Resins
Mel ami ne
Acrylics
Nylon 6 Resin and Fiber
Nylon 6 Resin
1800
20bO
1000
1100
1000
2130
3500
29400
16500
540
11250
5000
430
1480
220
160
3400
6500
(300-5000
(200-3500)
(0-3000
(0-1 /, 000)
(300-8000)
(0-5,000)
(0-3700)
(12,000-67,000)
((4000-23,000)
(0-20,000)
(0-18,250)
(2000-50,000)
(300-610)
(60-2400)
(300-6160)
15.0
8.3
9.2
8.3
17.8
29.2
245
138
4.5
10.4
41.7
3.62
12.34
1.8
1.3
28.4
54.2
2.5-41.72
1.67-24.03
0-25.03
0.141.8
2.50-66.75
0-41.72
0.30.87
100-559
33.38-191.9
0-167
0-152.3
16.69-417
2.5-5.1
0.5-20
2.50-50.87
84
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TABLE 15
PLASTICS AND SYNTHETICS INDUSTRY
RAW WASTE LOADS
All Units Expressed as Kg/kkg (lb/1000 Ib of Production)
oo
en
PRODUCT
Polyvinyl Chloride
ABS/SAN
PVAcetate
Polys tyrene
Polypropylene
LDPE
HOPE
Cellophane
Fayon (Zinc: 12-50)
Polyes ter
Nylon 6 & 66 Resins
Nylon 6 & 66 Fibers
Cellulose Acetate
Expoxy
Phenolic Resin
Urea Resin
Melamine
BODr
COD
Repor ted
Range
0. 1
2
0
0
0
0.2
0
20
20
3
1
0.1
6
57
15
- 48
- 20.7
- 2
- 2.2
- 10
- 4.4
- 1
-133
- 45
- 20
-135 ,
- 60 6
- 70
- 82
- 51
Observed
Value
5.
20.
1.
1.
4.
1.
22
22
20
6<15
55
--
__
7
7
4
0
4
0
-------
Table 16
Other Elements Compounds and Parameters
Phenolic Compounds
Nitrogen Compounds (organic, ammonia, and nitrate nitrogen)
Phosphates
Oil and Grease
Dissolved Solids
PH
Color
Turbidity
Alkalinity
Temperature
Sulfides
Cyanides
Mercury
Chromium
Copper
Zinc
Iron
Titanium
Cobalt
Cadmium
Manganese
Aluminum
Magnesium
Molybdenium
Nickel
Vanadium
Antimony
Toxic Organic Chemicals
The other elements and compounds listed in Table 16 were based on
surveys of -the Corps of Engineers permit applications for
discharge of wastewaters from a number of plants in the plastics
and synthetics industry, reviews with personnel in regional EPA
offices, the Industrial Waste Study of the Plastics Materials and
Synthetics Industry by the Celanese Research Company (8), the EPA
Interim Guideline Document(51), discussions with industry
representatives, literature data on process operations, and
internal industrial technical consultants.
86
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SECTION VI
SELECTION OF POLLUTANT PARAMETERS
Selection Criteria
Parameters selected for the purpose of effluent limitation
guidelines and standards of performance were based on the
following criteria:
a. Sufficient data on a parameter known to have deleterious
effects in the environment were available for all of the
product subcategories with regard to the raw waste load
and the observed degree of removal with demonstrated
technology.
b. The parameter is present in the raw waste load for an
individual product subcategory in sufficient quantity to
cause known deleterious effects in the environment and
there is demonstrated technology available to remove the
parameter.
Selected Parameters
The following parameters have been selected for the purpose of
effluent limitation guidelines and standards of performance based
on the criteria discussed above:
BOD5
COD~
TSS
Zinc
Phenolic Compounds
Total Chromium
PH
Biochemical Oxygen Demand JBODJ.
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,
87
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and the development of populations. Organisms undergo stress at
reduced D. O. concentrations that make 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
efficiency and growth rate, and reduced maximum sustained
swimming speed. Fish food organisms are likewise affected
adversely in conditions with suppressed DO. Since all aerobic
aquatic organisms need a certain amount of oxygen, the
consequences of total lack of dissolved oxygen due to a high BOD
can kill all inhabitants of the affected area.
If a high BOD is present, the quality of the water is usually
visually degraded by the presence of decomposing materials and
algae blooms due to the uptake of degraded materials that form
the foodstuffs of the algal populations.
£OD
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
sulf ate) . 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 non-biodegradable organic
material. In addition, the presence of inorganic reducing
chemicals (sulf ides, 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.
Suspended so..ds
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
88
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material that destroys the fish-food bottom fauna or the spawning
ground of fish. Deposits containing organic materials may
deplete bottom oxygen supplies and produce hydrogen sulfide,
carbon dioxide, methane, and other noxious gases.
In raw water sources for domestic use, state and regional
agencies generally specify that suspended solids in streams shall
not be present in sufficient concentration to be objectionable or
to interfere with normal treatment processes. Suspended solids
in water may interfere with many industrial processes, and cause
foaming in boilers, or encrustations on equipment exposed to
water, especially as the temperature rises. Suspended solids are
undesirable in water for textile industries, paper and pulp,
beverages, dairy products, laundries, dyeing, photography,
cooling systems, and power plants. Suspended particles also
serve as a transport mechanism for pesticides and other
substances which are readily sorbed into or onto clay particles.
Solids may be suspended in water for a time, and then settle to
the bed of the stream or lake. These settleable solids
discharged with man's wastes may be inert, slowly biodegradable
materials, or rapidly decomposable substances. While in
suspension, they increase the turbidity of the water, reduce
light penetration and impair the photosynthetic activity of
aquatic plants.
Solids in suspension are aesthetically displeasing. When they
settle to form sludge deposits on the stream or lake bed< they
are often much more damaging to the life in water, and they
retain the capacity to displease the senses. Solids, when
transformed to sludge deposits, may do a variety of damaging
things, including blanketing the stream or lake bed and thereby
destroying the living spaces for those benthic organisms that
would otherwise occupy the habitat. When of an organic and
therefore decomposable nature, solids use a portion or all of the
dissolved oxygen available in the area. Organic materials also
serve as a seemingly inexhaustible food source for sludgeworms
and associated organisms.
Turbidity is principally a measure of the light absorbing
properties of suspended solids. It is frequently used as a
substitute method of quickly estimating the total suspended
solids when the concentration is relatively low.
2S» Acidi^ a.nd Alkalinity
Acidity and alkalinity are reciprocal terms. Acidity is produced
by substances that yield hydrogen ions upon hydrolysis and
alkalinity is produced by substances that yield hydroxyl ions.
The terms "total acidity" and "total alkalinity" are often used
to express the buffering capacity of a solution. Acidity in
natural waters is caused by carbon dioxide, mineral acids, weakly
dissociated acids, and the salts of strong acids and weak bases.
Alkalinity is caused by strong bases and the salts of strong
alkalies and weak acids.
89
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The term pH is a logarithmic expression of the concentration of
hydrogen ions. At a pH of 7, the hydrogen and hydroxyl ion
concentrations are essentially equal and the water is neutral.
Lower pH values indicate acidity while higher values indicate
alkalinity. The relationship between pH and acidity or
alkalinity is not necessarily linear or direct.
Waters with a pH below 6.0 are corrosive to water works
structures, distribution lines, and household plumbing fixtures
and can thus add such constituents to drinking water as iron,
copper, zinc, cadmium and lead. The hydrogen ion concentration
can affect the "taste" of the water. At a low pH water tastes
"sour." The bactericidal effect of chlorine is weakened as the pH
increases, and it is advantageous to keep the pH close to 7.
This is very significant for providing safe drinking water.
Extremes of pH or rapid pH changes can exert stress conditions or
kill aquatic life outright. Dead fish, associated algal blooms,
and foul stenches are aesthetic liabilities of any waterway.
Even moderate changes from "acceptable" criteria limits of pH are
deleterious to some species. The relative toxicity to aquatic
life of many materials is increased by changes in the water pH.
Metalocyanide complexes can increase a thousand-fold in toxicity
with a drop of 1.5 pH units. The availability of many nutrient
substances varies with the alkalinity and acidity. Ammonia is
more lethal with a higher pH.
The lacrimal fluid of the human eye has a pH of approximately 7.0
and a deviation of 0.1 pH unit from the norm may result in eye
irritation for the swimmer. Appreciable irritation will cause
severe pain.
Occurring abundantly in rocks and ores, zinc is readily refined
into a stable pure metal and is used extensively for galvanizing,
in alloys, for electrical purposes, in printing plates, for dye-
manufacture and for dyeing processes, and for many other
industrial purposes. Zinc salts are used in paint pigments,
cosmetics, Pharmaceuticals, dyes, insecticides, and other
products too numerous to list herein. Many of these salts (e.g.,
zinc chloride and zinc sulfate) are highly soluble in water;
hence it is to be expected that zinc might occur in many
industrial wastes. On the other hand, some zinc salts (zinc
carbonate, zinc oxide, zinc sulfide) are insoluble in water and
consequently it is to be expected that some zinc will precipitate
and be removed readily in most natural waters.
In zinc-mining areas, zinc has been found in waters in
concentrations as high as 50 mg/1 and in effluents from metal-
plating works and small-arms ammunition plants it may occur in
significant concentrations. In most surface and ground waters,
it is present only in trace amounts. There is some evidence that
zinc ions are adsorbed strongly and permanently on silt,
resulting in inactivation of the zinc.
90
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Concentrations of zinc in excess of 5 mg/1 in raw water used for
drinking water supplies cause an undesirable taste which persists
through conventional treatment. Zinc can have an adverse effect
on man and animals at high concentrations.
In soft water, concentrations of zinc ranging from 0.1 to 1.0
mg/1 have been reported to be lethal to fish. Zinc is thought to
exert its toxic action by forming insoluble compounds with the
mucous that covers the gills, by damage to the gill epithelium,
or possibly by acting as an internal poison. The sensitivity of
fish to zinc varies with species, age and condition, as well as
with the physical and chemical characteristics' of the water.
Some acclimatization to the presence of zinc is possible. It has
also been observed that the effects of zinc poisoning may not
become apparent immediately, so that fish removed from zinc-
contaminated to zinc-»free water (after 4-6 hours of exposure to
zinc) may die 48 hours later. The presence of copper in water
may increase the toxicity of zinc to aquatic organisms, but the
presence of calcium or hardness may decrease the relative
toxicity.
Observed values for the distribution of zinc in ocean waters vary
widely. The major concern with zinc compounds in marine waters
is not one of acute toxicity, but rather of the long-term sub-
lethal effects of the metallic compounds and complexes. From an
acute toxicity point of view, invertebrate marine animals seem to
be the most sensitive organisms tested. The growth of the sea
urchin, for example, has been retarded by as little as 30 ug/1 of
zinc.
Zinc sulfate has also been found to be lethal to many plants, and
it could impair agricultural uses.
Phenols
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.
91
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Phenols also reduce the utility of water for certain industrial
uses, notably food and beverage processing, where it creates
unpleasant tastes and odors in the product.
Chromium
Chromium, in its various valence states, is hazardous to man. It
can produce lung tumors when inhaled and induces skin
sensitizations. Large doses of chromates have corrosive effects
on the intestinal tract and can cause inflammation of the
kidneys. Levels of chromate ions that have no effect on man1
appear to be so low as to prohibit determination to date.
The toxicity of chromium salts toward aquatic life varies widely
with the species, temperature, pH, valence of the chromium, and
synergistic or antagonistic effects, especially that of hardness.
Fish are relatively -tolerant of chromium salts, but fish food
organisms and other lower forms of aquatic life are extremely
sensitive. Chromium also inhibits the growth of algae.
In some agricultural crops, chromium can cause reduced growth or
death of the crop. Adverse effects of low concentrations of
chromium on corn, totacco and sugar beets have been documented.
Nitrogeneous Compounds
Nitrogeneous 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
and acrylics. Ammonia is a common product of the decomposition
of organic matter. Dead and decaying animals and plants along
with human and animal body wastes account for much of the ammonia
entering the aquatic ecosystem. Ammonia exists in its non-
ionized form only at higher pH levels and is the most toxic in
this state. The lower the pH, the more ionized ammonia is formed
and its toxicity decreases. Ammonia, in the presence of
dissolved oxygen, is converted to nitrate (NO3) by nitrifying
bacteria: Nitrite (N(>2) , 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
92
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containing more than 10 mg/1 of nitrate nitrogen (NO^-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 lev^l
present.
Ammonia can add to the problem of eutrophication by supplying
nitrogen through its breakdown products. Some lakes in warmer
climates, and others that are aging quickly are sometimes limited
by the nitrogen available. Any increase will speed up the plant
growth and decay process.
Dissolved Solids
Essentially inorganic salts, dissolved solids are an integral
part of many industry processes. The following manufacturing
processes are known to have the greatest unit loads of dissolved
solids.
Cellulose acetate resins
Cellophane
Polystyrene
ABS/SAN
Epoxy resins
Nylon
Rayon
Polyester resins
The major loads occur in the rayon and cellophane industries
where removal is sometimes carried out on selected, concentrated
streams.
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
93
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whereas they could not be in temperate climates. Waters
containing 5000 mg/1 or more 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 not exceed
500 mg/1.
Limiting concentrations of dissolved solids for fresh-water 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 fresh-water 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 brines. 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 cleaness, color, or taste of
many finished products. High contents of dissolved solids also
tend to accelerate corrosion.
Specific conductance is a measure of the capacity of water to
convey an electric current. This property is related to the
total concentration of ionized substances in water and water
temperature. This property is frequently used as a substitute
method of quickly estimating the dissolved solids concentration.
Toxic^and Hazardous Chemicals
The industry uses a large number of accelerators and inhibitors
which are considered proprietary and, consequently, no informa-
tion was obtainable. Some of these components may be on EPA's
recently established list of toxic substances shown below and the
guidelines must adhere to regulations established for their
usage.
Polychlorinated biphenyls
Eldrin
Dieldrin
Benzidine and its salts
Cyanide and all cyanide compounds
Mercury and all mercury compounds
Endrin
Toxaphene
DDT
DDD
DDE
94
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IronA_Aluminum, Nickel, Vanadium, Titaniumand^Molybdenum
The above metals were selected because they are known to be used
in the processes or to occur in the waste waters of specific
product subcategories. However, insufficient data were available
on raw waste loads or treated waste waters to permit establishing
guidelines at this time. In most cases where these metals are
used, biological treatment systems reduce or remove them to low
concentration levels; however, they should be considered to be
present in specific product subcategories as summarized in Table
17. Receiving water quality standards should determine if
limitations are necessary.
Oil and grease -Color -Turbidity-Phosphates -Sulfides -Copper -
Cadmium_ -Manganese -Magnesium-Antimony
These pollutants are known to be present in waste waters from
certain processes in varying amounts; however, no data was
available which would permit establishing raw or treated waste
loads. Consequently, they are listed so that appropriate
cognizance can be taken in determining if they may be present in
amounts requiring limitation by water quality standards.
95
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OTHER ELEMENTS AND COMPOUNDS SPECIFIC TO
PLASTICS AND SYNTHETICS PRODUCTS
TABLE 17
Subcategory
ABS/SAN
POLYSTYRENE
POLYPROPYLENE
HI DENSITY POLYETHYLENE
CELLOPHANE
RAYON
NYLON 6 & 66
ACRYLICS
Other Element
or Compound
Iron
Aluminum
Nickel
Total Chromium
Organic N
Iron
Aluminum
Nickel
Total Chromium
Vanadium
Titanium
Aluminum
Titanium
Aluminum
Vanadium
Molybdenum
Total Chromium
Dissolved Solids
Zinc
Dissolved Solids
Organic N
Organic N
Phenolic Compounds
96
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SECTION VII
CONTROL AND TREATMENT TECHNOLOGY
The control and treatment technology for the plastics and
synthetics industry can encompass the entire spectrum of water
treatment technologies since selection of specific waste water
treatment technologies must be on the basis of performance
capability. The control and treatment technology for the
plastics and synthetics industry can be divided into three major
categories. These are:
1. Presently used waste water treatment technology.
2. Potentially usable waste water treatment technology.
3. In-plant control of waterborne pollutants.
Categories 1 and 2 are often designated as end-of-pipe treatment;
however, selective applications to segregated streams prior to a
centralized wastewater treatment plant should be considered as an
integral part of waste water control. In-process control
technology is dependent upon two major considerations. (1)
process requirements for water usage and the pollutants resulting
from these operations, such as unreacted raw materials, partially
reacted by-products which must be removed to meet major product
specifications, catalysts or accelerators required for
controlling the reactions, and additives necessary to provide the
appropriate chemical characteristics; and (2J emission of
pollutants into water streams due to poor housekeeping practices,
excessive use of water for control of hazardous conditions such
as fires, leaks and spills due to inadequate equipment
maintenance, and accidental occurrences due to equipment failure
or personnel errors.
This survey found no waste water treatment technology unique to
the plastics and synthetics industry. The application of end-of-
pipeline waste water treatment technology throughout the industry
subcategories has a marked similarity in operational steps, but,
of course, a considerable variation in the results obtained.
Therefore, the waste water treatment technology presently used in
the industry is generally applicable across all industry
subcategor ies.
Presently. Used wastewater Treatment Technology
Wastewater treatment technology in the plastics and synthetics
industry relies heavily upon the use of biological treatment
methods. These are supplemented by appropriate initial treatment
to insure that proper conditions, especially by pH controls and
equilization are present in the feed to the biological system.
97
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Initital treatment for the removal of solids is not routinely
required in the industry and is installed on a selective basis
where the quantity of solids would interfere with subsequent
treatment. The initial step in wastewaster is often equalization
basins for control of pH. Consequently, the disposal of sludges
or solids from the initial treatment step is not the same type of
problem as encountered in municipal sewage systems espcially
since many of the solids that are removed are polymeric materials
which are not significantly affected by biological systems.
Biochemical-oxygen-demanding pollutants in the waste waters from
the industry are amenable to varying degrees of removal depending
upon the usual parameters associated with the specific
biochemical oxidation rates of the waste waters. Table 18
records pertinent operational parameters and average BOD5 COD and
TSS wastewater concentrations found among the waste water
treatment plants selected as exemplary of practical technology.
During the course of this survey, 19 plants were visited. These
plants were selected on the following bases: (1) being exemplary
of practical waste water treatment plant, and (2) being repre-
sentative of typical manufacturing processes. Operating data
from 12 of these plants was reasonably complete so that Tables 19
and 20 could be constructed. Data from the other plants were
inadequate for reasons such as: they discharge into municipal
sewage systems or treat for specific parameters such as phenolic
compound metals or phenolic compound removal; the plants have
only the equivalent of initial waste water treatment; or plant
waste water flows combine with waste waters from other process
units in a manner or quantity which prohibited determining any
meaningful information.
Examination of the waste water treatment plant flowsheet
indicated that the conditions prevailing did not fit into a
single operational category. Although all of the waste water
treatment plants employed biological systems, the treatability of
the different waste waters undoubtedly influence both the design
and established operational modes of practical waste water
treatment systems. In selection of the plants, efforts were
made, whenever possible, to choose plants from which relatively
long-term operational data, e.g. one-year, could be obtained.
While the dominant mode of operation of the biological system is
single-stage aeration, a significant number of the plants have a
two-stage system since long residence time polishing lagoons
follow the aeration step. However, in no instances were a two-
stage activated sludge system found or activated sludge in
combination with trickling filters although these modes of
operation are certainaly practicable. One large multi-product
chemical plant achieves excellent pollutant removal through a
series of anaerobic and facultative lagoons in which the total
residence time of the waste water is 150 days. However, this
type of installation often is not practical because of land
availability or soil conditions. Another multi-product plant,
known for the consistently low BOD.5 concentrations in its
affluents, is based on an elaborate system of monitoring, holding
ponds, waste equalization and/or segregation in conjunction with
98
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TABLE 18
PERFORMANCE OF OBSERVED WASTE WATER TREATMENT PLANTS
BOD
COD
SS
Cateogry A
Polyvinyl Chloride
Polyvinyl Acetate
Polystyrene
Polypropylene
Low Density Polyethylene
High Density Polvethylene
Inlet
(mg/liter)
380
167
110
517
530
33
Outlet Inlet Outlet
(mg/liter) (mg/liter) (mg/liter)
9
10
10
19
16
6
1590
1499
70
72
72
149
80
Inlet
(mg/liter)
1312
40
50
Outlet
(mg/liter)
35
11
20
32
32
25
vo
10
Category B
Cellophane
Rayon
ABS/SAN
91
160
1605
20
24
11
288
550
2077
197
350
109
960
400
70
16
Category C
Polyester
Nylon 6 6
Nylon 6
Cellulose Acetate
Epoxy
Phenolics
Urea
Melamine
4412
1267
545
1200
29
44
65
41
5790
2076
231
183
265
240
382
20
45
58
32
48
Category D
Acrylics
990
140
1735
647
75
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biological treatment. The success of this waste water treatment
plant for removing chemically-active substances is based on its
achieving a high degree of composition uniformity in the feed to
the biological portion. In short, no shortcut method for removal
of chemically-active substances was found when a biological
system was used. Operational success depends upon good design
coupled with competent operation.
Examination of the effluent BOD5 concentrations achieved by the
plants indicates that many are achieving BOD5 concentrations
comparable to those for municipal sewage secondary treatment
plants as proposed by the Environmental Protection Agency in the
Federal Register of April 30, 1973 26. However, because the
influent concentrations of biochemically active substances are
often much greater than in municipal sewage, especially the
soluble portions, the operational modes are different - most
immediately obvious is the much longer residence times. The
effects of influent concentration, residence time, biomass
concentration, aeration capacity and treatability of wastewaters
upon the effluent concentration of pollutants in treated waste-
waters from the synthetics and plastics industry cannot be
categorized as well as for municipal sewage treatment; neverthe-
less, biochemically active portions of these waste waters can be
removed by practicable biological treatment systems to con-
centration levels typical of those achieved in other situations
by the application of available technology. The practical
application of that technology will depend upon such things as
the occurrence of substances reducing or inhibiting the action of
the biological system, the operational nature of the waste water
generating processes, the operational flexibility of the waste
water treatment system, availability of land and the attention
given to operation and maintenance of the waste water treatment
system.
Although the operational conditions of the waste water treatment
plant surveyed were quite different, the general effect of long
residence time in the treatment facilities is increased
efficiency of BOD_5 removal. To provide a rough indication of the
magnitude of the effect of residence time on BOD5 removal
efficiency, data from the plants surveyed are shown in Figure 31.
In this Figure the total load of BOD5 removed has been computed
on the basis of the aeration basin volume and recorded as pounds
of BODJ5/1000 cu ft as a number besides the plotted point. The
effect of this procedure is, of course, to indicate higher values
for the long residence time system. It is recognized that this
procedure is meaningless from the basis of waste water treatment
plant theory; however, for aeration basins loaded in the range of
40 to 70 lbs/BOD5/1000 cu ft (0.6 to 1.1 kg BOD5/cu meter) figure
31 reflects practices in operational waste water treatment
plants. Regardless of the biological methods employed, these
data as well as design considerations reflect the necessity for
extensive facilities to effect high removal efficiencies of
biochemically oxygen demanding substances or to achieve low
concentrations in the treated waste waters. If large land areas
are available, the most practicable method of treating these
100
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TOTAL RESIDENCE TIME (hours)
ts
§
O
H
§
O
H
H)
CO
H
!Z
O
W
W
OJ
T3
m
33
O
m
33
m
o
-------
waste waters may be in long residence time systems; on the other
hand in space limitated locations waste water treatment based on
biological systems may require staged operations or be
supplemented by other treatment methods.
Although the waste water treatment data from different process
plants indicate that biological systems are capable of remvoing
BOD5 substances to roughly similar concentration levels despite
wide variations in influent concentrations, the removal of
carbonaceous substances, characterized by chemical oxygen demand
(COD) or total organic carbon (TOG) , is specific to a particular
industry.
In contrast to municipal sewage where the COD/BOD ratios are
generally less than 5 (32, 30, 37, 23) in the treated effluent,
the plastics and synthetics industry is more apt to have a ratio
in the range of 4 to 12, as shown in Tables 19 and 20. This
reflects the fact that the waste waters contain carbonaceous
substances which are not readily biodegradable, as typified by
the relatively large increase in the COD/BOD5. ratios from the
influent to the effluent of the waste water treatment plant.
These variations have been well established and are reported in
the literature for sewage as well as industrial waste. The waste
waters in the plastics and synthetics industry which were
surveyed during this study indicated the same types of
variability as other industrial waste water.
Considerably greater difficulty is encountered in the high-
efficiency removal of substances measured by the COD test. This
is relfected by the data shouwn in Figure 32. The wide
variations in removal efficiencies indicate that the limits of
biological systems for removal of components measured as COD
depend strongly upon the magnitude of the biologically refractive
portion of the incoming COD. Consequently, these data confirm
that COD is highly specific with respect to the composition of
the waste waters from the various industry subcategories.
Variations in the capabilities of biological systems for removing
biochemically-active substances is especially apparent among the
nylon, polyester and acrylic plants. In effect, two of the
wastewater treatment plants have two-stage biological treatment
due to the long total residence time (554 and 852 hours) in
polishing ponds. The other two plants have single-stage
biological systems. Although insufficient data were available to
determine what portion of the BOD5_ was removed in the polishing
ponds of the plants surveyed, it is apparent that the
difficulties of removing pollutants from acrylic plants are more
severe than from Nylon 66 and polyester plants.
The refractory nature of waste waters from acrylic plants was
further supported by data from a second acrylic plant where a
lightly-loaded biological waste water treatment system was
obtaining high removal efficiencies for BOD5 at low inlet
concentrations, but achieving only a 33 percent removal of COD -
whereas the plant reviewed in Tables 19 and 20 was achieving 62
102
-------
TOTAL RESIDENCE TIME (hours)
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ro
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-------
percent removal. Although the estimated raw waste BOD5 loads for
the second acrylic plant are approximately one-tenth of those for
the plant surveyed, consideration cf the processes indicate that
the lower BOD5 loads should be expected; however, its effluent
has a high concentration of zinc which must be removed prior to
discharge. This plant has an average BOD5 effluent concentration
of less than 10 mg/1.
In addition to the Nylon plants reported in Tables 19 and 20, a
small (0.01 MGD or 37 cubic meters/day), three-stage biological
treatment plant treating highly concentrated wastes from a Nylon
66 plant was surveyed. Although only a meager amount of data
were available, a small number of analyses indicated that the
waste water BOD5 concentrations were approximately three times
those of the plant reported in Tables 19 and 20. The total
residence time in the three sequential aerated basins (with 1.1
to 1.39 HP/1000 cu ft) was 679 hours, and the BOD5 concentration
was estimated (via differential balances on the total process
plant waste waters) to be approximately 160 mg/liter in the
effluent. Although the BOD5 removal efficiency was estimated to
be in the vicinity of 95 percent, the differences in inlet
concentration and, presumably, composition indicated outlet
concentrations nearly four times those of the Nylon 66 plant
chosen as exemplary for this study.
Based on the limited data available on operating waste water
treatment plants, a concensus of industry experiences on
treatability, and a knowledge of the processes generating the
waste waters, it seems that the treatment of waste water from
acrylic plants represents one of the most difficult treatment
problems in the industry.
Wastewater streams from cooling towers, steam generating
facilities and water treating systems are generally combined with
the process waste waters and sent to the treatment plant.
Although the proportion of the total waste water flow contributed
by these streams varies from plant to plant, once-through cooling
sometimes keeps the proportion low; however, where thermal
discharge regulations require the installation of cooling towers,
this portion can be expected to increase. Separate treatment of
cooling tower and boiler blow-downs for removal of corrosion
inhibiting chemicals was found infrequently in this survey. The
procedure for handling these blow-downs most frequently installed
or contemplated was the replacement of the more toxic corrosion-
inhibiting chemicals, such as chromates, with less toxic
substances. Generally, the plants rely upon obtaining
precompounded treatment chemicals and, consequently, depend upon
the supplier to provide information about the toxic aspects of
treatment plants and receiving waters. The choice of anti-
corrosion chemicals and other treating chemicals will depend upon
the operating conditions and construction materials in the
process plant. Since chrornate-based anti-corrosion systems are
usually more effective in controlling rate of corrosion, the
choice of using a less toxic anticorrosion system, where the
blowdown can be discharged to waste water or streams without
104
-------
TABLE No. 19
OPERATIONAL PARAMETERS OF WASTEWATER TREATMENT PLANTS
(Metric Units)
o
Ul
Type of plant
1. Type of Treatment
2. Hyd Load cu in/day
3. Res. !ue (Hrs.)
cu. Betex
5. COD ( " )<4)
6. PWR ( HP )
Cu Meter
7. Kg BOD Removed
HP - Hr.
8. Suspended Solids
(•g/liter)
9. Clarif Overflow
(•eters/day)
10. Bionass (MG/Liter)
11. Kg Removed/day
Kg HLSS
12. Typical Values
MB3N (out)
13. Typical Values
TK N (out)
14. BOD (in)
15. BOD (out)
16. COD/BOD (in)
17. COD (in)
18. COD (out)
19. COD/BOD (out)
20. Efficiency BOD(X)
21. Efficiency COD (%)
ACRYLICS
teut/Settl/
Cool Act. Al.
Slarif. Aerobic
Sludge Digest.
(plant in stup)
10370
(86* of desigi
{1>15 (63)
0. 66
0.94
0.032
0.81
53
N.C.
2000
0.38
906
145
1.91
1735
647
4.46
84
62
POLYESTER
Set tie /Equal
Act. Sl/Clarif
Polish Pond
3030
1(671 of design
(1)47 (852)
0.99
1.15
.039
1.04
45
16.7
3000
0.37
4412
28
1.31
5790
231
8.25
99.4
96
NYLON-66
AND
POLYESTER
Equal/Ext.
Aer Act. SI/
Clarif Aer
NYLON-6
Skinning, Mix.
Act. SI. Clar
Lagoon, sand )
Fi It/Pol Pond
1550
(1)24 (554)
0.86
1.33
3860
9 (21)
0.89
N.G.
.109 .062
1
0.32 0.54
58 53
1
N.G ; 21.2
500 j 2540
1.72 0.36
1267 , 387
44 48
1.63 1
2076
183 j
4.15 '
96.5 ; 87.6
91.4
RAYON
Neut Prin
Treatment Fig
inr Jfro.m Pla
( Second. Treat
31560
[67]
M
fozsl
C. J
(1. 13]
[30]
L J
37.7
N.G.
N.G.
[200]
go!
e-y
[500]
[350]
JIl.6]
[85]
[30]
CELLOBPANE
Act. SI.
Clarif.
26000
1.5
1.00
0.45
0.117
0.36
71
30.56
N.G.
N.G.
90
20
2.5
228
197
9.8
78
14
ABS
Act. SI. Plus
Aerobic SI.
Digeston
5450
56
0.38
0.86
.028
17
2k.f
N.G.
N.G.
57
61
1206
' i
1.76
2077
109
io
99.1
94.7
PVC
Equal/chem
Settle Act.
Sludge Clarif
2270
8.2
1. 17
5.17
0.113
0.45
38
3o.a«>
•I rr Vj2nd)
5550*
0.21
350
10
4. 5^
1590
70
7.0
97.5
PVA & PVC
Chem Settle
Act Sludge
Polish Pond
1020
24
0 45
B.C.
0.152
0.12
9
N.G.
7000<3)
.07(3>
1500
7
-
-
;
99.4
95.6 | N.G.
PVC
Chero Settle
Neut Act.
SI. Clarif.
1400
2.7.
3.59
0.194
Need RUL
N.G.
3^-. k
4000
Need RUL
-
65
816
416
Need RVL
51
LDPE
API Sep/Equal
& Cool/Aer
Lagoon/Clarif
Aer Lagoon/
Clarif/Pollsh
3030
(27.6 da
0. 13
.05
.006
.09
30
12.2(l81
T O o n<
•T^T
N.G.
-
-
376
17
3.98
1499
149
8.76
95.5
90.0
CELLULOSIC
Equal, Act.
Sludge
12870
64 (98)
0.48
N.G.
.025
0.86
68
\2k.k
3300
0.15
-
-
1324
37
-
196
5.3
97.2
N.G.
(1) First value is residence time in activated sludge plant. Vslue in ( ) is res
(2) Air injection: H.P. required calculated by ADL.
(3) About 70Z of HLSS are inorganic.
(4) Total BOD_ removed divided by volume of aeration basin.
in total systei
-------
TABLE No. 20
OPERATIONAL PARAMETERS OF WASTEWATER TREATMENT PLANTS
(English Units)
TYPE OF" PLANT
ACRYLICS
1. Type of Treatment fleut/Settl/
2. Hyd. Load (MGD)
3. Res. Time (Hrs.)
*• «» 'TiirfT^"
5. COD ( " )<4>
6. PWR(HP/1000 ft3)
#BOD Removed
'• H. P. -hour
8. Suspended Solids
(mg/Hter)
9. Clarif Q'flow
(GPD/ft2)
10. Biomass(MG/Liter)
#BOD Removed /Day
' JHLSS
12. Typical Values
NH3 N (out)
13. Typical Values
TK N (out)
14. BOD (in)
15. BOD (out)
16. COD/BOD (in)
17. COD (in)
18. COD (out)
19. COD/BOD (out)
20. Efficiency, BOD(7.)
21. Efficiency, COD(%)
(2) Air injection
(3) About 707. of I
cool act.al.
clarif. Aerobic
Sludge Digest.
(plant in
startup)
2.74
(867. of design)
(1)15 (63)
> 41
59
0.9
1.8
53
N.G.
2000
0.38
906
145
1.91
1735
647
4.46
84
62
POLYESTER
ettle/Equal
ct. Sl/clarif
olish Pond
0.8
67% of design
*47 (852
62
72
1.1
2.3
45
410
3000
0.37
4412
28
1.31
5790
231
8 25
99.4
96
NYLON-66
AND
POLYESTER"
Equal/Ext.
Aer Act. SI/
Clarif Aer
Lagoon, sand
Filters/Pol
Pond
0.41
(1)24 (554)
-
83
3.1
0.7
58
N.G.
500
1.72
1267
44
1.63
2076
183
4.15
96.5
91.4
NYLON-6
Skimming,
Mixing, Act.
Sludge, Clarif
1.02
9 (21)
56
N.G.
1.75
1.2
53
520
2540
0.36
387
48
-
-
_
-
87.6
RAYON
Neut Prin
treatment
Figures in £ J
from Planned
Secondary
Treatment
8.34
|67]
f43j
[38,1
[0.7]
[2.5]
[Mj
9?5(o'load)
N.G,
N.G.
[200]
M
f2 . 5 1
[Boof
f~350]
[11.6]
[85]
(30 1
CELLOPHANE
Act. SI.
Clarit.
ABS
Act. PI. Plus
Aerobic SI.
Digeston
6.87
1.5
63
28
3.3
0.8
71
750
N.G.
N.G.
90
20
2.5
228
197
9.8
78
14
1.44
56
24
54
0.8
17
606
N.G.
N.C.
57
61
1206
11
1.76
2077
109
7.2
99.1
94.7
PVC
Equal /Chem
Settle Act.
Sludge
Clarif.
0.6
8.2
73
323
PVA & PVC
Chem Settle
Act Sludge
Polish Pond
0.27
24
28
N.G.
3.2 4.3<2>
1.0 0.27(2)
38
9
756(lst)
427(2nd)
5550
0.21
N.G.
7000<3>
,07(3>
350 1500
.1° ^
4. 54 '
1590
70 i
7.0
97.5 | 99.4
95.6 ' N.G.
PVC
Chem Settle
Neut Act. SI.
Clarifier
0.37
2.7
Need RWL
224
5.5
Need RWL
N.G.
918
4000
Need RWL
-
65
-
816
416
Need RWL
51
LDPE
API Sep/Equal
& Cool /Aer
^goon/Clar
Aer Lagoon/
C'irif /Polish
0.8
662)
0.81
3.1
0.17
0.2
30
300(lst)
300(2nd)
N.G.
N.G.
376
17
3.98
1499
149
8.76
95.5
90.0
CELLOLOSIC
Equal, Act.
Sludge
3.4
64 (98)
30
N.G.
0.7-
1.9
68
600
3300
0.15
-
-
1324
37
-
-
196
5.3
97.2
N.G.
H.P. required calculated by ADL.
*LSS are inorganic.
(4) Total BOD removed divided by volume of aeration b .:..:..
-------
prior treatment, or using a chromate system which requires the
treatment of blowdown before discharging it to wastewater
treatment plants or streams is predominantly an economic one.
Although only one instance was found in which a system treats
blowdown from a cooling tower, the technology and availability of
equipment for removal of chromium is well established and widely
available. The treatment and/or removal of other constituents is
less well established, although biological treatment systems will
have the capability of removing some of these substances because
they tend to degrade at point of usage, such as in cooling
towers. Obviously, these blowdowns will be high in total
dissolved solids because of the concentrating effects that occur
in the operations.
End-of-pipe treatment technology is based on well-established
chemical methods, such as neutralization and biological
treatment, which can be carried out in various types of equipment
and under a wide variety of operating conditions. The
operability of the end-of-pipe treatment systems for the
synthetics and plastics industry is probably most affected by
intermittent highly-concentrated waste loads, due to the periodic
nature of certain pollutant-generating operations or to
inadvertent spills and leaks. Since one result of these "slugs"
of pollutants is the creation of momentary overloads or
conditions toxic to the micro-organisms, due principally to
concentration effects, the only effective control methods are
preventing their occurrence or providing sufficient volumetric
capacity in equalization basins to ameliorate their effect.
A combination of methods may be used depending upon the nature of
the process operations, safety requirements (such as the dumping
of reactors to prevent runway reactions and possible explosions),
and the availability of land area for the construction of
equalization basins. For presently-operating plants, the most
practical solution is the installation of an equalization basin
of sufficient volume and residence time to insure that any
"slugs" of pollutants can be mixed into larger volumes. This
will usually guarantee that concentration levels are lowered to
the point where the operability of the ensuing treatment step,
usually the biological system, will not be overly affected unless
the pollutants are highly toxic to the microorganisms.
The importance of equalization prior to biological treatment
cannot be overstressed when the potential exists for large
variations in either flow or concentrations of waste waters.
Design and operability of an equalization basin involves the
application of sound hydrodynamic considerations to insure that
mixing of the "slugs" with large volumes of waste waters with
lower concentrations. Consequently, equalization basin designs
may vary from simple basins, which prevent short circuiting of
inlet waste waters to the basin outlet going into the waste water
treatment plant, to basins which are equipped with mixers to
insure rapid and even mixing of influent waste water flows with
the basin volume. In either case, the operability and
reliability of an equalization basin should be high with minimal
-------
expenditure of operating labor and power. The results are well-
designed and well-operated equalizations basins that insure that
the subsequent treatment steps, especially those steps sensitive
to fluctuating conditions (i.e., biological treatment), are not
confronted with widely-varying conditions which may drastically
affect overall performance.
The operability, reliability and consistency of biological waste
water treatment systems are subject to a host of variables. Some
of the most important are the nature and variability of both the
flow and the waste water composition. The best overall
performance of biological treatment systems is realized when the
highest consistency of flow and waste water composition occurs.
While it must be recognized that no waste water stream can be
expected to have constant flow at constant composition, it is
possible to insure that these effects are ameliorated with the
institution of the previously described equalization basins, in
which sufficient capacity has been incorporated in order to
minimize surge flows. In this manner hydraulic flows, at least,
can be varied in an orderly way so that the biological system is
not "shocked" by either high flow rates or high concentrations.
In other words this insures that the most consistent conditions
prevail at all times for the micro-organisms. Because there are
so many variables, that can affect the operation of wastewater
systems based on biological activities, and because biological
activity is often affected by climatic conditions, especially
temperature, the effects of these variables must be recognized
and action taken to minimize them. Since acclimatization of
biological systems is important in achieving and maintaining
maximum performance, it follows that equalization, coupled with
attention to such items as the possible occurrence of chemical
species toxic to micro-organisms, is the basis for achieving the
maximum potential in operability, reliability, and consistency of
biological systems. Although in-line instrumentation such as pH,
dissolved oxygen, total organic carbon analyzers, etc., are
available, their usage, except for pH and, infrequently,
dissolved oxygen, for in-line control is minimal. In other
words, the reliability of some in-line instrumentation for con-
trol has not been developed to a degree where it is frequently
used. Therefore, control of the biological waste water treatment
process relies principally on adequate designs and judicious
attention to the physical aspects of the plant. Consequently,
well-trained, conscientious operators are most important in
achieving the maximum potential reliability and consistency in
biological treatment plants.
Achieving a high degree of operability and consistency in a
wastewater treatment plant is contingent upon the application of
good process design considerations and an effective maintenance
program. The most important factor is the incorporation of dual
pieces of equipment where historical experience indicates that
high maintenance or equipment modification is apt to occur. (For
example, sludge pumps, and provisions for either parallel
treatment facilities or surge capacities large enough to permit
effective repair.) Of course, shutdown of the production plant
108
-------
is a possibility in the case of a malfunctioning waste water
treatment plant; however, it is usually more economical to
provide the required spare equipment to handle conditions that
might reduce the operability of the waste water treatment plant.
Although the highest degree of performance reliability would
probably be achieved by installing two independent waste water
treatment facilities, each capable of handling the entire waste
water load, practical installations and operating costs as well
as the well-demonstrated operability of municipal sewage
treatment plants, indicate that a judicious blend of parallelism,
surge capacity, and spare equipment are the major factors to be
considered. Some of the most critical parameters that should be
incorporated in the design of waste water treatment for the
synthetics and plastics industry are as follows:
1. Provision for surge capacities in equalization basins or
special receiving basins to permit repair and maintenance of
equipment.
2. Installation of excess treatment capacity or provisions
for rapidly overcoming effects which may destroy or
drastically reduce the performance of biologically based
treatment systems.
3. Installation of spare equipment, such as pumps and
compressors, or multiple units, such as surface aerators, so
that operations can be continued at either full or reduced
capacity.
H. Layout of equipment and selection of equipment for ease
of maintenance.
Water recycle has not been used with any consistency or frequency
as a method for miniirizing water usage and possibly assisting in
reducing the size, if not the total pollution load, of the waste
water treatment system. Two of the major reasons for this are
(1) the industry, except for the cellulosics, is a relatively low
user of water per unit of product; and (2) high-quality process
water is often required in order to maintain product quality.
Consequently, the recycling of water into the process has not
been encountered. In one instance, however, intermittent usage
of treated waste waters for washdown of process areas was found.
The major potential for reduced water usage lies in the judicious
control of process steps using water for washing, scrubbing, and
so on, by employing countercurrent flow operations and by strict
attention to housekeeping operations. The effects of recycling
treated waste waters in which buildup of refractory substances is
permitted has never been determined. Consequently, recycle of
treated waste water as it might influence control and treatment
technology is limited to utilization of a lower-quality water
commensurate with lowered requirements, such as might be
encountered in the washing of floors or in hydraulic transport
systems where product quality is unaffected.
109
-------
The waste waters in the synthetics and plastics industry are
generally deficient in the nitrogen and phosphorus needed to
maintain a viable mass of micro-organisms. Consequently, it is
often necessary to add nitrogen and phosphorus, usually in the
form of liquid ammonia and liquid phosphoric acid. In some
instances, such as waste water from ABS/SAN, urea and melamine
manufacturing, the nitrogen content in the chemicals results in
an overabundance of nitrogen. In general, the addition of
nitrogen and phosphorus is difficult to control because of the
waste water composition and variations in the biological treat-
ability coupled with the lack of satisfactory in-line
instrumentation. Consequently nutrient additions are often at
either a constant rate or in proportion to the volumetric flow
rate with the result that these nutrients often appear in
appreciable quantities in the treated effluent due to either
excessive feed or because the variability in waste composition
caused these excesses to occur. When nutrients are required, it
can be expected that their concentration levels will be within
the ranges found in municipal sewage treatment plant effluent,
except that the ammonia nitrogen content will probably be
greater. Effluent leadings of BOD5, COD, and TSS from observed
exemplary operating biological treatment plants for each product
subcategory are summarized in Table 21. For the product
subcategories of epcxy resins, phenolic resins, urea resins, and
melamine resins the waste loadings are estimated based on levels
of attainable concentrations associated with other products that
have similar waste constituents.
It is apparent that presently used waste water treatment
technology for the plastics and synthetics industry has been
demonstrated sufficiently so that effective treatment of the
biologically degradable portions can be achieved. The design and
operational bases for effective biological waste water treatment
systems are well understood; however, because each plant of the
industry may generate waste water pollutants that have unique
biological refractoriness, the removal of COD substances to the
same degree as BODjj is not achievable in biological systems.
E°i§Htiaii.Y Usable Wastewater Treatment Technology
Technologies for removal of pollutants from water or, conversely,
water from pollutants have been widely investigated in recent
years. As a result, a voluminous literature exists on waste
water treatment; however, the categorization of these
technologies is readily effected on the basis of the physical,
chemical and biological operations involved. The technologies
described in the ensuing paragraphs are not now being utilized in
any significant number for the treatment of waste waters in the
industry. Three of the technologies with most promise for near
future application of waste water treatment are believed to be
adsorption, suspended solids removal and chemical precipitation.
110
-------
TABLE 21
Observed Treatment and Average Effluent Loadings
From Plant Inspections
PRODUCT
Control and Treatment
Technology Currently
In Use
Observed Average
Effluent Loadings
(Kg/Tonne (lb/1000 Ib
Production)
COD
SS
PRODUCT
Control and Treatment
Technology Currently
In Use
Observed Average
Effluent Loadings
(Kg/Tonne (lb/1000 Ib
Production)
BOD5
COD
SS
PVC
Equalization
Chemical Treatment
Settling Activated
Sludge Clarification
ABS/SAN
PVAcetate
Polypropylene
LDPE
Equalization Equalization Discharge
Activated Sludge Chemical Treatment Into
Aerobic Sludge Activated Sludge Multi-Plant
Clarification Clarification Effluent
Polishing Pond
Screen API Separator
Equalization Equalization
Chem. Treatment Aerobic Lagoop
Artivated Sludge
Polishing Pond
HOPE
Screen
Chemical
Treatment
Aeration Pond
0.14
1.0
0.80
Cellophane
Equalization
Activated Sludge
Clarification
0.184
1.83
0.52
Rayon
Chem. Treatment
Equalization
Activated Sludge
Clarification
0.08
0.60*
0.09
Polyester
Settle Chemical
Treatment
Equalization
Activated Sludge
Clarification
0.09 0.33
0.66* 0.66
0.18* 0.57
Nylon 66 Nylon 6
Equalization Skimming
Chem. Treat. Equalization
Activated SI. Chem. Treatment
Clarification Activated Sludge
Aerated Lagoon Clarification
Polishing Pond
0.13 0.18
0.87 1.0
0.26 .31
Phenolic Urea
Epoxie Resin Resin Melamine"
No separate treatment facilities
encountered. Most plants discharge
to municipal systems or are part of
a major complex.
Cellulose
Acetate
Equalization
Chem. Treatment
Settling
Activated Sludge
Clarification
Acrylic
Equalization
Chem. Treatment
Settling
Activated Sludg.
Clarification
4.9
41
3.5
3.3**
38**
4.1
.13
1.5
0.20
0.55
2.0
0.66
3.7
15*
1.8
0.16*
0.80*
0.32*
0.55* 0.08*
2.8* 0.40*
1.1* .16*
0.06* 1.7
0.30* 14
.12* 2.8
4.0
17
1.5
* Estimated value
** Estimated value for proposed system
-------
Adsorption
Removal of soluble substances, such as characterized by
the COD or TOG measurements, is relying increasingly on
the use of adsorptive techniques either by the use of a
solid adsorbent usually contained in a fixed bed or the
use of adsorbent floes such as the hydroxides of
aluminum and iron. For soluble substances the fixed bed
adsorption system such as typified by granular activated
carbon has been most widely used in the waste water
treatment industry although the use of powdered
activated carbon is technically feasible. Adsorptive
floes are more frequently used for the less soluble
substances although floes are known to be effective for
removal of color bodies under certain conditions.
However, granular activated carbon is believed to be the
leading technology for removal of soluble organic
species since it has been demonstrated for the removal
of phenolic compounds, although its efficiency varies
widely. (18, 19, 31, 41r 56) Consequently, it is
necessary to establish removal capabilities through
either pilot plant tests or laboratory determinations of
adsorption isotherms before design and operating
conditions can be determined. Process designs for
carbon adsorption systems are readily available from
consultants and equipment manufactures. Also, process
design procedures (67, 68) are available in the
literature. Table 22 illustrates a number of
applications of granular activated carbon systems
currently in use by industry. Table 22A gives a summary
of EPA research, development and demonstration projects
utilizing activated carbon adsorption technology.
Although granular activated carbon adsorption for the
removal of refractory organic species from waste waters
is proving to be effective, there is an economic
necessity that the spent granular activated carbon be
regenerated without undue loss of carbon or adsorptive
capacity. Consequently, the activated carbon systems
usually include a method for carbon regeneration
(thermal regeneration is used most frequently) or
arrangements are made for custom regeneration. The
operation of activated carbon systems for removal of
pollutants in this industry is not presently practiced
although activated carbon is being used for the
selective removal of phenols (56) which are a
constituent of some of the industry wasterwaters. Like
all technologies, activated carbons adsorption is not
without problems, e.g., the occurrence of biological
growths in the activated carbon bed is well known.
Since these may often occur under anaerobic conditions
the generation of hydrogen sulfide and other odoriferous
substances is encountered. Furthermore, since thermal
regeneration is most frequently used, care must be taken
112
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TABLE 22
SUMMARY OF
INDUSTRIAL SOURCES USING GRANULAR ACTIVATED CARBON SYSTEMS
Industry
Location
Principal Product
Contaminant(a) Removed
1.
2.
3.
4.
5.
6.
7...
Velvet Textiles
BASF Wyandotte
Chemical Corp.
ARCO-Watson
Refinery
Stephen Leedom
Reiohhold
Chemicals/ Inc.
Schnectady
Chemicals, Inc.
Chipman Div. of
Blacks tone, VA
Washington, NJ
Wilmington, CA
Southhampton , PA
Tuscaloosa, AL
Rotterdam, NY
Portland, OR
Velvet
Polyethers
Refinery Products
Carpet Mill
Phenol , Formalydehyde ,
Pentaerythritol ,
Orthophenylphenol, synthetic
resins, and plastics
Phenolic Resins
Herbicides-2,4-D acid, MCPA
Dyes, Detergents,
Organics
Polyethers (MW 1000-
3000)
COD
Dyes
COD, Phenols
Phenols
COD, Phenols
Rhodia, Inc.
8. Sherwin-Williams
Co.
9. Mobay Chemical Co.
10. Burlington Army
Ammunition Plant
11. Stepan Chemical
Co.
Chicago, IL
Houston, TX
Burlington, IA
Bordentown, NJ
acid, 2, 4-DB acid and ester?
of these products
p-Cresol
Explosives
Intermediate Detergents
p-Cresol
Color
TNT
Color and organics
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
Georgia Pacific
Stauffer Chemical
General Electric
Co.
C.H. Masland &
Sons
St. Regist Paper
Co.
Monsanto Indus-
trial Chemicals
Hercules, Inc.
Dow Chemical
Hardwicke
Chemical Co.
Crompton and
Knowles Corp.
Conway, NC
Skaneatelfis Falls,
NY
Selkirk, NY
Wakefield, RI
Pensacola, FL
Anniston, AL
Hatiesburg, MS
Midland, MI
Elgin, SC
Gibraltar, PA
Phenolic Resins
Strong Alkaline Detergents
Plastics
Carpet Yarn
Kraft products
Intermediate Organic Chemicals
(polynitrophenol)
Acid Resins, turpines & solvents
Phenol
Intermediate and Specialty
Organic chemicals
Dyes
l 1 ->
Phenols
COD
Phenols and COD
Color and COD
Color
Polynitrophenol
Organics
Phenols and Acetic Acid
COD, Color
Dye , COD
-------
TABLE 22a.
Summary of EPA Research Development and
Demonstration Projects Utilizing Activated
Carbon Adsorption Technology
(1) EPA Advanced Wastewater Treatment Demonstration
Grant No. 17080 EDV, "Terticry Treatment by Lime
Addition at Santee, California, "Santee County
Water District, Santee, California, January 12, 1966.
(2) EPA Advanced Wastewater Treatment Demonstration Grant
No. 802719, "Interim Wastewater Treatment Plant
Demonstration, Covington Kentucky, "Campbell and Kenton
Counties Sanitation District, July 23, 1973.
(3) EPA Advanced Wastewater Treatment Demonstration
Grant No. 80265, "Physical Chemical Treatment Evaluation,"
Metropolitan Sewer Board Minneapolis, St. Paul Minn.,
January 1 , 1974.
(4) EPA Storm and Combined Sewer Research Grant No, 802433
Rice University, Houston, Texas, "Maximum Utilization of
Water Resources in a Planned Community, July 16, 1973.
(5) EPA Industrial Research Grant No. 17020 EPF, "Adsorption
from Aqueaus Solution," University of Michigan, Ann Arbor
Michigan, October 1, 1969.
(6) EPA Industrial Demonstration Grant No. 12050GXE, "Treatment
of Oil Refinery Wastewaters for Reuse Using a Sand Filter
Activated Carbon System, B.P. Oil Company, Marcus Hook,
Pennsylvania January 1, 1971.
(7) EPA Industrial Demonstration Grant No. 12020EAS "Recondition
and Reuse of Organically Contaminated Waste Sodium Chloride
Brines, Dow Chemical Company, Midland, Michigan, January 6, 1959.
(8) EPA Advanced Wastewater Treatment Demonstration Grant No.
11060 EGP," Advanced Waste Treatment at Painesville, Ohio,
City of Painesville, Ohio, December 15, 1969.
(9) EPA Research Grant Mo. 12040 HPK, "Organic Compunds
in Pulp Mill Lagoon Discharge," University of Washington.
(10) EPA Research Study No. 21ACU07, "Development of Analog
Chemical Treatment," EPA NERC Cincinnati, Ohio, January 7, 1972.
114
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(11) EPA Research Study No. 21 ABD 06, "Process Modification
to Enhance Removal of Heavy Metals, NERC Cincinnati, Ohio,
January 4, 1973.
(12) EPA Advanced Wastewater Treatment Demonstration Grani;
No. 11010 EHI, "Teritory Treatment of Combined Storm
Water Sanitary Relief Discharge and Sewage Treatment
Plant Effluent," Sanitary District of East Chicago,
January 12, 1966.
(13) EPA Advanced Waste Treatment Demo Grant No. 11010 DAB,
"Chemical Clarification and Carbon Filtration and Adsorption
as Secondary Treatment for Rocky River Wastewater Treatment
Plant, Cuyahoga County, Ohio Sewer Dicstrict, August 16, 1968.
(14) EPA Industrial Demonstration Grant No. 801431, "An Activated
Carbon Secondary Treatment System for Purification of a
Chemical Plant Wastewater for maximum Reuse, "Hercules, Inc.,
January 3, 1973.
(15) EPA Demonstration Grant No. 800554, "Carbon Adsorption and
Regeneration for Petrochemical Waste Treatment," University
of Missouri, Columbia, Misssouri, January 6, 1972.
(16) EPA Research Contract No. 68-01-0183 "Physical Chemical
Treatment of Municipal Waste," Envirotpch Corporation
Salt Lakp City, Utah, July 4. 1972.
(17) EPA Research Contract No. 68-01-0137, "Development
and Demonstration of Device for on Board Treatment
of Wastes from Vessels," AWT Systems Inc, Wilmington
Delaware, March 6, 1971.
(18) EPA Research Contract No. 68-01-0130, "Device for On
Board Treatment of Wastes from Vessels," Fairs banks
Morse, Inc., Beloit, Wisconsin, March 6, 1971.
(19) EPA Research Contract No. 68-01-0104, "Recreational
Water Craft Waste Treatment System," Ametek/Calmec
Tnc., Los Angeles California, March 6, 1971.
(20) EPA Research Contract No. 68-01-0099, "Development of
Modular Transportable Prototype System for Treating
Spilled Hazardous Materials," Hernord, Inc., Milwaukee,
Wisconsin, June 29, 1971.
115
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(21) EPA Research Contract No. 68-01-0077, "Process for
Housing and Community Development Industries," Levitt
and Son, Nassau County, New York, June 15, 1971.
(22) EPA Research Contract No. 68-01-0013, "Waste Heat
Utilization in Waste Water Treatment," URS Research
Company, San Mateo, California, December 31, 1970.
(23) EPA Research Contract No. 58-01-0901, "Study of
Improvements in Granular Carbon Adsorption Process,"
FMC Corporation, Princeton, New Jersey, June 26, 1970.
(24) EPA Advanced Waste Treatment Contract No. 58-01-0444,
"Carbon Adsorption and Electro dialipes for Demineralization
at Santee California," Santee County Water District,
Santee California, June 29, 1968.
(25) EPA Research Contract No. 58-01-0400, "Activated Carbon
Powder Treatment in Slurry Clarifiers," Infilco, Fullers
Company, Tucson, Arizona, June 9, 1968.
(26) EPA Research Contract No. 58-01-0075, "Study of Powdered
Carbons for Waste Water Treatment, "West Virginia Pulp
and Paper Company, Covington, Virginia, June 29, 1967.
(27) EPA Research Study No. 21ABK-31, "Treatability of Organic
Compounds," EPA NERC Cincinnati, Ohio, January 7, 1973.
(28) EPA Research Study No. 21 ABK 16, "Treatability of Organic
(29) EPA Research Study No. 21 ACP 09, "Removal of Toxi Metals
in Physical Chemical Pilot Plant," EPA NERC Cincinnati, Ohio
January 1, 1972.
(30) EPA Research Study No. 16 ACG-05, "Identify Pollutants
in Physical Chemical Treated Wastes," EPA NERC Corvallis,
Oregon, January 8, 1971.
(31) EPA Advanced Waste Treatment Demonstration Grant No. 800685,
"A Demonstration of Enhancement of Effluent from Trickling
Filter Plant," City of Richardson, Texas, December 24, 1971.
(32) EPA Advanced Waste Treatment Demonstration Grant No. 801026,
"Removal of Heavy Metals by Waste Water Treatment Processes,"
City of Dallas, Texas, January 2, 1972.
(33) EPA Advanced Waste Treatment Demonstration Grant No. 801401,
116
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"Piscataway Model advanced Waste Treatment Plant," Washington
Suburban Sanitary Commission, Hyattsville, Maryland, January
1, 1967.
(34) EPA Research Grant No. 800661, "Oxidation Mechanisms on
Supported Chromia Catalysts, "Purdue Research Foundation,
Lafayette, Indiana, January 6, 1970.
(35) EPA Research Grant No. 12130 DRO, "Deep Water Pilot Plant
Treatability Study," Delaware River Basin Commission,
Trenton, New Jersey, July, 1971.
117
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to insure that the gaseous products from regeneration do
not cause air pollution.
Suspended Solids Removal
Suspended solids removal from the effluent of biological
waste water treatment plants has not been widely
practiced in the plastics and synthetics industry.
Although a wide variety of methods can be used for
removing suspended solids from liquids, the application
of these methods to wastewaters inevitably containing
biochemically active substances requires special
consideration because biological growths and slimes can
result in poorly operating systems. Process designs for
suspended solids removal systems applicable to municipal
waste waters have been reviewed (69) and the same
equipment will be applicable for suspended solids
removal in this industry's waste waters. In-depth media
filtration is most frequently utilized for the removal
of suspended solids from waste waters because the media
can be cleaned by suitable hydraulic methods. Other
methods for suspended solids removal that might be
applicable are precoated filters, wherein a material
such as diatomaceous earth is used and subsequently
discarded, and membrane filtration. However, neither of •
these are expected to take precedence over the more
conventional in-depth media filters that have been
widely used in water treatment. The selection of
suspended solids removal equipment is dependent,
obviously, upon the physical and chemical nature of the
solids and the degree of removal to be achieved.
Chemical Precipitation
By changing the chemical characteristics of waste waters
it is often possible to effect removal of soluble
substances by rendering them insoluble at which point
the problem becomes one of removing suspended solids.
The most common technique is alkaline precipitation used
for the removal of metallic species. The removal of
zinc in the rayon and acrylic industries by alkaline
precipitation is the only instance of its practice in*
this industry. Zinc removal has been the subject of a
demonstration project (65) although the technology for
removal of other metals is well known and has been
reviewed by Patterson & Minear (47) in some detail.
Since many of the precipitated substances are in the
form of hydrous oxides, removal of the precipitated
solids are often difficult with the frequent result that
concentrations in the treated effluents are greater than
would be indicated by the solubility products of the
chemical species. An excellent example is the
aforementioned project (47) where the effluent
concentration of zinc varied widely over an extended
period for reasons as yet not completely understood.
118
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Prior chemical reactions may be required to effect
removal of certain species such as the conversion of
Cr+6 to Cr+3 by sulfur dioxide followed by precipitation
with an alkali such as lime. Obviously, where chemical
precipitation changes the pH of the treated waste waters
to a value outside the specified limits for discharge,
subsequent readjustment of pH will be required. Another
area where chemical precipitation is finding increasing
usage is for the removal of phosphates from the
effluents of biological waste water treatment plants.
Phosphate precipitation relies primarily on the use of
calcium, iron, or aluminum compounds and has been the
subject of widespread investigations which are well
reviewed in a design manual(70) and mathematical
model(71). Since the results of chemical precipitation
are dependent upon the complex interrelationships of
chemical species, equilibrium constants and kinetics,
the degree of applicability of chemical precipitation
for the removal of pollutants from waste waters cannot
be generalized and its effectiveness must be determined
for each application.
Among waste water treatment technologies, the following have
reached various stages of development or can be readily
transferred from other fields when their unique capabilities are
required.
Anaerobic Process
Although anaerobic processes has been most widely used
for the digestion of biological sludges, the removal of
nitrates from waste waters is receiving increasing
attention (72, 73, 74). To effect removal of nitrogen
values, it is necessary that a biological treatment
plant be operated in a manner which results in a
nitrified waste water such as from extended aeration
treatment plants. Denitrification usually requires the
addition of a supplementary carbon source and methanol
or molasses has been found especially useful. The
largescale demonstration of biological denitrification
is being pursued at a number of municipal installations.
Because excess supplementary carbonaceous substances are
usually required to provide adequate food supply for the
denitrification bacteria, the effluent from biological
denitrification often has a greater concentration of
BOD5 or COD than the influent. However, because of the
difficulties of removing nitrogen substances due to high
solubilities and the complex interactions in secondary
biological treatment systems, denitrification is
expected to be utilized more frequently where low
concentrations of nitrogenous substances in treated
waste waters is necessary.
Air Stripping
119
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The removal of ammonia from alkaline solution is the
major potential application for air stripping (22, 34) in
this industry. Although the process has been
demonstrated in moderately large operations, its
selection will depend upon the nature of the waste
waters and receiving stream requirements for the removal
of nitrogenous substances. Scale formation in
equipment, typically of a cooling tower configuration,
can cause severe operational problems or demand close
control of the chemistry of the system. In addition,
air stripping of ammonia is very temperature sensitive -
i.e., proceeding at very slow rates at low temperatures.
The stripped substances are usually in such low
concentrations that they are not considered to be air
pollutants.
Chemical Oxidation
Chlorine, permanganate, hypochlorite, ozone and so on
may be used to chemically oxidize some pollutants.
Breakpoint chlorination for destruction of ammonia in
treated waters from municipal sewage plants has long
been recognized and ozone has been used for the
treatment of potable water. The application of
oxidative chemicals requires that specific determination
be made of their effectiveness in removing the
pollutants and, in particular, to determine if the
reaction products are innocuous. As a particular
example, the chloramines produced by chlorine and
ammonia are more toxic to aquatic life than the ammonia.
similarly, the toxic aspects of manganese, ozone, etc.,
must be carefully evaluated to insure that the removal
of one type of pollution does not result in creating a
different or, perhaps, even more severe pollution
problem. Consequently, it is expected that chemical
oxidation will be employed on a highly selective basis
such as in the destruction of cyanide where its overall
effectiveness is assured.
Foam Separation
Surfactants added to a waste water followed by air
blowing to produce a foam can effect a concentration of
various substances often found in waste waters.
However, successful development above the pilot plant
scale has not been demonstrated and its usefulness as a
treatment technology will probably be extremely limited.
Algal Systems
Nutrient removal by the growing of algae is well known;
however, it has not achieved any significant acceptance
due primarily to (1) the necessity of having a
relatively warm climate with high incidence of sunshine
120
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and (2) the difficulties of removing the algae from the
waste water before discharge.
Incineration
Destruction of pollutants by combustion or incineration
is technically feasible regardless of the concentration
insofar as the products of combustion do not create an
air pollution problem. At the present time,
incineration of concentrated liquid wastes containing
phenolic compounds is being practiced. Equipment is
available for achieving incineration of virtually any
type of waste; however, the use of supplementary fuel is
usually required. Incineration is not frequently used
because of the high cost of energy. In some instances
where the removal of pollutants cannot be achieved in a
less costly manner or because disposal of the removed
pollutants still presents a severe problem, incineration
may be the best method of water pollution control.
Wet Air Oxidation
The oxidation of organic pollutants by introducing air
or oxygen into water under pressures of from 300 to 1800
psig that has been primarily used for the destruction of
sludges. For the oxidation to proceed autogenously, it
is necessary that a sufficient concentration of
oxidizable substances be present to provide the
exothermic energy necessary to maintain the required
temperatures. Partial oxidation of concentrated
biological streams such as the sludges from initial and
biological treatment results in a stabilized solid which
can be used as a soil conditioner. Wet air oxidation
will probably continue to be considered primarily for
the destruction of concentrated pollutants such as
slurries or sludges.
Liquid-*Liquid Extraction
The transfer of mass between two immiscible phases,
known as liquid-liquid extraction, is often capable of
achieving high degrees of removal and recovery of
selected components. The technology has been well
developed in the chemical and nuclear fuel industries
but has been infrequently applied to the treatment of
waste water streams. Liquid-liquid extraction would
usually be employed to remove a relatively valuable
component or a particular noxious substance from a waste
water stream prior to additional treatment. A typical
example is the recovery of phenolic compounds. rs Loss
of the extracting liquid to the water stream must be
considered since it may then be a pollutant which
requires further removal before discharge of the treated
waste water.
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Ion-Exchange
The removal of ions from water by the use of ion-
exchange resins has been well established in the field
of water treatment. Man-made resins or naturally
occurring minerals such as zeolites or clinoptilolite
have been used. The removal of zinc from viscose rayon
wastes by ion-exchange has been demonstrated; however,
successful long-time operation has not been achieved.
Ion exchange has been used for the removal of nitrates
and clinoptilolite has been shown to be effective in the
removal of ammonium ion from waste waters. Although ion
exchange can be an effective method for the removal of
ionic species from waters, the economic necessity for
regeneration of the ion-exchange media results in a
concentrated liquid stream for which further disposal
must be considered. It is expected that the use of ion
exchange in waste water treatment would be limited to
the selective removal or concentration of pollutants for
which more economically effective methods are not
available. Since ion-exchange regenerates add mass to
the waste stream from the regeneration, ultimate
disposal of concentrated streams from ion-exchange
systems will contain more total dissolved solids than
removed from the waste waters.
Reverse Osmosis
Desalination research and development efforts have been
responsible for the development of reverse osmosis as a
method for removal of ionic species from waste waters.
Also, non-ionic species can be removed; however, control
of membrane fouling must be given special consideration.
The major process advantage of reverse osmosis is its
low energy demand when compared with evaporation and
electrodialysis; however, the costs of replacement
membranes may be an offsetting factor to the total cost
picture. The applicability of reverse osmosis to the
treatment of waste water streams can only be determined
by laboratory and pilot plant tests on the waste water
of concern. As in the case of ion exchange reverse
osmosis produces a concentrated stream containing the
removed pollutants and further consideration must be
given to its disposal.
Freeze-Thaw
Controlled freezing followed by separation and thawing
of the ice crystals has undergone extensive development
as a desalination method. As in the case of reverse
osmosis, it must be evaluated for specific situations.
Again, the ultimate disposal of a liquid stream highly
concentrated in pollutants must be taken into
consideration when evaluating the overall waste water
disposal problems.
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Evaporation
Evaporation has been well developed and widely used for
the desalination of seawater. Furthermore, it is a well
developed operation in the chemical process industries.
Unfortunately, direct evaporation is the most energy
consuming of the water removal processes; therefore,
elaborate multi-stage systems are required to effect
energy economy. Its application to the concentration of
selected waste water streams is established; however,
evaporation is usually used in conjunction with other
process operations where the energy demands and
resulting concentrated solutions can be justified on the
basis of most economic overall performance.
This approach can be expected to continue in the face of
rising energy costs and increasingly stringent
limitations on waste water discharges. The technical
feasibility of evaporation will have to be determined
for specific situations since a highly concentrated
waste water may cause fouling of heat transfer
substances. Also, volatile species which can be removed
by the steam stripping action and, consequently, appear
in the condensate would mean further treatment before
reuse or discharge. Again, the disposal of highly
concentrated streams of pollutants (primarily inorganic
species) must be considered.
Electrodialysis
Developed for the desalination of water, electrodialysis
is a separation technique that would be expected to
compete with ion exchange, reverse osmosis, freezing and
evaporation for the removal of pollutants from waste
water streams. As in the case of all of these,
electrodialyses for waste water treatment must be chosen
on the basis of achieving the necessary performance
under required operating conditions.
In-Plant Control of Waterborne Pollutants
Pollutants removed frcm process streams in the course of removing
water generated by reactions, or water required for effecting
reactions or purifying products, are specific to particular
processes. However, an ubiquitous source of waterborne
pollutants is attributable to spills, leaks and accidents, within
process plants handling liquids. The synthetic and plastic
industry is, of necessity, required to handle and process liquids
under a wide variety of conditions, although the major products
are usually solids. Consequently, all segments of the industry
will be found to contribute waterborne pollutants due especially
to spills and leaks in process operations as well as support
operations. The importance of this subject has been reviewed in
123
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several articles based on work funded by the Environmental
Protection Agency. (60, 61)
The major way to control the emission of pollutants from spills
and leaks is to recognize the potential that exists in various
areas of the plant. The following matrix was developed in the
previously referenced work as a method for controlling and
ranking the main functions of areas in liquid handling
facilities.
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TABLE 23
MAi.tlX FOR EVALUATING LIQUID
HANDLING FACILITIES
Probability of Spillage
Loading and
Storage Transfer Unloading
Inventory of
Contained Liquid
Frequency of
Operating Cycles
Very
High
Low
Ratio:
Temporary Connections Very
Permanent Connection Low
Volumetric Transfer
Rate Low
Dependence Upon
Human Factor High
Low Very Low
Moderate Very High
Very Low Very High
High High
Low Very High
Processing
Low
Moderate
Moderate
Variable
High
125
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The following list of spill prevention and control techniques are
commonly found throughout the liquid handling industries (15,. 21,
44) and apply equally well to the synthetic and plastics
industry:
1. Diked areas around storage tanks. For flammable
substances these are required; however, as a passive barrier
to tank rupture, and tank and pipe connection leaks, a diked
tank storage area is considered the first-line barrier to
containing and reducing the spread of large-volume spills.
2. Tank level indicators and alarms. The sounding of alarms
at prescribed levels during tank filling could be expected to
minimize the ccmmon occurrence of overflow when reliance is
on manual gauging for control.
3. Above-ground transfer lines. Above-ground installation
permits rapid detection of pipeline failures and minimizes
hazardous polluting substances from polluting ground waters.
Although increasing the possible mobility into surface
waters, long-term considerations are believed to favor above-
ground transfer lines.
4. Curbed process areas. Spills from processing equipment
must often be removed rapidly from the area but prevented
from spreading widely in the immediate area; consequently,
curbed areas connected to collecting sewers are indicated.
5. Area catchment basins or slop tanks. For containment of
small spills and leaks in the immediate area thereby
effecting removal at the highest concentrations, local
catchment basins can provide significant flexibility in
preventing spills from entering water courses.
6. Holding lagoons for general plant area. Lagoons which
can be used to segregate spills and prevent them from passing
as slugs into waste water treatment plant or water courses,
give the surge capabilities necessary for handling large
volume or highly toxic spills.
7. Initial waste water treatment. For removal of floating
substances or for the chemical neutralization or destruction
of spilled materials, the initial waste water treatment
plants serve to ameliorate the more drastic effects of spills
in receiving waters.
8. Biological waste water treatment. The removal of soluble
substances usually through biological action, where possible,
can insure that the plant waste water discharges have a high
degree of uniformity at acceptable quality regardless of in-
plant variations such as would occur from spills.
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9. Availability of spill cleanup equipment. Vacuum trucks,
booms, neutralizing chemicals and so on, represent obvious
contingency planning to cope with spills.
10. Routine preventative maintenance schedules. Because
literature sources indicated that the cause of many fires in
the chemical industry could be traced to failures that might
have been avoided by a thorough preventative maintenance
program, it was recognized that this program would be an
indicator of the possible reduction in spill potential.
11. Spill control plan. The formalization of a plan for
coping with spills and the training of personnel in courses
of action similar to plant safety programs, was reasoned to
be a prime indicator of the operational possibility of coping
with spills in a manner which would avoid entry into water
courses.
The application of ancilary control techniques requires judicious
planning of operational philosophy, organization, and specific
measures such as discussed below.
Operational Philosophy
Each plant management needs to formulate a "Spill Exposure Index"
which will reveal potentially-serious problems in connection with
its operation. Once the problems are defined, rememdies and the
costs of implementing them are not difficult to determine. The
next step is establishing priorities, a budget, and a commitment
to capital and operating expenditures. As new production
projects are proposed for a plant site, each should incorporate
adequate measures for spill prevention as an integral part of its
design. Capital investment in this category should be considered
to be fully as necessary as investment in process equipment or,
alternatively, in more elaborate waste water handling procedures.
One approach is the development of a classification index (taking
into consideration the minimum aquatic biological toxicity, etc.)
which establishes ratings of hazardous polluting substances and
recommends the minimum acceptable containment measures.
Organization
Since most of the prevention and control measures represent added
inconvenience and costs in the eyes of the plant operating staff,
even when wholeheartedly accepted, establishment of an
independent group with a direct assignment to minimize spills and
authorized to take action is especially desirable.
Specific Measures
In a facility with a "high spill exposure index" there should be
a review of the designs and conditions to determine the potential
consequences of spills and leaks in a truly objective manner.
The review should consider the design of the process and
127
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equipment and should involve a piece-by-piece physical
inspection. In common with most successful projects, there is no
substitute for careful attention to details. All possible
accidents and departures from routine should be considered and
then analyzed in terms of the hazard, and the corrective action
or control measures which could be applied.
All plant facilities need to be included, both process and
service units. One frequently neglected item is the condition of
underground lines cf sewers. A number of potential sources of
leaks and spills can frequently be eliminated without real
inconvenience to the process.
In the process area, a number of spill exposure conditions are
often found. One of the most serious is limited storage between
coupled process units which may not be in balanced operation.
Intermediate storage of this type is most often designed on the
basis of surge volume provided. But often operating rates are
difficult to adjust, and overflow of the surge tank results.
When spill prevention per se, becomes an important criterion, a
major revision in standard operating procedure, and perhaps a
revised standard for the size of storage may be called for.
Small leaks at shafts of pumps, agitators, and valve stems is
frequently tolerated; and in the case of rotating equipment, is
desirable for shaft lubrication and cooling. In the aggregate
such losses may be significant spills and should be prevented or
contained. Sampling stations and procedures should also be
reviewed to curtail unnecessary discard of small quantities of
process fluids. Vent systems are potential points of accidental
spill and, on hot service, may allow a continuous spill due to
vaporization and condensation.
The major hazard in storage areas is catastrophic failure of the
tank, an accident which on economic grounds alone justifies
careful attention to tank design, maintenance, and inspection.
Containment of a large spill is desirably provided by diking or
curbing, but these systems need analysis as to proper operation
both in standby status and in the event of a spill; safety
principles and operating convenience can both be in conflict with
spill prevention and the differences must be reconciled. Venting
and tank overflow problems can be severe because of the cyclic
nature of storage operations; accessories such as heating or
cooling systems, agitators, instrumentation, and fire prevention
control systems all can represent potential for spill.
Loading, unloading, and transfer operations are particularly
accident prone. Where materials with obviously high hazard are
involved - a high degree of reliability of the transfer system is
achievable at a cost which is really quite reasonable. This
success is due to provision of adequate equipment but also in
large measure to strict adherence to well-thought-out procedures.
Carelessness and shortcuts in operation do not often occur. The
same philosophy applied to less dangerous materials can be
fruitful, and we have seen a number of good installations of this
kind.
128
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Permanent piping, swing joint systems, and flexible hoses are all
used successfully for transfer and each has its place. There is
a need to recognize that each has inspection and maintenance
problems as well. The design of transfer lines must consider
such questions as leaving them full or empty when idle, purging
before and after use, protection with check valves, and
manifolding. Multiple use of a transfer line should be avoided
but when necessary on economic or other grounds the design should
provide a clear indication to the operator that valves are
properly set. Remote setting of valves, and panel indication of
valve position are practical systems that could be more widely
employed.
In addition to active spill-prevention measures, curbing, diking
and collection systems are desirable and are common at land-based
transfer points. Where marine transfer is involved, passive
safeguards are difficult to apply and their adoption is new even
in the petroleum industry where the apparent need has been
highest. The plastics and synthetics industry can and should
follow suit. Watersoluble and heavier-than-water fluids both
obscure and complicate the problem. In any event all such
passive systems which contain rather than prevent spills should
be looked upon as back-up measures and not as a crutch to permit
neglect of active spill prevention.
The emphasis on ancillary process control technology must be
based equally on adequate, well-maintained equipment and on
operational vigilance and supervision. Attention to these
details will often result in reducing significantly not only the
total loads on wastewater treatment plants but, most importantly,
reducing the variability of pollutant flows with a concomitant
improvement in the quality of treated waste waters emitted to
receiving bodies.
Procedures and Operating Methods for Elimination or
Reduction of Pollutants
Consideration of the process operations employed throughout the
plastics and synthetics industry indicates a high degree of
commonality in that the usual process flowsheet is developed
around a judicious combination of batch and continuous
operations. Only in the case of high volume materials, such as
the polyolefins, do truly continuous process operations seem to
predominate. Skillful process designs and operations in the
other industry segments provide essentially continuous flow of
product from the process; however, this is frequently due to the
effects of multiple-batch operations in conjunction with
appropriate storage and surge of process streams. Where the
process operations have been put on a continuous operational
basis, it is found that the basic process utilized is less
demanding of process water usages or is based on technology that
does not require water or does not generate water from reactions.
The principal example of this, of course, is the particle form
process for the production of polyethylene. But, generally, the
similarity of basic process operations throughout the plastics
129
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and synthetics industry indicates that similar philosophical
approaches to the elminiation or reduction of pollutants can be
employed and that their application must be approached on a
piant-by-plant basis.
The reduction or elimination of waterborne pollutants in the
plastics and synthetics industry will depend upon the following
factors.
1. The replacement of present technology with technology
which generates less waterborne pollutants. Examples of this
are the particle form process of polyethylene and the mass
polymerization process for polystyrene, ABS/SAN and polyvinyl
chloride. The possibilities for applying this approach will
require assessment of the availability of new technology and
the capital investment required for retiring present plants
and erecting new plants. It will also require determining if
the quality range of products produced can meet the require-
ments of the market. In those product categories, such as
the ones listed above, where less water use and lower
pollutant-generating processes exist, the replacement
approach is dependent upon a socioeconomic decision, i.e., is
the early retirement of more polluting processes and their
replacement with less polluting processes going to result in
effectively reducing the emission of environmental pollutants
in a manner in which the greatest benefits/cost ratios result
for the environment and society. At the present time,
significant reductions in pollutant loads can be achieved, in
the above-listed products by replacing one production method
with another. In general, however, the plastics and
synthetics industry considered in this survey is a mature
industry, and there appears little potential for dramatic
breakthroughs in the production technology. The most
probable results will be replacement of some products with
newer products.
2. The age of the plant and equipment. In some segments of
the plastics and synthetics industry, notably rayon and
cellophane, the age of the plants and equipment is one of the
most important aspects of reducing loads of waterborne
pollutants. These plants were designed and built in an era
when there was little concern about the emission of water
pollutants and, consequently, the process, equipment and
plant layout designs did not provide for incorporating tech-
niques for reducing water flows, and segregating and
preventing pollutants from entering the water streams. The
process conditions and engineering applicability of
techniques such as countercurrent washing, segregation of
non-process water streams from process waste water streams,
water usage in housekeeping, and so on, are well known;
however, incorporation of these procedures into old plants
becomes, again, more a question of economics and less a
question of applying methods of water conservation and
reduction in pollutant loads.
130
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3. Process Operational Changes. Certain obvious process
operational changes can be made such as replacement of direct
water condensers with surface condensers, better control of
reactions, and, possibly, less generation of wastes either
because of less offspecification product or more efficient
reactions, replacement of water scrubbing systems by non-
aqueous methods, and so on. Engineering design procedures
and equipment necessary to accomplish these improvements are
usually available; however, it is the hour-by-hour operating
details, such as the functioning of controllers or operator
attention and skill, that determines the overall success of
these changes.
U. Maintenance and Housekeeping. It is well-established
that in the chemical processing industries the pollutional
load imposed on the waste water treatment plant can
frequently be reduced significantly by improved maintenance
and equipment, i.e., repair of leaking pump seals, valves,
piping drips, instrumentation and so on. Housekeeping
practices which utilize procedures other than water for the
flushing of samples, the disposal of offspecification
product, the disposal of samples, etc., can reduce
pollutional loads. It must be made clear to operating
personnel that the difficulties inherent in applying the best
and most economical methods for removal of pollutants from
water streams to be emitted from the plant are never as
useful as preventing the pollutants from entering the water
stream in the first place.
131
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SECTION VIII
COST, ENERGY, AND NON-WATER QUALITY ASPECTS
Approximately 280 company operations participate in the
manufacture of the eighteen products for which guidelines and
standards are recommended (see Table 24). The actual number of
plants involved is not known, but there are believed to be more
than 300 of them. Seme of the 280 company operations include
multi-plant divisions; some represent multi-product plants. By
comparison, 240 permit applications have been received by EPA
from plants in this industry which discharge into streams.
Again, counting those that discharge into municipal sewers, the
total number of plants is probably over 300.
Total production in 1972 for these products is estimated at 12
million kkg or 26 billion pounds per year. Overall, production
of these products is expected to grow at 10 percent per year.
Current water usage (1972) is estimated at 1035 thousand cubic
meters per day (275 MGD). Assuming that hydraulic loads (unit of
flow/unit of production) remain constant, water usage is expected
to grow to 1440 thousand cubic meters per day (380 MGD) or at 6.7
percent per year through 1977.
The first part of this section summarizes the costs (necessarily
generalized) and effectiveness of end-of-pipe treatment systems
either currently in use or recommended for future use in the
plastics and synthetics industry. In order to reflect the very
different treatment economics of existing versus new plants or
small versus large ones, costs have been developed for,
typically, two plant sizes in each product subcategory. These
appear later in this section. The purpose of this discussion is
to describe the basic cost analyses upon which the product-
specific estimates are based.
The final part of this section reports updated inputs for EPA's
Industrial Waste Treatment Model. The estimated total volume of
waste waters discharged for product subcategories have been
provided for 1972 and 1977. Also, general estimates of the
current level of treatment in different industry segments have
been made.
Alternative Treatment Technologies
The range of components used or needed to effect best practicable
control technology currently available (BPCTCA), best available
technology economically achievable (BATEA) , and best available
demonstrated technology for new source performance standards
(BADT-NSPS) in this portion of the plastics and synthetics
industry have been combined into eight alternative end-of-pipe
treatment steps. These are as follows:
A. Initial Treatment^ For removal of suspended
solids and heavy metals. Includes equaliza-
tion, neutralization, chemical coagulation
133
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TABLE 2k
PERSPECTIVES ON THE PLASTICS AND SYNTHETICS INDUSTRY
- WATER USAGE -
Guideline
Sub category
Product
A
PVC
ABS/SAN
P Styrene
PV Acetate
LDP Ethylene
HDP Ethylene
Polypropylene
B
Cellophane
Rayon
Subtotal - A & B
C
Cellulose Acetates
* Epoxy
* Melamine )
* Urea Resins J
* Phenolics
Polyester
Nylon 66 1
Nylon 6 j
D
Acrylics
Subtotal - C & D
Number of
Company
Operations (1)
23
8
19
26
12
13
g
4
7
121
7
8
11
81
19
20
11
157
TOTAL - 18 PRODUCTS 278
Percent
of Total 18
Product
Production (2)
1972
14.7
3.1
12.4
1.7
19.4
8.4
5.5
1.2
3.5
69.9
3.3
0.7
3.5
4.7
8.9
6.9
2.1
30.1
100.0
Percent of
Water Used by
18 Products
1972
7.4
1.6
4.2
0.7
7.2
4.6
4.0
13.9
19.1
62.7
16.8
0.1
0.2
0.4
8.5
9.5
1.8
37.3
100.0
Percent of Growth
in Water Usage
of 18 Products (3)
1972-1977
14.6
4.1
5.9
0.4
14.3
12.2
10.4
(5.1)
7.8
64.6
4.5
0.1
0.4
0.4
22.4
6.8
0.8
35.4
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 18-product production in 1972: 12 million kkg (26 billion Ibs ).
(3) Result of projected product growth at current hydraulic loads.
* See footnote, p. 136.
134
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or precipitation, API separators, and primary
clarification.
B. Biological Treatment: Primarily for removal of
BOD. Includes activated sludge (or aerated
stabilization basins), sludge disposal, and
final clarification.
C. Multi-Stage Biological: For further removal of
BOD loadings. Either another biological treat-
ment system in series or a long-residence-time
polishing lagoon.
D. Granular Media Filtration^ For further removal
of suspended solids (and heavy metals) from
biological treatment effluents. Includes some
chemical coagulation as well as granular media
filtration.
E. Physical-Chemical Treatment; For further removal
of COD, primarily that attributable to refractory
organics, e.g., with activated carbon adsorption.
F. Liguid Waste Incineration: For complete treat-
ment of small volume wastes.
G- Zinc Removal and Recovery: For two-stage precipi-
tation and recycle of zinc used in production of
rayon.
H. Phenol Extraction; For removal of phenol compounds,
e.g. from epoxy, acrylics, and phenolics wastes.
Costs of Treatment Technology Now in Practice
Information on actual treatment cost experience in the plastics
and synthetics industry was not plentiful from the exemplary
plants visited. Data of varying degrees of completeness were
available from twelve of those plants. To both verify, the
reasonableness of the data received and to provide a broader
basis for estimation, a costing model was developed based on
standard waste water treatment practice. This model covers both
capital and operating costs for the equivalent of what appears to
be the best technology currently practiced by the industry:
essentially initial and biological treatment from either
activated sludge or aerated stabilization pond systems. Over a
plant size range of 2 to 12 thousand cubic meters per day (0.5 to
3.0 MGD), the cost experience data from the plants visited came
within i 20 percent of that predicted by the cost model. The
costs calculated from the model, therefore, are believed to be a
realistic basis for estimating the replacement value of existing
facilities and the economic impact of further secondary-type
treatment requirements.
135
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For the purposes of these cost analyses, the products were
initially grouped according to their chemical, rather than waste
water, nature.
Group I:* epoxies, melamine, urea resins, and phenolics.
Group II: PVC, ABS/SAN, polystyrene, PV acetate.
Group III: low-density polyethylene, high-density
polyethylene, polypropylene.
Group IV: acrylics, polyesters, nylon 6, nylon 66.
Group V: cellophane, rayon, cellulose acetates.
Cost curves developed from the cost model are presented in Figs.
33 and 34. Fig. 33 presents the capital costs of activated
sludge and aerated stabilization pond systems as a function of
hydraulic load. Fig. 34 presents the operating and maintenance
costs over the ranges of production found in the five product
groups studied. The initial capital cost of biological treatment
systems is mainly dependent upon (and here related to) the
hydraulic load, the other factors making only minor variations in
the total cost. Operating costs, on the other hand, have been
viewed as dependent on pollutant as well as hydraulic loads.
Costs for representative plants in the product subcategories were
developed using these curves together with as many product-
specific differences as were known. "Representative" plants
defined here for the purpose of determining overall industry
costs are not to be confused with "exemplary" plants which were
sought as a basis for setting guidelines. Cost data from
exemplary plants were used to validate our cost model, which
could then be used to estimate the costs for representative-sized
plants, i.e., the costs required in order for the rest of the
industry to catch up.
The two principal biological waste treatment processes considered
to best represent the options available are the aerated
stabilization basin and the activated sludge system. Of the two,
the aerated stabilization basin is much preferred on an initial
cost basis when land is readily available. The following items
were determined for the individual treatment steps.
*Revisions and updating of the cost analysis for the epoxy
resins, phenolic resins, urea and melamine resins will be
incorporated into the Development Document for the Synthetic
Polymers Segment of the Plastics and Synthetics Industry.
136
-------
10-0
5.0
02.0
ACTIVATED SLUDGE TREATMENT
o
1.0
-AERATED STABILIZATION TREATMENT
0.2
0.1
l I
llll
I
I
I l
I I
llll
0.1
0.2
0.5 1.0 2.0 5.0 10.0
TREATMENT PLANT CAPACITY (MGD)
20.0
50.0
100.0
FIGURE 33
BIOLOGICAL TREATMENT IN THE PLASTICS AND SYNTHETICS INDUSTRY -
CAPITAL COSTS
-------
8£T
OPERATING COST
w
H
o
tr1
O
O
H
O
M
I
H
2
O
n
o
en
t-3
en
H
(-3
ffi
M
cn
H3
H
O
en
a
en
ffi
H
h3
H
n
en
H
2
§
cn
t-3
H
O
G
U)
-------
(1) construction cost as a function of hydraulic load at a given
pollutant level; (2) operating and maintenance labor as a
function of hydraulic load; (3) chemical requirements as a
function of hydraulic and pollutant load; (4) power requirements
as a function of hydraulic and pollutant load; (5) additional
material and supply cost as a function of hydraulic load. An
estimate of land requirements 4s provided for each total
treatment system. The cost data used were derived from varied
industrial and municipal applications. They are adjusted where
possible to reflect specific changes necessary for the plastic
industry. Costs have been adjusted to a national average cost
level of January 1973 using the ENR Construction Cost Index (16).
The estimated cost curves have been adjusted to exclude unusual
construction or site-specific requirements. The curves include
all elements of construction cost which a contract bidder would
normally encounter in completing the waste water treatment.
Included are building materials, labor, equipment, electrical,
heating and ventilation, normal excavation and other similar
items. Also included are engineering costs. The annual
operating costs include operation and maintenance labor,
chemicals, power, material and supplies.
Biological treatment systems as practiced in the plastics and
synthetics industry are not large users of energy. The amounts
needed in the initial and biological steps are indicated in Figs.
35 and 36.
Cost of Advanced Treatment Technologies
Although not presently practiced by the most exemplary waste
water treatment plants in the plastics and synthetics industry/
the technology exists to achieve very low concentrations of
suspended solids. The technology chosen for capital and
operating cost estimates is granular media filtration although
other types of filtration systems and, in certain instances, long
residence time lagoons might be effective, however, the
uniformity of effluent is not as controllable in the latter.
Granular media filtration used with chemical precipitation and
coagulation should be further effective in reducing the
concentration of metals and insoluble BOD5. The capital costs
(operating costs and energy requirements are minimal) for
granular media filtration used in our estimates are shown in Fig.
37 for the five product groups studied. Costs have been calcu-
lated on the basis of hydraulic loads and annual production
rates.
The question of capital and operating costs required to achieve,
by 1983, best available treatment of the organics which escape
biological treatment is difficult to address on the basis of
present technical knowledge. Review of the waste water treatment
technology field seems to indicate that activated carbon
adsorption applied following the secondary (biological) treatment
is the most probable technology.
139
-------
500,000
200,000
o
UJ
(E
= 100,000
5
UJ
tn
K 50flOO
i
30,000
10,000
PRIMARY TREATMENT
1000
2000
5000 lOflOO 20,000
BOD REMOVAL (ibs/ day)
50,000
100,000
FIGURE 35
BIOLOGICAL TREATMENT IN THE PLASTICS AND SYNTHETICS INDUSTRY
ENERGY REQUIREMENTS - PRIMARY TREATMENT
-------
500,000
200,000
o
UJ
-------
ZfrT.
CAPITAL INVESTMENT
-------
This assumes that the nature of the wastes is such that the
refractory organic substances (measured as COD or TOG) would not
be susceptible to treatment by" other adsorptive methods, such as
floes, or that high dosages of lime would be ineffective.
Because the removal of COD can be expected to be highly specific
to the type of pollutant in the waste waters (31r 41), the
applicability of carbon adsorption across the industry is
technically still in doubt. Nevertheless, in order to provide an
indication of the probable magnitude of advanced waste water
treatment, activated carbon adsorption has been chosen as a
process which would be considered as an add-on to biological
treatment. The assumption is made, based on meager data in the
literature, that only 60 percent removal of the COD would be
achieved and that the carbon loading would be 0.07 Ib COD/lb of
carbon (kg COD/kg of carbon) at a bed volume per hour flow rate
of 0.5, i.e., 120 minutes contact time in the adsorbers. Capital
and operating costs have been prepared using the input parameters
of hydraulic load and COD per day applied to the activated carbon
system (1, 22, 20).
Fuel consumption was taken as 6,000 Btu/lb of dry carbon
regenerated and carbon makeup as 5 percent of carbon regeneration
rate. These costs (capital and operating) are indicated in Figs.
38 and 39.
Non-Water Quality Aspects of Alternate Treatment Technologies
The non"water 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 byproduct of commercial value, (3) disposal
of off-specification and scrap products, and (4) the creation of
problems of air pollution and land utilization.
Disposal of Solids and Slurries
Biological sludges are the principal disposal problem resulting
from end-of-pipe treatment of waste waters. Occasionally
chemical sludge (such as from neutralization and precipitation of
an inorganic chemical) is of concern. Biological sludges are
most frequently subjected to some type of continued biological
degradation. Aerobic digestion is the most frequently used
method, when lagoons are operated in the extended-aeration mode,
the solids accumulate in these lagoons or in polishing lagoons.
The long-term consequence of these operations is a gradual
filling of the lagoons. They then must be dredged or abandoned.
Presently, sludges from end-of-pipe wastewater treatment plants
are stabilized by biological means and disposed of to landfills.
Prior treatment to dewater the biological sludges by chemical or
mechanical means will probably be increasingly employed.
However, the problem of landfill disposal remains. Consequently,
one of the long-term aspects of waste water treatment is
ascertaining that appropriate landfill sites have been obtained.
The cost of sludge disposal from plastics and synthetics plants
143
-------
10.0
200
10 20 50 100
MILLIONS OF POUNDS/ YEAR PRODUCT
FIGURE 38
ACTIVATED CARBON ADSORPTION FOR THE PLASTICS AND SYNTHETICS INDUSTRY
CAPITAL INVESTMENT
500 1000
-------
10.0
*>.
en
GROUP II
GROUP IV
GROUP I
10 20 50 100 200
MILLION POUND PRODUCT / YEAR
FIGURE 39
ACTIVATED CARBON ADSORPTION FOR THE PLASTICS AND SYNTHETICS INDUSTRY -
OPERATING COSTS
500
1000
-------
will be essentially equivalent to the cost of sludge disposal
from municipal sewage treatment plants. The same type of
disposal methods are applicable, but there will be significant
variations in the amounts of sludge generated. Estimates based
on raw waste loads reported in the Celanese report (8) indicate
the range of dry solids to be disposed of would be as follows:
(1)
(2)
(3)
Type of Plant
Cellulesic-based
UnitsAl OOP/Units of Product
25-50
Phenolics, epoxy, nylon
acrylics, polyesters
Polystyrene, PVC, ABS/SAN,
polyethylene, polypropylene
10-25
1-10
Burd (11) reports that lagooning or landfilling cost (capital and
operating) lie in the range of $1 to $5 per ton of dry solids.
Utilizing the higher value, the range of disposal costs per pound
of product becomes:
(1)
(2)
(3)
Type of Plant t/Pound of Product
Cellulosic-based 0.00625-0.0125
Phenolics, epoxy,
nylon, acrylics,
polyesters
0.00250-0.00625
Polystyrene, PVC, 0.00025-0.0025
APS/SAN, polyethylene,
polypropylene
Q£ Product
0.0138-0.0276
0.00551-0.0138
0.00055-0.00551
Burd also reports capital and operating costs for incineration to
be $10 to $50 per ton ($11-$55/kkg). Due to the rapid increase
in fuel costs and the relatively small volume of sludge at
individual plants, $50.00 per ton is probably more nearly the
cost that will prevail in this industry. Consequently, sludge
incineration costs might be expected to be in the following
ranges:
(1)
(2)
(3)
Type of Plant g/Pound of Product
Cellulosic-based 0.0625-0.125
Phenolics, epoxy,
nylon acrylics,
polyesters
0.250-0.0625
Polystyrene, PVC, 0.00250-0.0250
ABS/SAN, polyethylene
polypropylene
g/kg of Product
0.1378-0.2756
0.00551-0.0138
0.00551-0.0551
146
-------
The yearly volume of biological sludges (acre feet) generated for
each 10,000,000 Ibs of product is estimated to be the following:
Type of Plant Biological Sludges Only
~ ~ ~" Acre Feet/Year Cu Meters/Year
(1) Cellulesic-based 0.4-0.80 493-986
(2) Phenolics, epoxy, 0.10-0.40 123-493
nylon acrylics,
polyesters
(3) Polystyrene, PVC, 0.04-0.10 49-123
APS/SAN, polyethylene,
polypropylene
The most significant sludge disposal problem is the volume of
sludge generated during the removal of zinc from rayon plant
waste waters. These sludges, mixed with calcium sulfate, are
presently being lagooned. An EPA demonstration project for zinc
removal and recovery has been completed. Undoubtedly, the future
disposal of zinc sludge will depend upon economics as well as the
need to meet effluent limits. Although large diked land areas
are required for lagooning and, consequently, large-scale
flooding might be considered a hazard, zinc sludge, tends to
attain a jelly-like consistency, which would prevent this. This
means that, if a dike wall breaks, large amounts of the contained
sludge will not flow from the filled lagoon.
Generation of Commercially-Valuable By-Products
Within the plastics and synthetics industry, only cellophane and
rayon plants recover a by-product from their waste water which
has appreciable commercial value. This is sodium sulfate or
Glaubers salt, which is sold largely to the pulp and paper
industry. Although this might be viewed as transferring part of
the problem of disposing of inorganic dissolved salts to another
industry, within the framework of this industry the sale of
Glauber salt can be considered a valuable by-product.
Costs of Sulfate Recovery - The opportunity for reclamation of
byproduct values as opposed to disposal or treatment appears in
the rayon and cellophane subcategories. One such instance of
recovery - that of sodium sulfate - is in spin bath reclamation.
Rayon is made by spinning viscose into a bath of sulfuriq acid,
sodium sulfate, and, in most cases, zinc sulfate. The sulfuric
acid reacts with the alkaline viscose to produce sodium sulfate
and water. This neutralization is a continuous operation.
Because of the speed at which the rayon filaments are spun
(several hundred meters per minute) and the need to achieve a
quick reaction to set the fibers, a large amount of acid must be
used, and the acid must not change appreciably in composition
from one end of the bath to the other. For example, a typical
inlet composition might contain 13 percent acid, 22 percent
147
-------
1.20
11' NET COST = GROSS
COST-BY-PRODUCT AND
RECYCLE CREDITS.
WATER WASH
STREAMS
ACID WASH
STREAMS
1 2 3
S04 CONC. IN WASH STREAM (%)
FIGURE 40
NET COST OF RECOVERING DILUTE WASH SOLUTIONS
148
-------
sodium sulfate, and 6 percent ZnSO4, and the exit composition 12-
1/2 percent acid, 23 percent sodium sulfate, and 5.8 percent
ZnSO4. This acid is returned to acid recovery where some of the
sodium sulfate is removed by evaporation and crystallization, and
the remaining sodium sulfate, zinc sulfate, and acid (with new
acid and zinc sulfate added) is recirculated back to the spin
bath. To the extent that rayon carries acid (and zinc) from the
spin bath into subsequent acid and water washes, acid and zinc
are lost from the system. These chemicals are washed out of the
rayon in such dilute solutions (the most concentrated is
approximately one-tenth the strength of the original spin bath)
that at current prices for zinc and sodium sulfate, reclamation
is not economic.
Different rayons require different bath compositions. A typical
bath for tire cord contains 6.5 percent sulfuric acid, 15 percent
sodium sulfate, and 7 percent zinc sulfate. For regular staple a
typical bath contains 13 percent sulfuric acid, 22 percent sodium
sulfate, and 1 percent zinc sulfate. Table 25 shows the
comparative concentrations from typical streams associated with
the spin bath.
149
-------
TABLE 25
TYPICAL STREAM COMPOSITIONS
(Basis (kg/kkg)
Exit from Spin Bath
Most Cone. Most Oil.
First Acid Wash
Water Wash
Na2SO4
ZnSOU
(Avg)
230 30 10 0.05
58 5 0 0.4
(To sewer) (To sewer) (To sewer)
Recycle to acid
recovery)
A rule-of-thumb cut-off point used by one rayon company in
determining which streams are economic to recover, is 2 percent
sulfuric, 3 percent sodium sulfate, 0.5 percent zinc. We have
calculated the economics of recovery in Table 26.
TABLE 26
BY-PRODUCT CREDIT VALUE FOR BREAK-EVEN STREAM
(Basis: 1000 Ibs (453.6 kg) H2O Solution, or 700 Ibs (317.5 kg)
evaporation capacity)
H2SO4
Na2SO4
ZnSO4
20
30
5
55
(9.07 kg)
(13.61 kg)
(2.27 kg)
(24.95 kg)
Net Values, recycle or feed
Ibs. to reclaim operation (0/lb)
0.9 (2.0
0.5* (1.1
ls.75 (21.5 (Z/kg)
11.15 (24.6 iz/kg)
Total (0/lb)
18 (40 */kg)
15 (33 (Z/kg)
48.2.7(106.5 (Z/kg)
(Fl.7 (179.5
-------
TABLE 27
OPERATING COST PER 1000 LBS (453. 6 kg) H2O RECYCLED
(Basis: Evaporation of 700 Ibs (317.5 kg) H2O to
3-1/3 fold concentration, i.e., same as Table 26 above*)
Ibs recycled
Utilities (steam 6% of CI) 2.. 2 _ I 4.9)
TOTAL COST 81.3 (179.6)
*This assumes concentrating the acid wash stream of Table 18 to
the most dilute of typical spin bath compositions, namely 1%
H2SO4, 10% Na2SO4, 1.558 ZnSO.4.
**Based on single-effect evaporators designed to handle 32,000
gal/hr (121 cu.m./hr) acid wash stream (approximately one-fourth
to one-third of total acid washwater from a typical large rayon
plant) .
The component of chief environmental concern is the dissolved
salts, primarily sodium sulfate, which is the neutralized product
of sulfuric acid plus caustic. The major side-stream component
which is of any economic value to recycle and reclaim is zinc
sulfate; but to the extent that a company disposes of zinc, the
various state laws and proposed federal guidelines require that
zinc be precipitated and not discharged into receiving waters.
There is no inexpensive way of minimizing the sulfate in the
final effluent other than by further evaporation and reclamation
of some of the dilute streams. We have, therefore, taken the
data on acid and water wash streams in Table 25 above and
calculated approximate compositions of various intermediate
streams (relative to Na2SO4, H2SO4, and ZnSO4_) in order to
examine various wash stream combinations from different grades of
rayon being processed. The by-product value and cost of recovery
for these streams was calculated, and the net cost versus
composition expressed in terms of Na^SO4_, is plotted in Fig. 40.
The acid wash stream represents approximately one-quarter of all
the water in the plant effluent and three-quarters of all the
dissolved solids in the effluent. If an average integrated acid
wash stream has 1.5 percent Na2S04, then, from Fig. 40, the net
cost of recycling this stream would be $0.72/1000 Ibs ($1.59/kkg)
of solution recycled. At a total water usage of 16.5 gal/lb of
rayon, the cost is 2.40 per Ib (5.30/kg) of rayon.
These cost estimates are based on use of single-effect
evaporators, which represent current U.S. practice. we
151
-------
understand double-effect evaporators are used in some European
rayon operations. The use of double-effect evaporators would
reduce steam consumption, but would be partially off-set by the
higher capital investment required; so that even then total cost
of treating this full acid wash stream would be on the order of
l.U to 1.90/lb (3.1 to 4.2*/kg) of rayon. Clearly what is needed
to make significant inroads on the dissolved solids problem is a
study of the judicious application of multiple effect evaporation
technology to the more concentrated of these acid wash streams.
Disposal of Off-Specification and Scrap Products
The disposal of solid wastes resulting from off-specification
products and solids removed by in-plant separation processes
prior to the waste water treatment plant present problems to the
industry. These wastes are, we believe, generally disposed of to
landfills which are often on company property. Since most of the
waste solids can be expected to be resistant to biological
degradation, their disposal will probably not have significant
potential for ground water pollution.
Other Non-Water Quality Pollution Problems
Other non-water 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 wastewater
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.
Industry cos.£ Perspectives
As the primary purpose of this program was to study exemplary
treatment systems and not to audit the range of treatment in the
industry, this overview is based on information from available
sources on the degree of treatment generally practiced in the
plastics and synthetics industry. Rough estimates were made of
the current degree of BOD removal across each of five product
groups. These ranged from 30 percent average removal in Group V
to 60 percent in Group IV. (Other current BOD removal estimates
are 30 percent in Group I, 50 percent in Group II, and <*0 percent
in Group III.) Using these estimates, a weighted average removal
of 42 percent was calculated for the entire industry in 1972. By
1977, the similar weighted average implicit in the BPCTCA (best
152
-------
practicable control technology currently available) guidelines to
be achieved is 95 percent removal. That would imply a
significant annual increase in removal efficiency, i.e., 18
percent per year. The technology exists and is in practice to
achieve this broad requirement.
The expected annual costs for existing plants in the plastics and
synthetics industry in 1977 consistent with the BPCTCA guidelines
are $66 million. This is a sum of estimates by product
subcategory (Table 28) calculated from: estimates of the mix of
existing plants between large and small sizes; the average costs
(per cubic meter or thousand gallons) considering plant size
effects; and the flow (in 1972) associated with these existing
plants. Similarly, by 1983, the estimated costs for existing
plants to comply with BATEA (best available technology
economically achievable) guidelines are $192 million. It should
be noted that these costs are associated with end-of-pipe
treatment only. Costs for in-plant additions or modifications
are not included.
For the purpose of gauging the implicit level of additional
needs, a working estimate of current annual costs was developed.
A rough estimate of $110 million (replacement value) of installed
investment was developed assuming that existing secondary
treatment facilities remove 80 to 85 percent of BOD as opposed to
the 95 percent generally required by BPCTCA. This level of
removal was associated with initial investment costs equal to
two-thirds the per-unit costs of BPCTCA technology.
Similar consideration was given to the proportion of the industry
having either no treatment or primary treatment only. Primary
treatment facilities were costed at one-fourth the per-unit costs
of BPCTCA technology. Finally, with an assumption that annual
costs run about 22 percent of the investment costs, the annual
costs for existing plants in 1972 was estimated at $25 million.
The above annual cost estimates for 1972, 1977, and 1983 indicate
average increases cf 21 percent per year between 1972 and 1977,
and 19 percent per year between 1977 and 1983 for existing
plants.
To those costs for existing plants in the plastics and synthetics
industry must be added the costs associated with new plants -
governed by BADT (best available demonstrated technology) new
source performance standards. Assuming the production volume of
new plants to be equal to the expected growth in production, the
potential annual cost associated with new plants in 1977 was
estimated at $35 million. Altogether, that means that the
industry's annual costs are expected to increase 32 percent per
year (from $25 million in 1972 to $101 (66 + 35) in 1977) -
supported by a sales growth of 10 percent per year. This assumes
a balancing out of factors like expansion of existing facilities,
the replacement of existing facilities by new plants, and
industry utilization rates over time. A similar estimate for
153
-------
1983 was precluded by the lack of a meaningful forecast of
product growth.
The average costs cf treatment over the industry consistent with
the figures in Table 28 for BPCTCA, BATEA, and BADT
technologies respectively are: $0.19 ($0.73), $0.56 ($2.11), and
$0.27 ($1.02) per cubic meter (thousand gallons).
One measure by which to gauge the importance of the costs in
Table 28 is to relate them to the sales price of the products as
is done in Table 29. A range of costs as a percentage of sales
was calculated (1) from a lower level associated with a large
representative plant with basis (i.e., associated with the
suggested guidelines) water usage to (2) a higher level
associated with a small representative plant with high water
usage.
On average, BPCTCA costs for the smaller plants with higher water
usage were 4.0 times higher than the larger plant in each
subcategory. The average range was 0.7 percent to 2.8 percent of
sales price. On average, BATEA costs for the smaller plants with
higher water usage were 3.9 times higher than the larger plants
in the industry. The average range of BATEA costs was 2.1 to 8.1
percent of sales price. BADT costs (for a large plant at basis
water usage) were 0.9 percent.
£££££ Effluent Treatment Costs
Table 30 and its 34 associated tables (arranged by product
groups) portray the costs of major treatment steps required to
achieve the recommended technologies. In fourteen of the
eighteen product subcategories, costs are indicated for two
different plant sizes which are representative of the mix of
production facilities. In the cases of cellophane, cellulose
acetates, and rayon, only one representative plant size was
needed to adequately describe industry costs. In the acrylics
subcategory, on the other hand, three plant sizes were
appropriate.
The use of different economics for two plant sizes is, at best,
only a step better than using a single treatment plant economics.
Current and future treatment costs for an overall industry
subcategory should ideally reflect an average cost consistent
with the plant-size mix. The costs for new plants were tied to
the economics of the larger representative plant.
In each of the 34 installments to Table 30, the representative
plant is 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 closer to 20 or 25 years.
154
-------
TABLE 28
PERSPECTIVES ON THE PLASTICS AND SYNTHETICS INDUSTRY
- TREATMENT COSTS -
Guideline Sub category
Product
Total Annual Costs, $ Mi Hi on
Existing Plants New Plants
1977 1983
1973-1977
PVC
ABS/SAN
PV Acetate
Polystyrene
LDP Ethylene
HDP Ethylene
Polypropylene
Cellophane
Rayon
Subtotal
6.6
1.4
1.1
5.3
4.5
3.3
2.9
3.7
6.8
35.6
5.2
0.3
1.2
4.4
7.6
19.9
5.0
3.8
17.1
14.6
9.4
6.8
10.6
18.8
106.0
15.0
1.0
4.4
16.6
17.2
4.2
1.3
0.2
2.4
3.3
2.9
2.7
0.0
1.1
19.0
Cell. Acetates
it Epoxies
•^ Melamine
* Urea Resins
* Phenolics
Polyester
Nylon 66 \
Nylon 6 /
5.2
0.3
1.2
4.4
7.6
10.2
15.0
1.0
4.4
16.6
17.2
28.0
0.9
0.1
0.7
1.2
9.6
3.0
Acrylic
Subtotal
Industry Total
66.4 192.1
_OL3_
15.8
34.8
*See footnote, p. 136.
155
-------
TABLE 29
PERSPECTIVES ON THE PLASTICS AND SYNTHETICS INDUSTRY
-COSTIMPACT-
Guideline Subcategory
Product
BPCTCA
%
Control Cost Range as % of Sales Price
BATEA
%
BADT
%
01
CTl
PVC
ABS/SAN
P Styrene
PV Acetate
LDP Ethylene
HDP Ethylene
Polypropylene
12
25
14
20
12
13.5
17
1.1-4.8
0.7-1.2
0.8-2.1
0.6-3.0
0.5-3.4
0.7-3.0
0.9-4.7
3.5-13.6
1.9- 4.5
2.1- 7.9
1.5-12.8
1.6-10.3
2.2- 7.9
2.1-10.8
1.3
0.8
0.9
0.7
0.6
0.9
1.0
B
Cellophane
Rayon
60
32
1.5-3.5
2.2-3.1
4.1- 9.4
5.6- 8.1
1.7
2.5
Cell. Acetates
** Epoxies
* Melamine/Urea
* Phenolics
Polyester
Nylon 66
Nylon 6
60
60
20
22
60
70
70
0.3-3.0
0.2-0.4
0.4-0.5
1.3-3.3
0.1-5.0
0.2-2.9
0.6-1.6
0.8- 8.0
6.7- 1.2
1.5- 2.3
4.3-12.3
0.3-11.9
0.5- 7.7
1.8- 4.8
0.5
0.2
0.4
1.3
0.3
0.4
1..4
Acrylics
*See footnote, p.
35 0.5-1.7
UNWEIGHTED AVERAGE 0.7-2.8
136.
1.2- 4.1
7.1- 8.1
0.7
0.9
-------
Cost-effectiveness relationships are implicit in the use of these
costs together with the effluent levels achieved by each
treatment step in each major relevant pollutant dimension. These
effluent levels are indicated at the bottom of each
representative plant sheet.
Industrial Waste Treatment Model Data
The general practice in these larger volume plastics and
synthetics products is to treat the entire waste stream (mostly
process water) . Without significant separation of streams,
therefore, data are provided for EPA's Industrial Waste Treatment
Model in terms of total flows. Each product subcategory is
covered on a table with other members of its product group
(Tables 31-35).
Total discharges for each product subcategory are estimated for
1972 and 1977. The quality of effluents remaining untreated in
1977 is indicated as that consistent with the application of
BACTCA 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.
157
-------
GO
Group No.
TABLE 30
SUMMARY OF WATER EFFLUENT TREATMENT COSTS FOR
REPRESENTATIVE PLANTS IN THE PLASTICS AND SYNTHETICS INDUSTRY
Representative Plant Size
BPCTCA Costs
BATEA Costs
BADT Costs
Product
* Group I2
Epoxies
Melamine
Urea
Phenol ics
Group 1 1
PVC
ABS/SAN
Polystyrene
PV Acetate
-------
en
VD
Group No.
Representative Plant Size
TABLE 30 (cent)
BPCTCA Costs
BATEA Costs
BADT Costs
„ . Millions
Product >„/,„.
Group III
LDP Ethylene
HDP Ethylene
Polypropylene
Group IV
Acrylics
Polyester
Nylon 6
Nylon 66
Group V
Cellophane
Cell. Acetate
Rayon
90
180
57
115
45
90
23
45
90
23
90
11
45
23
90
45
90
68
Millions
#/yr
200
400
125
250
100
200
50
100
200
50
200
25
100
50
200
100
200
150
$/stere1
.21
.16
.29
.18
.26
.19
.46
.30
.22
.40
.23
.30
.18
.53
.25
.08
.09
.11
$71000 gal
.81
.60
1.09
.69
.99
.73
1.76
1.15
.84
1.49
.86
1.15
.66
2.02
.97
.31
.33
.43
$/stere
.66
.50
.76
.53
.61
.45
1.12
.76
.56
.94
.50
.88
.51
1.42
.66
.22
.26
.30
$71000 gal
2.48
1.88
2.88
1.99
2.29
1.71
4.24
2.87
2.12
3.57
1.89
3.33
1.94
5.39
2.48
.84
.98
1.12
S/stere1
.24
.18
.32
.21
.29
.22
.67
.44
.32
.57
.33
.47
.27
.82
.40
.09
.16
.13
$71000 gal
.92
.68
1.23
.79
1.10
.83
2.53
1.67
1.21
2.15
1.24
1.79
1.03
3.09
1.52
.35
.61
.49
1. Stere = cubic meter.
2. Costs for Group I are estimated industry charges for discharging into larger municipal systems.
-------
TABLE 30-1
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD)
Costs -$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Epoxies (small plant) *
11
3.6
0.12
(25)
(0.43)
(0.033)
Alternative Treatment Steps *
A B H I
240 560 205 227
19
24
6
1
45
56
25
9
16
20
4
2
18
23
21
139
50
135
42
201
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Phenolic Compounds
Raw
Waste
Load
70
110
15
N/A
Resulting Effluent Levels
(Units per 1000 Units of Product)
H F
B
0.2
1
0.7
0.06
0.4
0.04
0.002 0.0004
* Steps A and B only are based upon a dilution factor of 10; 1.2 thousand cubic meters per day (0.33 MGD).
Step F is incineration of total undiluted waste stream. Calculation of costs per thousand gallons assumes
pay-your-way user charges equal to 0.5 of steps A and B, corresponding to waste load share on municipal
system.
**See footnote, p. 136.
160
-------
TABLE 30-2
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year :
Hydraulic Load
cubic meters/metric ton of product (gal/lb) :
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Epoxies (large plant) **
45 (100)
3.6 (0.43)
0.49 (0.13)
Alternative Treatment Steps*
A § H[ _E
375 875 465 1165
30
38
11
3
70
88
67
33
37
46
6
3
93
117
115
9
102 238
Effluent Quality (Expressed in terms of yearly averages)
Raw
Waste
Load
92 334
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B
H
B.O.D. 70
C.O.D. 110
Suspended Solids 15
Phenolic Compounds N/A
0.2
0.1
0.06
0.4
0.04
0.002 0.0004
Steps A, B and E are based upon a dilution factor of 10; 4.9 thousand cubic meters per
day (1.3 MGD). Calculations of costs per thousand gallons assumes pay-your-way user charges
equal to 0.5 of steps A and B corresponding to waste load share on municipal system.
**See footnote, p. 136.
161
-------
TABLE 30-3
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory : Melamine (small plant) ***
Representative Plant Capacity
million kilograms (pounds) per year
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD)
Costs-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
1.3
(15)
(0.16)
0.03 (0.007)
Alternative Treatment Steps *
A B** _F
240 560 100
19
24
2
1
46
45
56
24
4
129
9
11
16
30
66
Effluent Quality (Expressed in terms of yearly averages)
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 B F
0.06
0.3
0.04
0.02
0.1
0.01
* Steps A and B only are based upon a dilution factor of 50; 1.5 thousand cubic meters
per day (0.35 MGD). Step F is incineration of total undiluted waste stream. Costs per
thousand gallons assumes pay-your-way user charges equal to 0.1 of steps A and B, corres-
ponding to waste load share on municipal system.
** No raw waste load data available; costs based upon BOD load of 2200 Ib/day.
***See footnote, p. 136.
162
-------
TABLE 30-1*
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year :
Hydraulic Load
cubic meters/metric ton of product (gal/lb) :
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Melamine (large plant)***
27
1.3
0.11
22
27
4
2
55
(60)
(0.16)
(0.029)
Alternative Treatment Steps
**
£
A B
270 630 220
50
63
38
14
165
18
22
21
122
183
Effluent Quality (Expressed in terms of yearly averages)
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)
0.06 0.02
0.3 0.1
0.04 0.01
Steps A and B only are based upon a dilution factor of 20; 2.2 thousand cubic meters
per day (0.58 MGD). Step F is incineration of total undiluted waste stream. Costs
per thousand gallons assumes pay-your-way user charges equal to 0.25 of steps A and B,
corresponding to waste load share on municipal system.
Raw waste load unavailable; costs based upon BOD loading of 9100 Ib/day.
***See footnote, p. 136.
163
-------
TABLE 30-5
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year
Hydraulic Load
cubic meters/metric ton of product (gal/lb) :
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs -$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Urea (small plant) ***
7 (15)
1.8 (0.22)
0.04 (0.01)
Alternative Treatment Steps'
A B ** p
260 600 126
21
26
3
1
51
48
60
24
4
136
10
13
16
42
81
Effluent Quality (Expressed in terms of yearly averages)
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 B F
0.08
0.4
0.02
0.03
0.2
0.02
* Steps A and B only are based upon a dilution factor of 50; 2.0 thousand cubic meters
per day (0.5 MGD). Step F is incineration of total undiluted waste stream. Costs per
thousand gallons assumes pay-your-way user charges equal to 0.1 of steps A and B,
corresponding to waste load share on municipal system.
** No raw waste load data available; costs based upon BOD load of 2,200 Ib./day.
***See footnote, p. 136.
164
-------
TABLE 30-6
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD)
Costs-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Urea (large plant)
***
27
1.8
(60)
(0.22)
0.15 (0.04)
Alternative Treatment Steps «
A B** F
294 686 250
24
29
8
3
64
55
69
36
15
175
20
25
24
168
237
Effluent Quality (Expressed in terms of yearly averages)
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 B F
0.08
0.4
0.02
0.03
0.2
0.02
*Steps A and B only are based upon a dilution factor of 20; 3.0 thousand cubic meters per day
(0.8 MGD). Step F is incineration of total undiluted waste streams. Costs per thousand gallons
assumes pay-your-way user charges equal to 0.25 of steps A and B, corresponding to waste load
share on municipal system.
"*No raw waste load data available; costs based upon BOD loading of 9100 Ib/day.
***See footnote, p. 136.
165
-------
TABLE 30-7
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory
Representative Plant Capacity
million kilograms (pounds) per year
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD)
Costs -$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Phenolics (small plant) * *
11
12.3
0.42
(25)
(1.48)
(0.11)
Alternative Treatment Steps *
A B H E
330 770 420 1065
26
33
3
2
62
77
34
6
34
42
5
3
85
107
95
2
64
179
84
289
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Phenolic Compounds
Raw
Waste
Load
35
50
4
N/A
Retailing Effluent Levels
(Units per 1000 Units of Product)
A B H E
0.6
3
0.4
0.006
0.09
0.6
0.06
0.0006
Steps A, B and E are based upon a dilution factor of 10; 4.2 thousand cubic meters per day
(1.1 MGD). Costs per thousand gallons assumes pay-your-way user charges equal to 0.1 of
steps A and B, corresponding to flow share on municipal system.
**See footnote, p. 136.
166
-------
TABLE 30-8
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory
Representative Plant Capacity
million kilograms (pounds) per year
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD)
Costs-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Phenolics (large plant)
**
45
177
(100)
12.3 (1.48)
1.70 (0.45)
Alternative Treatment Steps *
A § I H
900 2100 2425 975
72
90
11
4
168
210
88
20
194
243
115
9
78
98
21
10
588 561
207
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Phenolic Compounds
Raw
Waste
Load
35
50
4
N/A
Resulting Effluent Levels
(Units per 1000 Units of Product)
X B H E
0.6
3
0.4
0.09
0.6
0.06
0.006 0.0006
Steps A, B and E are based upon a dilution factor of 10; 17.0 thousand cubic metefs per
day (4.5 MGD). Costs per thousand gallons assumes pay-your-way user charges equal to
0.1 of steps A and B, corresponding to flow share on municipal system.
**See footnote, p. 136.
167
-------
TABLE 30-9
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD)
Costs -$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Polyvinyl Chloride (small plant)
45 (100)
13.3 (1.60)
1.82 (0.48)
Alternative Treatment Steps
A B JD JE
255 595 107 790
20
26
3
0.5
48
60
24
3
9
11
2
—
63
79
146
22
49.5
135
22
310
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
6
25
30
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B D E
0.3
3
0.09
0.4
0.5 0.04
168
-------
TABLE 30-10
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory
Representative Plant Capacity
million kilograms (pounds) per year
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD)
Colts-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Polyvinyl Chloride (large plant)
90 (200)
13.3 (1.60)
3.67 (0.97)
Alternative Treatment Steps
A B D E_
315 735 170 1260
25
32
4
1
60
74
36
5
14
17
2
—
101
126
203
44
62
175
33
474
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
6
25
30
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B D E
0.3
3
0.09
0.4
0.5 0.04
169
-------
TABLE 30-11
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory
Representative Plant Capacity
million kilograms (pounds) per year
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD)
Costs-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
ABS/SAN (small plant)
23 (50)
15.6 (1.87)
1.06 (0.28)
Alternative Treatment Steps
* § E. JL
113 284 75 560
g
11
2
0.5
23
28
35
3
6
8
2
—
45
56
118
11
22.5 89
16
230
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
20
30
10
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B D E
0.4
4
0.5
0.1
0.9
0.09
170
-------
TABLE 30-12
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory;
Representative Plant Capacity
million kilograms (pounds) per year
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs -$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
ABS/SAN (large plant)
90 (200)
15.6 (1.87)
4.28 (1.13)
Alternative Treatment Steps
A § J( 1
345 885 185 1350
28
35
4
1
71
89
72
6
15
19
2
—
108
135
203
44
68
238
36
490
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
20
30
10
Resulting Effluent Levels
(Units per 1000 Units of Product)
V B D E
0.4
4
0.5
0.1
0.9
0.09
171
-------
TABLE 30-13
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year :
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Polystyrene (small plant)
23
(50)
9.67 (1.16)
0.68 (0.18)
Alternative Treatment Steps
A B ^ E.
102 258 56 475
8
10
2
0.5
21
26
31
2
4
6
2
_
38
48
113
11
20.5
80
12 210
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
1
3
4
Resulting Effluent Levels
(Units per 1000 Units of Product)
B
0.1
O.OF
0.3
0.2 0.03
172
-------
TABLE SO-lll
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory;
Representative Plant Capacity
million kilograms (pounds) per year :
Hydraulic Load
cubic meters/metric ton of product (gal/lb) :
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs -$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Polystyrene (large plant)
90 (200)
9.67 (1.16)
2.7 (0.7)
Alternative Treatment Steps
* I £ J.
285 725 135 960
23
29
3
0.5
58
73
50
2
11
14
2
—
77
96
146
22
55.5 183
27
341
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
1
3
4
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B D E
0.1
1
0.05
0.3
0.2 0.03
173
-------
TABLE 30-15
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs -$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Polyvinyl Acetate (small plant)
11
(25)
12.5 (1.50)
0.42 (0.11)
Alternative Treatment Steps
A B D _E
90 210 40 405
7
9
2
0.5
17
21
15
0.5
3
4
2
_
32
41
98
3
18.5
53.5
174
Effluent Quality (Expressed in terms of yearly averages)
B.O.D. (Units/1000
COD of Pr°duct)
Suspended Solids
Raw
Waste
Load
1
2
1
Resulting Effluent Levels
(Units per 1000 Units of Product)
D E
B
0.1
1
0.06
0.4
0.3 0.04
174
-------
TABLE 30-16
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year :
Hydraulic Load
cubic meters/metric ton of product (gal/lb) :
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Polyvinyl Acetate (large plant)
45 (100)
12.5 (1.50)
1.70 (0.45)
Alternative Treatment Steps
A § £ J
255 595 102 685
20
26
2
0.5
48
60
24
1
8
10
2
—
55
69
118
11
48.5 133
20
253
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
1
2
1
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B D E
0.1
1
0.06
— 0.4
0.3 0.04
175
-------
TABLE 30-17
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD)
Costs - $1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Low Density Polyethylene (small plant)
90 (200)
10.7 (1.29)
2.95 (0.78)
Alternative Treatment Steps
A B D E
290 680 145 1070
23
29
11
0.5
54
68
21
2
12
15
2
—
85
107
176
33
63.5 145
29 401
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
2
30
2
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B D E
0.1
1
0.06
0.4
0.3 0.04
176
-------
TABLE 30-18
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory
Representative Plant Capacity
million kilograms (pounds) per year
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Effluent Quality (Expressed in terms of yearly averages)
Low Density Polyethylene (large plant)
180 (400)
10.7 (1.29)
6.1 (1.6)
Alternative Treatment Steps
A § D E
435 1015 235 1670
35
44
4
1
81
102
44
4
19
24
3
_
134
167
263
65
84
231 46
629
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
2
30
2
Resulting Effluent Levels
(Units per 1000 Units of Product
A B n E
0.1
1
0.06
0.4
0.3 0.04
177
-------
TABLE 30-19
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory :
Representative Plant Capacity
million kilograms (pounds) per year :
Hydraulic Load
cubic meters/metric ton of product (gal/lb) :
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs -$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
High Density Polyethylene (small plant)
57 (125)
10.9 (1.30)
1.9 (0.5)
Alternative Treatment Steps
A B JD _E
255 595 110 725
20
26
2
0.5
48
60
23
1
9
11
2
-
58
73
128
14
48.5 132 22
273
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
1
2
2
Resulting Effluent Levels
(Units per 1000 Units of Product)
D E
B
0.1
1
0.06
0.4
0.2 0.04
178
-------
TABLE 30-20
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year :
Hydraulic Load
cubic meters/metric ton of product (gal/lb) :
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs -$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
High Density Polyethylene
115
10.9
3.8
(25)
(1.30)
(1.0)
Alternative Treatment Steps
A B D E
315
735
175
1160
25
32
3
0.5
59
74
32
1
14
18
2
—
93
116
160
27
60.5 16P
34
396
Effluent Quality (Expressed in terms of yearly averages)
Raw
Waste
Load
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B D E
B.O.D.
C.O.D.
Suspended Solids
0.1
1
0.2
0.06
0.4
0.04
179
-------
TABLE 30-21
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year :
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs- $1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Polypropylene (small plant)
45
(100)
21.0 (2.52)
2.88 (0.76)
Alternative Treatment Steps
A § D E
294 747 145 880
24
29
3
0.5
60
75
53
3
12
15
2
_
70
88
126
13
56.5 191
29
297
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
4
10
N/A
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B D E
0.3
1
0.5
0.1
0.9
0.09
180
-------
TABLE 30-22
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year :
Hydraulic Load
cubic meters/metric ton of product (gal/lb) :
Treatment Plant Size:
thousand cubic meters per day (MGDj :
Costs-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Polypropylene (large plant)
90 (200)
21.0 (2.52)
5.7 (1.5)
Alternative Treatment Steps
A B D E
420 1076 250 1400
34
42
4
1
86
108
82
5
20
25
2
—
112
140
160
27
81
281
47
439
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
4
10
N/A
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B D E
0.3
1
0.5
0.1
0.9
0.09
181
-------
TABLE 30-23
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year :
Hydraulic Load
cubic meters/metric ton of product (gal/1 b)
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Acrylics (small plant)
23 (50)
25 (3.0)
1.70 (0.45)
Alternative Treatment Steps
A B C D E
255 643 595 102 685
20
26
3
1
51
64
43
7
48
60
27
6
8
10
2
—
55
69
118
11
50
165
141
20
253
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
25
50
2
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B C D E
1
6
0.5
0.1
0.8
0.08
182
-------
TABLE 30-2U
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory
Representative Plant Capacity
million kilograms (pounds) per year
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD)
Costs-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Acrylics (medium plant)
45
25
(100)
(3.0)
3.4 (0.9)
Alternative Treatment Steps
A B C D E
306 783 714 160 1050
24
31
5
1
63
78
69
12
57
71
42
11
13
16
2
—
84
105
146
22
61
222
181
31
357
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
25
50
2
Resulting Effluent Levels
iUnits per 1000 Units of Product)
A B C D I
1
6
0.5
0.1
0.8
0.08
183
-------
Table 30-25
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory :
Representative Plant Capacity
million kilograms (pounds) per year :
Hydraulic Load
cubic meters/metric ton of product (gal/lb) :
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs -$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Acrylics (large plant)
90 (200)
25 (3.0)
6.8
(1.8)
Alternative Treatment Steps
A B C D E
480 1230 1120 255 1640
38
48
5
1
98
123
94
7
90
112
49
6
20
26
3
—
131
164
203
44
92
322
257
49
542
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
25
50
2
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B C D E
1
6
0.5
0.1
0.8
0.08
184
-------
TABLE 30-26
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year :
Hydraulic Load
cubic meters/metric ton of product (gal/lb) :
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs -$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Polyester (small plant)
23 (50)
31 (3.7)
2.12 (0.56)
Alternative Treatment Steps
A B C D E
270 682 630 117 765
22
27
3
1
55
68
47
6
50
63
27
5
9
12
2
—
61
77
113
11
53
176
145
23
262
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
20
25
1
RMulting Effluent Levels
(Units per 1000 Units of Product)
A B C D E
0.3
5
0.06
0.4
0.2 0.04
185
-------
TABLE 30-27
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory :
Representative Plant Capacity
million kilograms (pounds) per year
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD)
Costs- $1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Polyester (large Plant)
90 (200)
31 (3.7)
8.5
(2.2)
Alternative Treatment Steps
A B C D E
570 1465 1330 290 1670
46
57
8
2
117
147
126
18
106
133
70
17
23
29
3
—
134
167
145
22
113
408
326
55
468
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
20
25
1
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B C D E
0.3
5
0.06
0.4
0.2 0.04
186
-------
TABLE 30-28
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year
Hydraulic Load
cubic meters/metric ten of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD)
Costs-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Nylon 6 (small plant)
11
67
2.3
(25)
(8)
(0.6)
Alternative Treatment Steps
A B C D IE
270 630 630 120
840
22
17
2
0.5
50
63
23
3
50
63
23
3
10
12
2
—
67
84
136
18
51.5 139
139
24
305
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
20
N/A
N/A
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B C D E
2
20
0.3
2
0.2
187
-------
TABLE 30-29
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory :
Representative Plant Capacity
million kilograms (pounds) per year :
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Nylon 6 (large plant)
45 (100)
67 (8)
9.1
(2.4)
Alternative Treatment Steps
A B C D E
600 1400 1400 300 2050
48
60
7
1
112
140
62
9
112
140
62
9
24
30
3
—
164
205
278
72
116
323
323
57
719
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
20
N/A
N/A
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B C D E
2
20
0.2
0.3
2
0.2
188
-------
TABLE 30-30
WATER EFFLUENT TREATMENT COSTS
PI ASTICS AND SYNTHETICS INDUSTRY
Product Subcategory :
Representative Plant Capacity
million kilograms (pounds) per year :
Hydraulic Load
cubic meters/metric ton of product (gal/lb) :
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Nylon 66 (small plant)
23 (50)
16.7 (2.0)
1.1
(0.3)
Alternative Treatment Steps
A B C D E
231 539 539 78 575
18
23
2
0.5
43
54
23
3
43
54
23
3
6
8
2
—
46
58
113
11
43.5 123
123
16
228
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
10
15
N/A
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B C D E
0.4
2
0.07
0.5
0.2 0.05
189
-------
TABLE 30-31
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year :
Hydraulic Load
cubic meters/metric ton of product (gal/lb) :
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs -$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Nylon 66 (large plant)
90 (200)
16.7 (2.0)
4.5
(1.2)
Alternative Treatment Steps
A B £ D E
360 840 840 190 1200
29
36
8
2
67
84
67
27
67
84
67
27
15
19
2
—
96
120
145
22
75 245
245
36
383
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
10
15
N/A
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B C D E
0.4
2
0.07
0.5
0.2 0.05
190
-------
TABLE 30-32
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year :
Hydraulic Load
cubic meters/metric ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Costs-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Cellophane (all plants)
45 (100)
325 (39)
44.7
(11.8)
Alternative Treatment Steps
A B D E
1620 3780 880 5550
130
162
20
2
302
378
181
20
70
88
7
—
444
555
692
209
314
881 165 1900
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
50
150
50
Resulting Effluent Levels
(Units per 1000 Units of Product)
D E
B
5
50
10
2
10
1
191
-------
TABLE 30-33
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory:
Representative Plant Capacity
million kilograms (pounds) per year :
Hydraulic Load
cubic meters/metric ton of product (gal/lb) :
Treatment Plant Size:
thousand cubic meters per day (MGD) :
Com - $1000
Cellulose Acetate
90 (200)
157 (18.8)
43.2 (11.4)
Alternative Treatment Steps
A B C D E
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Effluent Quality (Expressed in terms of yearly averages)
1590 3710 3710 850
4840
126
159
28
3
297
371
204
40
297
371
204
40
68
85
7
_
387
484
395
109
317
912 912 160
1375
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
50
75
15
Resulting Effluent Levels
(Unite par 1000 Unite of Product)
A B C D E
3
30
0.5
3
0.3
192
-------
TABLE 30-3^
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory: Rayon (all plants)
Representative Plant Capacity
million kilograms (pounds) per year : 68 (150)
Hydraulic Load
cubic meters/metric ton of product (gal/lb) : 151 (18.1)
Treatment Plant Size:
thousand cubic meters per day (MGD) : 31.0 (8.2)
Com-$1000 Alternative Treatment Steps
6 § G 9 §
Initial Investment 1320 3380 1210 700 4650
Annual Costs:
Capital Costs (8%) 106 270 97 56 372
Depreciation (10%) 132 333 121 70 465
Operation and Maintenance 15 273 485 6 692
Energy and Power 2 16 28 - 209
Zinc Recovery Credit (681)*
Total Annual Costs 255 897 50 132 1738
Effluent Quality (Expressed in terms of yearly averages)
Raw Resulting Effluent Levels
WMte (Units per 1000 Units of Product)
A B G D E
B.O.D. 25 3 - - 1
C.O.D. 50 - 40 - 7
Suspended Solids N/A 6 0.7
Zinc 30 - 0.3 - 0.07
'Assumes 75% recovery of zinc values at $.20/lb.
193
-------
TABLE 31
INDUSTRIAL WASTE TREATMENT MODEL DATA
PLASTICS AND SYNTHETICS INDUSTRY
(Product Group #1) *
Product Subcategory
Epoxies Melamine/Urea Phenolics
Total Industry Discharge
1000 cubic meters/day or
(million gallons/day)
1972 0.8(0.2) 2.3(0.6) 21.0(5.5)
1977 1.1(0.3) 3.8(1.0) 28.0(7.4)
Flow Through Components Employed
One hundred percent of total flow in each industry subcategory is assumed
to pass through each treatment step or component.
Quality of Untreated Wastewater in 1977
(Expressed in terms of yearly averages.)
Parameters:
(in units/1000 units of product)
B.O.D. 0.2 0.07 0.6
C.O.D. 1 0.3 3
S.S. 0.1 0.03 0.4
Phenolic Compounds 0.002 - 0.006
Number of Companies in
Subcategory Q „ 81
Percent of Treatment in 1972
Treatment Steps:
(in percent now treated) Estimate
A. Initial Treatment 55
B. Biological Treatment 30
*See footnote, p. 136.
194
-------
TABLE 32
INDUSTRIAL WASTE TREATMENT MODEL DATA
PLASTICS AND SYNTHETICS INDUSTRY
(Product Group #2)
Product Subcategory
PVC
ABS/SAN PStyrene PV Acetate
Total Industry Discharge
1000 cubic meters/day or
(million gallons/day)
1972
1977
76.1(20.1)
134.0(35.4)
Flow Through Components Employed
16.3(4.3)
32.7(42.4)
43.4(11.5)
66.9(17.7)
7.6(2.0)
9.1(2.4)
One hundred percent of total flow in each industry subcategory is assumed
to pass through each treatment step or component.
Quality of Untreated Wastewater in 1977
(Expressed in terms of yearly averages.)
Parameters:
(in units/1000 units of product)
B.O.D.
C.O.D.
S.S.
Number of Companies in
0.3
3
0.5
0.4
4
0.5
0.1
1
0.2
0.1
1
0.3
Subcategory 23
19
26
Percent of Treatment in 1972
Treatment Steps:
(in percent now treated) Estimate
A. Initial Treatment 90
B. Biological Treatment 45
195
-------
TABLE 33
INDUSTRIAL WASTE TREATMENT MODEL DATA
PLASTICS AND SYNTHETICS INDUSTRY
(Product Group #3)
Product Subcategory
LDP Ethylene HDP Ethylene Polypropylene
Total Industry Discharge
1000 cubic meters/day or
[million gallons/day]
1972 74.2(19.6] 47.7(12.6) 40.9(10.8)
1977 130.6[34.5] 95.8(25.3) 82.1(21.7)
Flow Through Components Employed
One hundred percent of total flow in each industry subcategory is assumed
to pass through each treatment step or component.
Quality of Untreated Wastewater in 1977
(Expressed in terms of yearly averages.)
Parameters:
(in units/1000 units of product)
B.O.D.
C.O.D.
S.S.
Number of Companies in
0.1
1
0.3
0.1
1
0.2
0.3
1
0.5
Subcategory 12 13
Percent of Treatment in 1972
Treatment Steps:
(in percent now treated) Estimate
A. Initial Treatment 55
B. Biological Treatment 35
196
-------
TABLE 3^
INDUSTRIAL WASTE TREATMENT MODEL DATA
PLASTICS AND SYNTHETICS INDUSTRY
(Product Group #4)
Product Subcategory
Acrylic
Polyester
Nylons
Total Industry Discharge
1000 cubic meters/day or
(million gallons/day)
1972
1977
18.9(5.0)
22.0(5.8)
87.2(23.1.) 97.2(25.7)
175.6(46.5) 124.0(32.8)
Flow Through Components Employed
One hundred percent of total flow in each industry subcategory is assumed
to pass through each treatment step or component.
Quality of Untreated Wastewater in 1977
(Expressed in terms of yearly averages.)
Parameters:
(in units/1000 units
B.O.D.
C.O.D.
S.S.
of product)
1
6
0.5
0.3
5
0.2
[6] /[66]
2/0.4
20/2
2/0.2
Number of Companies in Subcategory 11
Percent of Treatment in 1972
Treatment Steps:
19
Estimate
(in percent now treated)
A. Initial Treatment 99
B. Biological Treatment 60
20
197
-------
TABLE 35
INDUSTRIAL WASTE TREATMENT MODEL DATA
PLASTICS AND SYNTHETICS INDUSTRY
(Product Group #5)
Product Subcategory
Cellophane Cellulose Acetate Rayon
Total Industry Discharge
1000 cubic meters/day or
(millions gallons/day)
1972 143.1(37.8) 171.8(45.4) 195.4(51.7)
1977 123.0(32.5) 189.6(50.1) 226.6(59.9)
Flow Through Components Employed
One hundred percent of total flow in each industry subcategory is assumed
to pass through each treatment step or component.
Quality of Untreated Wastewater in 1977
(Expressed in terms of yearly averages.)
Parameters:
(in units/1000 units of product)
8.O.D. 5 33
C.O.D. 50 30 40 ;
S.S. 10 1 6
Zinc — .3
Number of Companies in
Subcategory 4 77
Percent of Treatment in 1972
Treatment Steps:
(in percent now treated) Estimate
A. Initial Treatment 60
B. Biological Treatment 30
198
-------
SECTION IX
BEST PRACTICAELE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
GUIDELINES AND LIMITATIONS
Definition of Best. Practicable Control Technology
Currently Available^_f BPCTCA j
Based on the analysis of the information presented in Sections
IV-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 equilization, 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 BOD.5 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 house-
keeping practices.
The best practicable control technology currently available has
been found to be capable of achieving effluent concentrations of
BOD.5 comparable to the secondary treatment of municipal sewage.
The design and operational conditions of these biological systems
are, of course, significantly different than for municipal
sewage. The capabilities of biological treatment for industrial
wastes are specific to a particular plant's waste waters.
However, as discussed in Section VII, end-of-pipe treatment for
the removal of biologically active substances from waste waters
has been demonstrated successfully in different sections of the
plastics and synthetics industry. This technology has proven
applicable regardless of the age or size of the manufacturing
plant. Depending upcn the treatability of the wastewaters, it
has been demonstrated to be practical in maintaining
concentrations of biologically active substances in the effluent
stream within reasonable limits. However, variations due to the
vagaries of micro-organisms as well as process and climatic
conditions are normal for any biological waste water treatment
plant. The Guidelines for best practicable control technology
take these factors into consideration and recognize that certain
unique properties such as measured by COD exists in the waste
waters from the industry. Besides BODS, COD, and S3, certain
metals, phenolic compounds, and nitrogen compounds are among the
parameters of major concern to the industry.
199
-------
Table 21, Section VII of this report describes effluent loadings
which are currently being attained by the product subcategories
of the industry for BOD5, COD, and suspended solids. The results
of this work show that exemplary, practical waste water treatment
plants are presently in operation and that their operational
procedures are comparable with those of biological systems in
other industries. Consequently, the most significant factors in
establishing effluent limitation guidelines on a basis of units
of pollutants per unit of production are (1) the waste water
generation rates per unit of production capacity and (2) the
practicable treatment levels of the waste waters from the
particular manufacturing process.
The Guidelines
The guidelines in terms of kg of pollutant per kkg of production
(lb/1000 Ib) are based on attainable effluent concentrations and
demonstrated waste water flows for each product and process
subcategory.
Attainable Effluent Ccncentrations
Based on the definition of BPCTCA the following long term average
BOD5 and T.S.S. concentrations were used as a basis for the
guidelines.
BOD5 T.S.S.
Major Subcategory I 15 30
Major Subcategory II 20 30
Major Subcategory III 45 30
Major Subcategory IV 75 30
The BOD5 and T.S.S. concentrations are based on the exemplary
plant data presented in Table 18, Section VII, and in some cases
technology transfer such as multi-stage biological systems as
presented in Section VII.
The COD characteristics of process wastes in the plastics
industry vary significantly from product to product, and within a
plant over time. The ratio of COD to BOD5 in plant effluents is
shown in Table 36 to range from a low of 2 in polypropylene to a
high of 11.8 in polyester. The COD limits for BPCTCA are based
on levels achieved in the exemplary plants for which data were
available. They are expressed as ratio to the BOD5 limits in
Table 37. Considering the variability of the COD/BODjj ratio
between plants the upper limits of COD/BOD.5 of 5, 10, and 15 were
used for determining limitations. Upon applying the variability
factors discussed below to determine the BOD5. limitations, the
COD/BOD5 factors as applied to the BOD5_ limitations result in a
COD limitation that is liberal. The resulting COD limitations do
not determine the technology required but in effect require that
COD wastes be treated along with the BOD5 wastes.
200
-------
TABLE 36
COD/BOD RATIOS IN EFFLUENT STREAMS
Product COD/BOD
Polyvinyl chloride 7.5
ABS/SAN 9.5
LD Polyethylene 6.7
Polypropylene 2.0
HD Polyethylene 5.7
Cellophane 8,. 5
Rayon 11.7
Polyester 11.8
Nylon 66 U.2
Cellulose acetate 8.5
Acrylics 4.3
201
-------
TABLE 37
COD/BOD Guideline Bases
Product COD/BOD
Polypropylene, Nylon 66, and
Acrylics
Polyvinyl chloride, ABS, polyvinyl 10
acetate, polystyrene, low density
and high density polyethylene,
cellophane, cellulose acetate and
Nylon 6
Polyester, Rayon 15
The removal of phenolic compounds is based on an attainable
concentration level of 0.5 mg/liter monthly limit as demonstrated
by dephenolizing units (75) (76), activated carbon (18) (19) (56) (47)
or biological degradation (47) (76).
The removal of total chromium is based on an attainable
concentration level of 0.25 mg/liter monthly limit as
demonstrated by various chemical precipitation techniques
followed by biological degradation (47) (76).
The removal of zinc is based on an attainable concentration of
1.4 mg/liter as demonstrated by an alkaline chemical
precipitation process (65) (76) .
Demonstrated Wastewater Flows
The waste water flow basis for BPCTCA is based on demonstrated
wastewater flows found within the industry for each product and
process subcategory. Wastewater flows observed at exemplary
plants were used as the basis when they fell at the approximate
middle of the wastewater flow ranges reported by previous
industry and EPA surveys. When the observed flows fell outside
of the middle range, a waste water flow within this range was
used as the basis.
The waste water flow basis includes process water, utility
blowdowns and auxiliary facilities such as laboratories, etc.
The waste water flow basis is summarized in Table 38. It is
essential to note that the waste water flow is often an integral
part of the basic design and operation of the plant or the
process and may therefore be subject to significant reduction
only at large expense. In general, the hydraulic load is larger
for older plants. However, the availability of water also
influences design as does the philosophy of the company
constructing the plant. No simple formula for relating hydraulic
load to plant age, size or location can be established.
Demonstrated wastewater flows which fall in the middle of the
reported range of wastewater flow is the best available basis for
use in determining guidelines.
202
-------
Statistical Variability of a Properly Designed and Operated Waste
Treatment Plant
The effluent from a properly designed and operated treatment
plant changes continually due to a variety of factors. Changes
in production mix, production rate, climatic conditions and
reaction chemistry influence the composition of raw wasteload
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 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 sub-
categories as discussed above, a statistical analysis was made of
plants where sufficient data was available to determine these
variances for day-to-day and month-to-month operations. The
standard deviations for day-to-day and month-to-month operations
were calculated. For the purpose of determining effluent
limitation a variability factor was defined as follows:
Standard deviation = Q monthly, Q daily
Long-term average (yearly or design) = x
Variability factor = y monthly, y daily
y monthly = x_+ 2Q monthly
x
y daily = x + 3p daily
The variability factor is multiplied by the long-term yearly
average to determine the effluent limitation guideline for each
product subcategory. The monthly effluent limitation guideline
is calculated by use of a variability factor based on two
standard deviations and is only exceeded 2-3 percent of the time
for a plant that is attaining the long-term average. The daily
effluent limitation 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 limitation guidelines as discussed in
this paragraph should never be exceeded by a properly designed
and operated waste treatment facility.
203
-------
TABLE 38
Demonstrated Wastewater Flows
Wastewater Flow Basis
ccm/kkg gal/1000//
P olyvinyl chloride
Suspension
Emulsion
Bulk
Polyvinyl Acetate
Polystyrene
Suspension
Bulk
Polypropylene
Lo Density Polyethylene
Hi Density Polyethylene
Solvent
Polyform
Cellophane
Rayon
ABS/SAN
Polyester
Resin
Fiber
Resin and Fiber Continuous
Resin and Fiber Batch
Nylon 66
Resin
Fiber
Resin and Fiber
Nylon 6
Resin and Fiber
Resin
Fiber
Cellulose Acetate
Resin
Fiber
Resin and Fiber
Epoxy
Phenolics
Urea Resins
Melamine
Acrylics
15.02
5.42
2.50
8.34
9.18
1.67
17.52
8.34
12.52
2.17
242
133
17.52
7.93
7.93
7.93
15.86
6.67
5.84
12.52
56.94
37.55
19.39
41.72
41.72
83.44
3.59
12.3
1.84
1.34
16.69
1800
650
300
1000
1100
200
2100
1000
1500
260
29,000
16,000
2,100
950
950
950
1900
800
700
1500
6800
4500
2300
5000
5000
10,000
430
1480
220
160
2000
204
-------
The following table summarizes the basis for the BOD5_ variability
factors.
TABLE 39
Demonstrated Variability
Influent
Concentration
Major
Subcategory mg/1
Long-Term
Effluent
Concentration
mg/1
Variability
Factor
Monthly Daily
I
II
III
IV
33
380
380
1206
91
1267
__
6
9
17
11
20
44
__
1.80
1.33
1.80
1.76
1.77
2.2
2.2*
3.0
2.1
3.3
3.3
3.8
4.0*
4.0*
*estimated values
205
-------
Based on the table of demonstrated variability the following vari-
ability factors were applied to determine the effluent limitation
guidelines.
TABLE 40
Variability Factor
Major
Subcategory Monthly Daily
I 1.6 3.1
II 1.8 3.7
III 2.2 4.0
IV 2.2 4.0
The variability factors for suspended solids removal is based on
the variabilities presented in table 40A for suspended solids
removal. The monthly variability was calculated at 2.2 and daily
estimated at 4.0.
206
-------
TABLE 40A
Suspended Solids Removal
Demonstrated
monthly
Product Variability
Cellulose Acetate 2.2
Nylon 6 1.7
Polyester 2.2
Nylon 66 2.2
Acrylics 2.6
Polyvinyl Chloride 1.9
The variability for total chromium and phenolic compounds are
based on the monthly limits and a variability factor of 2.0 for
the daily maximum.
The variability of zinc concentrations is based on the
variability encountered by the EPA demonstration project(65).
The analysis of variability set the zinc limits at 4.0 mg/1
monthly and 6.8 mg/1 daily.
Based on the factors discussed in this Section the effluent
limitation guidelines for BPCTCA are presented in Tables 41 and
42.
207
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-------
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
Definition of Best Available Technology Economically. Achievable
fBATEA)
Based on the analysis of the information presented in Sections
IV-VIII, the basis for BATEA is defined below.
Best available technology economically achievable (BATEA) for
existing point sources is based on the best in-plant practices of
the industry which minimize the volume of waste generating water
as typified by segregation of contact process waters from
noncontact waste water, maximum waste water recycle and reuse,
elimination of once-through barometric condensers, control of
leaks, good housekeeping practices, etc., and end-of-pipe
technology, for the further removal of suspended solids and other
elements typified by media filtration, chemical treatment, etc.,
and further COD removal as typified by the application of
adsorption processes such as activated carbon and adsorptive
floes, and incineration for the treatment of highly concentrated
small volume wastes and additional biological treatment for
further BOD5 removal when needed.
Best available technology economically achievable can be expected
to rely upon the usage of those technologies which provide the
greatest degree of pollutant control per unit expenditure.
Historically, this has been the approach to the solution of any
pollution problem - as typified by the mechanical and biological
treatment used fcr removal of solids and biochemically-active
dissolved substances, respectively. At the present state of
technological development it is possible to achieve complete
removal of pollutants from waste water streams. The economic
impact of doing this must be assessed by computing cost benefits
to specific plants, entire industries, and the overall economy.
The application of best available technology will demand that the
economic achievability be determined, increasingly, on the basis
of considering water for its true economic impact. Unlike best
practicable technology, which is readily applicable across the
industry, the selection of best available technology economically
achievable becomes uniquely specific in each process and each
plant. Furthermore, the human factors associated with
conscientious operation and meticulous attention to detail become
increasingly important if best available technology is to achieve
its potential for reducing the emission of pollutants from
industrial plants.
209
-------
The Guidelines
Achievable Effluent Concentrations
Suspended Solids
The removal of suspended solids from waste water effluent is
based on well-understood technology developed in the chemical
process industries and in water treatment practices. Application
of filtration to the effluents frcm 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 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. 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
algael 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 ing/liter); the capital and operating
cost for this technology adds significantly to waste water
treatment costs. The concentration basis for BATEA is 10 mg/1
for all product and process subcategories. (1) (22) (47)
Oxygen-Demanding Substances
Removal of biochemical-oxygen-demanding substances to
concentration levels less than the range proposed for municipal
sewage treatment plants will require the utilization of physical-
chemical processes. It is expected, however, that the chemical-
oxygen-demanding substances will present a far greater removal
problem than BOD, because the biochemically-treated waste water
will have proportionally much higher ratios of COD to BOD than
entered the waste water treatment plant. To reduce the COD in a
treated effluent, it will be necessary either to alter processes
so that nonbiodegradable fractions are minimized or attempt to
remove these substances by some method of waste water treatment.
Both of these approaches may be difficult. Alteration of
processes so that they produce less refractory wastes may not be
possible within the constraints of the required chemical
reactions. However, reduction in the quantities of wastes
generated by spills^ leaks, and poor housekeeping practices can
contribute significantly to reducing the total COD discharges,
especially where a large fraction of the pollutants are
refractory to biological degradation. Consequently, one of the
first steps in a program to reduce emissions should be a thorough
evaluation of the process operation alternatives and techniques
for preventing pollutants from entering the waste water streams.
In other methods for removal of oxygen demanding substance,
adsorption by surface-active materials, especially activated
210
-------
carbon, has gained preeminence. Although the effectiveness of
activated carbon adsorption has been well demonstrated for
removing BOD and COD from the effluents of conventional municipal
sewage treatment plants, its effectiveness for the removal of the
complex chemical species found in the waste water of this
industry can be expected to be highly specific. Evidence of the
low adsorption efficiency of activated carbon for a number of
different chemical species is beginning to appear 'in the
technical literature. However, the only way to determine if
activated carbon adsorption is an effective method for removing
COD is to make direct determinations in the laboratory and in
pilot plants. In some instances, activated carbon adsorption may
be used to remove substances selectively (for example, phenols)
prior to treatment by other methods. Although activated carbon
adsorption is proving to be a powerful tool for the removal of
many chemicaloxygen-demanding and carbonaceous substances from
waste water streams, it is not a panacea. Its use must be
evaluated in terms of the high capital and operating costs,
especially for charcoal replacement and energy, and the benefits
accrued.
Removal of carbonaceous and oxygen-demanding substances can some-
times be achieved through oxidation by chlorine, ozone,
permanganates, hypochlorites, etc. However, not only must the
cost benefits of these be assessed but certain ancillary effects,
such as (1) the production of chlorinated by-products which may
be more toxic than the substance being treated, (2) the addition
of inorganic salts and (3) the toxic effects of the oxidants
themselves must be taken into account. Consequently, when
chemical oxidation is employed for removal of COD, it may be
necessary to follow the treatment with another step to remove the
residuals of these chemicals prior to discharge to receiving
waters.
Degradation of oxygen-demanding substances may take place slowly
in lagoons if sufficiently long residence time can be provided.
If space is available, this may be an economic choice. Also, the
use of land irrigation, or the "living filter" approach to water
purification, is receiving selected attention. Ultra-filtration
and reverse osmosis, both of which are membrane techniques, have
been shown to be technically capable of removing high molecular
species, but they have not been shown to be operationally and
economically achievable. With these techniques the molecular
distribution of the chemical species determines the efficiency of
the separation. They probably have limited potential in the
plastics and synthetics industry, due to the particular spectrum
of molecular weights occuring in the waste waters.
The concentration basis for BATEA for COD is 130 mg/1 as
demonstrated in an activated carbon-pilot plant (77) or the
concentrations which are attainable by biological treatment in
the exemplary plants as expressed in Table 18, Section VII, and
for BOD5 is 15 mg/1 for major sutcategory I and II product
subcategories and 25 mg/1 for major subcategory III and IV
product subcategories.
211
-------
The removal of phenolic compounds is based on the application of
dephenolizing units, or activated carbon followed by biochemical
degradation. The concentration basis for phenolic compounds is
0.1 mg/1 for the Acrylic product subcategory.
The removal of total chromium is based on an attainable
concentration level of 0.25 mg/liter as demonstrated by various
chemical precipitation techniques followed by biological
degradation (47).
The removal of zinc from the rayon subcategory wastes is based on
an achievable concentration of 1.0 mg/1 as demonstrated by the
EPA demonstration project (65) .
Waste Load Reduction Basis
The waste load basis for BATEA is based on overall loading
reduction through the use of the best achievable concentrations
and the reduction of waste water flows from BPCTCA to a level
between the BPCTCA waste water flows and the identified BADT
waste water flows as described in Section XI. Increased
efficiency in the utilization of water combined with closer
operational control on preventing 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 factors for BATEA guidelines are 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 40B. The TSS
factors are based on data obtained from multi- media filters used
in the petroleum refining industry. The other parameters are
based on the achievable concentration for monthly maximum and a
variability factor of 2 to determine the daily maximum.
TABLE 40B
Variability Factors BATEA
BOD5 and COD TSS
Monthly Daily Monthly Daily
Major Subcategory I 1.6 2.4 1.7 2.0
Major Subcategory II 1.8 2.8 1.7 2.0
Major Subcategory III 2.2 3.0 1.7 2.0
Major Subcategory IV 2.2 3.0 1.7 2.0
212
-------
Based on the factors discussed in this section, the Effluent
Limitation Guidelines for Best Available Technology Economically
Achievable, BATEA, are presented in tables 43 and 44.
213
-------
-------
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
BEST AVAILABLE DEMONSTRATED TECHNOLOGY
Definition of New Source Performance Standards Best Available
Demonstrated Technology (NSPS-BADT)
Based on the analysis of the information presented in sections
IV-VIII, the basis for NSPS-BADT is defined below.
Best available demonstrated technology (BADT) for new source
performance standards (NSPS) are based on BPCTCA and the maximum
possible reduction of process waste water generation and the
application of media filtration and chemical treatment for
additional suspended solids and other element removal and
additional biological treatment for further BOD5_ removal as
needed.
The Standards
Achievable Effluent Concentrations
The concentration basis for NSPS-BADT is the same as for BATEA
for all parameters except COD. They are discussed in section X.
The COD concentration basis for NSPS - BADT is based on the
concentrations which were attainable in exemplary plants as
expressed in Table 18, Section VII. The acrylics COD
concentration for a plant designed for 25 ppm average BOD5_ was
estimated from plant data at 480 mg/1. To determine limitations,
the variability factors determined from BPCTCA (Table 40, Section
IX) 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 BOD5_ wastes.
Waste Load Reduction Basis
The waste water flow basis for NSPS - BADT is based on the lowest
identified as to primary source flows associated with each
product. The waste water basis ranges from 0 to 50 percent of
the BPCTCA basis and is product specific. These waste water
flows are summarized in Table 40C.
It is apparent that effluent limitation standards requiring
significant reductions over that attainable by best practicable
control technology currently available (BPCTCA) requires
considerable attention to both the process generation of
waterborne pollutants as well as the water use practices of the
plant.
Variability
The variability factors for BADT standards are based on the
variability factors determined for BPCTCA for BOD5_ and COD. The
215
-------
TABLE NO. 40 C
Product Subcategory
Lowest Demonstrated Waste Water Flows
gal/1000 Ib production ccm/kkg
Polyvinyl chloride suspension
emulsion
bulk
Polyvinyl Acetate
Polystyrene suspension
bulk
Polypropylene
Polyethylene Low Density
High Density Solvent
High Density Polyform
Cellophene
Rayon
ABS/SAN
Polyester resin
Fiber
resin and fiber continuous
resin and fiber batch
Nylon 66 resin
Nylon 6 resin
Fiber
Resin and Fiber
Fiber
Resin and Fiber
Cellulose Acetate resin
Fiber
Resin and Fiber
Acrylics
950
650
300
900
1100
200
1100
900
1500
260
16,000
9000
1900
950
950
550
1900
800
700
1500
3300
1700
5000
2500
2500
5000
1900
7.92
5.42
2.50
7.51
9.17
1.67
9.17
7.51
12.51
2.17
133.44
75.06
15.85
7.92
7.92
4.59
15.85
6.67
5.84
12.51
27.52
14.18
41.70
20.85
20.85
41.70
15.85
216
-------
TSS variability factors are 1.7 monthly and 2.5 daily as
demonstrated by multi-media filtration data obtained from the
petroleum industry. The other parameters are based on the
achievable concentration for monthly maximum and a variability
factor of 2 to determine the daily maximum.
Based on the factors discussed in this section, the New Source
Performance Standards for Best Available Demonstrated Technology
NSPS-BADT are presented in tables 45 and 46.
217
-------
TABLE NO. 41
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
EFFLUENT LIMITATIONS GUIDELINES
Subcategory
kg/kkg (lb/1000 Ib of production)
BODS
Maximum Average
of daily values
for any period
of thirty
consecutive days
Polyvinyl chloride
Suspension 0.36
Emulsion 0.13
Bulk 0.06
Polyvinyl Acetate 0.20
Polystyrene
Suspension 0.22
Bulk 0.04
Polypropylene 0.42
Polyethylene
Low Density 0.20
High Density Solvent 0.30
High Density Polyform 0.052
Cellophane 8.7
Rayon 4.8
ABS/SAN 0.63
Polyester
Resin 0.78
Fiber 0.78
Resin and Fiber Continuous 0.78
Resin and Fiber Batch 1.56
Nylon 66
Resin 0.66
Fiber 0.58
Resin and Fiber 1.24
Nylon 6
Resin 3.
Fiber 1.
Resin and Fiber 5,
Cellulose Acetate
Resin A.13
Fiber 4.13
Resin and Fiber 8.26
Acrylics 2.75
71
90
61
Maximum
for any
one day
.70
.26
.12
.39
.43
.08
.81
.39-
.53
.10
17.8
10
1.30
1.4
1.4
1.4
2.8
1.20
1.1
2.3
6.8
3.5
10.3
7.5
7.5
15.0
5.00
COD
Maximum Average
of daily values
for any period
of thirty
consecutive days
3.6
1.3
0.60
2.0
2.2
0.40
2.1
2.0
3.0
0.52
87
72
6.3
11.
11,
11,
23.4
3.3
3.0
6.2
37.1
19
56.1
41.3
41,
82.
Maximum
for any
one day
7.0
2.6
1.2
3.9
4.30
.80
4.10
3.9
5.8
1.0
178
150
13.0
21.5
21.5
21.5
43.00
6.0
5.3
11.3
68,
35.
103.
75,
75.
150,
SS
Maximum Average
of daily values
for any period
of thirty
consecutive days
0.99
0.36
0.16
0.55
0.61
0.11
1.16
0.55
0.83
0.14
16
8.8
1.16
0.52
0.52
0.52
1.04
0.44
0.39
0.83
48
27
75
13.8
25.0
2.75
2.75
5.5
1.1
Maximum
for any
one day
1.8
.65
.29
1.00
1.1
.20
2.11
1.00
1.31
.25
29.10
16.0
2.1
.95
.95
.95
1.90
.80
,110
1.52
4.51
2.31
6.81
5.0
5.0
10.0
2.0
oo
rH
CVJ
-------
TABLE NO. 42
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
EFFLUENT LIMITATIONS GUIDELINES
kg/kkg (lb/1000 Ib of production)
Product
Parameter
Polystytene suspension
High Density Polyethylene Solvent
ABS/SAN
Rayon
Acrylics;
Total Chromium
Total Chromium
Total Chromium
Zinc
Phenolic Cmpds
Maximum Average
of daily values
for any period
of thirty
consecutive days
0.0023
0.0031
0.0044
0.534
0.0083
Maximum
for any
one day
0.0046
0.0062
0.0088
0.91
0.017
(N
-------
TABLE NO. 43
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
EFFLUENT LIMITATION GUIDELINES
Subcategory
kg/kkg (lb/1000 Ib of production)
BOD5_
Maximum Average Maximum
of daily values for any
for any period one day
of thirty
consecutive days
COD
Maximum Average
of daily values
for any period
of thirty
consecutive days
Maximum
for any
one day
SS
Maximum Average
of daily values
for any period
of thirty
consecutive days
Maximum
for any
one day
Polyvinyl chloride
Suspension 0.28
Emulsion 0.13
Bulk 0.06
Polyvinyl Acetate 0-19
Polystyrene
Suspension 0.22
Bulk 0.040
Polypropylene 0.32
Polyethylene
Low Density 0.19
High Density Solvent 0.30
High Density Polyform 0.052
Cellophane 5.1
Rayon 2.8
ABS/SAN .45
Polyester
Resin .44
Fiber .44
Resin and Fiber Continuous .34
Resin and Fiber Batch .87
Nylon 66
Resin .37
Fiber .32
Resin and Fiber .69
Nylon 6
Resin 1.8
Fiber .92
Resin and Fiber 2.7
Cellulose Acetate
Resin 1.7
Fiber 1.7
Resin and Fiber 3.4
Acrylics < 39
0.41
0.20
0.09
0.29
0.33
0.06
0.48
0.29
0.45
0.078
7.9
4.4
.70
.59
.59
.47
1.20
.5
.44
.94
2.45
1.25
3.7
2.35
2.35
4.7
1.2
1.28
0.61
0.28
0.89
1.03
0.19
2.14
1.65
1.60
0.28
43.9
24.4
3.3
2.3
2.3
1.8
4.5
1.9
1.7
3.6
9.3
4.8
14.1
8.9
8.9
17.8
4.7
1.92
0.92
0.42
1.33
1.55
0.29
3.21
2.48
2.40
0.42
68.3
37.9
5.1
3.1
3.1
2.4
6.2
2.6
2.3
4.9
12.
6.
19.2
12.
12.
24.4
6.3
0.19
0.092
0.042
0.14
0.16
0.028
0.23
0.14
0.21
0.037
3.19
1.77
0.28
0.13
0.13
0.11
0.27
0.11
0.10
0.21
0.55
0.28
0.84
53
53
06
0.27
0.23
0.11
0.05
0.16
0.18
0.033
0.27
0.16
0.25
0.043
3.75
2.08
0.33
0.16
0.16
0.13
0.32
0.13
0.12
0.25
0.65
0.33
0.98
0.63
0.63
1.26
0.33
o
(N
CM
-------
TABLE NO. 44
BEST AVAILABLE TECHNONOGY ECONOMICALLY ACHIEVABLn
EFFLUENT LIMITATIONS GUIDELINES
kg/kkg (lb/1000 Ib of production)
Product
Parameter
Polystyrene suspension Total Chromium
High Density Polyethylene Solvent Total Chromium
ABS/SAN Total Chromium
Rayon Zinc
Acrylics Phenolic Cmpds
Maximum Average
of daily values
for any period
of thirty
consecutive days
0.0023
0.0031
0.0042
0.105
0.0016
Maximum
for any
one day
O.OU46
0.0062
0.0084
0.210
0.0032
CN
CM
-------
TABLE NO. 45
BEST AVAILABLE DEMONSTRATED TECHNOLOGY FOR
NEW SOURCE PERFORMANCE STANDARDS
kg/kkg (lb/1000 Ib of production)
Subcategory
BOD5_
Maximum Average Maximum
of daily values for any
for any period one day
of thirty
consecutive days
COD
Maximum Average
of daily values
for any period
of thirty
consecutive days
SS
Maximum Maximum Average Maximum
for any of daily values for any
one day for any period one day
of thirty
consecutive days
Polyvinyl chloride
Suspension
Emulsion
Bulk
Polyvinyl Acetate
Polystyrene
Suspension
Bulk
Polypropylene
Polyethylene
Low Density
High Density Solvent
High Density Polyform
Cellophane
Rayon
ABS/SAN
Polyester
Resin
Fiber
Resin and Fiber Continous
Resin and Fiber Batch
Nylon 66
Resin
Fiber
Resin and Fiber
Nylon 6
Resin
Fiber
Resin and Fiber
Cellulose Acetate
Resin
Fiber
Resin and Fiber
Acrylics
0.19
0.13
0.06
0.18
0.22
0.04
0.22
0.18
0.30
0.054
3.6
2.02
.43
.44
.44
.25
.87
.37
.32
.69
1.51
.78
2.29
1.15
1.15
2.29
.87
0.37
0.26
0.12
0.35
0.43
0.08
0.43
0'.35
0.58
0.10
.41
.17
,88
.79
.79
.46
1.58
.67
.58
1.25
2.75
1.42
4.17
2.08
2.08
4.17
1.58
0.89
0.61
0.28
0.84
1.03
0.19
1.47
1.80
1.60
0.28
48
47
3.1
0
0
32
8.0
2.6
2.3
4.95
15.7
8.1
23.9
11
11
22
16.7
70
20
54
60
2.00
0.37
2.9
3.47
3.10
.54
98
97
6.5
7.3
7.3
4.2
14.6
4.8
4.2
9.0
28.6
14.7
43.4
20
20
40
30.4
0.13
0.092
0.042
0.13
0.16
0.028
0.16
0.13
0.21
0.036
2.27
1.28
0.27
0.13
0.13
0.078
0.27
0.11
0.10
0.21
0.47
0.24
0.71
0.35
0.35
0.71
0.27
.19
.14
.06
.19
.24
.04
.24
.19
.31
.05
3.3
1.92
.40
.19
.19
.12
0.40
.16
.15
.31
.69
.35
1.1
.51
.51
1.1
0.40
-------
TABLE NO. 46
BEST AVAILABLE DEMONSTRATED TECHNOLOGY FOR
NEW SOURCE PERFORMANCE STANDARDS
Product
Parameter
Polystyrene suspension
High Density Polyethylene Solvent
ABS/SAN
Rayon
Acrylics
Total Chromium
Total Chromium
Total Chromium
Zinc
Phenolic Cmpds
kg/kkg (lb/1000 Ib of production)
Maximum Average
of daily values
for any period
of thirty
consecutive days
0.0023
0.0031
0.0040
0.075
0.0016
Maximum
for any
one day
0.0046
0.0062
0.0080
0.150
0.0032
CM
-------
-------
SECTION XII
ACKNOWLEDGEMENTS
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, Terry Rothermel and C. M. Mohr as the Principal
Investigators. Industry subcategory leaders were Harry Lambe, W.
V. Keary, Stanley Dale, Robert Eller, and Richard Tschirch. J.
E. Oberholtzer was the sampling and analytical leader,
David L. Becker, Project Officer, Effluent Guidelines Division,
through his assistance, leadership, advice, and reviews has made
an invaluable contribution to the preparation of this report.
Mr. Becker provided a careful review of the draft report and the
original Development Document and suggested organizational,
technical and editorial changes.
Allen Cywin, Director, Effluent Guidelines Division, Ernst Hall,
Assistant Director, Effluent Guidelines Division and Walter J.
Hunt, Chief Effluent Guidelines Development Branch, offered many
helpful suggestions during the program.
The members of the working group/steering committee who
coordinated the internal EPA review are:
Walter J. Hunt - Effluent Guidelines Division (Chairman)
Allen Cywin - Effluent Guidelines Division
David Becker - Effluent Guidelines Division (Project Officer)
Taylor Miller - Office of General Counsel
John Savage - Office of Planning and Evaluation
Robert Wooten - Region IV
Walter Lee - Region II
Frank Mayhue - Office of Research and Monitoring (Ada)
Wayne Smith - National Field Investigation Center (Denver)
Lawrence Roslinski - Office of Categorical Programs
Paul Des Rosiers - 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. Kit Krickenberger, Sharon
Ashe, Kay Starr, and Nancy Zrubek - Effluent Guidelines Division.
Anne Witkos, Mary Jane Demarco, Martha Hanaman and Violet Gaumont
- Arthur D. Little, Inc.
Appreciation is extended to staff members from EPA's Regions I,
II, III, IV, V, and VI offices for their assistance and
cooperation.
225
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Appreciation is extended to the following State organizations for
assistance and cooperation given to this program.
Alabama-Water Improvement Commission
Illinois Division of Water Pollution Control
Illinois Environmental Protection Agency
Louisiana-Stream Control Commission
New Jersey-Water Resources Division
State Department Environmental Protection
North Carolina-Office of Water and Air Resources
Ohio Environmental Protection Agency
South Carolina Pollution Control Authority
Appreciation is extended to the following trade associations and
corporations for assistance and cooperation given to this
program.
American Enka
Borden Company
Celanese Fibers Company
Dart Industries
Dow Chemical Company
E.I. du Pont de Nemours and Company
Exxon Chemicals
Fiber Industries
FMC Corporation
B. F. Goodrich Chemical Company
The Goodyear Tire 6 Rubber Company
Hercules Incorporated
Manufacturing Chemists Association
Marbon Division Borg-Warner Chemicals and Plastics Group
Monsanto
Northern Petrochemical Company
Reichhold Chemicals, Inc.
Rohm & Haas
Sinclair-Koppers
Tenneco Chemicals
Tennessee Eastman company
Union Carbide Corporation
226
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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. "Aerobic Digestion of Organic Waste Sludge," EPA Water
Pollution Control Research Series Report No. 17070 (December
1972) .
3. Albright, Lyle F., "Vinyl Chloride Polymerization by
Emulsion, Bulk and Solution Processes," Chemical Engineering,
Modern Chemical Technology, Part 16 (July 3, 1967).cc
4. "An Act to Amend the Federal Water Pollution Control Act,"
Public Law 92-500, Ninety-Second Congress, S. 2770 (October
18, 1972).
5. Arthur D. Little, Inc., "Technical Proposal: Effluent
Limitation Guidelines for the Plastics and Synthetics
Industry to the Environmental Protection Agency," Cambridge,
Massachusetts (November 16, 1972).
6. Aston, R.S., "Recovery of Zinc from Viscose Rayon Effluent,"
Presented at Purdue Industrial Waste Conference (May 1968).
7. Baloga, J.M., F.B. Hutto, Jr., and E.I. Merrill, "A Solution
to the Phenolic Pollution Problem in Fiberglass Plants: A
Progress Report," Chemical Engineering Progress Symposium
Series, No. 97^ Water - 1969 65, 124 (1969) .
8. Barson, Norman and James W. Gilpin, "Industrial Waste Study
of the Plastic Materials and Synthetics Industry," Draft
report prepared by Celanese Research Company for the Water
Quality Office, Environmental Protection Agency, Contract No.
68-01-0030 (undated).
9. Bibliography of Water Quality Research Reports, Environmental
Protection Agency, Office of Research and Monitoring,
Washington, D.C. (June 1972).
10. Black, H.H., "Planning Industrial Waste Treatment," J.. Water
PSilaiion Control Federation !i, 1277-1284 (1969).
11. Burd, R.S., "A Study of Sludge Handling and Disposal,"
Federal Water Pollution Control Administration Publication WP
20-4, Washington, D.C. (1968).
12. "Can Plants Meet EPA's New Effluent Guidelines?", Chemical
Week, pp. 59-60 (November 22, 1972) .
227
-------
13. Chemical Engineering Flowsheets, Prepared by the editors of
Chemical and Metallurgical Engineering, McGraw-Hill, New York
(1940) .
14. "Chemical Bugs Tame Process Wastes," Env.. Sci_.. Technol. 4
637^638 (1970).
15. Clarke, James S., "New Rules Prevent Tank Failures,"
Hydrocarbon Processing 5C)(5) , 92-94 (1971) .
16. "Construction Scoreboard," Engineering News •* Record 1.9_0(3), 32
(1973) .
17. Contract for Development of Data and Recommendations for
Industrial Effluent Limitation Guidelines and Standards of
Performance for the Plastics and Synthetics Industry," No.
68-01-1500, Issued to Arthur D. Little, Inc., Cambridge,
Massachusetts (December 1972) .
18. Conway, R.A. , et al. , "Conclusions from Analyzing Report
1 Treatability of Wastewater from Organic Chemical and
Plastics Manufacturing - Experience and Concepts',"
Unpublished document (January 1973) .
19. 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) .
20. Cost and Performance Estimates for Tertiary Wastewater
Treatment Purposes, Report NO. TWRC-9, PB 189953, Robert A.
Taft Water Research Center, Environmental Protection Agency,
Cincinnati, Ohio (June 1969) .
21. Crocker, Burton B., "Preventing Hazardous Pollution During
Plant Catastrophes," (4, 1970). 22. Gulp, Gordon L. and
Robert W. Gulp, Advance^ Wastewater Treatment , Van Nostrand
Reinhold CompanyT New York, N.Y. (1971).
23. Davis, Ernest M., "BOD vs. COD vs. TOC vs. TOD," Water and
Engineering, pp. 32-38 (February 1971) .
24. Devey, D.G. and N. Harkness, "Some Effluents from the
Manufacture and Use of Synthetic Resins and Other Polymers,"
Ef£li WJter Treaty J. ^1, 320-321 and 323-334 (1971) .
25. Eisenhauer, H.R. , "The Organization of Phenolic Wastes," JA
Water Pollution Control Federation 40, 1887-1899 (1968) .
26. "Environmental Protection Agency ±40 CFR Part 1331 secondary
Treatment Information, Notice of Proposed Rulemaking, "
Federal Register 38 (82) , 10642-10643 (April 30, 1973).
228
-------
27. Environmental Protection Agency, Toxic and Hazardous
Chemicals Designations, Report in progress.
28. Faith, W.L., Donald B. Keys, and Ronald L. Clark, Industrial
Chemicals, Third Ed.r Jchn Wiley and Sons, Inc., New York,
N.Y. (1965).
29. Federal Water Pollution Control Act Amendments of 1972, House
of Representatives, Report No. 92-1465, U.S. Government
Printing Office, Washington, D.C. (September 28, 1972).
30. Ford, D.L., "Application of Total Carbon Analyzer for
Industrial Wastewater Evaluation," Proc. of Twenty-Third
Industrial Waste Conf^, Part Two, Purdue University,
Lafayette, Indiana, pp. 989-99 (May~1968).
31. Ford, D.L., "The Applicability of Carbon Adsorption in the
Treatment of Petrochemical Wastewaters," Presented at
Conference on Application of New Concepts of Physical-
Chemical Wastewater Treatment (September 1972).
32. Ford, Davis L., "Total Organic Carbon as a Wastewater
Parameter," Public Works, pp. 89-92 (April 1968).
33. Golding, Brage, Polymers and Resins: Their Chemistry
Chemical Engineering, Van Nostrand Reinhold Company, New
York,
34. Gonzales, John G. and Russell L. Gulp, "New Developments in
Ammonia Stripping," Public Works, pp. 78-84 (May 1973) .
35. Hackert, R.L., "Spray Irrigation Disposal of Industrial
Wastes," Presented at Fourteenth Annual A.S.M.E. Plant
Engineering and Maintenance Conf., Milwaukee, Wisconsin
(October 1971).
36. Industrial and Engineering Chemistry, Modern Chemical
Processes, Reinhold Publishing Corp., New York, N.Y. (1950).
37. Jones, Robert H., "TOC: How Valid Is It?", Water and Wastes
Engineering, pp. 32^33 (April 1972) .
38. Kwie, William W., "Ozone Treats Wastestreams from Polymer
Plant," Water and Sewage Works Ilj5, 74 (1969).
39. Lamb, A. and E.L. Tollefson, "Toxic Effects of Cupric,
Chromate and Chromic Ions on Biological Oxidation," Water
Research 7, 599-613 (1973).
40. Lash, L.D. and G.L. Shell, "Treating Polymer Wastes,"
Chemical Engineering Progress 6j>(6) , 63-69 (1969) .
41. Lawson, Cyron T. and John A. Fisher, "Limitations of
Activated Carbon Adsorption for Upgrading Petrochemical
229
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Effluents." Presented at the Sixty-Fifth Annual Meeting of
the A.I.Ch.E., New York, N.Y. (November 1972).
42. Lundgren, Hans., "Air Flotation Purifies Wastewater from
Latex, Polymer Manufacture," Chemical Engineering Progress
S^msosium Series, NoA 97, Water - 1 96 9 65, 191 (1969).
43. Matthews, George, et. al., Vinvl and Allied Polymers ,
Chemical Rubber Co. Press, Cleveland, Ohio, pp. 13-40 (19727-
44. McDermott^ G.N., "Industrial Spill Control and Pollution
Incident, Prevention," J, Water Pollution Control Federation
43(8), 1629 (1971).
45. "National Pollutant Discharge Elimination System, Proposed
Forms and Guidelines for Acquisition of Information from
Owners and Operators of Point Sources," Federal Register 37
(234) , 25898
46. Naughton, P., "Bug Husbandry is the Secret of Waste Disposal
Plant Success," Process Engineering^ pp. 67068 (March 1971).
47. Patterson, J. W. and R. A. Minear, Wastewater Treatment
Second Edition, pp. 216-162, State of Illinois
Institute of Environmental Quality (January 1973) .
48. "Dipper-Type sampler for Collecting Samples of Sewage, Indus-
trial Waste or other Liquids," Prepared by Phipps and Bird,
Inc., Providence, Rhode Island.
49. Poon, C. P. C.g "Biodegradability and Treatability of
Combined Nylon and Municipal Wastes," J, Water Pollution
Control Federation 42X 100-105 (1970) .
50. "Pretreatment Guideline^ for the Discharge of Industrial
Wastes to Municipal Treatment Works," Draft report prepared
by Roy F. Westor., Inc., for the Environmental Protection
Agency, Contract No. 68-01-0346 (November 17, 1972) .
51. "Procedures, Actions, and Rationale for Establishing Effluent
Levels and Compiling Effluent Limitation Guidance for the
Plastic Materials and Synthetics Industries," Unpublished re-
port of the Environmental Protection Agency and the
Manufacturing Chemists Association, Washington, D.C.
(November 1972) ,
52. ^rocesj; industries Pictured Flowsheets , Prepared by the
editors of chemical and Metallurgical Engineering, McGraw-
Hill, New York, N.Y. (1945) .
53. Robinson, Donald M. and Dennis R. Bolten, "From Problem to
Solution with ABS Polymer Wastewater," Presented at 17th
Ontario Industrial Waste Conference, Niagara Falls, Ontario
(June 7-10, 1970) „
230
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54. Santoleri, J. J. "Chlorinated Hydrocarbon Waste Disposal and
Recovery Systems," Chemicaj, Engineering Progress 69± 68
(1973).
55. Shreve, R. Norris< Chemical Process Industries^ Third Ed.,
McGraw-Hill, New York, N.Y. (1967).
56. Shumaker, T. P., "Granular Carbon Process Removes 99.0-99.2%
Phenols," Chemical Processing (May 1973).
57. sittig, Marshall, Organic Chemical Process Encyclopedia,
Second Ed., Noyes Development Corporation, Park Ridge, N. J.
(1969) .
58. Smith, W. Mayo, Ed., Manufacture of Plastics^ Vol. 1,
Reinhold Publishing Corp., Park Ridge, N.J. (1964).
59. Steinmetz, C. E. and William J. Day, "Treatment of Waste from
Polyester Manufacturing Operations," Chemical Engineering
Progress Symposium Seriest No^ .97A Water f 1969 65A 188
719697.
60. Stevens, J. I., "The Roles of Spillage, Leakage and Venting
in Industrial Pollution Control," Presented at Second Annual
Environmental Engineering and Science Conference, University
of Louisville (April 21, 1972) .
61. Stevens, J. I. and W. v., Keary, "Industrial Utilization of
Techniques for Prevention and Control of Spills," Presented
at American Institute of Chemical Engineers Workshop,
Charleston, West Virginia (October 1971).
62. "Waste-Water Treatment Costs for Organics 1969-1973," Envir.
Sci. Technol. 3^ 311-313 (1969) .
63. "Water Pollution Abatement Costs, Plastic Materials and
Synthetic Rubber Industries (SIC 282)," Unpublished report
provided by the Environmental Protection Agency.
64. Woodruff, P. H., W. J. Moore, W. D. Sitman. G. A, Omohundro,
"Viscose Waste-Profile of a Successful Pollution Control
Program." Water Sewage Works 115jt 44-450 (1968) .
65. "Zinc Precipitation and Recovery from Viscose Rayon
Wastewaters," EPA Water Pollution Control Research Series,
Report 12090. ESG (January 1971) .
66. Bess, F.C., J.C. Hovious, R.A. Conway and B.H. Cheely,
"Proposed Method for Establishing Effluent Guidelines for the
Organic and Plastics Manufacturing Industry," Letter and
Attachment to Dr. Martha Sager, Chairman, Effluent Standards
and Water Quality Information Advisory Committee, June 12,
1973.
231
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67. Swindell-Dressier Company, "Processs Design Manual for Carbon
Adsorption," Environmental Protection Agency, Contract 14-12-
928, October 1971.
68. Weber, W. J., "Physicochemical Processes for Water Quality
Control," Wiley Interscience, New York 1972.
69. Burns & Roe, Inc., "Process Design Manual for Suspended Solid
Removal," Environmental Protection Agency, Contract 14-12-
930, October 1971.
70. Black & Veatch, "Process Design Manual for Phosphorous
Removal," Environmental Protection Agency, Contract 14-12-
936, October 1971.
71. Seiden, L. and K. Patel, "Mathematical Model of Tertiary
Treatment by Lime Addition," Robert A. Taft Water Research
Center, Report Nc. TWRC-14, September 1969.
72. Barker, J. E., and R. J. Thompson, "Biological Removal of
Carbon and Nitrogen Compounds from Coke Plant Wastes," EPA-
R2-73-167, April 1973.
73. Eliasson, R. and G. Tchobanglous, "Removal of Nitrogen and
Phosphorous Compounds from Wastewaters," Environmental
Science and Technology, 3, No. 6, p. 536-541, June 1969.
74. Gould, R. F., Editor, "Anaerobic Biological Treatment
Processes," American Chemical Society, Advances in Chemistry
Series No. 105, February 1970.
75. Supplement B - Detailed Record of Data Base for the
"Development Document for proposed Effluent Limitations
Guidelines and New Source Performance Standards for the
Steelmaking Segment of the Iron and Steel Manufacturing Point
Source Category," EPA 440/1-73/024, February 1974.
76. Supplement B - Detailed Record of Data Base for the
"Development Document for Effluent Limitations Guidelines and
New Source Performance Standards for the Synthetic Resins
Segment of the Plastics and Synthetics Manufacturing Point
Source Category," March 1974.
77. "Reuse of Chemical Fiber Plant Wastewater and Cooling Water
Blowdown," EPA Water Pollution Control Research Series Report
12090EUX (October 1970).
78. Hager, D.G., "A Survey of Industrial Wastewater Treatment by
Granular Activated Carbon," Presented at the 4th Joint
chemical Engineering Conference, American Institute of
Chemical Engineers, Canadian Society for Chemical
Engineering, Vancouver, British Columbia, September 10, 1973.
232
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SECTION XIV
GLOSSARY
Acetvl
Refers to that portion of a molecular structure which is derived
from acetic acid.
Aerobic
A living or active biological system in the presence of free,
dissolved oxygen.
Alkvl
A general term for monovalent aliphatic hydrocarbons.
Alumina
The oxide of aluminum.
Anaerobic
Living or active in the absence of free oxygen.
Arvl
A general term denoting the presence of unsaturated ring
structures in the molecular structure of hydrocarbons.
Autoclave
An enclosed vessel where various conditions of temperature and
pressure can be controlled.
Bacteriostate
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
is of Water and Wastes^ ~"
Catalyst
233
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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.
Cellulose Xanthate
An intermediate in the production of rayon by the viscose
process, formed by reaction of carbon disulfide with alkali
cellulose. The solution of this material in dilute aqueous
caustic is termed "viscose."
Chain Terminator
An agent which, when added to the components of a polymerization
reaction, will stop the growth of a polymer chain, thereby
preventing the addition of MER units.
COD
Chemical Oxygen Demand - Determined by methods explained in the
references given under BODS.
Copolymer
The polymer obtained when two or more monomers are involved in
the polymerization reaction.
Delusterant
A compound (usually an inorganic mineral) added to reduce gloss
or surface reflectivity of plastic resins or fibers.
Dialysis
The separation of substances in solution by means of their
unequal diffusion through semipermeable membranes.
Diatomaceous Earth
A naturally-occurring material containing the skeletal structures
of diatoms - often used as an aid to filtration.
Double-Effect Evaporators
Two evaporators in series where the vapors from one are used to
boil liquid in the other.
Effluent
The flow of wastewaters from a plant or wastewater treatment
plant.
234
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Emulsifier
An agent which promotes formation and stabilization of an
emulsion, usually a surface-active agent.
Emulsion
A suspension of fine droplets of one liquid in another.
Facultative Lagoon or Pond
A combination of aerobic surface and anaerobic bottom existing in
a basin holding biolcgically-active wastewaters.
Fatty Acids
An organic acid obtained by the hydrolysis (saponification) of
natural fats and oils, e.g., stearic and palmitic acids. These
acids are monobasic and may or may not contain some double bonds.
They usually contain sixteen or more carbon atoms.
Filtration
The removal of particulates from liquids by membranes on in-depth
media.
Formalin
A solution of formaldehyde in water.
GPP
Gallons per day.
GPM
Gallons per minute.
Halogen
The chemical group containing chlorine, fluorine, bromine,
iodine.
Humectant
An agent which absorbs water. It is often added to resin
formulations in order to increase water absorption and thereby
minimize problems associated with electrostatic charge.
Influent
The flow of wastewaters into a treatment plant.
M
235
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Thousands (e.g., thousands metric tons).
MM
Millions (e.g., million pounds).
Monomer
A relatively simple compound which can react to form a polymer.
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 C6H5OH.
Polymer
A high molecular weight organic compound, natural or synthetic,
whose structure can be represented by a repeated small unit ±the
(MER) 1.
PolYmerization
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 wastewaters prior to discharge to a publicly owned
wastewater treatment plant.
Primary Treatment
First stage in sequential treatment of wastewaters - essentially
limited to removal of readily- settlable solids.
S^flux
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 semi-solid organic products of natural
or synthetic origin, generally of high molecular weight with no
definite melting point. Most resins are polymers.
236
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scrubber
Equipment for removing condensable vapors and particulates from
gas streams by contacting with water or other liquid.
Secondary Treatment
Removal of biologically-active soluble substances by the growth
of micro-organisms.
Slurry
Solid particles dispersed in a liquid medium.
Spinnerette
A type of extrusion die consisting of a metal plate with many
small holes through which a molten plastic resin is forced to
make fibers and filaments.
Staple
Textile fibers of short length, usually one-half to three inches.
TDS
Total dissolved solids - soluble substances as determined by
procedures given in reference under BOD5.
TOC
Total Organic Carbon - a method for determining the organic
carbon content of wastewaters.
Tow
A large number of continuous filaments of long length. Tow is
•the usual form of fibers after spinning and stretching and prior
to being chopped into short lengths of staple.
Vacuum
A condition where the pressure is less than atmospheric.
237
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TABLE 47
METRIC UNITS
CONVERSION TABLE
MULTIPLY (ENGLISH UNITS)
ENGLISH UNIT ABBREVIATION
acre ac
acre - feet ac ft
British Thermal
Unit BTU
British Thermal BTU/lb
Unit/pound
cubic feet/minute cfm
cubic feet/second cfs
cubic feet cu ft
cubic feet cu ft
cubic inches cu in
degree Fahrenheit °F
feet ft
gallon gal
gallon/minute gpm
horsepower hp
inches in
Inches of mercury in Hg
pounds Ib
million gallons/day mgd
mile mi
pound/square inch psig
(gauge)
square feet sq ft
square inches sq in
tons (short) ton
yard yd
by TO OBTAIN; (METRIC UNITS)
CONVERSION ABBREVIATION METRIC UNIT
hectares
cubic meters
0.405
1233.5
0.252
0.555
0.028
1.7
0.028
28.32
16.39
0.555(°F-32)*
0.3048
3.785
0.0631
0.7457
2.54
0.03342
0.454
3,785
1.609
ha
cu m
kg cal
kg cal/kg
cu m/min
cu m/min
cu m
1
cu cm
°C
m
1
I/sec
kw
cm
atm
kg
cu m/day
km
(0.06805 psig +l)*atm
0.0929
6.452
0.907
0.9144
sq m
sq cm
kkg
kilogram-calories
kilogram calories/
kilogram
cubic mp.ters/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 tons
(1000 kilograms)
meters
Actual conversion, not a multiplier
238
<*U.S. GOVERNMENT PRINTING OFFICE: 1974 546-318/338 1-3
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