EPA -^0/1 -7 3-010
Development Document for Proposed
Effluent Limitations Guidelines and
New Source Performance Standards
for the
SYNTHETIC RESINS
Segment of the Plastics and
Synthetic Materials Manufacturing
Point Source Category
U.S. ENVIRONMENTAL PROTECTION AGENCY
AUGUST 1973
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Publication Notice
This is a development document for proposed effluent limitations
guidelines and new source performance standards. As sucn, this raport
is subject to changes resulting from comments received during the period
of public comments of the proposed regulations. This document in its
final form will be published at the time the regulations tor this
industry are promulgated.
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DEVELOPMENT DOCUMENT
for
PROPOSED 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
Robert L. Sansom
Assistant Administrator for Air & Water Programs
Allen Cywin
Director, Effluent Guidelines Division
David L. Becker
Project Officer
September, 1973
Effluent Guidelines Division
Office of Air and Water Programs
U.S. Environmental Protection Agency
Washington, D.C. 20460
Chicago } Illinois bGGOti
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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 92-100).
Guidelines and standards were developed for the following major
products:
APS/SAN Nylon 66
Acrylics Phenolics
C°llophan^ Polyester
Cellulose Acetate Polypropylene
Epoxy Polystyrene
Hiah-Density Polyethylene Polyvinyl Acetate
Low-Density Polyethylene Polyvinyl Chloride
Melamine Payon
Nylon 6 Urea
Effluent limitation guidelines contained herein set forth tne degree of
reduction of pollutants in effluents that is attainable tnrouah th*--
aDplica^ion of best practicable control technology currently available
(BPCTCA), and the degree of reduction attainable through the application
of best available •'-echnology 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
cost for 8&DT for new sources is estimated at $35,000,000.
Supporting data and rationale for the develoment of proposed effluent
limitation guidelines and standards of performance are contained in this
development document.
ii
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CONTENTS
Section Pagi
I Conclusions •,
II Recommendations 3
III Introduction -,-,
Purpose and Authority j_j
Methodology ^2
General Description of the Industry 13
Plastics -jj
Synthetic Fibers 15
Cellophane jg
Product and Process Technology ig
Typical Polymerization Products ^g
Emulsion and Suspension Polymerization ig
Atmospheric or Low-Pressure Mass Poly- 22
mer izat ion
High-Pressure Mass Polymerization-Low 25
Density Polyethylene
Polyolefins - Solution Polymerization 27
Polyolefins - Ziegler Process 29
Polyolefins - Particle Form Process 31
Polyacetal Resins 31
Cellophane 33
Rayon 34
Polyester Resin and Fiber 40
Nylon 66 Resin and Fibers 44
Cellulose Acetate Resin 45
Cellulose Acetate Fibers 50
Cellulose Triacetate Fibers 50
Epoxy Resins 50
Phenolic Resins 57
Amino Resins - Urea and Melamine 53
Acrylic Fibers 70
Nylon 6 Resins and Fibers 71
IV Industry Categor izai ton 77
V Waste Characterization gl
Raw Waste Loads g^
VI Selection of Pollutant Parameters g5
Selection Criteria g5
Selected Parameters g5
BODS 85
COD 86
Suspended Solids 86
Zinc 86
iii
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Phenolic Compounds 86
Chromium 87
Iron, Aluminum, Nickel, Vanadium, 87
Titanium, Molybdenum, and Cobalt
Nitrogeneous Compounds 87
Dissolved Solids 88
Toxic and Hazardous Chemicals 88
Oil and Grease, Alkalinity, Color, 88
Turbidity, Phosphates, Sulfides, Copper,
Cadmium, Manganese, Magnesium, Antimony
pH 89
VII Control and Treatment Technology 91
Presently Used Wastewater Treatment 91
Technology Potentially Usable Wastewater 104
Treatment Technology
Adsorption 104
Suspended Solids Removal 106
Chemical Precipitation 108
Anaerobic Process 109
Air Stripping 109
Chemical Oxidation 110
Foam Separation 110
Algae Systems 110
Incineration 110
Liquid-Liquid Extraction 111
Ion Exchange 111
Reverse Osmosis 112
Freeze Thaw 112
Evaporation 112
Electrodialysis 113
In-Plant Control of Waterborne Pollutants 113
Operational Philosophy 116
Organization 116
Specific Measures 116
Procedures and Operating Methods for 118
Elimination or Reduction of Pollutants
VIII Cost, Energy and Non-Water Quality Aspects 121
Alternative Treatment Technologies 121
Costs of Treatment Technology Now in 123
Practice
Non-Water Quality Aspects of Alternate Tre t- 131
ment Technologies
Disposal of Solids and Slurries 131
Generation of Commerically-Valuable 135
By-Products
Disposal of Off-Specification and Scrap 140
Products
Other Non-Water Quality Pollution Problems 140
Industry Cost Perspectives 140
Water Effluent Treatment Costs 142
IV
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Industrial Waste Treatment Model Data 145
IX Best Practicable Control Technology Cur- 187
rently Available Guidelines and Limitations
Definition of Best Practicable Contol 187
Technology Currently Available (BPCTCA)
The Guidelines 188
Attainable Effluent Concentrations 188
Demonstrated Wastewater Flows 190
Statitcal Variability of a Properly 191
Designed and Operated Waste Treatment
Plant
X Best Available Technology Economically 195
Achievable
Definition of Best Available Technology 195
Economically Achievable (BATEA)
The Guidelines 195
Achievable Effluent Concentrations 195
Suspended Solids 195
Oxygen Demanding Substances 196
Waste Load Reduction Basis 198
Variability 198
XI New Source Performance Standards - Best 199
Available Demonstrated Technology
Definition of New Source Performance 199
Standards - Best Available Demonstrated 199
Technology (NSPS-BADT)
The Standards
Achievable Effluent Concentrations 199
Waste Load Reduction Basis 199
Variability 199
XII Acknowledgments 207
XIII References 209
XIV Glossary 215
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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
vi
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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
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 74
29 Typical Polymerization Reactions to Form 75
Nylon 6 Resin and Fiber
30 Nylon 6 Production 76
31 BOD Removal as Function of Total System 95
Residence Time
32 COD Removal as Function of Total System 97
Residence Time
33 Biological Treatment in Plastics and 125
Synthetics Industry - Capital Costs
34 Biological Treatment in the Plastics 126
and Synthetics Industry - Operating Costs
35 Biological Treatment in the Plastics and 128
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
and Synthetics Industry - Capital Investment
38 Activated Carbon Adsorption for the Plastics
and Synthetics Industry - Capital Investment
39 Activated Carbon Adsorption for the Plastics 133
and Synthetics Industry - Operating Costs
40 Net Cost of Recovering Dilute Wash Solutions 136
vii
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TABLES
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 8
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 79
Plants
13 Industry Subcategorizat ion 60
14 Wastewater Loading for the Plastics and 82
Synthetics Industry
15 Plastics and Synthetics Industry Raw Waste Loads 83
16 Other Elements, Compounds and Parameters 84
17 Other Elements and Compounds Specific to Plastics 90
and Synthetics Products
18 Performance of Observed Waste Water Treatment 93
Plants
19 Operational Parameters of Wastewater Treatment 99
Plants (Metric Units)
viii
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Number Title Page
20 Operational Parameters of Wastewater Treatment 100
Plants (English Units)
21 Observed Treatment and Average Effluent 105
Loadings From Plant Inspections
22 Summary of Industrial Sources Using Granular 107
Activated Carbon Systems
23 Matrix for Evaluating Liquid Handling Facilities 114
24 Perspectives on the Plastics and Synthetics 122
Industry - Water Usage
25 Typical Stream Compositions 138
26 By-Product Credit Value for Break-Even Stream 138
27 Operating Cost Per 1000 Ibs (4536 kg) H20 139
Recycled
28 Perspectives on the Plastics and Synthetics 143
Industry - Treatment Costs
29 Perspectives on the Plastics and Synthetics 144
Industry - Cost Impact
30 Summary of Water Effluent Treatment Costs for 145
Representative Plants in the Plastics and
Synthetics Industry
30-1 Water Effluent Treatment Costs - Plastics 147
and Synthetics Industry - Epoxies (small)
30-2 Water Effluent Treatment Costs - Plastics 143
and Synthetics Industry - Epoxies (large)
30-3 Water Effluent Treatment Costs - Plastics 149
and Synthetics Industry — Melamine (small)
30-4 Water Effluent Treatment Costs - Plastics 150
and Synthetics Industry - Melamine (large)
30-5 Water Effluent Treatment Costs - Plastics 151
and Synthetics Industry - Urea (small)
30-6 Water Effluent Treatment Costs - Plastics 152
and Synthetics Industry - Urea (large)
30-7 Water Effluent Treatment Costs - Plastics 153
and Synthetics Industry - Phenolics (small)
ix
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Number Title Page
30-8 Water Effluent Treatment Costs - Plastics 154
and Synthetics Industry - Phenolics (large)
30-9 Water Effluent Treatment Costs - Plastics 155
and Synthetics Industry - Polyvinyl Chloride
(small)
30-10 Water Effluent Treatment Costs - Plastics 156
and Synthetics Industry - Polyvinyl Chloride
(large)
30-11 Water Effluent Treatment Costs - Plastics 157
and Synthetics Industry - ABS/SAN (small)
30-12 Water Effluent Treatment Costs - Plastics 158
and Synthetics Industry - ABS/SAN (large)
30-13 Water Effluent Treatment Costs - Plastics 159
and Synthetics Industry - Polystyrene (small)
30-14 Water Effluent Treatment Costs - Plastics 160
and Synthetics Industry - Polystyrene (large)
30-15 Water Effluent Treatment Costs - Plastics 151
and Synthetics Industry - Polyvinyl Acetate
(large)
30-16 Water Effluent Treatment Costs - Plastics 152
and Synthetics Industry - Polyvinyl Acetate
(large)
30-17 Water Effluent Treatment Costs - Plastics 163
and Synthetics Industry - Low Density
Polyethylene (small)
30-18 Water Effluent Treatment Costs - Plastics 164
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 166
and Synthetics Industry - High Density
Polyethylene (large)
30-21 Water Effluent Treatment Costs - Plastics 167
and Synthetics Industry - Polypropylene (small)
30-22 Water Effluent Treatment Costs - Plastics 168
and Synthetics Industry - Polypropylene (large)
x
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Number Title Page
30-23 Water Effluent Treatment Costs - Plastics 169
and Synthetics Industry - Acrylics (small)
30-24 Water Effluent Treatment Costs - Plastics 170
and Synthetics Industry - Acrylics (medium)
30-25 Water Effluent Treatment Costs - Plastics 171
and Synthetics Industry - Acrylics (large)
30-26 Water Effluent Treatment Costs - Plastics 172
and Synthetics Industry - Polyester (small)
30-27 Water Effluent Treatment Costs - Plastics 173
and Synthetics Industry - Polyester (large)
30-28 Water Effluent Treatment Costs - Plastics 174
and Synthetics Industry - Nylon 6 (small)
30-29 Water Effluent Treatment Costs - Plastics 175
and Synthetics Industry - Nylon 6 (large)
30-30 Water Effluent Treatment Costs - Plastics 175
and Synthetics Industry - Nylon 66 (small)
30-31 Water Effluent Treatment Costs - Plastics 178
and Synthetics Industry - Nylon 66 (large)
30-32 Water Effluent Treatment Costs - Plastics 179
and Synthetics Industry - Cellophane
30-33 Water Effluent Treatment Costs - Plastics 180
and Synthetics Industry - Cellulose Acetate
30-34 Water Effluent Treatment Costs - Plastics 181
and Synthetics Industry - Rayon
31 Industrial Waste Treatment Model Data -
Plastics and Synthetics Industry (Product
Group #1)
32 Industrial Waste Treatment Model Data - -,00
Plastics and Synthetics Industry (Product
Group #2)
33 Industrial Waste Treatment Model Data - ,o/
Plastics and Synthetics Industry (Product
Group #3)
34 Industrial Waste Treatment Model Data -
Plastics and Synthetics Industry (Product
Group #4)
XI
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Number Title Page
35 Industrial Waste Treatment Model Data - 18f.
Plastics and Synthetics Industry (Product
Group #5)
36 COD/BOD Ratios in Effluent Streams 189
37 COD/BOD Guideline Basis 190
38 Demonstrated Wastewater Flows 192
39 Demonstrated Variability 193
40 Variability Factor 193
41 Best Practicable Control Technology 201
Currently Available Effluent Limitation
Guidelines
42 Best Practicable Control Technology Currently 202
Available Effluent Guidelines for Other Elements
Best Available Technology Economically 203
43 Achievable Effluent Limitation Guidelines
44 Best Available Technology Economically 204
Achievable Effluent Guidelines for Other
Elements or Compounds
45 Best Available Demonstrated Technology for 205
New Sources Performance Standards
46 Best Available Demonstrated Technology for 206
New Source Performance Standards for Other
Elements or Compounds
47 Metric Units Conversion Table 221
xii
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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-volump
produc-*- subcat egories . The 1972 production for these products was
estimated at 12 million kkg (26 billion pounds) per year. Tiie 1972
water usage was estimated to be 1035 thousand cubic meters per day (275
MGD) . Wa-'-er usage (at current hydraulic loads) was projected ic
increase at- 6.7 percent per year through 1977, while production was
oro jeered +-0 increase at 10 percent per year in the same period.
For -^he purposc of setting effluent limitations guidelines and standards
of ner f ormance, the industry parameters giving tne most ettectiv-.
categorization were found to be waste water characteristic?,
i f ically:
Raw weste load, wi+:h a BOD5 value of more than or less than 10
kg/kka 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 nerein as the
basis for BPCTCA. ^hree groupings were defined with avarage
effluent concentrations under 20 mg/1 (low attainable EO05_
concentration) , from 30 to 75 mg/1 (medium attainable EODS_
concentration) , and over 75 mg/1 (high attainable
concentration) .
on these •'-wo dimensions of categorization, lour
subcat Dories were defined:
Major Subcateqory T - low waste load, low attainable BOD5 concentration
(5 products: polyvinyl chloride, polyvinyl acetate,
polystyrene, polyethylene, and polypropylene).
H§.J2£ Sub-category II - high waste load, low attainable BOD5
concentration (3 products: ABS/SAN, cellophane, and
rayon) .
^jor Subca-*-egory III - high waste load, medium attainable BOD5
concentration treatability (8 products: polyesters. Nylon
66, Nylon 6, cellulose acetates, expoxies, pheaolics,
urea, and trelamine) .
MS32S pubca-»-egory IV - high waste load, low treatability (1 product:
acrylics) .
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Additional subcategorizati on within the above four major subeategories
wr;s necessary -*-o account for the waste water generation which is
specific to +-h° individual products and their various proems sina
m^hodR. The separation of each individual product into Separate
subcat
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SECTION II
R ECOMMENDATIONS
COD and suspended solids are the critical constituents requirinq
guidelines and standards. Other constituents are even more specific *-u
the product subcateaory, and are sumarized below.
Subcat<=gory Other Flement or Compound
ABS/SAN Iron
Aluminum
Nickel
Total Chromium
Organic Nitrogen
POLYSTYRENE Iron
Aluminum
Nickel
Total Chromium
POLYPROPYLENE Vanadium
Titanium
Aluminum
HT-DENSTTY POLYETHYLENE Titanium
Aluminum
Vanadium
Molybdenum
Total Chromium
CELLOPHANE Dissolved Solids
RAYON Zinc
Dissolved Solids
?POXY PESINS Phenolic Compounds
PHENOLIC RESINS Phenolic Compounds
UPEA PESINS Organic Nitrogen
Nickel
Cobalt
MELAMINE Organic Nitrogen
NYLON 6 and 66 Organic Nitrogen
ACRYLICS Phenolic Compounds
Effluent limitations guidelines and standards of performance are
oroposed 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,
molyb^denum, and cobalt 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.
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water quality standards should determine if limitations are
necessary.
Best practicable control technology currently available (BPCTCA) for
^xis+inq point sources is based on the application of end-of-pipe
technology such as biological treatment for EOD reduction as typifi?d by
activated sludge, aerated lagoons, trickling filters, aerobic-anaerobic
lagoons, etc. With appropriate preliminary treatment typified by
eomalization, to dampen shock loadings, settling, clarification, and
chemical treatment, for removal of suspended solids, oils, other
elements, and pH control, and subseguent treatment typified by
clarification and polishinq processes for additional BOD ana 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 «nd-of-pipe technology, for the further removal of suspended solids
and other elements typified by media filtration, chemical treatment,
Qtc., and further COD removal as typified by the application of
adsorption processes such as activated carbon and adsorptive floes, arid
incineration for the treatment of highly concentrated small volum"
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 as defined in BATEA 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 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 LIMITATION GUIDELINES
All Units are Kg/kkg (lb/1000 Ib)
BOD
Monthly'
Average
Daily
Maximum
COD
Monthly"
Average
Daily
Maximum
Monthly
Average
Daily
Maximum
Polyvinyl 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
Phenol ics
Urea Resins
Melamine
Acrylics
.31
.11
.053
.18
.20
.035
.36
.18
.27
.045
8.6
4.9
0.63
0.78
0.78
0.78
1.56
0.66
.58
1.24
5.61
3.71
1.90
4.12
4.12
8.24
0.36
1.22
0.18
.13
2.75
.44
.16
.076
.26
.28
.050
.52
.26
.38
.065
13.4
7.6
0.98
1.06
1.06
1.06
2.12
.90
.79
1.69
7.64
5.06
2.58
5.62
5.62
11.24
0.49
1.66
.25
.18
3.75
3.1
1.1
.53
1.8
2.0
.35
1.8
1.8
2.7
0.45
86
72.9
6.3
11.7
11.7
11.7
23.4
3.30
2.95
6.25
56.1
37.1
19.0
41.2
41.2
82.4
1.80
6.10
.90
.65
13.8
4.4
1.6
.76
2.6
2.8
.50
2.6
2.6
3.8
.64
134
113
9.8
15.9
15.9
15.9
31.8
4.50
3.94
8.44
76.4
50.1
26.3
56.2
56.2
112.4
2.45
8.30
1.25
.90
18.8
.62
.22
.11
.36
.39
.07
.73
.36
.53
.09
17.3
9.7
0.73
0.33
0.33
0.33
0.66
0.28
.25
.53
.38
.58
.80
1
1
3.
.75
,75
,50
0.15
0.57
0.077
0.056
0.70
.88
.32
.15
.52
.56
.10
1.0
.52
.76
.12
26.8
15.1
1.05
0.48
0.40
0.48
0.96
.40
,35
,75
40
25
1.15
2.
2.
5.
,50
,50
.00
.22
.74
.11
.08
1.0
Monthly Average: Maximum average of daily values for any period of 30 consecutive
days.
Daily Average: Maximum for any one day.
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TABLE NO. 2
EFFLUENT GUIDELINES
FOR OTHER ELEMENTS OR COMPOUNDS
- BPCTCA
Sub category
ABS/SAN
POLYSTYRENE
POLYPROPYLENE
HI DENSITY POLYETHYLENE
CELLOPHANE
RAYON
EPOXY RESINS
PHENOLIC RESINS
UREA RESINS
MELAMINE
NYLON 6 & 66
ACRYLICS
Other Element
Or Compound
Iron
Aluminum
Nickel
Total Chromium
Organic N
Iron
Aluminum
Nickel
Total Chromium
Vanadium
Ti tanium
Aluminum
Titanium
Aluminum
Vanadium
Molybdenum
Total Chromium
Dissolved Solids
Zinc
Dissolved Solids
Phenolic Compounds
Phenolic Compounds
Organic N
Nickel
Cobalt
Organic N
Organic N
Organic N
Phenolic Compounds
Kg/kkg (lb/1000 Ib prod.)
BPCTCA
Monthly Ave. Daily Max.
Present
Present
Present
. 0031
Present
Present
Present
Present
. 00027
Present
Present
Present
Present
Present
Present
Present
.0031
Present
.534
Present
. 0018
.0062
Present
Present
Present
Present
Present
Present
.0083
Present
Present
Present
. 0037
Present
Present
Present
Present
. 00033
Present
Present
Present
Present
Present
Present
Present
. 0037
Present
.667
Present
.0036
.012
Present
Present
Present
Present
Present
Present
.017
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TABLE 3
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
EFFLUENT LIMITATION GUIDELINES
BOD
Polyvinyl 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
Kesin and Fiber
Resin
Fiber
Cellulose Acetate
Resin
Fiber
Resin and Fiber
Epoxy
Phenolics
Urea Resins
Mel amine
Acrylics
Kg/KKg (lb/1000 Ib prod.)
COD SS
Daily
Maximum
0.15
U.054
0.050
0.084
0.092
0.034
0.18
Monthly
Average
0.110
0.040
u.038
0.06b
0.070
0.0^5
0.130
0.06b
o.oys
0.032
1.8
1.0
0.13
0.060
0.060
0.060
0.120
0.050
0.044
0.094
0.43
0.28
0.15
0.32
0.32
0.64
0.055
0.090
0.028
0.020
0.125
Daily
Maximum
0.23
U.080
0.07&
0.13
0.14
0.050
0.26
0.13
0.19
0.065
3.6
2.0
0.26
0.12
0.12
0.12
0.24
0.10
0.088
0.188
0.86
0.56
0.30
0.63
0.6J
1.28
0.11
O.IH
0.0b5
0.040
0.2b
Monthly
Averaqe
0.75
0.27
0.25
0.42
0.46
0.17
0.88
0.42
0.6J
0.22
12.
6.7
0.88
0.40
0.40
0.40
0.80
0.33
0.29
0.62
Z.9
1.9
1.0
2.1
2.1
4.2
0.36
0.62
0.18
0.13
0.83
Daily
Maximum
1.5
U.54
0.50
0.84
0.9^
0.34
1.7b
U.84
1.26
0.44
24.
13.4
1.76
0.80
0.8U
0.80
1.60
0.66
0.58
1.24
5.8
3.8
2.0
4.2
4.2
8.4
0.72
1.24
0.36
0.26
1.66
Monthly
Average
0.075
0.027
U.025
O.U42
0.046
0.017
0.088
0.042
0.06?
0.022
1.2
0.67
0.088
0.040
0.040
0.040
0.080
0.033
O.OZ9
0.062
o.2y
0.19
0.10
0.21
0.21
0.42
U.036
U.062
0.018
0.013
U.083
0.13
U.044
2.4
1.34
.176
0.080
0.080
0.080
0.160
0.06b
0.058
0.124
0.58
0.38
0.20
0.42
0.42
0.84
0.072
0.12
0.036
0.026
0.17
-------
TABLE 4
EFFLUENT GUIDELINES FOR OTHER
ELEMENTS OR COMPOUNDS
Subcategory
ABS/SAN"
POLYSTYRENE
POLYPROPYLENE
HI DENSITY POLYETHYLENE
CELLOPHANE
RAYON
EPOXY RESINS
PHENOLIC RESINS
UREA RESINS
MELAMINE
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
Vanad ium
Molybdenum
Total Chromium
Dissolved Solids
Zinc
Dissolved Solids
Phenolic Compounds
Phenolic Compounds
Organic M
Nickel
Cobalt
Organic N
Organic N
Organic N
Phenolic Compounds
Kg/kkg (lb/]000 Ib prod.)
BATEA
Monthly Ave. DaiJy Max.
-PRESENT--
-PRESENT —
-PRFSENT--
.0022
-PRESENT--
-PRESENT--
-PRESENT--
-PRESENT--
. 00]2
-PRESENT--
-PRESENT--
-PRESENT--
-PRESENT--
-PRESENT--
-PRESENT--
-PPESFNT--
.00]6
-PRESENT--
.0667
.00036
.00062
-PRESENT--
-PRESENT--
-PRESENT--
-PRESENT--
-PRESENT--
-PRESENT--
.00083
"""5 SftlT
- -PRESENT -
--PRESENT
.0044
- -PRESENT -
— PRESENT-
— PRESENT-
--PRESENT
. 0024
--PRESENT -
--PRESENT -
— PRESENT-
— PRESENT-
— PRESENT-
— PRESENT-
— PRESENT-
.0032
— PRESENT -
.]33
—PRESENT
. 00072
.00]2
— PRESENT-
— PRESENT-
— PRESENT
— PRESENT -
—PRESENT -
— PRESENT-
.00]7
-------
TABLE NO.
BEST AVAILABLE DEMONSTRATED TECHNOLOGY FOR
NEW SOURCE PERFORMANCE STANDARDS
kg/kkg (lb/JOOO lb of production)
BOD
COD
Folyvinyl chloride
Suspension
Emulsion
Bulk
Polyvinyl Acetate
Polystyrene
Suspension
Bulk
Polypropylene
Lo Density Polyethylene
Hi Density Polyethylene
Solvent
Poly form
Cellophane
Rayon
ABS/SAN
Polyest er
Resin
Fiber
Resin and Fiber
Resin and Fiber
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
Acrylic s
Continuous
Batch
onthly
o. ]]o
0.040
0.038
0.065
0.070
0.025
0. ]30
0. 065
0.095
0.032
1.8
].o
0. ]3
0.060
0.060
0. 060
0. ]20
0. 050
0.044
0. 094
0.43
0.28
O.J5
0.32
0. 32
0.64
0. 055
0.090
0.028
0. 020
0. ]25
Daily
0. 23
0.080
0.075
0.]3
0. ]4
0.050
0. 26
0. ]3
0. ]9
0.065
3.6
2. 0
0. 26
0. ]2
0. ]2
0. ]2
0.24
0. ]0
0.088
0. ]88
0.86
0. 56
0. 30
0. 63
0. 63
] .28
o.]]
0. ]8
0.055
0.040
0.25
Mont hly Daily
]8
]5
40
38
65
70
25
,88
65
95
32
.90
.90
.90
] -8
. 33
.29
0.62
4.3
2.8
3.2
3. 2
6.4
.36
. 62
• 18
• ]3
.83
2. 2
.80
.76
].30
] .40
. 50
].76
] .30
] .90
.64
36.
30.
2.6
] .80
] .80
] .80
3.0
. 66
.58
].24
8.6
5.6
3.0
6.4
6.4
]2.8
. 72
].24
.36
.26
] .66
SS
Monthly
075
,027
025
,042
046
0]7
,088
042
,063
022
67
088
040
040
040
080
033
,029
062
29
19
.2]
.2]
.42
.036
. 062
.0]8
.0]3
.083
Daily
. 054
.050
.084
. 092
.034
.084
• 13
.044
.4
.34
.176
.080
.080
.080
. ]60
.066
.058
,58
38
20
42
42
84
072
12
036
026
]7
-------
TABLE 6
BEST AVAILABLE DEMONSTRATED TECHNOLOGY
FUR NEW SOURCE PERFORMANCE STANDARDS
FOK OTHER bOUKCES OR COMPOUNDS
Subcategory
ABS/SAN
POLYSTYRENE
POLYPKOPYLENE
HI DENSIIY POLYETHYLENE
CELLOPHANE
RAYON
EPOXY RESINS
PHENOLIC RESINS
UREA RESINS
MELAMINE
NYLON 6 & 66
ACRYLICS
Other Element
Or Compound
Iron
Aluminum
Nickel
Total Chromium
Organic N
iron
Aluminum
Nickel
Total Cnromium
Vanadium
i itaniurn
Aluminum
Titanium
Alumi num
Vanadium
Molybdenum
Total Chromium
Dissolved Solids
Zinc
Dissolved Solids
Pnenolic Compounds
Phenolic Compounds
Organic N
Nickel
Cobalt
Organic N
Organic N
Organic N
Pnenolic Compounds
Kg/Tonne (lb/1000 lb prod.)
BADT
nonthly Ave. Daily Max.
—PRESENT—
—PRESENT—
—PRtSENT—
.0022 .0044
—PRtSENT—
—PRESENT—
—PRESENT—
— PRESENT—
.OU12 .0024
—PRESENT—
— PRESENT—
—PRESENT—
— PRESENT—
—PRESENT—
— PRESENT—
—PRESENT—
.0016 .0032
--PRtSENT—
.0567 .133
—PRESENT—
.00036 .00072
.00062 .0012
—PRESENT—
—PRESENT—
—PRESENT—
—PRESENT—
— PRESENT—
— PRESENT—
.00083 .0017
10
-------
SECTION III
INTRODUCTION
Purpgsg_ 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
oublicly owned treatment works, which are based on the application of
the best practicable control technology currently available as defined
by -t-he Administrator pursuant to Section 304 (b) of the Act. Section
301 (b) also requires the achievement by not lat°r 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 avail-
able 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 3Of
of th<= 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 throuah the application of th<=
best available demonstrated control technology, processes, operating
methods, or other alternatives, including, where practicable, a standard
p-rmitting no discharge of pollutants.
Section 30U(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 measure-rf and
procedure innovations, operation methods and other alternatives. Thf-
regulat-ions proposed herein set forth effluent limitations guid-'-lines
tmrsuant to section 301(b) of the Act for the largest volume products of
••-he elastic 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 (?8 F.P. 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
-------
^he 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
le-i-^rmining whether separate limitations and standards are appropriate
for its different segments. Considerations in the industry
Fubca-'-egori zation process included raw materials, products,
manufacturing process°s, raw waste characteristics and raw waste
•"-readability and attainable effluent concentrations.
Thc raw waste characteristics for each subcategory were identified
throuah analyses of (1) the sources and volumes of water and wast"
waters and (2) the constituents (including thermal) of all waste waters
including •'-oxic or hazardous constituents and other constituents which
result in taste, odor, color, or are toxic to aquatic organisms. Tho
constituents of waste waters which should be subject to effluent
guidelines and standards of performance were identified.
^h0 full rangc of control and treatment technologies existing witnin th~-
industry was identified. This included an identification of each
distinct control and treatment technology, including both in-plant and
°nd-of-process technologies, which are existent or capable of beina
designed for each subcategory. It also included an identification, in
tertns of th° amount of constituents (including thermal) and the
chemical, physical, and biological characteristics of pollutants, of the
°ffluent levcl resulting from the application of each of the treatment
and control technoloaies. The problems, limitations, and reliability of
cach 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
technoloaies upon other pollution problems, including air, solid waste,
noise, and radiation were identified. The energy requirements of each
of thc control and treatment technologies were identified as well as the
cost of the application of such technologies.
ThQ information, as outlined above, was then evaluated in order to
d^termin^ what levels of technology constituted the "best practicable
control technology currently available," "best available tecnnology
economically achievable," and the "best available demonstrated control
••-ecrnology, 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
Affluent 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
(includina energy requirements), the treatability of the wastes, water
use practices, and other factors.
12
-------
The d'ata for identification and analyses were derived rrom a number of
sources. Thes» sources included EPA research information, EPA nermit
applications, records of selected state agencies, published literature,
previous FPA technical quidance for plastics and synthetics manutac-iur*',
a survey of wast^ watcr treatment practice by the Manufacturing Gn^mis^s
Association, qualified technical consultation, and on-site visits and
int^rvi ^-ws a4- plastics and synthetics manufacturing facilities
prac^-icinq exemplary waste water treatment in plants within the United
States. Samples for analyses were obtained from selected plants ir
order to establish the reliability of the data obtained. All references
u^ed in developing the guidelines for effluent limitations and standards
of performance or new sources reported herein are listed in Section XIII
of -t-his docum=n*.
Ge_neral_DescriD^iion_of_the_I.ndustry_
The plastics and synthetics industry is composed of three separate
segments: the manufacture of the raw material or monomer; the conversion
of +:hi? monomer into a resin or plastic material; and the conversion of
the plastic r^sin into a plastic item such as a toy, synthetic fib'-r,
packacrino film, adhesive, paint, etc. This analysis is concerned
urimarily wi^h the manufacture of -t-he basic plastic or synthetic r^sin
(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).
Th° present report segment deals with 16 of the major resins, all of rh~
rnajor synthetic fibers, all of the cellulosic fibers, and cellophane
film, and covers over 90 percent of the total consumption of th~
plastics and syn^h-rics industry.
Plastics
Thr- synthetic plastics industry for this segment, accounts for
approximately 12 million kkg (26 billion Ibs) of material having a
dollar value of about "55 billion. This is an increase over tne 1962
consumption of 3.18 million kkg (7 billion Ibs) for an average growth
ra-*-e over th^ 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 ov-r 400 plants. of these 300 producers, there are about 35
major corporations having individual sales of over $500 million. These
=jre orimarily 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
i-t-ems are fabricated by the basic resin producers. A large number of
h° basic resin producers are integrated to raw material production. In
many cases, a given installation will produce both monomer, polymer, and
4-
13
-------
••-he end-use, items, and i+- is difficult to isolate the sourc« of
pollution between th^- three separate segments. At the small end of "-.he-
scale, the plastics industry includes many companies having sal^s of
less than $1 million per year, often producing one resin in small
quantities for a specific customer. Such companies might average no
mor° 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.
Th° 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. ThQ automotive industry, including trim,
steering wheels, outside grill, etc.
Th°se -i-hr<=e industries account for somewhat over 50 percent of the to^al
production of plastic materials.
The type of plant constructed depends primarily on the specific r°sins
heina produced. The large volume commodity resins, polyvinyl chloride,
polystyrene and the polyolefins are generally produced in plants Banging
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.
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
segmen^ 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
14
-------
TABLT 7
1972 CONSUMPTION OF PLASTICS AND SYNTHETICS
Consumption Number of
Products J0£0_kkg Companies
'Jr-=a and Melamine 411 11
nolyvinyl Acetate 198 26
Low D^nsi-t-y Poly-thylene 2,372 12
Piah Density Polyethylene 1,026 13
Polypropylene 767 9
Polys-t-yrene 1,196 19
431 8
Polyvir.yl Chloride 1,975 23
Phenolic 652 81
Acrylic Resins 208 5
Polyos-*-0r Resins 30 4
Nylon ^esins 110 6
Acrylic Fibers 286 6
Polyester Fibers 1,040 15
Nylon Fibers 896 14
Cellulose £cetat°s* 257 7
Cellophane 145 4
Rayon 430 7
Total 12,508 278
*Includes fibers and resins.
15
-------
readily shipped from producing points. Thus a manufacturer 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
Allied Chemical
American Cyanamid
Ashland Oil
Rorden
Bora-Warner (Marbon)
Celanese Occidental
Dart Industries
Diamond Shamrock
Dow
DuPont
Eastman
Ethyl
Foster Grar.t
General Electric
B.F. Goodrich
W.R. Grace
Gulf
MAJOR RESIN PRODUCERS
Hercules
Koppers
Mobay (Bayer)
Monsanto
National Distillers
Petroleum (Hooker)
Phillips Petroleum
Peichhold
Rohm & Haas
Shell
Standard Oil (Indiana)
Standard Oil (New JErsey)
Standard Oil (Ohio)
Stauffer Chemical
Tenneco
Union Carbide
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 table showing the producers of synthetic fibers is found
Table 9
Allied chemical
American Cyanamid
American Fnka
Cclanese
Courtalds
Dow Badische
DuPont
Passman
Peaunit
Midland
Firestone
loodyear
Hvstron
Monsanto
Phillips Fibers
Rohm & Haas
Union Carbide
SYNTHETIC FIBEP FRODUCEFS
Nylon
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.
Tr aeneral synthetic fibers have been growing in importance
whereas the cellulose acetate and rayon fibers have been
•Inclining in imoor^ance over the years.
Capacity by producer for the cellulosic based fibers is shown below:
Table 10
CAPACITY
1000 kkg/Year (MM Ibs/Year)
Comp.§.DY
American Cyanamid
Akzona
(American Enka)
Celanese
Courtaulds
DuPont
Eastman
^1 Paso (Beaunit)
FMC
Rayon
Filament
33
45
11
41
(73)
(100)
(24)
(90)
Payon
Acetate
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
ar° not expected. The profitability of the cellulose and rayou 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 comneting clear films, such as polypropylene, polyester and
loolybutylene, consumption of cellophane has dropped uninterruptedly
sincr- 196U, reaching a level of 145,000 kkg (320 million Ibs) in 1971.
C^ntinuPd decline is expected with consumption reaching as low as 12,300
kka (270 million Ibs) by 197S. Further inroads from other synthetic
films as well as a shift to the use of thinner gauges of cellophan^,
possible in combination with other packaging films, can be expected to
fur^-h^r reduce demand. Cellophane production is carried out by three
companies (Olin, FMC Corporation, and Du Pont) in relatively old plants.
Produc^ and Process Technology
Typical Polymerization Products
Polymers are characterized by vinyl polymerizations. Tne 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. m°thyl 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 th«
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 polymerization reaction itself,
18
-------
Polyethylene
Polypropylene
Polyvinyl Chloride
Polystyrene
Polyvinyl Acetate n I C = C I "-' H
FIGURE I TYPICAL POLYMERIZATION REACTIONS FOR POLYETHYLENE,
POLYPROPYLENE, POLYVINYL ACETATE, POLYVINYL CHLORIDE,
POLYSTYRENE
19
-------
Polyacrylonitrile n | C = C 1 if H
Polybutadiene
FIGURE 2 TYPICAL POLYMERIZATION REACTIONS
FOR POLYACRYLONITRILE AND POLYBUTADIENE
20
-------
OR
n/3
n/3
- O -
H
I
C - O
I
H
trioxane
FIGURE 3 TYPICAL POLYMERIZATION REACTION FOR POLYACETAL RESINS
21
-------
bur thes<= do not have a bearing on the potential aqueous pollution
nroblem. Therefore both methods will be covered by this discussion.
Products of this process include:
Polystyrene (PS)
Acrylcn itril^, butadiene, styrene (ABS)
Styrene, acrylonitrile (SAN)
Polyvinyl chloride (PVC)
Polyvinyl acetate (PVA)
A. ba-'-ch process, as shown in Fig. 4, is commonly used. Typical reactor
size ip 5,000 to 30,000 aal (18.9 to 113.5 cu m). The batch oycl~
conpis+-s of the continuous introduction of a water-monomer emulsion to
•t-h- stirred reactor. Polymerization occurs at about the rate of monomer
addition; the hea^ of reaction is removed to coolingtower water
circulated throuah th~ jacket. The reactor is vented through a
conder.p^r for monomer recovery; and the condensate, including any water,
is r=>turri°d directly to the vessel. On completion of the batch, a shor-
"soaking" time is allowed for completion of the reaction, and water is
then aided to dilute to the desired end composition. The batch is drawn
oft -t-h.rouah a screen to product storage. Oversize screenings (a very
small amount) arc disposed of to landfill.
Monomers, the principal raw materials, are often protected during
shior>ina and storage by an inhibitor, such as catechol, which may b«-
removed prior to polymerization by washing. This contributes to the
wast-^ water load.
A number of products, polyvinyl acetate for example, are marketed in
+-nis la-t-<=x 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 °mulsion 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
r^ac-t-ion, control its rate, and influence the final molecular weight.
These materials are used in very small amounts, and their residue
remains in tha product. Removal of the heat of reaction is a difficult
problem in this process and limits the type of equipment which can be
uped.
Products of this process include:
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Polystyrene (PS)
Acrylonitrile, butadiene, styrene (ABS)
Styrr-ne , acrylonitrile (SAN)
Polyvir.yl chloride (PVC) .
I+- is usually necessary to protect the purified monomers from auto-
nolymer iza+-ion in storage. The inhibitor used for this purpose is
remover? by distillation or washing. This frequently results in an
3ou=ous wast^. ^he reaction system is usually continuous, or multi-
staae, and th^ first stcp is to bring the monomer to reaction
~-mr>'-r:*4-urp by indirec4- heating. A heat-transfer oil or fluid such as
nowth-rn1, circulated from a fired heater, is used. Once reaction begins
-h- h-^-t- is removed by •'-ransfer to a cooling oil circulated tnrouan
ceils or in a jacket. The circulated oil is cooled by wa~er in
conventional heat-exchange equipment.
On leaving th~ reactor, the polymer contains unreacted monomer ana small
amounts of contaminants and by-products. These materials are rerrov-d by
vacuum strinpina.
Vaoors from this unit pass through an oil-cooled tar condenser. The
v^n4: from ••-nis condenser is connected to a steam jet ejector, ana sf-am
and volatile hydrocarbons condense in a water-cooled surfac- condr-nser.
Trsolut le oils are decanted and recovered, and contaminated
ones to •'•he orocess sewer.
Pure nolymer from the bottom of the stripper is forced througn mul
oriflc- extruders to make strands of polymer, which are cooled in -.
waf-r bath before pelletizinq for storage and shipment.
niqh Prcssure Mass Polymerization - Low Density Polyethylene
T'he high pr-ssure process for low density polyethylene is a very simple
on-?, as illustrated in Fig. 6. Ethylene gas is mixed with a. very small
auantity of air or oxygenated organic compounds as a catalyst, ana witn
recycled ^thylene, and raised to high pressure in reciprocating com-
t>rc:ssors. The operating pressure is considered to be confident inl
information, but the trend in the industry has been to the nighes4-,
oractical pressures, and literature references to design ratings of
40,000 psi (2722 atm) and up are common. At the operating pressure and
a-*- an appropriate temperature, polymerization is carried out in jacketed
reactors. The hear of reaction is removed to hot water in the
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
oumped througn 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 recycle. A purge stream of this
water is removed and replaced with high-quality, clean water. The purge
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
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IF a-1- a rate sufficient ^o remove polymer fines generated in chipping.
Tb° guartity of fin^s depends on the grade of polymer produced and with
some grades is negligible. Wet polymer from the screen is drieci and
stor~d in silos.
Polyole^ins - Solution Polymerization
In *-he solution process for polyolefins shown in Fig. 7, tne polymer is
dissolved in the reaction solvent as it is formed, and t.he catalyse is
nr^s^nt as a separate solid phase. The catalyst system is activated
chromium oxide deposited on a carrier such as alumina. This process is
OP.C of two for polyolefins which first came into prominence in the late
IS^O's; +-he oth°r is the Ziegler process, in wnicn the polymer
precipitates as i- is formed. Products of the solution system include
hiab density polyethylene and a limited number of co-polymers.
\s *-he concentration of polymer, or the molecular weight of tne polymer
ir solution, increases, the viscosity of the solution also increases
markedly. This pnenonv=non places severe limitations on tne piocoss-
a*~i li-y of the re-action mass. Temperature control is accompli sned by
ir./iirect cooling with refrigerated water, and the viscosity must not br;
all ow-d to ^xceed a reasonable limit for efficient heat transfer.
y if also an important limitation in the next step, whicn is the
of the catalyst by filtration or centrif ugation. 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
nroc^ss^d in a skimmer and solid catalyst removed to land fill.
Th° agueous phasc is recycled to the steam stripper. Vapor from -t-he
s-t-^am strippcr is combined with other recovered solvear for
ouri f icat ion.
The catalyst-free polymer solution is processed in a system which
concentrates and precipitates the polymer, and then removes ta° last
- races of solvent by st°am stripping, leaving the polymer as a slurry in
wa-'-er. The slurry is filtered or centrifuged, and the filtrate recycled
+-o th° strinper.
n-1- recovered in the concentrator and vapors from the steam
~triopers are processed by distillation in the solvent recovery section.
A.11 process water used in the catalyst and polymer separation ar^a
appears as an agueous waste stream from this distillation unit. It
contains small guantities of dissolved hydrocarbons, but in at least on°
plant it is used as boiler feed water.
Dry polymer crumb or flake is blended, melted, extruded and pelletized.
^his pelletizing operation is carried out under water, with cooling and
•t-rar.sport accomplished with recirculated, clean, softened water. &
purge stream amounting to a few percent of the circulation rat*1- is
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withdrawn to waste. This system is the samc as already described for
the low-density polyethylene process.
Polyolefins - Ziegl^r Process
This process depends on a catalyst system discovered and patented by Dr.
Karl ^iegler. There have b°en a number of improvements by companies
usinq the basic principle, and the name in fact applies to the ca-t-alyr^
systcm. Each user has had to design his own plant. It is convenient,
however, to group under this name all polyolefin processes which cmploy
a reaction solvent ir which the polymer precipitates as it is torm-'d.
vig. P derails "-.his type of polyolefin production. The catalysr is a
r^la+iv^ly complex alkyl, or alkyl halide, of metals such as titanium
and aluminum.
Products of -t-his process include:
Hiah Density Polyethylenc
Polybuten"
Copolymers.
Catalyst preparation, monomer addition, and reaction proceed as already
d-scribed for the solution process. Temperatures and pressures are
Icw^r; and, because the polymer does no-*- dissolve, problems caused by
siv0 viscosity do not arise.
The ncxt step is the removal of the catalyst, which historically has
b°en thc- most troublesome part of the system. The residual catalyst
content of t-.he final polymer must be very low, and for tnis reason a
syst~-m is employed which allows transfer of catalyst to a separate
liauid chase. Aqueous alcohol is used for this purpose and tne catalyst
is rcmovcd in solution, leaving the polymer slurried in the hydrocarbon
solvent.
Th= agueous alcohol phas= is treated to precipitate the catalyst as th^-
oxid-s (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, bu+-
consolidati on of the sludge left behind has been a problem. Alconol is
recovered for reuse by distillation. The agueous phase remaining is th°
principal waste product of the plant. This water contains a finite
amoun+- of dissolved alcohol, and this chemical constitutes the laraest
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, arid th0
hydrocarbon solvent is purified by distillation. A small quantity of
agueous waste is recycled to the alcohol unit.
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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 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 practice of 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 Fesins
These resins are polymerization products of formaldehyde. At present
they are manufactured at two U.S. plants, operated by different com-
panies 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.
31
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32
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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.
Cellophane
Cellophane is produced in a wide variety of grades. However, these
variations primarily represent differences in film thickness, plasti-
cizer 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:
Steep__ing
R (cell) OH + NaOH - «»R(cell) ONa + H20
cellulose alkali cell.
Xanthation
R(cell) ONa + CS2 - ^R(cell) OCSSNa
cell, xanthate
R(cell) OCSSNa + H2SO4 - *»R(cell) OH + CS2 + Na2 SO4
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.
33
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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.
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:
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High tenacity continuous filament (tire and
industrial type yarn)
Regular tenacity continuous filament (textile
yarn)
Regular tenacity staple
High performance (e.g., high wet modulus) staple.
The •'rypes 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 furtner below.
The basic reactions involved are represented by the following:
Steering
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 SOU 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.
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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.
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 -co
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
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
38
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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-
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.
39
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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 8S percent by weight ester of a dihydric alcohol (usually
ethylene glycol) and terephthalic acid. 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-
cyclohexanedimQthanol rather than ethylene glycol.
Molecular weights in the region of 15,000 are required for useful
textile fiber properties. Most products contain a aelusterant,
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
cyclohexanedim°thylene 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 aihydric
alcohol are that it be quite pure and particularly free from color-
formina 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
40
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(1) Via dimethyl terephthalate (DMT) route:
a — Alcoholysis with ethylene glycol
DMT
2CH2OH-CH2OH
ethylene glycol
2CH3OH
t
monomer
b — Polymerization of "monomer"
260-300° F^ r
"Monomer"Vacuum » HO |_C2H4OOC
C2H4OH +
polyethylene terephthalate (PET)
_n_ HOC2H4OH |
2
ethylene glycol distilled off
(2) Via terephthalic acid (TPA) route:
C-
HO
O
\
OH
2CH2OH-CH2OH-
PET +
H20 |
terephthalic acid
ethylene glycol
FIGURE 12 TYPICAL POLYMERIZATION REACTION
FOR POLYESTER RESINS AND FIBER
41
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•nore common. Th^re 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
orocess generates only ethylene glycol.
Titanium dioxide is used in polyester fibers as a delusterant. Optical
brighteners are often used. These arQ applied either topically (by the
textile finisher) or via addition of fluorescent dyes to the molten
polymer prior ^o melt spinning.
Th-= exac*- nature of the catalysts used in the polymerization process
varies somewhat and is regarded as proprietary information. They are,
however, known to include acptates 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
fa-i-ty acids, emulsifiers, bacteriostats, and humectants.
The end product from ?. polyester fiber plant is in the form or 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 batcn poly-
merization process, continuous polymerization and direct spinnina
combinations are more common for new facilities.
A ^ypical 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 tha 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.
^he spinning operation involves forcing the molten polymer (at about
2Q0°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
threadlir.es, each containing 250 to 1000 filaments can be brought
tcaethsr, passed over capstans and through an air ejector, and coiled in
a larae can for subsequent drawing. For continuous filament yarns, the
42
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43
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spun threadline comprising 15 to 50 filaments is either wound on Dobbins
for subsequent draw twisting or drawn directly at high speed and woun-3
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 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 UOOO
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
drawina. 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, -hereby
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 (Tio2), 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
44
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(a) Formation of nylon "salt"
HOOC-(CH2)4 -COOH + H2N(CH2)6 IMH2 *- -^ H3N (CH2)6 NH3OOC(CH2)4 COO
HMDA,
hexamethylene
diammonium adipate or
nylon salt
(b) Polymerization of salt
HMDA -2H2O /HN (CH2)6 NHOC (CH2 )4 CO-Y
v XX
FIGURE 14 TYPICAL POLYMERIZATION REACTIONS
FOR NYLON 66 RESINS AND FIBER
45
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but with slightly different process conditions. For the purposes of
this study, we have included nylon 66 resins and fibers are included 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 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 poly-
condensation 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 Pesin
Process Description - Cellulose acetate resin (flake) is produced by a
batch ^ype 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 acetylation
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.
46
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47
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The clear, viscous solution is then transferred to a hydrolysis reactor
where dilute aqueous acetic acid is added, and the acetate hydrolized
back *-o the soecified acetyl content. Some magnesium acetate may be
added to adjust t he 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:
ylat ion
R(cell) (OH) 3 + ?(CH1CO)2 0
R(cell) (OCOCH3)3 + 3 CH3COOH
cell, triacetate
R(C?11) (OCOCH3) 3 + xH20 - ^*- R (cell) (OCOCH3) (OH) X * XCH3COOH
3-x
cell, -"-riaceta-1- e cell, acetate
Cellulose aceta-e flake is recovered from the reaction solution on a
continuous precipitator by precipitation with weak acetic acid solution
from the counter curren*- wash step that follows. The
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 use3 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 Fia. 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.
48
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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 of wheels to orient the fibers before being wound
on a bobbin. The filaments pass over a small roll applicaror 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
cellules0 acetate fibers except that the solvent employed for triacetate
in a mixture of methancl and me-thylene chloride.
Epoxy Pesins
Epoxy resins are characterized by the presence of the epoxy group within
their structure. Father than an end resin in itself, the epoxy family
shovild 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 formal-
dehyde. It is also possible to produce epoxy resins by introducing the
50
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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. Bisphenol 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.
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 Eg. 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, p., 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.
52
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(1) 2CH2-CHCH2CI
\ /
O
Epichlorohydrin
pH > 7
+ HO
(2)
OCH2CHCH,
I I
OH Cl
CH3
Diglycidyl Ether of Bisphenol A
OCH2CHCH2
\ /
0
HO
2NaOH
2NaCl t 2H,O
CH, , .
\UT\
c
I
CH,
OH
CH2CHCH2
\l
CH,
CH,
CH,
CH,
\l
FIGURE 18 REACTIONS BETWEEN EPICHLOROHYDRIN AND BISPHENOL A
53
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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 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 epoxidation 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 s^nt to storage.
The solid resins, which have a high molecular weight, are usually
produced by batch techniques in resin kettles. In producing these
materials wher^ the repeating part of the epoxy chain is a high number
ranging from l.fl to 16, the mole ratio of epichlorohydrin to bispnenol 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.
54
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CATALYST
BISPHENOL A
EPICHLOROHYDRIN
(2)
50% NaOH
WATER
METHYL ISOBUTYL
KETONE
i
1st. STEP
POLYMERIZATION
EPICHLOROHYDRIN
REMOVAL
2nd STEP
POLYMERIZATION
WASHING
WASH
'WATER
(&}
SOLVENT
REMOVAL
\
LIQUID EPOXY
RESIN
0 BISPHENOL A
©EPICHLOROHYDRIN
(3) 50% CAUSTIC
NaOH
H20
0WASH WATER
© LIQUID RESIN
© 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
n= 0.2
FIGURE 19
LIQUID EPOXY RESIN PRODUCTION
55
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BISPHENOL
EPICHLOROHYDRIN
50% NaOH
WATER
METHYL ISOBUTYL
KETONE
POLYMERIZATION
-*J WASHING
DECANTING
SOLVENT
RECOVERY
WASTE
WATER
RESIN
SOLIDIFICATION
0BISPHENOL A
(DEPICHLOROHYDRIN
(3) 50% CAUSTIC
NoOH
H20
© WASH WATER
(5) SOLID RESIN
(6) WASTE WATER
H20
NaCt
lbs/1000lbs
PRODUCT
777.6
367.6
318.0
159.0
159.0
2218.0
1000.0
2681.0
2449.0
232.0
RESIN
GRINDING
T
SOLID
RESIN
PRODUCT
n = 5
FIGURE 20
SOLID EPOXY RESIN PRODUCTION
56
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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 resin?
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 pnenol such
as creosol or resorcinol, and an aldehyde such as £ormaldenyj'r or
acetaldehyde. Nearly all industrially-significant resins, nowever, are
based upon the reaction of phenol with formaldehyde.
Phenol, commonly known as carbolic acid, is a solid at room temperature
but mel-f-s 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.
Ther» are two broad types of resins produced by tnis industry for
subsequent utilization by their customers. In the first category are
the one-step resins, sometimes termed resols. These are cnaracterized
by being formed from a mixture of phenol and formaldehyde which contains
more -*-han one mole of formaldehyde per mole of phenol. Often th= mole
ratio is abou^ 1.5 to 1. An alkali such as sodium hydroxide is used ^o
catalyze the polymerization which takes place at a pH of between 8 and
11. The reaction is shown in Fig. 21.
Th~ 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
^he 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).
57
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Alkaline
Catalyst
6HCHO
OH
HO-CH2 X ^SX CH
HO-CH2
CH2OH
3H20
FIGURE 21 TYPICAL REACTION TO FORM ONE-STEP RESINS OR RESOLS
58
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The second category of resins is -the novolaks. These are formed trom 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 us-s
where a high ortho 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 durina
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.
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 usina
hexamethylenetc-tramine. 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 oy 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 -*:he basic manufacturing processes to any significant
degree.
Manufacturing Processes for Typical Resins - Altnough continuous
processes for th° production of phenolic resins have been developed,
they are seldom used. The production of these continuous units must b^
high, and the industry calls for such a wide variety of materials tna-r
it is seldom possible to have a large enough run on a single grai-~ of
polymer to justify their use.
The standard producing unit of the industry is typically a batch r-=sin
kettle arrangement, such as is shown in Fig. 23, The heart of th =
process, the r^sin 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.
59
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OH
5 I -f 4HCHO
V * '
Acid Catalyst
OH OH OH
CH2 f/' N. CH2
OH
CH,
CH,
OH
FIGURE 22 TYPICAL REACTION TO FORM NOVOLAK RESIN
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In a typical cycle for a one-step resin, the phenol is cnarged 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 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
9B°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.
Tf 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 guickly 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.
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
62
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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 qround, 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 wast^
water generation.
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^Al though called
amino resins, in the case of most of the compounds used they are morp 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 hicrhly 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 r^actants) to form materials such as monomethylol urea and
dimethylol urea which are the reactive monomers involved in the final
polymer. As indicated in Eg. 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
63
-------
u ii
(1) H2N-C-NH2 + CH20 —»• H2N-C-NH-CH2OH
Urea Formaldehyde Monomethylolurea
0 O
II II
(2) H2N-C-NH2 + 2CH20 »• HOCH2-NH-C-NH-CH2OH
Dimethylolurea
O O
(3) H2N-C-NH-CH2OH + HOCH2-NH-C-NH-CH2OH
HOCH2
\ II
0 N-C-NH-CH2OH +H2O
H2N-C-NH-CH2
FIGURE 24 TYPICAL POLYMERIZATION FOR UREA
AND FORMALDEHYDE
64
-------
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 formal-
dehyde 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.
^, 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 an ether linkaae 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 molecular 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. Thc 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
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Table 11
Markets for Amino Resins
Percentage of
Amino Resins
Adhesives 36%
Textile and Paper Treating and Coating 22%
Laminating and Protective Coatings 18%
Moulding Compounds and All
Other Applications _24%
100%
66
-------
NH2
NHCH,OH
N N
II)
H2N
NH2
3 CH2O
N N
NOH2CHN - C C — NHCH,OH
Tnmethylol Melamine
NH2
\
N N
(2)
6 CH2O
C C
x%Nx\
H, N NH2
HOCH,
CH,OH
HOH,C
CH.OH
N
HOH,C CH,OH
Hexamethylol Melamine
NH,
N N
(3)
NH,
NH2
NHCH2OH
NH
CHjOH
NH2
I
<^C\
N N
NHCH,OH
NH CH2 NH
NH2
NHCH,OH
N N
H,O
NHCH,OH
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
eaually 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 mills, 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, wnere 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 =>ach 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
68
-------
!=>
O
e
69
-------
this initial heating period the pH drops to about U as the reaction
between 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 piaments, 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 or 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 polyacrylonitrile. 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
70
-------
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 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 sulfo-
cyanide 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
'{CH2-CHCN)n
acryloni tri1e polyacryloni tri1e
Polymer and solvent are then mixed to form a spinning dope which is
forced through spinnerettes into a coagulating bath (solvent + H2O) 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 loath.
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
-------
CN
g
cn
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w
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23
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PL,
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72
-------
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 ether fibers, TiO2 is added in the poly-
merization step as a delusterant, spin finishes are used in processing
and thermal stabilizers are added. End products from rhe 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 H^O 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
staqe. In the third step the chain stopping agenr (usually a
monofunctional acid, such as acetic acid, or occasionally a mono-
functional amine) terminates the growing chains. Tne 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 con-
tinuous 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. Tne strands
are continuously cut into chips which must be subseguently 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 freguently 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 nylcn 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. The Vickers-Zimmer process is thus based on two main units:
the polymerization reactor column and a thin-film evaporator.
73
-------
RECOVERED MONOMER
HOPPER
DEHYDRATION
AND CATALYST
RECOVERY
RECOVERED
WATER AND
CATALYST
AQUEOUS-SUSPENSION ACRYLONITRILE POLYMERIZATION
PUMP
POLYACRYLONITRILE
SOLVENT
SPINNERET STRETCH1NG
HEATED
WALL
EVAPORATION
CHAMBER
HEATED
CHAMBER
WASHING
FIGURE 28
ACRYLIC FIBER PRODUCTION - DRY SPINNING PROCESS
CRIMPING
SETTING
DRYER
I
YARN TOW STAPLE
74
-------
(a) Initiation and addition to form aminocaproic acid
HN (CH2 >5 C=O + H2 O —»-H2 N (CH2 )s COOH
caprolactam e — aminocaproic acid
(b) Polycondensation
O
II
C
H J N
Nylon 6
T H 1
H2 N (CH2)5 COOH —»- H 4- N - (CH2)5 - C 4- OH + (n-1) H20
*- LJ -I M
FIGURE 29 TYPICAL POLYMERIZATION REACTIONS TO FORM
NYLON 6 RESIN AND FIBER
75
-------
O
CO
W
76
-------
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 major subcategories representing combinations
of the waste characteristics discussed above.
Major_S_ubcatec[ory__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.
Sub_cJi£§_2O.Ey._!.! - High raw waste load; raw waste load
areater than 10 kg/tonne product; attainable low
BOD5 concentrations.
MSi2£_Subcateg.ory__IlI - High raw waste load; attainable medium
BOD5 concentrations - in the 30-75 mg/liter range.
egory__IV - High raw waste load; attainable high BOD5_
concentrations over 75 mg/liter.
The attainable BODjj concentration in the effluent is influenced by ~he
treatability and, for a specific plant, by the variations in the
influent concentrations. In major sutcategory 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
plantsin major subcategory II are characterized by high raw waste loads
but the waste waters can be treated to low attainable BOD5_
concentrations. Raw and effluent loads are a factor of 10 higher than
for the SD§J2£ subcategory I plants, largely because of the high water
usage for Rayon and Cellophane and the high BOD5 influent concentration
for ABS/SftN resins. Major subcategory III plants are cnaracterized 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
77
-------
by 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
mehtods. The separation of each individual product in-co 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.
78
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TABLE 13
INDUSTRY SUBCATEGORI2ATION
Major
Subcategory I
Major
Subcategory II
Polyvinyl chloride Cellophane
Suspension Rayon
Emulsion ABS/SAN
Bulk
Polyvinyl Acetate
Polystyrene
Suspension
Bulk
Polypropylene
Polyethylene
High Density
Solvent
Polyform
Low Density
Major
Subcategory III
Polyester
Resin
Fiber
Pesin & Fiber
Continuous
Resin 6 Fiber
Batch
Nylon 66
Resin
Fiber
Resin & Fiber
Nylon 6
Resin & Fiber
Resin
Fiber
Cellulose Acetate
Resin
Fiber
Resin & Fiber
Epoxy
Phenolics
Urea Resins
Melamine
Major
Subcategory IV
Acrylics
80
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SECTION V
WASTE CHAPACTEPIZATION
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 analysts for
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 wat*=r 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 reguired
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.
Paw_Waste_Loads
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 ana 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 33U for COD, and from 0 70
for suspended solids.
Data from the above sources are recorded in Tables 14 and 15 for waste
water flows, BOD5, COD and 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.
81
-------
TABLE NO. 14
WASTEWATER LOADING FOR THE PLASTICS AND SYNTHETICS INDUSTRY
Wastewater Loading
(gal/1000#)
Observed Reported
Flow Range
Wastewater Loading
(cu m/tonne)
Observed Reported
Flow Range
Product
Polyvinyl Chloride—Suspension
Polyvinyl Chloride—Emulsion
Polyvinyl Chloride—Bulk
ABS/SAN
Polyvinyl Acetate
Polystyrene—Suspension
Polystyrene—Bulk
Polypropylene
Lo Density Polyethylene
Hi Density Polyethylene—Solvent
Hi Density Polyethylene—Polyform
Cellophane
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
Melamine
Acrylics
Nylon 6 Resin and Fiber
Nylon 6 Resin
1800 (300-5000)
15.0
29400 (12,000-67,000)
16500 ((4000-23,000)
540 (0-20,000)
11250 (0-18,250)
5000 (2000-50,000)
10.4
430
1480
220
160
3400
6500
82
(300-610)
(60-2400)
(300-6160
3.62
12.34
1.8
1.3
28.4
54.2
2.5-41.72
2060
1000
1100
1000
2130
3500
(200-3500)
(0-3000)
(0-17,000)
(300-8000)
(0-5,000)
(0-3700)
8.3
9.2
8.3
17.8
29.2
1.67-24.03
0-25.03
0-141.8
2.50-66.75
0-41.72
0-30.87
245 100-559
138 33.38-191,
4.5 0-167
0-152.3
41.7 16.69-417
2.5-5.1
0.5-20
2.50-50.87
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-------
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.
84
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SECTION VI
SELECTION OF POLLUTANT PARAMETERS
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 tor an
individual product subcategory in sufficient quantity to caus°
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
ss
Zinc
Phenolic Compounds
Total Chromium
BOD5
The biochemical oxygen demand was selected because it is an indicator of
the potential oxygen depleting effects of the waste waters in the
receiving waters. BOD5 has been used widely for characterizing the
quality of waste waters and is the parameter for which the greatest
amount of data is available. The organic chemicals on which the
industry is based are known to have a wide range of biochemical oxygen
demand, varying from highly biodegradable to highly refractory.
Concentrations of BOD5^ in the raw wastes may vary from less than 100
mg/liter to approximately 5000 mg/liter. The lower values are typical
of processes where there is low process water usages or where process
contaminants and water of reaction are removed. The biochemical oxygen-
demanding portion of the waste water stream is treatable; however, the
effects of non-degradable substances as well as the specific nature of
the organic chemical determines the ease and degree of removal. BOD was
selected as a parameter for all product subcategories.
85
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COD
The chemical oxygen demand -test has been used widely to provide an
indication of the presence of carbonaceous substances, many of which are
non-biodegradable in practicable biologically based waste water
treatment plants. COD data are nearly as widely available as BOD5 data
and since some measure of gross non-biodegradable carbonaceous
pollutants is required, especially for wastewater with low BOD5, it has
been selected as a parameter. The variability of COD in the raw waste
load is even greater than that of BOD, ranging from a low of about 100
mg/liter to 6000 mg/liter or even more. The removal of chemical oxygen
demand to the same efficiencies as BOD in a biological system is not
attainable. Removals range are from under 30 percent to over 95
percent. The efficiency of COD removal is specific to the individual
process operation characteristics and cannot be generalized for the
industry. COD was selected as a parameter for all product
subcategories .
Solids
The third parameter for which a significant data Dase exists is
suspended solids. Because of the variable effects of suspended solids
on the receiving water quality and aesthetics, it was chosen as a
parameter. The suspended solids in raw waste loads are not well known
and vary widely with the type of manufacturing process. Furthermore,
the biological treatment process and polishing lagoons generate micro-
organisms which contribute to suspended solids loads. Suspended solids
removal is largely based on gravity sedimentation and, consequently,
wide variations in the concentration of suspended solids is often found
in operating plants. However, technology is available which can control
suspended solid effluents to very low levels. Suspended solids was
chosen as a parameter for all product subcategories.
.Zinc
Of all metals, zinc is used in the largest quantities, principally in
the manufacture of rayon. Reported raw waste loading of zinc is known
to cause deleterious effects on receiving waters. The removal of zinc
from waste waters has been demonstrated in operating plants and
demonstration projects. Zinc was chosen as a parameter for the product
subcategory rayon.
Phenolic compounds are widely used as raw materials in the plastics and
synthetics industry; consequently, these are often found in waste water.
Because the deleterious effects of phenolic compounds in receiving
waters are well known, phenolic compounds were chosen as a parameter for
those processes manufacturing phenolic resin, acrylics and epoxies. The
86
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removal of phenolic compounds by biological and phy Biochemical means has
been demonstrated. Phenolic compounds was chosen as a parameter for the
phenolic resin, epoxy resin and acrylics product subcategories.
Chromium
The use of chromium compounds as catalysts, as chromium inhibiting
chemicals, and in materials of construction is widespread throughout
industry. The toxic effects of chromium in receiving waters has been
widely investigated and is known to be highly deleterious; therefore, it
was chosen as a parameter for ABS/SAN, polystyrene, and hi density
polyethylene where it has been identified in the waste waters and where
it is known to be used in process streams. The technology for chromium
removal has been widely demonstrated in other industries.
l£°-D.» Aluminum, Nickel, VanadJLum, Titanium, Molybdenum and Cobalt
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.
Compounds
The effects of biological nutrients such as nitrogeneous compounds on
receiving water guality is well known. 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. The removal of nitrogeneous compounds such as
ammonia and nitrates has been demonstrated in other industries; however,
the removal of organic nitrogen has not been demonstrated in this
industry. Consequently, receiving stream water quality standards should
determine if limitations are necessary.
87
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Dissolved Solidg
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.
Although technology for removal of dissolved solids is well known, its
application in the industry has not been economically practical.
Toxic_and_Hazardous_Chemicals
The industry uses a large number of accelerators and inhibitors which
are considered proprietary and, consequently, no information was
obtainable. Some of these components may be 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
Oil §nd arease -Alkalinity. -Color -Turbidity. -PJ3°.Ii]2]}ates ~Sulfides
Cop_p_er -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.
88
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EM
The effects of low and high pH values on receiving waters is well known
and water quality standards which have been promulgated for receiving
waters should govern.
89
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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
EPOXY RESINS
PEHNOLIC RESINS
UREA RESINS
MELAMINE
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
Phenolic Compounds
Phenolic Compounds
Organic N
Nickel
cobalt
Organic N
Organic N
Organic N
Phenolic Compounds
90
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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 (2) 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 subcategories.
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.
91
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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 treat-
ment 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 SS 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 representative 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 mean-
ingful 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 BOD5^
concentrations in its effluents, is based on an elaborate system of
monitoring, holding ponds, waste equalization and/or segregation in
92
-------
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conjunction with 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 wastewaters from the
synthetics and plastics industry cannot be categorized as well as for
municipal sewage treatment; nevertheless, biochemically active portions
of these waste waters can be removed by practicable biological treatment
systems to concentration 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 BOD5 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 BOD^/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 UO 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
94
-------
5JUV
800
700
'e 600
1
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? 500
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X(,
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.LULOSICS1
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'OLYESTER
X(28)PVA AND PVC
0 20 30 40 50 60 70 80 90 95 98 99 99.8 99.9 99.99
PERCENT BOD REMOVAL
FIGURE 31
BOD REMOVAL AS FUNCTION OF TOTAL SYSTEM RESIDENCE TIME
95
-------
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 BODI5 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
(TOC), 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
96
-------
900
800
700
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to
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600
500
400
300
200
100
(X)
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10 20 30 40 50 60 70 80 90 95 98 99
PERCENT COD REMOVAL
99.8 99.9
99.99
FIGURE 32
COD REMOVAL AS FUNCTION OF TOTAL SYSTEM RESIDENCE TIME
97
-------
20 was achieving 62 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 of the processes indicate
that BOD5 loads should be expected; however, its effluent has a high
concentration of zinc which must be removed prior to discharge.
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 BODJ5 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 some 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
coolinq 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
chromate-based anti-corrosion systems are usually more effective in
controlling rate of corrosion, the choice of using a less toxic anti-
corrosion system, where the blowdown can be discharged to waste water or
streams without prior treatment, or using a chromate system which
requires the treatment of blowdown before discharqinq it to wastewater
treatment plants or streams is predominantly an economic one. Although
98
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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.
101
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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
hiah 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 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
102
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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 rhe 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.
U. 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 minimizing 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.
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
103
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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 loadings of BOD5, COD, and SS from observed exemplary operating
biological treatment plants for each product subcategory are summarized
in Table 21. For the product subcategories of epoxy 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 BOD5 is not achievable in biological systems.
Potentially. Usatde was_tewater_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.
6 Adsorption
Removal of soluble substances, such as characterized by the COD
or TOC 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
104
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N H C 4-J -H
•H H CO It-i
r-J • .—I > -H
-H . T-l > -H
co e 4-> -H )--
D 01 -U 4-1 (0
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.-H i- at
1-1 4-> ,
to to
o. N
tfl l-i -H l-i
V- O) O G
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H 4-1 -
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at .-i - >
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t. 3 OJ 4-.
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O 4-1 r/i vH &o P-i
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O i-i C/l -H P-,
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4-1 ID (0 fcO
rt ^H ai o c
N n3 4J -H T-*
•H u ra 4-1 .c
i-l U i-t > -
4J CO tfl -H
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4-1 -O tO
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ra -H o
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105
-------
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 freguently 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 comppunds, although its efficiency varies
widely.(18, 19, 31, Ul, 56) Consequently, it is necessary to
established 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 in use by
industry.
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 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
106
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SUMMARY OF
INDUSTRIAL SOURCES USING GRANULAR ACTIVATED CARBON SYSTEMS
Industry
1. Velvet Textiles
2 . BASF Wyandotte
Chemical Corp.
3 . ARCO-Watson
Refinery
4. Stephen Leedom
5. Reichhold
Chemicals, Inc.
Location
Blackstone, VA
Washington, NJ
Wilmington, CA
Southhampton, PA
Tuscaloosa, AL
6. Schnectady Rotterdam, NY
Chemicals, Inc.
7.. Chipman Div. of Portland, OR
Rhodia, Inc.
Principal Product
Velvet
Polyethers
Refinery Products
Carpet Mill
Phenol, Formalydehyde,
Pentaerythritol,
Orthophenylphenol, synthetic
resins, and plastics
Phenolic Resins
Contaminant(s) Removed
Dyes, Detergents,
Organics
Polyethers (MN 1000-
3000)
COD
Dyes
COD, Phenols
Phenols
Herbicides-2,4-D acid, MCPA COD, Phenols
acid, 2, 4-DB acid and esters
of these products
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
12. Georgia Pacific Conway, NC
13. Stauffer Chemical
14. General Electric
Co.
15. C.H. Masland &
Sons
16. St. Regist Paper
Co.
17. Monsanto Indus-
trial Chemicals
18. Hercules, Inc.
19. Dow Chemical
20. Hardwicke
Chemical Co.
21. Crompton and
Knowles Corp.
Skaneateles Falls,
NY
Selkirk, NY
Wakefield, RI
Pensacola, FL
Ann is ton, AL
Hatiesburg, MS
Midland, MI
Elgin, SC
Gibraltar, PA
p-Cresol
Explosives
Intermediate Detergents
Phenolic Resins
Strong Alkaline Detergents
Plastics
Carpet Yarn
Kraft products
p-Cresol
Color
TNT
Color and organics
Phenols
COD
Phenols and COD
Color and COD
Color
Intermediate Organic Chemicals Polynitrophenol
(polynitrophenol)
Acid Resins, turpines & solvents Organics
Phenol Phenols and Acetic Acid
COD, Color
Intermediate and Specialty
Organic chemicals
Dyes
107
Dye, COD
-------
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 ±691 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 -che 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 (U7) 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. 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
108
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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, tne 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.
6 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.
6 Air Stripping
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
109
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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 Seperation
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 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
110
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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. 75 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.
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
111
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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 wh^n
compared with evaporation and electrodialysis; however, th»
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.
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
112
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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.
Control of_ Waterborne Pollutants
Pollutants removed from 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 l^aks in process operations as well as support operations.
The importance of this subject has been reviewed in 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
MATRIX FOR EVALUATING LIQUID
HANDLING FACILITIES
Probability of Spillage
Inventory of
Contained Liquid
Frequency of
Operating Cycles
Storage
Very
High
Loading and
Transfer Unloading
Low
Ratio:
Temporary Connections Very
Permanent Connection Low
Volumetric Transfer
Rate
Dependence Upon
Human Factor
Low
High
Low
Moderate
Very Low
High
Low
Very Low
Very High
Very High
High
Very High
Processing
Low
Moderate
Moderate
Variable
High
114
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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.
he application of ancilary control techniques requires judicious
'lanning of operational philosophy, organization, and specific measures
uch as discussed below.
perational Philosophy
ach plant management needs to formulate a "Spill Exposure Index" which
ill reveal potentially-serious problems in connection with its
peration. Once the problems are defined, rememdies and the costs of
mplementing them are not difficult to determine. The next step is
stablishing priorities, a budget, and a commitment to capital and
perating expenditures. As new production projects are proposed for a
ilant site, each should incorporate adequate measures for spill
irevention as an integral part of its design. Capital investment in
his category should be considered to be fully as necessary as
nvestment in process equipment or, alternatively, in more elaborate
aste water handling procedures.
ne approach is the development of a classification index (taking into
onsideration the minimum aquatic biological toxicity, etc.) which
stablishes ratings of hazardous polluting substances and recommends the
inimum acceptable containment measures.
rganization
ince most of the prevention and control measures represent added
nconvenience and costs in the eyes of the plant operating staff, even
hen wholeheartedly accepted, establishment of an independent group with
direct assignment to minimize spills and authorized to take action is
specially desirable.
pecific Measures
-------
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 durina tank filling could be expected to minimize
the common occurrence of overflow when reliance is on manual gauginc
for control.
3. Above-ground transfer lines. Above-ground installation permit?
rapid detection of pipeline failures and minimizes hazardous
polluting substances from polluting ground waters. Although
increasing the possible mobility into surface waters, long-tern
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 spreadinc
widely in the immediate area; consequently, curbed areas connectec
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 a-
the highest concentrations, local catchment basins can provid*
significant flexibility in preventing spills from entering wate-
courses.
6. Holding lagoons for general plant area. Lagoons which can b<
used to segregate spills and prevent them from passing as slugs intc
waste water treatment plant or water courses, give the surg<
capabilities necessary for handling large volume or highly toxi<
spills.
7. Initial waste water treatment. For removal of floatin<
substances or for the chemical neutralization or destruction o
spilled materials, the initial waste water treatment plants serve ti
ameliorate the more drastic effects of spills in receiving waters,
8. Biological waste water treatment. The removal of solubl
substances usually through biological action, where possible, ca.
insure that the plant waste water discharges have a high degree o
uniformity at acceptable quality regardless of inplant variation
such as would occur from spills.
-------
In a facility with a "high spill exposure index" there should be a
review of the designs and conditions to determine the potential
conseauences of spills and leaks in a truly objective manner. The
review should consider the design of the process and 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 of sewers. A number of potential sources of leaks and spills can
frequently b° 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 -f-olerated; and in the case of rotating equipment, is
desirable for shaft lubrication and cooling. In tne 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
117
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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.
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, curcing, 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.
and Operating Methods for E^ijnJ.nat.i.on or
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
118
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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 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 plant-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 arr- 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 requirements 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,
ecruipment and plant layout designs did not provide for incorporatinq
techniques 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.
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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 off-
specification product or more efficient reactions, replacement of
water scrubbing systems by nonaqueous 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.
H. 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.
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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. Some 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 Technologj.es
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:
Initial !l£§§.£ni6Il£i For removal of suspended
solids and heavy metals. Includes equaliza-
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TABLE 2k
PERSPECTIVES ON THE PLASTICS AND SYNTHETICS INDUSTRY
- WATER USAGE -
Guideline
Sub category
Product
Number of
Company
Operations (1)
Percent
of Total 18
Product
Production (2)
Percent of
Water Used by
18 Products
Percent of Growth
in Water Usage
of 18 Products (3)
1972
1972
1972-1977
PVC
ABS/SAN
PStyrene
PV Acetate
LDP Ethylene
HDPEthylene
Polypropylene
23
8
19
26
12
13
9
14.7
3.1
12.4
1.7
19.4
8.4
5.5
7.4
1.6
4.2
0.7
7.2
4.6
4.0
14.6
4.1
5.9
0.4
14.3
12.2
10.4
Cellophane
Rayon
Subtotal- A&B
4
7
121
1.2
3.5
69.9
13.9
19.1
62.7
(5.1)
7.8
64.6
Cellulose Acetates
Epoxy
Melamine )
Urea Resins J
Phenolics
Polyester
Nylon 66 I
Nylon 6 )
D
Acrylics
Subtotal - C & D
7
8
11
81
19
20
11
157
TOTAL - 18 PRODUCTS 278
3.3
0.7
3.5
4.7
8.9
6.9
2.1
30.1
100.0
16.8
0.1
0.2
0.4
8.5
9.5
1.8
37.3
100.0
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 (2.6 billion Ibs ).
(3) Result of projected product growth at current hydraulic loads.
122
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tion, neutralization, chemical coagulation
or precipitation, API separators, and primary
clarification.
B- Ml2l2ai£3.i Treatment: Primarily for removal of
BOD. Includes activated sludge (or aerated
stabilization basins), sludge disposal, and
final clarification.
C. Multi,-Stac[§_ Biological: For further removal of
BOD loadings. Either another biological treat-
ment system in series or a long-residence-time
polishing lagoon.
D- Granvrlar M£^ii. Hiiiration.: For further removal
of suspended solids (and heavy metals) from
biological treatment effluents. Includes some
chemical coagulation as well as granular media
filtration.
TE.§i£2!§Di! For further removal
of COD, primarily that attributable to refractory
organics, e.g., with activated carbon adsorption.
Waste Incineration: For complete treat-
ment of small volume wastes.
2inc Reniova.1 and Recovery.': For two-stage precipi-
tation and recycle of zinc used in production of
rayon.
E!l§.2.2l Extraction: For removal of phenol compounds,
e.g. from epoxy, acrylics, and phenolics wastes.
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 + 20 percent of that
predicted by the cost model. The costs calculated from the model,
123
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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.
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 -che 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.
(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
124
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function of hydraulic load. An estimate of land requirements is
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 2f. 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 vQry 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 calculated 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.
This assumes that the nature of the wastes is such that the refractory
organic substances (measured as COD or TOC) 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 (31, 41), the applicability of carbon adsorption across the
industry is technically still in doubt. Nevertheless, in order to
127
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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 lb GOD/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 (U) 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 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:
131
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!Y.2§ of Plant ynits/I^OOO/Unitg of Product
(1) Cellulosic-based 25-50
(2) Phenol ics, epoxy, nylon
acrylics, polyesters 10-25
(3) Polystyrene, PVC, ABS/SAN,
polyethylene, polypropylene 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:
3!y.E§. of E!a.Q.t fL/Pound of Product £/k_2 of Product
(1) Cellulosic-based 0.00625-0.0125 0.0138-0.0276
(2) Phenolics, epoxy, 0.00250-0.00625 0.00551-0.0138
nylon, acrylics,
polyesters
(3) Polystyrene, PVC, 0.00025-0.0025 0.00055-0.00551
APS/SAN, polyethylene,
polypropylene
Burd also reports capital and operating costs for incineration to be
$10 to $50 per ton ($1 1-$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:
of Poduct
(1) Cellulosic-based 0.0625-0.125 0.1378-0.2756
(2) Phenolics, epoxy, 0.250-0.0625 0.00551-0.0138
nylon acrylics,
polyesters
(3) Polystyrene, PVC, 0.00250-0.0250 0.00551-0.0551
ABS/SAN, polyethylene
polypropylene
The yearly volume of biological sludges (acre feet) generated for
each 10,000,000 Ibs of product is estimated to be the following:
134
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TY.E§ 9.L Ei§nt Biological Sljodcjejs Or
Acre Feet/Year Cu Meters/Year
(1) Cellulosic-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. Althougn 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 sulfuric 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 sodium sulfate, and 6 percent ZnSO4_,
135
-------
1.20
NET COST = GROSS
COST-BY-PRODUCT AND
RECYCLE CREDITS.
ACID WASH
STREAMS
WATER WASH
STREAMS
1 2 3
N02 804 CONC. IN WASH STREAM (%)
FIGURE 40
NET COST OF RECOVERING DILUTE WASH SOLUTIONS
136
-------
and -the exit composition 12-1/2 percent acid, 23 percent sodium sulfate,
and 5.8 percent ZnSO^J. 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 zir.c 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.
137
-------
TABLE 25
TYPICAL STREAM COMPOSITIONS
(Basis (kg/kkg)
Exit_from_S]2in_Bath
Most Conc.
First Acid Wash
(Avg)
Water Wash
Na2SO4
Zr.SO4
230
58
30 10 0.05
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)
Net Values, recycle or feed
to reclaim operation (2/lb) Total (£/lb)
18 (40 iz/kg)
H2SO4
Na2SO4
ZnSOU
20
30
5
55
Ibs.
(9.07 kg)
(13.61 kg)
(2.27 kg)
(24.95 kg)
0.9 (2.0 0/kg)
0.5* (1.1 2/kg)
9^75 (21.5 0/kg)
1T.15 (24.6 0/kg)
15 (33 !Z/kg)
48^7(106.5
-------
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*)
g/1000 Ibs recycled
Utilities (steam a> $1.00/1000 Ibs)
Labor (5) $5.50/hr including fringe)
Overhead (ft 100% of labor)
Depreciation ($950,000** a) 10 yrs)
Insurance and Taxes (5) 2% of CI)
Maintenance (a 6* of CI)
TOTAL COST
0
70.0
2.4
2.4
3.6
7
2^2
81.3
(154 0/kg)
( 5.3)
( 5.3)
( 7.9)
0.2)
1 __ 4..91
(179.6)
*This assumes concentrating the acid wash stream of Table 18 to the most
dilute of typical spin bath compositions, namely 7% H.2SO4, 10* Na2SO^»,
1.5* ZnSO4.
**Based on single-effect evaporators designed to handle 32,000 gal/hr
(121 cu.m./hr) acid wash stream (approximately one-fourtn 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 ZnS04) 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^SOU, 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 Na2_SO£, 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
139
-------
total water usage of 16.5 gal/lb of rayon, the cost is 2.40 per Ib
(5. 3£/kg) of rayon.
These cost estimates are based on use of single-effect evaporators,
which represent current U.S. practice. We 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 1.4 to 1.90/lb (3.1 to 4.20/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. Tnese 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.
i£Y £°§£ Pgrspectiygs
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.
140
-------
Pouah 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
40 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
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
aalions) 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.
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 tech-
nology. 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 of 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
141
-------
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 1983 was precluded
by the lack of a meaningful forecast of product growth.
The average costs of 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 iO.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.
Water Ef.fluent 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
142
-------
TABLE 28
PERSPECTIVES ON THE PLASTICS AND SYNTHETICS INDUSTRY
- TREATMENT COSTS -
Guideline Sub category
Product
Total Annual Costs, $ Million
Existing Plants
1977 1983
New Plants
1973-1977
PVC
ABS/SAN
PV Acetate
Polystyrene
LDPEthylene
HDP Ethylene
Polypropylene
Cellophane
Rayon
Subtotal
Cell. Acetates
Epoxies
Melamine
Urea Resins
Phenolics
Polyester
Nylon 66 \
Nylon 6 /
Acrylic
Subtotal
Industry Total
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
10.2
1.9
30.8
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
28.0
4.5
86.1
66.4 192.1
4.2
1.3
0.2
2.4
3.3
2.9
2.7
0.0
19.0
0.9
0.1
0.7
1.2
9.6
3.0
0.3
15.8
34.8
143
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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.
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Model Data
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145
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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/1 b)
Treatment Plant Size:
thousand cubic meters per day (MOD)
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
(25)
(0.43)
0.12 (0.033)
Alternative Treatment Steps1
A B H ^
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)
V B _H _F
0.2 - 0.06
1 - 0.4
0.7 - 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.
148
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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 B » _E
375 875 465 1165
30
38
11
3
70
88
67
33
37
46
6
3
93
117
115
9
102 238
92 334
Effluent Quality (Expressed in terms of yearly averages)
Raw
Waste
Load
B.O.D. 70
C.O.D. 110
Suspended Solids 15
Phenolic Compounds N/A
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B H E
0.2
1
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 stejps A and B corresponding to waste load share on municipal system.
149
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TABLE 30-3
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 (MOD)
Costs-$1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Melamine (small plant)
(15)
1.3
(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 Leveh
(Units per 1000 Units of Product)
V 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.
150
-------
TABLE 30-lj.
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
50
63
38
14
165
220
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.
151
-------
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 (MGO)
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 ** F
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
Watts
Load
N/A
N/A
N/A
Resulting Effluent Levels
(Units per 1000 Units of Product)
X 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 MOD). 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.
-------
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
(60)
1.8 (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)
B
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 rubic meters per day
(0.8 MGD). Step F is incineration of total undiluted waste streams. Costs per thousand gallons
assumes pay your-way usei charges equal to 0.25 of steps A and B. corresponding to waste load
share on municipal system
"No niw waste load data available, costs based upon BOD loading of 9100 Ib/day
153
-------
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
8b
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
ISI/A
Retultinq Effluent Levels
(Units per 1000 Units of Product)
A B H E
0.6
3
0.4
009
0.6
0.06
0.006 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.
154
-------
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
12.3
1.70
A
900
(100)
(1.48)
(0.45)
Alternative Treatment Steps*
177
B
2100
E_
2425
H
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)
- & Ji JL
0.6 - 0.09
3 - 0.6
0.4 - 0.06
0.006 0.0006
Steps A, B and E are based upon a dilution factor of 10; 17.0 thousand cubic meters 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.
155
-------
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 J> ^
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 par 1000 Units of Product)
A B D E
0.3
3
0.09
0.4
0.5 0.04
156
-------
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
A B D^ £
113 284 75 560
9
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 Levtls
(Units per 1000 Units of Product)
A B D E
0.4 -
4
0.5
0.1
0.9
0.09
158
-------
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)
Costs-$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)
X B
0.3
3
JO £
0.09
0.4
0.5 0.04
157
-------
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 § _D _E
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)
A B D E
0.4
4
0.5
0.1
0.9
0.09
159
-------
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)
Corts - $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)
Altar native Treatment Steps
A B D £
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)
BJO.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
1
3
4
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B D £
0.1
- , n.05
0.3
0.2 0.03
160
-------
TABLE 30-1*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
Polystyrene (large plant)
90 (200)
9.67 (1.16)
2.7
(0.7)
Alternative Treatment Steps
A B D JE
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
T
0.05
0.3
0.2 0.03
161
-------
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 JE
90 210 40 405
7
9
2
0.5
17
21
15
0.5
3
4
2
—
32
41
98
3
185
53.5
174
Effluent Quality (Expressed in terms of yearly averages)
B.Q.O. (Units/1000
of Product>
Suspended Solids
Raw
Waste
Load
1
2
1
Remlting Effluent Levels
(Units per 1000 Units of Product)
D E
B
0.1
1
0.3
Q.Q6
-< .0.4?.',
0.04
162
-------
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
Polystyrene (large plant)
90 (200)
9.67 (1.16)
2.7 (0.7)
Alternative Treatment Steps
A B D ^
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
161
-------
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 2 .§.
90 210 40 405
7
9
2
0.5
17
21
15
0.5
3
4
2
_
32
41
98
3
185 53.5
174
Effluent Quality (Expressed in terms of yearly averages)
B.O.D. (Units/1000
CO'b of Product)
Suspended Solids
Raw
Waste
Load
1
2
1
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B D E .
0.1
1
O.06
- '- L« • • Oh*
0.3 0.04
162
-------
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) :
Com-$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
£ § J) 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 Leveta
(Units per 1000 Units of Product)
B
0.1
1
0.3
0.06
0.4
0.04
163
-------
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/It))
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
164
-------
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 § p. 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)
B
0.1
1
0.06
0.4
0.3 0.04
165
-------
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 D 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)
B
0.1
1
0.06
0.4
0.2 0.04
166
-------
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
60.5 166
34
396
Effluent Quality (Expressed in terms of yearly averages)
Raw
Waste
Load
B.O.D.
C.O.D.
Suspended Solids
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B D E
0.1
1
0.06
0.4
0.2 0.04
167
-------
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 B 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
168
-------
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 (MGD) :
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
169
-------
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/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 (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
170
-------
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
Effluent Quality (Expressed in terms of yearly averages)
Acrylics (medium plant)
45
25
(100)
(3.0)
3.4 (0.9)
Alternative Treatment Steps
A
306
24
31
5
1
B
783
63
78
69
12
C
714
57
71
42
11
D
160
13
16
2
—
E
1050
84
105
146
22
61
222
181
31
357
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 I
1
6
0.5
0.1
0.8
0.08
171
-------
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 § 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 Lewis
(Units per 1000 Units of Product)
A B C D E
1
6
0.5
0.1
0.8
0.08
172
-------
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 (MOD)
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
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B C D E
0.3
5
006
0.4
0.2 0.04
173
-------
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
570 1465
C
1330
D
290
E
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
174
-------
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 ton of product (gal/lb)
Treatment Plant Size:
thousand cubic meters per day (MOD) :
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
270
B
630
C
630
D
120
E
840
22
27
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)
B
2
20
0.3
2
0.2
175
-------
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
176
-------
TABLE 30-30
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 (small plant)
23 (50)
16.7 (2.0)
1.1 (0.3)
Alternative Treatment Steps
A B C D
231 539 539 78
E
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
0.4
2
0.07
0.5
0.2 0.05
177
-------
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
178
-------
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)
A B D E
5
50
10
2
10
1
179
-------
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) :
Costs - $1000
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
Cellulose Acetate
90 (200)
157 (18.8)
43.2 (11.4)
Alternative Treatment Steps
A B C D E
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
Effluent Quality (Expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw
Waste
Load
50
75
15
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B C D E
3
30
0.5
3
1 0.3
180
-------
TABLE 30-3^
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
Rayon (all plants)
68 (150)
151 (18.1)
31.0 (8.2)
Alternative Treatment Steps
ABODE
Initial Investment
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Zinc Recovery Credit
Total Annual Costs
Effluent Quality (Expressed in terms of yearly averages)
1320 3380 1210 700
4650
106
132
15
2
270
338
273
16
97
121
485
28
(681)*
56
70
6
_
372
465
692
209
255
897
50 132
1738
B.O.D.
C.O.D.
Suspended Solids
Zinc
Raw
Waste
Load
25
50
N/A
30
Resulting Effluent Levels
(Units per 1000 Units of Product)
A B G D E
3
40
0.3
1
7
0.7
0.07
'Assumes 75% recovery of zinc values at $.20/lb.
181
-------
TABLE 31
INDUSTRIAL WASTE TREATMENT MODEL DATA
PLASTICS AND SYNTHETICS INDUSTRY
(Product Group #1)
Product Subcategory
Epoxies Melamine/Urea Phenol ics
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 - g „
Percent of Treatment in 1972
Treatment Steps:
(in percent now treated) Estimate
A. Initial Treatment 55
B. Biological Treatment 30
81
182
-------
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)
16.3(4.3)
32.7(42.4)
43.4(11.5)
66.9(17.7)
7.6(2.0)
9.1(2.4)
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.
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
Percent of Treatment in 1972
Treatment Steps:
(In percent now treated)
23
Estimate
A. Initial Treatment 9°
B. Biological Treatment 45
19
26
183
-------
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. 0.1 0.1 0.3
C.O.D. 1 1 1
S.S. 0.3 0.2 0.5
Number of Companies in
Subcategory 12 13 9
Percent of Treatment in 1972
Treatment Steps:
(in percent now treated) Estimate
A. Initial Treatment 55
B. Biological Treatment 35
184
-------
TABLE 3U
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 18.9(5.0) 87.2(23.1) 97.2(25.7)
1977 22.0(5.8) 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/1 000 units of product)
Number of
B.O.D.
C.O.D.
S.S.
Companies in Subcategory
1
6
0.5
11
0.3
5
0.2
19
[6] /[66]
2/0.4
20/2
2/0.2
20
Percent of Treatment in 1972
Treatment Steps:
(in percent now treated) Estimate
A. Initial Treatment 99
B. Biological Treatment 60
185
-------
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)
B.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
186
-------
SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
GUIDELINES AND LIMITATIONS
Def initionr_of _Bgst _Pract j.cabl6 Control Technology
CurrentlY_Available (BPCTCA]_
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
technoloay 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 eguilization, to dampen shock loadings, settling, clarification, and
chemical treatment, for removal of suspended solids, oils, other
elements, and pH control, and subseguer.t 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 housekeeping practices.
The best practicable control technology currently available has been
found to be capable of achieving effluent concentrations of BOD5
comparable to the secondary treatment of municipal sewage. The design
and operational condition? 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, ena-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
upon 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 unigue
properties such as measured by COD exists in the waste waters from the
industry. Besides BODS, COD, and SS, certain metals, phenolic
compounds, and nitrogen compounds are among the parameters of major
concern to the industry.
187
-------
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 concentrations
Based on the definition of BPCTCA the following long term average
and S.S. concentrations were used as a basis for the guidelines.
BOD5
BOD5
S.S.
Major Subcategory I
Major Subcategory II
Major Subcategory III
Major Subcategory IV
15
20
U5
75
The BOD5 and S.S. concentrations
presented in Table 18, Section VII.
30
30
30
30
are based on exemplary plant data
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 BOD limits in Table 37. Considering the variability of the COD/BOD
ratio between plants the upper limits of COD/BOD of 5, 10, and 15 were
used.
188
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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 Polyethylen^ 5.7
Cellophane 8.5
Rayon 11.7
Polyester 11.8
Nylon 66 U.2
Cellulose acetate 8.5
Acrylics U.3
189
-------
TABLE 37
COD/BOD Guideline Bases
Product COD/BOD
Polypropylene, Nylon 66, epoxy 5
Phenolics, urea, melamine and
Acrylics
Polyvinyl chloride, ABS, polyvinyl 10
acetate, polystyrene, low density
and high density polyethylene,
cellophane, cellulose acetate and
Nylon 6
Polyester, Bayon 15
There is a real need for more data in most industries to provide a
basis for better understanding of how the COD load can be reduced.
In the interim, the purpose of the BPCTCA guidelines is simply to
reflect the removal of COD to be expected along with best practicable
BOD5 removal.
The removal of phenolic compounds is based on an attainable concen-
tration level of 0.5 mg/liter monthly limit as demonstrated by
dephenolozing units (75) , activated carbon(18) (19) (56) (HI) or biological
degradation (47) .
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 technigues followed by biological degradation(47).
The removal of zinc is based on an attainable concentration of 1.4
mg/liter as demonstrated by an alkaline chemical precipitation process
(65).
Demonstrated,Wastewater_Flows
The waste water flow basis for BPCTCA is based on demonstrated waste-
water 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
190
-------
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.
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 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 never be exceeded, provided
that the plant is designed and run in the proper way to achieve the
desired long-term average load. It is these short-term limits on which
the effluent guidelines are based.
In order to reflect the variabilities associated with properly designed
and operated treatment plants for each of the major subcategories as
discussed abov^, 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-^o-
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
Long-term average (yearly or design) = x
Variability factor = y
Y = x_±_22
x
The variability factor is multiplied by the long-term yearly average to
determine the effluent limitation guideline for each product
subcategory. The effluent limitation guideline as calculated by use of
the variability factor based on two standard deviations is only exceeded
2-3 percent of the time for a plant that is attaining the long-term
average. The data used for the variability analysis came from plants
191
-------
TABLE 38
Demonstrated Wastevater 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
192
-------
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.
The following table summarizes the basis for the variability factors.
TABLE 39
Demonstrated Variability
Influent Long-Term
Concentration Effluent Concentration Variability Factor
Major
Subcategory ______ 2J2/I
I
II
III
IV
380
1206
91
1267
__
9
11
20
44
— —
1.33
1.71
1.76
1.77
2.2
2.2*
2.50
2.84
3.0*
3.0*
*estimated values
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
I
II
III
IV
Monthly
1.4
1.8
2.2
2.2
Daily
2.0
2.8
3.0 -
3.0
The variability for suspended solids was estimated for all categories as
follows: monthly 1.4 — daily 2.0.
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.
193
-------
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 5 mg/1 daily.
Based on the factors discussed in this Section the effluent limitation
guidelines for BPCTCA are presented in Tables U1 and 42.
194
-------
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
°f _§Sst_Available_TechnologY_Economi.callY_Achievable (BATEA)
Based on the analysis of the information presented in Sections IV-VIII,
the basis for BATEA is de#fined 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 for 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, tne human factors
associated wi^h 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.
Achievable_Ef fluentCncentration
195
-------
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 from waste water treatment plants has not been applied often,
although its feasibility has been demonstrated in projects sponsored by
the Environmental Protection Agency. The operation of filtration
systems, such as the in-depth 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 mg/liter) ; the capital and operating
cost for this technology adds significantly to waste water treatment
costs. The concentration basis for BATEA is 10 mg/1 for all product and
process subcategorics. (1) (22) (47)
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 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
196
-------
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 sometimes be
achieved through oxidation by chlorine, ozone, permanganates,
hypochlorites, etc. However, not only must the cost benefits of these
be assessed but certain ancillary effects, such as (1) the production of
chlorinated by-products which may be more toxic than the substance being
treated, (2) the addition of inorganic salts and (3) the toxic effects
of the oxidants themselves, must be taken into account. Consequently,
when chemical oxidation is employed for removal of COD, it may be
necessary to follow the treatment with another step to remove the
residuals of these chemicals prior to discharge to receiving waters.
Degradation of oxygen-demanding substances may take place slowly in
lagoons if sufficiently long residence time can be provided. If space
is available, this may be an economic choice. Also, the use of land
irrigation, or the "living filter" approach to water purification, is
receiving selected attention. Ultra-filtration and reverse osmosis,
both of which are membrane techniques, have been shown to be technically
capable of removing high molecular species, but they have not been shown
to be operationally and economically achievable. With these techniques
the molecular distribution of the chemical species determines the
efficiency of the separation. They probably have limited potential in
the plastics and synthetics industry, due to the particular spectrum of
molecular weights occuring in the waste waters.
The concentration basis for BATEA for COD is 100 mg/1 and for BOD5 is 15
mg/1 for all product and process subcategories.
The removal of phenolic compounds is based on the application of
dephenolizing units, or activated carbon followed toy biochemical
degradation. The concentration basis for phenolic compounds is 0.1 mg/1
for the Epoxy resin. Phenolic resin and Acrylic product subcategories.
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).
197
-------
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 water flow basis for BATEA is based on overall loading
reductions through the use of the best achievable concentrations and the
waste water flows from the lowest range of waste water flows as reported
by the industry. In product subcategories where the waste water flows
were less than 4 cm/tonne (500 gal/1000 Ib) the flow basis did not
change. in no case was the waste water flow basis less than 50 percent
of the BPCTCA waste water flow basis in any subcategory. 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.
The BATEA guidelines are based on the achievable concentrations for each
parameter for determining the monthly averages and a variability factor
of 2 to determine the daily maximum.
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.
198
-------
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
BEST AVAILABLE DEMONSTRATED TECHNOLOGY
Definition of New Source Performance Standards Best Available
Demonstrated Techno^og^y. (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 as defined in BATEA 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.
T.]3S_.Standards
^ghievable_Fffluent Concentrations
The concentration basis for NSPS-BADT is the same as for BATEA for all
parameters except COD. They are discussed in section X. Tne COD
concentration basis for NSPS-BADT is based on the COD/BOD ratios
expressed in table 38 , section IX (BPCTCA).
In cases where the COD/BOD ratio reduced the concentration basis below
100 mg/liter (BATEA) the basis was established at 100 mg/lirer.
Waste Load Reduction Basis
The waste water flow basis for NSPS-BADT is based on the waste water
flows associated with BATEA, i.e. from the lowest range of reported
waste water flows for each product and process subcategory.
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 th<= plant. One approach that was considered is to require
new sources to meet the lowest value of unit of pollutants/unit of
product documented within an industry subcategory.
Variability
The NSPS-BADT are based on the achievable concentrations for each
parameter for determining the monthly average and a variability factor
of 2 to determine the daily maximum.
The Guidelines
199
-------
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.
200
-------
TABLE NO. 41
BEST PRACTICABLE CONTROL TECHNOLOGY
CURRENTLY AVAILABLE EFFLUENT LIMITATION GUIDELINES
All Units are Kg/kkg (lb/1000 Ib)
BOD
COD
Monthly
Average
.31
.11
.053
.18
.20
.035
.36
.18
.27
.045
8.6
4.9
0.63
0.78
0.78
0.78
1.56
0.66
.58
J.24
5.61
3.71
1.90
4.12
4.12
8.24
0.36
1.22
0.18
.13
2.75
Daily
Maximum
1 .44
.16
.076
.26
.28
.050
.52
.26
.38
.065
13.4
7.6
0.98
1.06
1.06
1.06
2.12
.90
.79
1.69
7.64
5.06
2.58
5.62
5.62
11.24
0.49
1.66
.25
.18
3.75
Polyvinyl 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
Mel amine
Acrylics
Monthly Average: Maximum average of daily values for any period of 30 consecutive
days.
Daily Average: Maximum for any one day.
Monthly
Average
3.1
1.1
.53
1.8
2.0
.35
1.8
1.8
2.7
0.45
86
72.9
6.3
11.7
11.7
11.7
23.4
3.30
2.95
6.25
56 J
37.1
19.0
41.2
41.2
82.4
1.80
6.10
.90
.65
13.8
Daily
Maximum
4.4
1.6
.76
2.6
2.8
.50
2.6
2.6
3.8
.64
134
113
9.8
15.9
15.9
15.9
31.8
4.50
.3.94
8.44
76.4
50.1
26.3
56.2
56.2
112.4
2.45
8.30
1.25
.90
18.8
^
Monthly Daily
Average Maximum
.62
.22
.11
.36
.39
.07
.73
.36
.53
.09
17.3
9.7
0.73
0.33
0.33
0.33
0.66
0.28
.25
.53
2.38
1.58
.80
1.75
1.75
3.50
0.15
0.57
0.077
0.056
0.70
.88
.32
.15
.52
.56
.10
1.0
.52
.76
.12
26.8
15.1
1.05
0.48
0.40
0.48
0.96
.40
.35
.75
3.40
2.25
1.15
2.50
2.50
5.00
.22
.74
.11
.08
1.0
201
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TABLE NO. 42
EFFLUENT GUIDELINES
FOR OTHER ELEMENTS OR COMPOUNDS - BPCTCA
Subcategory
ABS/SAN
POLYSTYRENE
POLYPROPYLENE
HI DENSITY POLYETHYLENE
CELLOPHANE
RAYON
EPOXY RESINS
PHENOLIC RESINS
UREA RESINS
MELAMINE
NYLON 6 & 66
ACRYLICS
Other Element
Or Compound
Iron
Aluminum
Nickel
Total Chromium
Organic N
Iron
Aluminum
NickeJ..
Total Chromium
Vanadium
Titanium
Aluminum
Titanium
Aluminum
Vanadium
Molybdenum
Total Chromium
Dissolved Solids
Zinc
Dissolved Solids
Phenolic Compounds
Phenolic Compounds
Organic N
Nickel
Cobalt
Organic N
Organic N
Organic N
Phenolic Compounds
Kg/kkg (lb/1000 lb prod.)
BPCTCA
Monthly Ave . Daily
Present
Present
Present
.0031
Present
Present
Present
Present
.00027
Present
Present
Present
Present
Present
Present
Present
.0031
Present
.534
Present
.0018
.0062
Present
Present
Present
Present
Present
Present
.0083
Present
Present
Present
.0037
Present
Present
Present
Present
.00033
Present
Present
Present
Present
Present
Present
Present
.0037
Present
.667
Present
.0036
.012
Present
Present
Present
Present
Present
Present
.017
202
-------
TABLE 43
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
EFFLUENT LIMITATION GUIDELINES
BUD
CuD SS
Polyvinyl chloride
Suspension
Emulsion
Bulk
Polyvinyl Acetate
Polystyrene
Suspension
Bulk
Polypropylene
Lo Density Polyethylene
Hi Density Holyethylene
Solvent
Polyform
Cellophane
Rayon
ABS/SAN
Polyester
Resin
Fioer
Resin and Fiber Continuous
Resin and Fiber Batch
Nylon 66
Kesin
Fiber
Resin and Fiber
Nylon 6
Resin and Fiber
Resin
Fiber
Cellulose Acetate
Resin
Fi ber
Resin and Fiber
Epoxy
Phenolics
Urea Resins
Melamine
Acrylics
monthly
Average
u.110
u.040
0.038
0.065
0.070
0.025
0.130
u.065
0.095
0.032
1.8
1.0
O.i3
0.1)60
O.ObO
0.060
0.120
0.05U
0.044
0.094
0.43
0.28
0.15
0.3*
0.32
0.64
0.055
0.090
0.028
0.02U
0.125
Daily
Maximum
0.23
0.080
0.075
U.13
0.14
0.050
0.26
0.13
0.19
0.065
3.6
2.0
0.26
U.lt
0.12
0.12
0.^4
0.10
O.OaS
0.188
0.86
U.56
U.30
0.63
0.63
1.28
0.11
0.18
0.055
0.040
0.25
Monthly
Average
0.75
0.27
0.25
0.42
0.46
0.17
0.88
U.42
0.63
u.22
12.
6.7
0.88
0.40
0.4U
0.40
0.80
0.33
0.29
0.62
2.9
1.9
1.0
2.1
2.1
4.2
0.36
0.62
0.18
0.13
0.83
Daily
Maximum
1.5
0.54
0.50
0.84
0.92
0.34
1.76
0.84
1.26
0.44
24.
13.4
1.76
0.80
0.80
0.8u
1.6U
U.6b
0.5s
1.24
5.8
3.8
2.0
4.2
4.2
8.4
0.72
1.24
0.36
0.26
1.66
Monthly
Average
0.075
0.027
0.025
0.042
0.046
0.017
0.088
0.042
0.063
0.022
1.2
0.67
0.088
u.o^n
0.040
0.040
0.080
0.033
0.029
0.0b2
0.29
0.19
0.10
0.21
0.21
0.42
0.036
0.062
0.018
0.013
0.083
Daily
Maximum
0.15
0.054
0.050
0.084
0.092
0.034
0.18
0.084
0.13
0.044
2.4
1.34
.176
0.08U
0.080
0.080
O.lbO
U.066
0.058
0.124
0.58
0.38
0.20
0.4*
QAt
0.84
0.072
u.12
0.036
0.026
0.17
203
-------
Subcategory
Table 44
STANDARDS OF PERFORMANCE FOR
OTHER ELEMENTS OR COMPOUNDS
Other Element
Or Compound
Kg/Tonne (lb/]000 Ib procT
BATEA
Moiithly Ave . _ Dailv_ Max^
ABS/SAN
POLYSTYRENE
POLYPROPYLENE
HI DENSITY POLYETHYLENE
CELLOPHANE
RAYON
EPOXY RESINS
PHENOLIC RESINS
UREA RESINS
MELAMINE
NYLON 6 & 66
ACRYLICS
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
Phenolic Compounds
Phenolic Compounds
Organic N
Nickel
Cobalt
Organic N
Organic N
Organic N
Phenolic Compounds
PRESENT
PRESENT
PRESENT
.0022
PRESENT
PRESENT
PRESENT
PRESENT
.00]2
PRESENT
PRESENT
PRESENT
PRESENT
PRESENT
PRESENT
PRESENT
.00]6
PRESENT
.0667
PRESENT
.00036
.00062
PRESENT
PRESENT
PRESENT
PRESENT
PRESENT
PRESENT
.00083
4947
PRESENT
PRESENT
.0044
PRESENT
PRESENT
PRESENT
PRESENT
.0024
PRESENT
PRESENT
PRESENT
PRESENT
PRESENT
PRESENT
PRESENT
.0032
PRESENT
.]33
PRESENT
.00072
.00]2
PRESENT
PRESENT
PRESENT
PRESENT
PRESENT
PRESENT
.00]7
204
-------
TABLE NO. 45
BEST AVAILABLE DEMONSTRATED TECHNOLOGY FOR
NEW SOURCE PERFORMANCE STANDARDS
kg/kkg (lb/]000 Ib of production)
Polyvinyl 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
Resin and Fiber
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
Continuous
Batch
BOD
Mpnthly Daily
COD
Monthly Daily
SS
Monthly
Daily
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
] .
].
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
no
040
038
065
070
025
]30
065
095
032
8
0
13
060
060
060
]20
050
044
094
43
28
15
32
32
64
055
090
028
020
125
0
0
0
0
0
0
0
0
0
0
3
2
0
0
0
0
0
0
0
0
0
0
0
0
0
]
0
0
0
0
0
.23
.080
.075
.13
• ]4
.050
.26
.13
-]9
.065
.6
.0
.26
.]2
.]2
.12
.24
• ]0
.088
. ]88
.86
.56
.30
> «>
.63
.63
.28
•]]
• ]8
.055
.040
.25
] • J
.40
.38
.65
.70
.25
.88
.65
.95
.32
18.
] 5 .
1.3
.90
.90
.90
] -8
.33
.29
0.62
4.3
2.8
1.5
3.2
3.2
6.4
.36
.62
.18
. ] 3
.83
2
]
]
]
]
]
36
30
2
]
]
]
3
]
8
5
3
6
6
]2
]
]
.2
.80
.76
.30
.40
.50
.76
.30
.90
.64
•
.
.6
.80
.80
.80
.0
.66
.58
.24
.6
.6
.0
.4
.4
.8
. 72
.24
.36
.26
.66
.075
.027
.025
.042
.046
.0]7
.088
.042
.063
.022
] . 2
.67
.088
.040
.040
.040
.080
.033
.029
.062
.29
. ] 9
.10
.2]
.2]
.42
.036
. 062
.0]8
.0]3
.083
. ] 5
.054
.050
.084
.092
.034
.18
.084
.13
.044
2.4
1.34
.]76
.000
.080
.080
. ]60
.066
.058
.124
.58
.38
.20
.42
.42
.84
.072
.12
.036
.026
.17
205
-------
TABLE 46
BEST AVAILABLE DEMONSTRATED TECHNOLOGY
FOR NEW SOURCE PERFORMANCE STANDARDS
FOR OTHER SOURCES OR COMPOUNDS
Subcategory
ABS/SAN
POLYSTYRENE
POLYPROPYLENE
HI DENSITY POLYETHYLENE
CELLOPHANE
RAYON
EPOXY RESINS
PHENOLIC RESINS
URtA RESINS
MELAMINE
NYLON b & 66
ACRYLICS
Other Element
Or Compound
Iron
Aluminum
Nickel
Total Chromium
Organic N
Iron
Aluminum
Nickel
Total Chromium
Vanadium
iitanium
Aluminum
Titanium
Aluminum
Vanadium
Molybdenum
Total Chromium
Dissolved Solids
Zinc
Dissolved Solids
Pnenolic Compounds
Phenolic Compounds
Organic N
Nickel
Cobalt
Organic N
Organic N
Organic N
Pnenolic Compounds
Kg/Tonne (lb/1000 Ib prod,
BADT
Monthly Ave. Daily Max.
.0022
.0012
.0016
.0667
.00036
.00062
.OU083
--PRESENI--
—PRESENT—
—PRESENT—
.0044
—PRESENT—
—PRESENT—
—PRESENT—
—PRESENT—
.0024
—PRESENT—
—PRESENT—
—PRESENT—
—PRESENT—
—PRtSENT—
—PRESENT—
—PRESENT—
.U032
—PRESENT—
.133
—PRESENT-
.00072
.0012
—PRESENT—
—PRESENT—
--PRESENT--
—PRESENT—
—PRESENT—
—PRESENT—
.0017
206
-------
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 and Terry
Rothermel as the Principal Investigators.
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 suggested organizational,
technical and editorial changes. He was also responsible for making
arrangements for the drafting, presenting, and distribution of the
completed report.
Allen Cywin, Director, Effluent Guidelines Division, Ernst Hall,
Assistant Director, Effluent Guidelines Division and Walter J. Hunt,
Chief Effluent Guidelines Development Branch, offered many helpful
suggestions during the program.
Acknowledgment and appreciation is also given to the secretarial staffs
of both the Effluent Guidelines Division and Arthur D. Little, Inc. for
their effort in the typing of drafts, necessary revisions, and final
preparation of the effluent guidelines document. The following
individuals are acknowledged for their contributions.
Kit Krickenberger - Effluent Guidelines Division Sharon Ashe - Effluent
Guidelines Division Kay Starr - Effluent Guidelines Division Nancy
Zrubek - Effluent Guidelines Division
Appreciation is extended to staff members from EPA's Regions I, II, III,
IV, V, and VI offices for their assistance and cooperation.
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
207
-------
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 & 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
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
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
208
-------
SECTION XIII
REFERENCES
"Advanced Wastewater Treatment as Practiced at South Tahoe," EPA
Water Pollution Control Research Series Report No. 17010 ELP,
Washington, D.C. (August 1971).
"Aerobic Digestion of Organic Waste Sludge," EPA Water Pollution
Control Research Series Report No. 17070 (December 1972) ,
Albright, Lyle F. , "Vinyl Chloride Polymerization by Emulsion,
Bulk and Solution Processes," chemical Engineering, Modern
Chendcal_TechnologY, Part 16 (July 3, 1967) .
"An Act to Amend the Federal Water Pollution Control Act," Public
Law 92-500, Ninety-Second Congress, S. 2770 (October 18, 1972).
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) .
Aston, R.S., "Recovery of Zinc from Viscose Rayon Effluent,"
Presented at Purdue Industrial Waste Conference (May 1968) .
Baloga, J.M., F.B. Hutto, Jr., and E.I. Merrill, "A Solution to
the Phenolic Pollution Problem in Fiberglass Plants: A Progress
g§EOgt^"_Chem^cal_Ejjgineering Progress^SYmEQsium Series A_No._97,
9_6 5 , 12 H (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._o£_Water_2uality_Research_Re2orts, Environmental
Protection Agency, Office of Research and Monitoring, Washington,
D.C. (June 1972) .
10. Black, H.H. , "Planning Industrial Waste Treatment," J. Water
P2lIu£ion_Control_Federation 4.1, 1277-1284 (1969) .
11. Burd, R.S., "A Study of Sludge Handling and Disposal," Federal
Water Pollution Control Administration Publication WP 20-U,
Washington, D.C. (1968) .
209
-------
12. "Can Plants Meet EPA's New Effluent Guidelines?11, Chemical Week,
pp. 59-60 (November 22, 1972).
13. Chemical Engineer ing FlQw sheets. Prepared by the editors of
Chemical and Metallurgical Engineering, McGraw-Hill, New York
(1940) .
14. "Chemical Bugs Tame Process Wastes , "^Eny . Sci. Technol. 4
637-638 (1970) .
15. Clarke, James S. , "New Pules Prevent Tank Failures," Hydrocarbon
Processing; 50(5), 92-94 (1971).
16. "Construction Scoreboard," Engineering News-Record 190(3) , 32
(1973).
17. Contract for Development of Data and Recommendations for Indus-
trial 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 'Treat-
ability of Wastewater from Organic Chemical and Plastics Manu-
facturing - 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) .
2 0 . Cost and Performance, Estimates, for Tertiary Wastewater Treatment
Purp_oses7 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. Culp, Gordon L. and Robert W. Gulp, Ady an ce d Wastewater ^Treatment ,
Van Nostrand Reinhold Company, New York, N.Y. (1971) .
23. Davis, Ernest M. , "BOD vs. COD vs. TOC vs. TOD, "_Water and^Wastes
IHaili§§£ill3 • 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 fl._.. Water
lieat-^J^ 11, 320-321 and 323-334 (1971) .
210
-------
25. Eisenhauer, H.R., "The Organization of Phenolic Wastes," J^
Pollution Control Federation ^0, 1887-1899 (1968).
26. "Environmental Protection Agency ±40 CFR Part 1331 Secondary
Treatment Information, Notice of Proposed Pulemaking," Federal
Register 3_8(82), 10642-10643 (April 30, 1973).
27. Environmental Protection Agency, Toxic and Hazardous Chemicals
Designations, Report in progress.
28. Faith, W.L., Donald B. Keys, and Ronald L. Clark, Industrial
ChSffiicals• Third Ed., John Wiley and Sons, Inc., New York, N.Y.,
(1965) .
29. gederal_Water Pollution Control Act Amendments of 1972, House of
Representatives, Report No. 92-1465, U.S. Government Printing
Office, Washington, B.C. (September 28, 1972).
30. Ford, D.L., "Application of Total Carbon Analyzer for Industrial
Wastewater Evaluation," Proc. of Twenty-Third Industrial Waste
ConfiJL_Part_Two, Purdue University, Lafayette, Indiana, pp. 989-99
(May 1968).
31. Ford, D.L., "The Applicability of Carbon Adsorption in the Treat-
ment 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
Che mi ca l_Engin eer i.ng, Van Nostrand Peinhold Company, New York,
34. Gonzales, John G. and Russell L. Culp, "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?", Waterrand Wastes
lD2iD.eg.EiH2» PP- 32-33 (April 1972) .
38. Kwie, William W., "Ozone Treats Wastestreams from Polymer Plant,"
Water_and_Sewage_Works 116, 74 (1969) .
211
-------
39. Lamb, A. and E.L. Tollefson, "Toxic Effects of Cupric, Chromare
and Chromic Ions on Biological Oxidation," Water_Re search 7,
599-613 (1973) .
40. Lash, L.D. and G.L. Shell, "Treating Polymer Wastes," Chemical
£5(6), 63-69 (1969).
41. Lawson, Cyron T. and John A. Fisher, "Limitations of Activated
Carbon Adsorption for Upgrading Petrochemical 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 Symposium
§§li§§i._Noi_97i_Water_I^196j9 65, 191 (1969).
43. Matthews, George, et. al.. Vinyl and Allied Polymers, Chemical
Rubber Co. Press, Cleveland, Ohio, pp. 13-40 (1972) .
44. McDermott, G.N., "Industrial Spill Control and Pollution Incident
Prevention," Ji_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 Engineer in g^ pp. 67068 (March 1971) .
47. Patterson, J. W. and R. A. Minear, Was_tewater Treatment Tech-
nolocjyx. Second Edition, pp. 216-162, State of Illinois Insti-
tute 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. , "Biodegradability and Treatability of Combined
Nylon and Municipal Wastes," J^. Water Pollution Control Feder-
ation il^ 100-105 (1970).
50. "Pretreatment Guidelines for the Discharge of Industrial Wastes
to Municipal Treatment Works, Draft report prepared by Roy F.
Weston, 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
212
-------
Plastic Materials and Synthetics Industries," Unpublished re-
port of the Environmental Protection Agency and the Manufacturing
Chemists Association, Washington, D.C, (November 1972).
52. Process 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. Eolten, "From Problem to
Solution with ABS Polymer Wastewater," Presented at 17th Ontario
Industrial Waste Conference, Niagara Falls, Ontario (June 7-10,
1970) .
54. Santoleri, J. J. "Chlorinated Hydrocarbon Waste Disposal and
Recovery Systems," Chemical 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 99.0-99.2fc
Phenols," Chemical Proces_sinc[ (May 1973).
57. sittig, Marshall, Organic Chemical Process Encycolpedia^ second
Ed., Noyes Development Corporation, Park Ridge, N.J. (1969).
58. Smith, W. Mayo, Fd., Manufacture of Plastics^ Vol. 1, Reinhold
Publishing Corp., Park Ridge, N.J. (1964).
59. SteinmPtz, C. E. and William J. Day, "Treatment of Waste from
Polyester Manufacturing Operations," Chemical Engineering Pro-
2I§§§ §Yffi22sium_Series,_No-._ 97L Water - 1969 65X 188 (1969) .
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," Enyir.
Sgii Technol^ 3X 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,
213
-------
"Viscose Waste-Profile of a Successful Pollution Control Program,"
Water Sewage Works 115X 44-450 (1968) .
65. "Zinc Precipitation and Recovery from Viscose Rayon Wasterwaters,"
EPA Water Pollution Control Research Series, Report 12090 ESG
(January 1971) .
66. Bess, F.C., J.C. Hovious, R.A. Conway and E.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.
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
No. 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, P. 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, P. F., Editor, "Anaerobic Biological Treatment Processes",
American Chemical Society, Advances in Chemistry Series No. 105,
February 1970.
214
-------
SECTION XIV
GLOSSARY
Acetyl
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.
A general term for monovalent aliphatic hydrocarbons.
Alumina
The oxide of aluminum.
Anaerobic
Living or active in -»-he absence of free oxygen.
Ary.1
A general term denoting the presence of unsaturated ring structures in
•"-he molecular structure of hydrocarbons.
Autoclave
An p-nclosed vessel where various conditions of temperature and pressure
can be controlled.
Bacteriostate
An aqent 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
P*ethods_, 19th Edition, Water Pollution Control Federation, or
215
-------
EPA's Manual 16020-07/71, Methods for Chemical Analysis of Water and
Wastes^
Catalyst
A substance which initiates primary polymerization or increases the rate
of cure or crosslinking when added in quantities which are minor as
compared with the amount of primary reactants.
Soda
A name for sodium hydroxide.
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."
Qh§i2 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 BOD5.
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.
Di_atomaceous Earth
A naturally-occurring material containing the skeletal structures of
diatoms - often used as an aid to filtration.
216
-------
Double-EfJect 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.
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.
F_a£u!t§£iy.§. Lagoon or Pond
A combination of aerobic surface and anaerobic bottom existing in a
basin holding biologically-active wastewaters.
Fatty. Aci^ds
An organic acid obtained by the hydrolysis (saponif icatior.) 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-deptn media.
Formalin
A solution of formaldehyde in water.
GPD
Gallons per day.
GPM
Gallons per minute.
Halogen
The chemical group containing chlorine, fluorine, bromine, iodine.
217
-------
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
Thousands (e.g., thousands metric tons).
MM
Millions (e.g., million pounds).
Monomer
A relatively simple compound which can react to form a polymer.
ES
A measure of the relative acidity or alkalinity of water on a scale of
0-1U. 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 .
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.
Pre treatment
Treatment of wastewaters prior to discharge to a publicly-owned waste-
water treatment plant.
218
-------
First stage in sequential treatment of wastewaters - essentially limited
to removal of readily-settlable solids.
Ref lux
Condensation of a vapor and return of the liquid to the zone from which
it was removed.
Pesi.n
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.
Scrubber
Equipment for removing condensable vapors and particulates from gas
streams by contacting with water or other liquid.
Treatment
Removal of biologically-active soluble substances by the growth of
micro-organisms .
Solid particles dispersed in a liquid medium.
Spinnerettg
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.
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.
219
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Tow
A large number of continuous filaments of long length. Tow is the usual
form of fibers after spinning and stretching and prior to being chopped
into short lengths of staple.
Vacuum
A. condition where the pressure is less than atmospheric.
220
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TABLE 20
METRIC UNITS
CONVERSION TABLE
MULTIPLY (ENGLISH UNITS) by TO OBTAIN (METRIC UNITS)
ENGLISH UNIT ABBREVIATION CONVERSION ABBREVIATION METRIC UNIT
acre ac
acre - feet ac ft
British Thermal
Unit BTU
British Thermal
Unit/pound BTU/lb
cubic feet/minute cfm
cubic feet/second cfs
cubic feet cu ft
cubic feet cu ft
cubic inches cu in
degree Fahrenheit F°
feet ft
gallon gal
gallon/minute gpm
horsepower hp
inches in
inches of mercury in Hg
pounds lb
million gallons/day mgd
mile mi
pound/square
inch (gauge) psig
square feet sq ft
square inches sq in
tons (short) t
yard y
0.405
1233.5
0.252
0.555
0.028
1.7
0.028
28.32
16.39
0.555(°F-32)*
0.3048
3.785
0.0631
0.7457
2.54
0.03342
0.454
3,785
1.609
(0.06805 psig -KL)*
0.0929
6.452
0.907
0.9144
ha hectares
cu m cubic meters
kg cal kilogram - calories
kg cal/kg kilogram calories/kilogram
cu m/min cubic meters/minute
cu m/min cubic meters/minute
cu m cubic meters
1 liters
cu cm cubic centimeters
°C degree Centigrade
m meters
1 liters
I/sec liters/second
kw killowatts
cm centimeters
atm atmospheres
kg kilograms
cu m/day cubic meters/day
km kilometer
atm atmospheres (absolute)
sq m square meters
sq cm square centimeters
kkg metric tons (1000 kilograms)
m meters
Actual conversion, not a multiplier
221
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