EPA 440/1-74/036
       Development Document for
 Proposed Effluent Limitations Guidelines
 and New Source Performance Standards
                 for the
         SYNTHETIC POLYMERS
             Segment of the
     PLASTICS AND SYNTHETIC
   MATERIALS MANUFACTURING
         Point Source Category

                 %
 UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
               SEPTEMBER 1974

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                  DEVELOPMENT DOCUMENT

                           for

        PROPOSED EFFLUENT LIMITATIONS GUIDELINES

                           and

            NEW SOURCE PERFORMANCE STANDARDS

                         for the
            SYNTHETIC POLYMER SEGMENT OF THE
     PLASTICS AND SYNTHETIC MATERIALS MANUFACTURING
                  POINT SOURCE CATEGORY
                    Russell E. Train
                      Administrator
                      James L. Agee
Assistant Administrator for Water and Hazardous Materials
                             «*v
                       Allen Cywin
         Director, Effluent Guidelines  Division
                     David L. Becker
                     Project Officer
                     September,  1974
              Effluent Guidelines Division
         Office of Water and Hazardous Materials
          U.S. Environmental Protection Agency
                 Washington, D.C.   20460
                                               60604

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                            ABSTRACT


This development document presents the findings of  an  extensive
study  of  the  synthetic  polymers  segment  of the plastics and
synthetics industry  for  the  purposes  of  developing  effluent
limitations  guidelines,  and  standards  of  performance for the
industry to implement Sections 304, 306, and 307 of  the  Federal
Water  Pollution Control Act of 1972 (PL 92-500).  Guidelines and
standards were developed for the following major products:

    Ethylene-Vinyl Acetate Copolymers
    Fluorocarbons
    Polypropylene Fiber
    Alkyds and Unsaturated Polyester Resins
    Cellulose Nitrate
    Polyamides (Nylon 6/12)
    Polyester Resins (thermoplastic)
    Silicones
    Multi-Product Plants
    Fluid-Product Plants

Effluent limitations guidelines contained herein  set  forth  the
degree of reduction of pollutants in effluents that is attainable
through  the  application  of best practicable control technology
currently  available  (BPCTCA) ,  and  the  degre;e  of   reduction
attainable  through  the application of best available technology
economically achievable (BATEA)  by  existing  point  sources  for
July  1,  1977,  and  July  1,   1983, respectively.  Standards of
performance for new sources are based on the application of  best
available demonstrated technology (BADT).

Annual  costs  for  this  segment  of the plastics and synthetics
industry for achieving BPCTCA control by 1977  are  estimated  at
$5,000,000,  and  costs  for  attaining BATEA control by 1983 are
estimated at $12,000,000.    The  annual  cost  of  BADT  for  new
sources in 1977 is estimated at $3,300,000.

Supporting  data  and  rationale  for the development of proposed
effluent limitations guidelines and standards of  performance  are
contained in this development document.
                            11

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                        TABLE OF CONTENTS


SECTION                                             PAGE

   I     CONCLUSIONS                                 1

  II     RECOMMENDATIONS                             3

 III     INTRODUCTION                               13

           PURPOSE AND AUTHORITY                    13
           METHODOLOGY                              14
           GENERAL DESCRIPTION OF THE INDUSTRY      15
           PRODUCT AND PROCESS TECHNOLOGY           23
             Acrylic Resins                         25
             Alkyd Molding Compounds                32
             Cellulose Derivatives                  33
             Cellulose Nitrate                      36
             Chlorinated Polyethylene               39
             Diallyl Phthalate Resins               42
             Ethylene-Vinyl Acetate Copolymers      44
             Fluorocarbon Polymers                  47
             Nitrile Barrier Resins                 54
             Parylene Polymers                      58
             Poly-Alpha-Methyl Styrene              62
             Polyamides                             64
             Polyaryl Ether (Arylcn)                 65
             Polybenzimidozoles                     69
             Polybenzotheazoles                     74
             Polybutene                             77
             Polycarbonates                         81
             Polyester Resins  (Thermoplastic)        86
             Polyester Resins  (Unsaturated)          89
             Polyimides                             94
             Polymethyl Pentene                     98
             Polyphenylene Sulfide                 100
             Polypropylene Fibers                  104
             Polysulfone Resins                    109
             Polyvinyl Butyral                     114
             Polyvinyl Carbazole                   118
             Polyvinyl Ethers                       120
             Polyvinylidene Chlorides              125
             Polyvinyl Pyrolidone                  127
             Silicones                             130
             Spandex Fibers                        136
             Urethane Prepolymers                  142

  IV     INDUSTRY CATEGORIZATION                   145

   V     WASTE CHARACTERIZATION                    149

           RAW WASTE LOADS                         149

  VI     SELECTION OF POLLUTANT PARAMETERS         155
                            ill

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           SELECTED  PARAMETERS                     155
           OTHER  POLLUTANT  PARAMETERS              158

 VII     CONTROL  AND TREATMENT TECHNOLOGY          165

           PRESENTLY USED WASTE WATER TREATMENT
           TECHNOLOGY                              166

VIII     COST, ENERGY,  AND  NONWATER QUALITY
         ASPECTS                                    177

           COST MODELS  OF TREATMENT TECHNOLOGIES   178
           COST EFFECTIVENESS PERSPECTIVES         178
           ANNUAL COST  PERSPECTIVES                178
           COST PER  UNIT PERSPECTIVES              179
           WASTE  WATER  TREATMENT COST ESTIMATES    179
           INDUSTRIAL WASTE TREATMENT MODEL DATA   179
           ENERGY COST  PERSPECTIVES                180
           NON-WATER QUALITY EFFECTS               180
           ALTERNATIVE  TREATMENT TECHNOLOGIES      181
                            IV

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                    TABLE OF CONTENTS  (CONT'D)

SECTION                                               PAGE

   IX   CURRENTLY  AVAILABLE GUIDELINES AND
        LIMITATIONS                                   219

          DEFINITION  OF BEST PRACTICABLE CONTROL
          TECHNOLOGY  CURRENTLY AVAILABLE  (BPCTCA)     219
          THE GUIDELINES                              220
          ATTAINABLE  EFFLUENT CONCENTRATIONS          220
          DEMONSTRATED WASTE WATER FLOWS              225
          STATISTICAL VARIABILITY OF A WELL-
          DESIGNED AND OPERATED WASTE WATER
          TREATMENT PLANT                             225

    X   BEST AVAILABLE TECHNOLOGY ECONOMICALLY
        ACHIEVABLE                                    233

          DEFINITION  OF BEST AVAILABLE TECHNOLOGY
          ECONOMICALLY ACHIEVABLE  (BATEA)             233
          THE GUIDELINES - ACHIEVABLE EFFLUENT
          CONCENTRATIONS                              234
          SUSPENDED SOLIDS                            234
          OXYGEN-DEMANDING SUBSTANCES                 234
          WASTE LOAD  REDUCTION BASIS                  236
          VARIABILITY                                 238

   XI   NEW SOURCE PERFORMANCE STANDARDS - BEST
        AVAILABLE  DEMONSTRATED TECHNOLOGY             243

          DEFINITION  OF NEW SOURCE PERFORMANCE
          STANDARDS - BEST AVAILABLE DEMONSTRATED
          TECHNOLOGY  (NSPS-BADT)                       243
          THE STANDARDS                               243
          ACHIEVABLE  EFFLUENT CONCENTRATION           243
          WASTE LOAD  REDUCTION BASIS                  243
          VARIABILITY                                 243
          ALKYDS AND  UNSATURATED POLYESTERS           245
                            V

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                    TABLE OF CONTENTS  (CONT«D)







SECTION                                               PAGE







  XII    ACKNOWLEDGMENTS                             249




 XIII    REFERENCES                                  251




  XIV    GICSSARY                                     255
                           VI

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                         LIST OF FIGURES
Figure No.                                         Page

 III-l   Typical Reactions tc Form Poly(Methyl
         Methacrylate)  - Including Monomer
         Manufacture                                26

 III-2   Acrylic Resin Production - Eulk Poly-
         merization Process                         27

 III-3   Acrylic Resin Production - Emulsion
         Polymerization Process                     29

 III-a   Acrylic Resin Production - Suspension
         Polymerization Process                     30

 III-5   Typical Reactions to Form Cellulose
         Derivatives                                34

 III-6   Cellulose Ethers Production                35

 III-7   Typical Reaction to Form Cellulose
         Nitrate                                    37

 III-8   Cellulose Nitrate Production               38

 III-9   Typical Reaction to Form Chlorinated
         Polyethylene                               40

 111-10   Chlorinated Polyethylene Production        41

 IH-11   Typical Reactions to Form Diallyl
         Phthalate                                  43

 111-12   Ethylene-Vinyl  Acetate  Copolymer
         Production                                 45

 HI-13   Polytetraf luoroethylene (PTFE) Pro-
         duction - TFE Monomer Process               49

 111-14   Typical Reactions  to Form Fluorocarbon
         Polymers                                   50

 111-15   Polytetrafluoroethylene (PTFE) Pro-
         duction -  PTFE  Polymer  Process              51

 111-16   Nitrile Barrier  Resin Production -
         Emulsion Polymerization Process             57
                         Vll

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                    LIST OF FIGURES (CONT'D)
Figure No.                                           Page

111-17    Typical Reactions -to Form Parylene
          Polymers                                    59

111-18    Parylene Production                         61

111-19    Typical Reaction to Form Alpha-Methyl
          Styrene                                     63

111-20    Typical Reactions to Form Folyaryl Ether    66

111-21    Typical Reactions to Form Polybenzimi-
          dazoles                                     70

111-22    Typical Reactions to Form Polybenzo-
          thiazoles                                   75

III-23    Typical Structures Produced in the
          Synthesis of Polybenzothiazoles             76

111-24    Typical Reaction to Form Polybutene         78

111-25    Polybutene Production - Huels Process       79

111-22    Typical Reaction to Form Polycarbonate      86

111-27    Polycarbonate Production - Semi-
          continuous Process                          84

111-28    Thermoplastic -Polyester Resin Production    88

I11-29    Typical Reaction and Raw Materials Used
          to Form Unsaturated Polyester Resins        90

111-30    Typical Reactions to Form Polyimides        95

111-31    Typical Reactions to Form Polymethyl
          Pentene                                     99

111-32    Typical Reaction to Form Polyphenylene
          Sulfide                                    101

111-33    Polyphenylene Sulfide Production           103
                         Vlll

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                    LIST OF FIGURES  (CONT • D)

 Figure No.                                          Page

 111-34   Polypropylene  Fiber Production               105

 111-35   Polypropylene  Monofilament Production        106

 111-36   Typical Reactions to Form Polysulfone
         Resins                                       110

 111-37   Polysulfone Resins Production                112

 111-38   Typical Reaction to Form Polyvinyl
         Butyral                                      115

 111-39   Polyvinyl Butyral Production - DuPont,
         Inc. Process                                 116

 111-40   Polyvinyl Butyral Production Monsanto,
         Inc. Process                                 117

 111-41   Typical Reaction to Form Polyvinyl
         Carbazole                                    119

 111-42   Typical Reactions to Form Polyvinyl
         Ethers - Including Monomer Manufacture       121

 111-43   Polyvinyl Ether Production - Solution
         Polymerization Process                       122

 111-44   Polyvinyl Ether Production - Bulk Poly-
         merization Process                           123

 111-45   Typical Reaction to Form Polyvinylidene
         Chloride                                     126

 111-46   Typical Reactions to Form Polyvinyl
         Pyrrolidone                                  128

111-47   Production of Silane Monomers,  Oligomers,
         and Dimethyl Silicone Fluid                  131

111-48   Production of Silicone Fluids,  Greases,
         Compounds Emulsions,  Resins,  and Rubber      132

111-43   Typical Reactions to Form Silicones          139
                       IX

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                    LIST OF FIGURES (CONT'D)


Figure No.                                          Page

111-50   Typical Reactions to Form Spandex Fibers    137

111-51   Spandex Fiber Production - Dry Spinning
         Process                                     138

III-52   Spandex Fiber Production - Wet Spinning
         Process                                     139

111-53   Spandex Fiber Production - Reaction
         Spinning Process                            141

111-54   Typical Reactions to Form Urethane Pre-
         polymers                                    143

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                         LIST OF TABLES
TABLE NUMBER                                         PAGE

  II-l    Best. Practicable Control Technology
          Currently Available Effluent Limitations
          Guidelines                                   6

  II-2    Best Practicable Control Technology
          Currently Available Effluent Limitations
          Guidelines (Other Elements and Compounds)    7

  II-3    Best Available Technology Economically
          Achievable Effluent Limitations Guidelines   8

  II-4    Best Available Technology Economically
          Achievable Efflument Limitations Guide-
          lines (Other Elements and Compounds)          9

  11*5    Best Available Demonstrated Technology -
          New Source Performance Standards            10

  II-6    Best Available Demonstrated Technology -
          New Source Performance Standards (Other
          Elements and Compounds)                      11

 III-l    Plastics and Synthetics Fcr Consideration   17

 III-2    Products to be Considered for Development
          of Effluent Guideline Limitations           20

 III-3    Products Eliminated from Consideration for
          Establishment of Effluent Guideline
          Limitations                                 22

 III-4    Manufacturers of Products to be Considered
          for Development of Effluent Limitations
          Guidelines                                  24

 III-5    Commercial Fluorocarbon Polymers            53

 III-6    Properties of Polyaryl Ethers               67

 III-7    Acids Whose Derivatives are Used in
          Polybenzimidazole Synthesis                 71

  IV-1    Industry Subcategorization                 147
                        XI

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                     LIST OF TABLES  (CONT'D)
TABLE NUMBER                                         PAGE

  V-l     Waste Water Loading for Synthetic Polymers
          Production                                  150

  V-2     Synthetic Polymers Production Raw Waste
          Loads                                       151

  V-3     Other Elements, Compounds, and Parameters   153

 VI-1     ether Elements and Compounds Specific to
          the Resins Segment of Plastics and
          Synthetic Industry                          164

VII-1     Operational Parameters of Waste Water
          Treatment Plants  (Metric Units)           167-168

VII-2     Operational Parameters of Waste Water
          Treatment Plants  (English Units)           169-170

VII-3     Performance of Observed Waste Water
          Treatment Plants                            171

VII-4     Observed Treatment and Average Effluent
          Loadings from Plant Inspections             172

VIII-1     Perspectives on the Production of Syn-
           thetic Polymers - Water Usage              182

VIII-2     Perspectives on Synthetic Polymers
           Production - Annual Treatment Costs        183

VIII-3     Perspectives on Synthetic Polymers
           Production - Cost Impact                   184

VIII-4     Summary of Water Effluent Treatment
           Costs - Cost Per Unit Volume Basis         185

VIII-4/1   Water Effluent Treatment Costs:  Ethylene
           Vinyl Acetate  (Small Plant - Large
           Industrial Complex)                        186

VIII-4/2   Water Effluent Treatment Costs:   Ethylene
           Vinyl Acetate  (Large Plant - Industrial
           Complex)                                   187
                        Xll

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                    LIST OF TABLES  (CONT'D)
TABLE NUMBER                                          PAGE

 VIII-4/3    Water Effluent Treatment Costs:
             Fluorocarbons  (Small Plant - Free
             Standing)                                 188

 VIII-4/4    Water Effluent Treatment Costs:
             Fluorocarbons  (Small Plant - Municipal
             Discharge)                                189

 VIII-4/5    WETC:  Fluorocarbons (Large Plant -
             Free Standing)                            190

 VIII-U/6    WETC:  Fluorocarbons (Large Plant -
             Municipal Discharge)                      191

 VIII-4/7    WETC:  Polypropylene Fibers (Free
             Standing Treatment Plant)                  192

 VIII-U/8    WETC:  Polypropylene Fibers (Municipal
             Discharge)                                193

 VTII-4/9    WETC:  Polyvinylidene Chloride (Small
             Plant - Industrial Complex)                194

 VIII-4/10   WETC:  Polyvinylidene Chloride (Large
             Plant - Industrial Complex)                195

 VIII-4/11   WETC:  Acrylic Resins (Small Plant -
             Industrial Complex)                        196

 VIII-4/12   WETC:  Acrylic Resins (Large Plant -
             Industrial Complex)                        197

 VIII-4/13   WETC:  Cellulose Derivatives (Small
             Plant - Industrial Complex)                198

 VIII-4/14   WETC:  Cellulose Derivatives (Large
             Plant - Industrial Complex)                199

 VIII-4/15   WETC:  Alkyds and Unsaturated  Polyester
             Resins (Large Plant  - Once-Through
             Scrubber - Free Standing)                  200

 VIII-4/16   WETC:  Alkyds and Unsaturated  Polyester
             Resins (Small Plant  - Recirculating
             Scrubber - Municipal Discharge)            201
                      Xlll

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                     LIST OF TABLES  (CONT ' D)
TABLE NUMBER                                           PAGE

 VIII-4/17    WETC:  Alkyds and Unsaturated Polyester
              Resins (Large Plant - Recirculating
              Scrubber - Free Standing)                 202

 VIII-4/18    WETC:  Alkyds and Unsaturated Polyester
              Resins (Large Plant - Recirculating
              Scrubber - Municipal Discharge)           203

 VIII-4/19    WETC:  Cellulose Nitrate  (Plant in
              Industrial Complex)                       204

 VIII-4/20    WETC:  Cellulose Nitrate  (Plant with
              Municipal Discharge)                      205

 VIII-4/21    WETC:  Polyamides  (Nylon 6/12) Pro-
              duction in a Complex                      206

 VIII-4/22    WETC:  Thermoplastic Polyester Resins
              (Large Plant - Industrial Complex)        207

 VIII-4/23    WETC:  Polyvinyl Butyral  (Free Standing
              Treatment Plant)                           208

 VIII-4/24    WETC:  Polyvinyl Ether  (Plant in
              Industrial Complex)                       209

 VIII-4/25    WETC:  Silicones (Fluids Only - Free
              Standing)                                  210

 VIII-4/26    WETC:  Silicones (Fluids Only - Indus-
              trial Complex)                            211

 VIII-4/27    WETC:  Silicones (Multi-product -
              Free Standing)                            212

 VIII-4/28    WETC:  Silicones (Multi-product -
              Industrial Complex)                       213

 VIII-4/29    WETC:  Nitrile Barrier Resins  (Plant
              in Industrial Complex)                    214

 VIII-4/30    WETC:  Spandex Fibers  (Plant in
              Industrial Complex)                       215
                       xiv

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                     LIST OF TABLES (CONT'D)
TABLE NUMBER                                          PAGE

 VIII-5/1    Industrial Waste Treatment Model Data
             Synthetic Polymers Production             216

 VIII-5/2    Industrial Waste Treatment Model Data
             Synthetic Polymers Production             217

 VIII-5/3    Industrial Waste Treatment Model Data
             Synthetic Polymers Production             218

   IX-1      COD/EOD5 Ratios                           222

   IX-2      COD/BOD5 Ratios Corresponding to
             Individual Products                       223

   IX-3      Demonstrated Waste Water Flows            226

   IX-4      Variability Factors for BOD5              228

   IX-5      Best Practicable Control Technology
             Currently Available Effluent Limita-
             tions Guidelines                        229-230

   IX-6      Best Practicable Control Technology
             Currently Available Effluent Limita-
             tions Guidelines                          231

    X-1      BATEA Waste Water Flow Rates              237

    X-2      Variability Factors EATEA                 238

    X-3      Best Available Technology Economically
             Achievable Effluent Limitations Guide-
             lines                                   239-240

    X-4      Best Available Technology Economically
             Achievable Effluent Limitations
             Guidelines (Other Elements and Compounds)  241

   XI-1      Lowest Demonstrated Waste Water Flows     246

   XI-2      Best Available Demonstrated Technology
             New Source Performance Standards          248

   XI-3      Best Available Technology Economically
             Achievable Effluent Limitations
             Guidelines                                249

  XIV-1      Metric Units Conversion Table             267
                      xv

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                            SECTION I

                           CONCLUSIONS
In   this  segment  of  the  plastics  and  synthetics  industry,
approximately 160 company  operations  are  responsible  for  the
manufacture  of  products  which  have  been grouped into fifteen
product  subcategories.   Annual  production  for   the   fifteen
products  was  estimated  to be 1.2 million kkg (2.6 billion Ibs)
per year or about one-tenth of the volume of the eighteen larger-
volume  resins  surveyed  earlier.   The  volume   of   effluents
currently discharged was estimated to be 90 thousand cu m/day (24
MGD).   Water usage (at current hydraulic loads) was projected to
increase at 10 percent per year through  1977,  while  production
was projected to increase at 14 percent in the same period.

For  the  purpose  of setting effluent limitations guidelines and
standards of performance, the industry parameters giving the most
effective  categorization  were   found   to   be   waste   water
characteristics,  specifically, raw waste load, with a BOD5 value
of more than or less than 10 kg/kkg of  product  separating  high
and   low   waste   load   subcategories;   and  attainable  BOD5
concentrations as demonstrated by plastics and synthetics  plants
using  technologies  which  are  defined  herein as the basis for
BPCTCA.  Three  groupings  were  defined  with  average  effluent
concentrations   under   20   mg/liter   (low   attainable   BOD5
concentration),  from 30 to 75 mg/liter  (medium  attainable  BOD5
concentration),   and  over  75  mg/liter  (high  attainable  BOD5
concentration.

Based on these  two  dimensions  of  categorization,  four  major
subcategories were defined.


    Major Subcategory I - low waste load, low attainable
    BOD5_ concentration (4 products:  ethylene vinyl
    acetate,  fluorocarbons, polypropylene fiber, and
    polyvinylidene chloride).

    Major Subcategory II  - high waste load,  low
    attainable BOD5 concentration (2 products:
    acrylic resins and cellulose derivatives).

    Major Subcategory III - high or low waste load,
    medium attainable BOD5 concentration (7  products:
    alkyd and unsaturated polyester resins,  cellulose
    nitrate,  polyamides,  saturated thermoplastic
    polyesters,  polyvinyl butyral, polyvinyl ethers,
    and silicones).

    Major Sufccategory IV  - high or low waste load,
    high attainable BOD5  concentration (2 products:
    nitrile barrier resins and spandex fibers).

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Additional   subcategorization   within   the  above  four  major
subcategories was  necessary  to  account  for  the  waste  water
generation  which  is  specific  to individual products and their
various processing methods.  The separation  of  each  individual
product into separate subcategories simplifies the application of
the  effluent limitations guidelines and standards of performance
by providing a clearly defined context  for  application  of  the
numerical  values.   The  advantages  of  this double-layered (by
waste characteristics and by-product)  subcategorization appear to
outweigh the advantages that  might  be  connected  with  product
group characterization alone.

Annual  costs  of  treatment for the synthetic polymer segment of
the plastics and  synthetics  industry  were  estimated  at  $1.8
million.   By  1977,  under  BPCTCA  guidelines and assuming full
payment of user charges by this industry for municipal treatment,
it was estimated that the  synthetic  polymers  industry  segment
should  expect  annual  costs of $5.0 million - an increase of 23
percent per year.  By  1983,  under  BATEA  guidelines,  existing
plants  would  be expected to have annual pollution control costs
of $12.0 million - an increase of 20  percent  per  year  between
1977  and  1983.   By 1977, under BADT-NSPS and projected product
growth, the annual costs for new plants  are  estimated  at  $3.3
million.   The  estimated  average  cost  of  treatment  over the
industry  for   BPCTCA,   BATEA,   and   BADT-NSPS   technologies
respectively  was:   $0.16   ($0.63),  $0.40  ($1.52),  and  $0.17
($0.66)  per cubic meter (per thousand gallons).

The average range of water pollution control costs  under  BPCTCA
was  estimated  at 0.3 to 1.3 percent of current sailes price.  On
average, the range of costs for applying EATEA to existing plants
was 0.6 to 3.3 percent of sales price.  The cost of BADT-NSPS was
estimated at 0.5 percent of sales price over the fifteen  product
groups.

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                           SECTION II

                         RECOMMENDATIONS
BODJ5,  COD,  and total suspended solids and pH are recommended as
the critical parameters requiring effluent limitations guidelines
and standards.  Guidelines  and  standards  for  total  suspended
solids,   pH,   and   fluorides  only  are  recommended  for  the
fluorocarbons subcategory  since  the  fluorocarbons  subcategory
wastes  are  similar  to  those  seen  in the inorganic chemicals
industry and contain only minimal BCD5 and COD in the raw  waste.
Other  pollutant parameters are specific to product subcategories
as indicated in the following list.  Some of these pollutants are
identified as being of potential concern,  and  others  as  being
ones  for which effluent limitations guidelines and standards are
recommended.
                                               Guidelines
                                              Recommended
Alkyd compounds and
unsaturated polyester
resins

Fluorocarbons

Spandex fibers
Acrylic resins

Polypropylene fibers


Nitrile barrier resins


Polyamides

Cellulose derivatives

Cellulose nitrate

Silicones
                          x

                          x
 Pollutant
Parameters

lead
cobalt
fluorides

cyanides
oils and grease
organic nitrogen

oils and grease

oils and grease
phosphates

organic nitrogen
cyanides

organic nitrogen

inorganic nitrogen

inorganic nitrogen
polychlorinated organics
copper                    x
fluorides
Polyvinylidene chloride  polychlorinated organics
Polyester resins
(thermoplastic)
cobalt
manganese
cadmium

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 Effluent limitations guidelines and standards of performance  are
 proposed   for   those  parameters  noted above as based on analogy
 with  other  industries,  since  there  was   insufficient   data
 available  to   determine  the magnitude of the raw waste loads or
 their concentration in treated waste  waters.   However  in  most
 cases  where  metals  are used, the combination of neutralization
 and biological  waste water treatment is  expected  to  reduce  or
 remove   them   to   low  concentrations  which  are  within  the
 recommended guidelines.  In the case of  mercury,  cyanides,  and
 cadmium  the  standards  for toxic and hazardous chemicals should
 apply.

 Best practicable control technology currently available  (BPCTCA)
 for existing point sources is based on the application of end-of-
 pipe  technology  at  the  production  site or the utilization of
 municipal  sewage  treatment  by  facilities   with   appropriate
 pretreatment methods.  End-of-pipe technologies are considered to
 be  based  on   biological  treatment  systems for BODS reductions
 (typified  by the activated  sludge  process,  trickling  filters,
 aerated  lagoons, aerobic - anaerobic lagoons, and so on).  These
 biological systems are presumed tc  be  preceded  by  appropriate
 treatment  such  as equalization basins to dampen shock loadings,
 settling,  clarification and chemical  treatment  for  removal  of
 solids  and  adjustment  of  pH, and subsequent treatment such as
 clarification or polishing ponds for additional removal  of  BOD5
 and suspended solids.  Also, in-plant application of technologies
 and  operational  methods  which may be helpful in meeting BPCTCA
 standards  include segregation of  process  contact  waste  waters
 from  noncontact water, elimination of direct condensers, control
 of  leaks,  minimization  of   housekeeping   water   usage   and
 establishment of nonwater using housekeeping practices.

 Best  available  technology  economically  achievable (BATEA)  for
 existing point  sources is based on the best in-plant practices of
 industry   which  minimizes  the   generation   of   waste   water
 pollutants.   These  are  typified  by  complete  segregation  of
 contact process  waters  from  noncontact  waste  water,  maximum
 recycle  and  reuse  of  treated  waste water, elimination of all
 possible contact of water with the processes  (for example,  by the
 elimination  of  barometric   condensers),    preventing   leaking
 materials   from  getting  into  waste  water  streams,   and  the
 application of other methods of removing pollutants (such as  the
 reduction  of  COD  through the use of adsorptive floes, granular
 media filtration, chemical treatment,  or activated  carbon).    In
 some   instances,  preventing  wastes   from  becoming  waterborne
 results in small volume,  highly concentrated streams which can be
 treated selectively or incinerated.


 Best available demonstrated  technology  (BADT)   for  New  Source
 Performance  Standards (NSPS)  is based on BPCTCA technologies and
the maximum possible reduction in process  waste  generation  and
 minimization  of  waste  water  flows  as outlined for BATEA.   The
 application of granular media filtration and  chemical  treatment
 for  additional  suspended solids and  other pollutant removal may

-------
be required  as  well  as  more  than  one  stage  of  biological
treatment.

The  levels  of technology considered above as BPCTCA, BATEA, and
BADT-NSPS are the bases for effluent limitations  guidelines  and
standards  of performance.  (Tables II-l, II-2, II-3, II-U, II-5,
and  11-6}.   The  tables  are  based  upon  documented  effluent
concentrations  attained by the techniques outlined above or upon
the engineering judgment that available technologies  from  other
industries can be transferred to this one.

Variations  in flow rates and the variabilities normally inherent
in well designed and  operated  treatment  facilities  have  been
taken into consideration.

-------
                                            TABLE II-l

     BEST PRACTICABLE CONTROL  TECHNOLOGY CURRENTLY AVAILABLE  EFFLUENT LIMITATIONS  GUIDELINE^
                                [kg/kkg (lb/]000 Ib) of  production]
Foot-
note
No.
1
2
3
4
5
«
7
8
9
10
11
12
13

Subcategory
Ethylene-Vinyl Acetate Copolymers
Fluorocarbons
Polypropylene Fiber
Polyvfnylidene Chloride
Acrylic Resins
Allcyds and Unsaturated Polyester Reains
Cellulose Nitrate
Polyamldes (Nylon 6/12 only)
Polyester Resins (thermoplastic)
Polyvinyl fiutyral
Polyvinyl Ethers
Silicones
Multi-Product Plants

Fluid Product Plants

BODj
Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Days
0.07 0.14
3.6 7.0
0.40 0.78
No nunerical guidelines-see discussion
in footnote
0.33 0.60
14 26
0.66 1.20
0.78 1.4
tfo numerical guidelines-see discussion
In footnote

14 26
8.2 15
3.3 6.0
No numerical guidelines-see dis-
COD

Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Days
0. 35
6. 7
2.0
No numerical guidelines-see
in footnote
1. 7
46
3.3
12
No numerical guidelines-see
in footnote

0. 70
13
3.9
discussion
3.0
85
6.0
22
discussion

70 127
41 75
17 30
No numerical guidelines-see dis-
niHR^on fn footnote
SUSPENDED SOLIDS
Maximum Average of Kaximun for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Davs
0.19 0.35
9.9 18.0
1.1 2.0
No numerical guidelines-see discussion
in footnote
0.22 0.40
9.4 17
0.44 0.80
0.52 0.9'5
No numerical guidelines-see discussion
in footnote

9.1 17
5.4 10
2.2 4.0
No numerical guidelines-see dis-
15
    Spandex Fibers

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                                         TABLE II-2
   BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE EFFLUENT LIMITATIONS GUIDELINES
                                    (Other Elements and Compounds)
           Product
      Parameter
          .kg/kkg (lbs/1000 Ibs of production)
                                               Maximum average of daily
                                               values for any period of
                                               thirty consecutive days
                                                      Maximum
                                                      For Any
                                                      One Day
Alkyds and unsaturated
polyester resins
Fluorocarbons

Spandex fiber

Nitrile barrier resins

Polypropylene fibers

Silicones
   Multi-product

   Al1ocati on for
     Barometri c
     Condensers

   Fluid-product

Polyester resins
(Thermoplastic)
Mercury

Fluorides

Cyanides

Cyanides

Oils & grease


Copper



Copper

Coppe r

Cadrni um
 Toxic and hazardous chemicals guidelines to apply

            0.6                   1.2

 Toxic and hazardous chemicals guidelines to apply
            0.5


           0 .071



           0.042

           0.017
 1.0


0 .1*


0.083

0.034
Toxic  and hazardous  chemicals guidelines
to apply

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                                                          TABLE  II-3



              AVAILABLE TECHNOLOGY  ECONOMICALLY ACHIEVABLE  EFFLUENT  LIMITATIONS  GUIDELINES

                                        [kg/kkg  (lb/1000  Ib) of  production]
Fe-.it- Subcategory
note
No.
1 Ll: , lene -Vin> 1 Acfct site Copo lycers
; Fiuorocarbors
3 Polyprcf. lene Fiber
3 A ryl Ic Resins
7 Aikvds and I'n saturated Polvester Resins
00 9 P^l.LiZUwts <\ Ion 0/12 only)
0 Pollster Resins ( theraoplast Ic)
11 Poly, in- 1 B Jt> ral
12 ?civv*.->i Ethurs
13 Silicones
fluid Pcodoct Plants
BOD,

Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Davs
0.06
2.2
0.22
No numerical guidelines-see
In footnote
0.10
6.9
0. 37
0.44
No numerical guidelines-see
in footnote
6.7
1.2
0.09
3.3
0.33
discussion
0.14
9.4
0.50
0.59
discussion
9.1
1.6

COD
Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Davs
0.19
4.0
0.40
No numerical
0.52
34
1 .9
2. 3
No numerical
35
6.3
0.29
5.9
0.59
guidelines-see discussion
in footnote
0. 74
47
2.6
3.1
guidelines-bee discussion
in footnote
47
8.5
Si .,. _D ,.,...
Kaxir.uT Average of N:LX;-.,- f : r ;
Daily V',:-jc? ft r A-.v G --c :..
Period til Ti i r ty
0.04 ', . ".
1.6
0.16
No nu.-c r i cal ^i. . -< . , • - —
0.03
2 .1
0.11
0. 14
No numerical gind> j , — (
la f, t , It
2.0 . -
0.37 , --
14      Jiitrile Barrier Resins                    No numerical guidelines-see di.cus.ion           No numerical guidelines-see discussion     Xo numerical g,J;d, ... o,-s

       c  J  «. .                                       in footnote                                in footnote                         in £o,.c;,-.t.
15      Spandex Fioers                               "                  "

-------
                                           TABLE II-4

         BEST AVAILABLE TECHNOLOGY ECONOMICALLY  ACHIEVABLE  EFFLUENT LIMITATIONS GUIDELINES
                                 (Other Elements and Compounds)
         Product
Alkyds and unsaturated
polyester resins
Fluorocarbons

Spandex fibers

Nitrile barrier resins

Polypropylene fibers

Silicones

   Multi-product

   Fluid-product

Polyester resins
(thermoplastic)
                               Parameter
Mercury

Fluorides

Cyanides

Cyanides

Oils and grease



Copper

Copper

Cadmium
                              kg/kkg (lbs/1000 Ibs of Production)
                                               Maximum average  of  daily
                                               values  for  any period of
                                               thirty  consecutive  days
                                                        Maximum
                                                        For Any
                                                        One Day
Toxic and hazardous chemicals guidelines to apply

            0.6                    1.2

Toxic and hazardous chemicals guidelines to apply
            0.092


            0.03
            0.011
0. 18


0.06
0.0055
Toxic and hazardous chemicals guidelines to apply

-------
                               TABLE II-5

BEST AVAILABLE  DEMONSTRATED  TECHNOLOGY NEW SOURCE  PERFORMANCE STANDARDS
                   [kg/kkg  (lb/1000 Ib) of production]
BOD5
yoot_ Subcategory Maximum Average of Maximum for Any
notc Daily Values for Any One Day
Ho Period of Thirty
Consecutive Days

2 Fluorocarbons °-8° i'6°
3 Polypropylene Fiber °-04 °-08
4 Polyvinylldene Chloride No numerical guidelines-see discussion
in footnote
5 Acrylic Resins
6 Cellulose Derivatives
7 Alkyds and Unsaturated Polyester Resins 0.02 0.03
O 8 Cellulose Nitrate 6.0 11
• rolT««ides (Fylon 6/12 only) 0.37 0.67
10 Polyester Resins (thermoplastic) 0.44 0.80
11 Polyvinyl Butyral
12 Polyvinyl Ethers No numerical guidelines-see discussion
in footnote
13 Slllcones

Multi-Product Plants 5.5 • "
Fluid Product Plants 0.57 1.0
14 Bltrlle Barrier Resins »o numerical guidelines-see discussion
in footnote
15 Spandex Fibers
COD Suspended Solids
Maximum Average of Maximum for Any Maximum Average of Maximum for Any
Daily Values for Any One Day Dally Values for Any One Day
Period of Thirty Period of Thirty
Consecutive Days Consecutive Days
0.22 0.40 0.04 0.05
1.4 2.9 0.57 0.83
0.07 0.14 0.03 0.04
No numerical guidelines-see discussion No numerical guidelines-see discussion
in footnote ^ *"> footnote
" ] "
00.11 0.20 0.0 06 0.008
30 54 1.8 2'7
1-9 3.4 0.11 °-17
6.5 12 0.14 0.20

No numerical guidelines-see discussion No numerical guidellnea-see discussion

46 82 1.7 2.5

4.7 8.5 0.18 0-26
No numerical guidelines-see discussion No numerical guidelines-see discussion
in footnote In footnote
„

-------
                                             TABLE II-6

              BEST AVAILABLE DEMONSTRATED TECHNOLOGY - NEW SOURCE PERFORMANCE STANDARDS
                                   (Other Elements and Compounds)
         Product
     Parameter
         kg/kkg (lbs/1000 Ibs of Production)
                                                Maximum average of daily
                                                values for any period of
                                                thirty consecutive days
                                                        Maximum
                                                        For Any
                                                        One Day
AlKyds and unsaturated
polyester resins
Fluorocarbons

Spandex fibers

Nitrile barrier resins

Polypropylene fibers

Silicones

   Multi-product

   Fluid-product

Polyester resins
(thermoplastic)
Keicury

Fluorides

Cyanides

Cyanides

Oils and grease



Copper

Copper

Cadmium
Toxic and hazardous chemicals guidelines to apply

            0.6                    1.2

Toxic and hazardous chemicals guidelines to apply
            0.017



            0.025
            0.0026
0.034


0.050
0.0052
Toxic and hazardous chemicals guidelines to  apply

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                                                                  FOOTNOTES   FOR
                                                                                               II-l,  II-3,  II-5
| — '
^
Ethylene -Vinyl Acetate  (EVA) Copolymer. Two of the five
known producers were contacted.  All plants are located
at polyethylene production facilities.  Water use and
vaste'Jater characteristics for EVA are essentially iden-
tical to those for low  density polyethylene.  However,
an emulsion polymerization process is known and produces
a distinctly different  waste load which Is essentially
that of poly vinyl acetate emul sion polymerization
reported in EPA 440/1-73/010.  Both multi-plant and
municipal sewage treatment is used.

Fluorocarbons . Three of the seven manufacturing plants
were visited.  A wide range of products are produced.
The cost ixportant is polyt etraf luorethylene (PTFE) and
these gu id el In ss are recommended for PTFE granular and
f I ne powder grades only .  The wastewater discharges
differ considerably depending upon the process recovery
echenes for h> dro chloric acid and the disposal of selec-
ted screams by deep well,  ocean dumping or off-site
contract methods.  The  use of ethylene glycol in a pro-
cess can significantly  affect the waste loads. Fluoride
concentrations in untreated wastewaters are generally
below levels attainable by alkaline precipitation,

Po_lypropy K'ne Fibers. Two of the three producers were
contacted. The volu.net.rlc flow ranges per unit of pro-
duction vary widely depending upon the type of coolinn
system used.  The waste loads are for plants where selec-
ted concentrated wastes are » eg rag a ted and disposed  of
by landfilling, etc. Primary treatment at one plant site
was obst-rved while the  other plant discharges to a
municipal sewage system.

F o 1> v i ny 1 i J e ne Ch 1 o ride. The two major manufacturers
were contacted. Both plant sites send was tew.it era to
multi -plant treatment plants of which the polyvinylidene
chloride is a saall port Ion.  Consequently, there was
Insufficient data to develop recommended guidelines .

Acrylic jtcsins. Three of the four manufacturers were
contacted.  Large r.unbers of product grades are produced
by bulk, solution, suspension and emulsion polymeriza-
tion.  The widely varying hydraulic loads for the large
nunber of products in addition to treatment of the waste-
waters by multi-plant wastewater treatment facilities
p roll ibi tea obtaining Sufficient meaningful data to
recommend ef fluent limitation guidelines.

Cellulose Derivatives.  Cellulose derivates investigated
included eth>l cellulose, hydroxyethyl cellulose,  methyl
cellulose and carboxymetbyl cellulose.  Wide variations
in unit flow rates for two plants producing the same
product, differences in manufacturing techniques  and the
availability of data prevented recommending guidelines.
The wastewaters from the three manufacturers are  being
treated in multi-plant wastewater treatment facilities
or will enter municipal sewage systems.
 7.  Alkyde and Unsaturated Polyester Resin^. Six carefully
     selected plants were visited to provide a crosa-section
     of the industry for size of operation, type of manufac-
     turing process and wastewater treatment methods. Hydrau-
     lic loads vary widely duperdtng upon the process designs
     Similarly, raw waste loads vary widely because some
     plants segragate wastes foi disposal in other manners.
     Generally, the industry discharges wastewatera into
     municipal sewaye sy^teras aid should continue.  Also,  tht
     type of air pollution control,  e.g. combustion or scrub-
     bing, has a significant effect on the wastewater loada.
     The recommended guidelines are for plants having their
     own wastewater treatment system - a very infrequent
     occurrence.

 8.  Cellulose Nttra_te_. The two major manufacturers of the
     four manufacturers were contacted.  These wastes require
     pH control and contain large amounts of nitrates. One
     plant discharges to a Municipal sewage system while the
     other goes into a multi-piant treatment complex.

 9.  j'ojjamities. Various polyamides are produced but only
     Nylon 6/12 produces significant amounts of wastewater,
     e.g. Nylon 11 uses no process water. Consequently,  the
     guidelines are restricted to Nylon 6/12 and were develop-
     ed on the basis of similarity with waste loads from
     Nylon 66 production.

10.  Polyester Thermoplastic Resins. There are three manu-
     facturers,  two of which produce polyCethylene,  terephtha-
     late) in quantities less than 21 of their total thermo-
     plastic production. The guidelines are recommended  for
     poly(ethylenc terephthalate)  since the other product
     polyCbutylene t erephth,-ilate)  is produced at only one
     plant and the waste waiter g^es into a municipal  sewage
     system, so no data on perfonnance could be obtained.
11.  Folyvinyl Butyral. Of three production sites,two have
     processes beginning with vinyl  acetate monomer  wnich
     generates much larger wastewater volumes than the pro-
     cess beginning with polyvinyl alcohol.  Since the manu-
     facturing sites where production starts with a  monomer
     discharge Iiito municipal  sewage systems,  there  was  no
     data available. Consequently,  the recommended  guide-
     lines are only for NSl'S-BADT  when starling witli poly-
     vinyl  alcohol since any other guidelines would  be
     tantamount  to establishing a  permit for the production
     sice.

12.  Polyvinyl ethers.  The three present planto use  differ-
     ent  processes each of which produces several  grades of
     product.    The different  chemical compositions  used in
     both  bulk and solution polymerization processes and the
     lack  of data  on. both  raw  and  treated wastewatera pre-
     vented  establishing guidelines.   The wastewatera are
     presently sent to either  multi-plant treatment  facilltla
     or municipal  sewage systems.
                                                                                                                                     13. Silicones. Four companies manufacture sillconea at five
                                                                                                                                         locations.  Three plants were visited and data were
                                                                                                                                         obtained from all plants. The major processing steps at
                                                                                                                                         the five plants are shown below.

                                                                                                                                                Major Processes at Five Silicone plants

                                                                                                                                            Plant No.            12345

                                                                                                                                         CH.C1                   x     xx
                                                                                                                                         Chlorosilane prod.      x  x  x  x  x
                                                                                                                                         Hydrolysis              x  x  x  x  x
                                                                                                                                         Fluids, greases,        x  x  x  x  x
                                                                                                                                          emulsions prod.
                                                                                                                                         Resin production        x  x  x
                                                                                                                                         Elastomer production    x  x  x     x
                                                                                                                                         Specialties prod.*      x  x  x
                                                                                                                                         Fumed silica prod.            x
                                                                                                                                         HC1 production                      x
                                                                                                                                           e.g. surfactants, fluorinated
                                                                                                                                           agents, and other materials.
                                                                                                                                                                          i Hi cone s, coupling
    Eased on the manufacturing process, the wastewater flows
    and the raw waste loads, the plants 1, 2, 3 vere desig-
    nated as multi-product plants while 4 and 5 vere desl.,-
    nated as fluid product plants.    Guideline   quantities
    based on  production  rates that  were  e&cicated
    from  sales volumes  for  BPT.


1A- Nitrlle Barrie_r_Restns.  Commercial scale production aid
    Bale of these resins has not yet begun. The co— >nies
    expected to have production facilities were contacted
    and two provided estimates of raw waste loads.  Because
    of the lack of demonstrated flows and raw waste loads
    It was impossible to establish effluent guideline
    llmitat ions.

i*. Spandex Fibers.  Three manufacturers eacTh produce
    Epandex fibers by significantly different processes.
    These  are dry,  wet and reaction spinning methods.
    Because of  limited data  on  raw waste  lends  ara
    because each plant operates  a different  process
    it was impossible to establish meaningful guidelines.

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                           SECTION III

                          INTRODUCTION

Purpose.and Authority

Section  301 (b)   of the Act requires the achievement by not later
than July 1, 1977, of effluent  limitations  for  point  sources,
other than publicly owned treatment works, which are based on the
application  of the best practicable control technology currently
available as defined by the  Administrator  pursuant  to  Section
30a (b)   of the Act.  Section 301 (b) also requires the achievement
by not later than July 1, 1983, of effluent limitations for point
sources,  other than publicly owned  treatment  works,  which  are
based  on  the  application  of  the  best  available  technology
economically achievable which will result in  reasonable  further
progress toward the national goal of eliminating the discharge of
all  pollutants,  as  determined  in  accordance with regulations
issued by the Administrator pursuant to  Section  305 (b)  of  the
Act.   Section 306 of the Act requires achievement by new sources
of a Federal standard of performance providing for the control of
the discharge of pollutants which reflects the greatest degree of
effluent reduction  which  the  Administrator  determines  to  be
achievable   through   the  application  of  the  best  available
demonstrated control technology, processes, operating methods, or
other alternatives,  including,  where  practicable,  a  standard
permitting no discharge of pollutants.

Section  304 (b)   of the Act requires the Administrator to publish
within one year of enactment of the  Act,  regulations  providing
guidelines  for  effluent limitations setting forth the degree of
effluent reduction attainable through the application of the best
practicable control technology currently available and the degree
of effluent reduction attainable through the application  of  the
best   control  measures  and  procedure  innovations,  operation
methods and other alternatives.  The regulations proposed  herein
set  forth  effluent  limitations  guidelines pursuant to Section
304 (b)  of the Act for the lower volume products of  the  plastics
and synthetic materials manufacturing source category.

Section  306  of  the  Act requires the Administrator, within one
year after a category of sources is included in a list  published
pursuant  to  Section 306 (b)  (1) (A)  of the Act, to propose regu-
lations establishing Federal standards of  performances  for  new
sources  within  such categories.   The Administrator published in
the Federal Register on January 16, 1973 (38 F.R. 1624),  a  list
of  27  source  categories.    Publication of the list constituted
announcement of the Administrator's  intention  of  establishing,
under  Section  306,  standards  of performance applicable to new
sources within the plastic and synthetic materials  manufacturing
source  category,  which  was  included within the list published
January 16, 1973.
                            13

-------
Methodolocfi

The effluent limitations guidelines and standards of  performance
proposed  herein  were  developed  in  the following manner for a
second group  of  specialty  plastics  and  synthetics  that  are
generally produced in smaller volumes than the first group.

Because  establishing guideline limitations for one or two plants
would be  tantamount  to  prescribing  the  limitations  for  the
plants'  discharge  permit  and because plants with less than one
million pounds per year of production are nearly always installed
at multi-product facilities, it was decided to include only those
products being produced at three or more plants in quantities  of
at least one million pcunds per year.  The products were examined
for  categorization  on  the  basis  of  raw  material, products,
manufacturing  processes,  raw  waste  characteristics,  and  the
demonstration   or   availability   of   waste   water  treatment
technology.

The  raw  waste  characteristics  for   each   subcategory   were
identified  through  analyses  of  (1)  the sources and volumes of
water and waste waters emitted from the processing plants and  (2)
the  thermal  conditions  and  pollutants  including   toxic   or
hazardous substances and other constituents which might result in
taste,  odor,  or color problems or toxicity to aquatic organism.
The constituents within each subcategory which should be  subject
to  effluent  limitations guidelines and standards of performance
were identified from information on process operating  conditions
and data on waste water analyses.

The  types  of  waste  water  control  and treatment technologies
existing in the  industry  were  identified.   This  includes  an
identification  of each distinct control and treatment technology
for both in-process and  end-of-process  technologies  which  are
existent or capable of being engineered for each subcategory.  It
also  includes  an  identificaticn  of the pollutants in terms of
chemical,  physical,  and  biological  characteristics,  and  the
effluent  concentration  levels resulting from the application of
each of the treatment and control  technologies.   The  problems,
limitations, and reliability of each treatment control technology
were   also   identified   as  well  as  the  time  required  for
implementation.    In   addition,    certain    other    nonwater
environmental  impacts  were  discussed,  such  as the effects of
control technologies on other pollution problem areas  (e.g., air,
solid  wastes,  noise,   and   radioactivity).    Energy   demand
requirements  for  each of the control and treatment technologies
were developed, and the cost  of  applying  such  technology  was
estimated.

The  information  outlined  above was then evaluated to determine
what levels of waste water treatment technologies constituted the
"best  practicable   control   technology   currently   available
 (BPCTCA) ," the "best available technology economiccilly achievable
 (BATEA) ,"   and   the   "best   available   demonstrated  control
technology, processes, operating methods, or other alternatives."
                            14

-------
In  identifying   such   technologies,   various   factors   were
considered.   These  include  the  total  cost  of  applying  the
technology in relation to the age of both the equipment  and  the
facility   involved,  the  processes  employed,  the  engineering
aspects of applying various types of control  techniques  through
process changes, nonwater quality environmental impact  (including
energy  requirements), the treatability of waste water, water use
practices, and other factors.

The data for identification of  industry  segments,  analyses  of
waste  water  generation  rates,  evaluation  of  process control
technology and determination of  waste  water,  treatment  techno-
logies  were  developed  from a number of sources.  These sources
included public  information  from  the  U.S.  EPA  research  and
development  efforts,  data  from  permits  filed  under the 1899
Refuse Act permit program, records of  selected  state  agencies,
published literature, a survey of waste water treatment practices
by  the  Manufacturing  Chemists Association, qualified technical
consultants, interviews  with  industry  personnel,  and  on-site
inspection  of  manufacturing processes and waste water treatment
facilities.   References  used  in  developing   guidelines   for
effluent  limitations and standards of performance of new sources
reported here for this segment of  the  plastics  and  synthetics
industry are essentially the same as those reported in EPA 440/1-
73/010  (16)  and  are  listed  in Section XIII of this document.
Because this segment of the industry  represents  generally  less
well  known  and  smaller volume products, significant amounts of
information on manufacturing processes  were  obtained  from  the
companies  and  are  included  in files developed to support this
Development Document.

General DescriptionnOf the_Industry

The  plastics  and  synthetics  industry  is  composed  of  three
separate  segments:   the  manufacture  of  the  raw materials or
monomers,  the conversion of these monomers into a  resin  plastic
material,   and  the  conversion  of  the  plastic  materials into
products  such  as  a  toy,  synthetic  fiber,   packaging   film,
adhesive,   and  so  on.   The  development document for the first
group  of  plastics  and  synthetics  (EPA   440/1-73/0lOa)    was
concerned  primarily with the manufacture of the basic plastic or
synthetic resins (SIC 2821);  however,  also  included  were  the
production of synthetic fibers such as nylon (SIC 2824), man-made
fibers such as rayon (SIC 2823), and cellulose film or cellophane
(SIC  3074).   The  first  industry grouping dealt with 16 of the
major resins, most of the major synthetic fibers, and all of  the
cellulose fibers and cellophane film, that is,  over 90 percent of
the  total  volume  of the industry.  Consequently, this group of
plastics and synthetic products deals  with  the  remaining  less
than  10  percent  of the industry.   The large number of products
(45)  encompassed in this segment of the industry is indicated  in
Table III-l, which lists the plastics and synthetics fibers to be
considered  in  the  second  phase  of the work on development of
effluent  limitations  guidelines  and  new  source   performance
standards.
                            15

-------
The   total  production  of  this  segment  of  the  industry  is
approximately  1.2  million  kkg  (2.6  billion  Ibs)   of   which
approximately  0.7 million kkg (1.5 billion Ibs)  is accounted for
in the production of unsaturated polyesters by over 40 producers.
The remaining products are generally produced by less  than  four
manufacturers.   Because many of the products are manufactured to
end use specifications, it is  not  possible  to  categorize  the
industry commercially except in a very general way, such as price
range, size product, size of market, or potential growth.  From a
commercial  point  of  view,  this  segment of the synthetics and
plastics industry can be divided  into  four  generally  distinct
groups.  The first group is the relatively new, high performance,
low  volume and high priced materials, e.g., selling generally at
over $6.60/kg ($3.00/lb), such as chlorinated polyethers,  methyl
pentene,   phenoxy   resins,   parylene  phosphonitrilic  resins,
polyaryl ether,  polybenzothiazoles,   polyethylene  amines,  poly-
benzimidazoles,    polyimides,   polymethylpentene,  polyphenylene
sulfide, poly alpha-methyl styrene,  and polyvinyl carbazol.

A second group is the older materials which  have  a  significant
market  and,  being  medium  priced,  are generally produced by a
limited number of companies.  These are  the  cellulosics,  poly-
vinyl  butyral,   diallyl  phthalates,  fluorocarbons,  silicones,
pyrrolidines, and vinylidene chloride.  A relatively new and fast
growing third group encompasses ionomers, nitrile barrier resins,
polyphenylene oxide, and polybutenes.  The fourth group is  those
relatively  large  volume resins which can anticipate good growth
such as methacrylates, polyesters, polycarbonates, and  ethylene-
vinyl acetate.
                           16

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                           TABLE III-1

            PLASTICS AND  SYNTHETICS FOR CONSIDERATION
Alkyd Molding Compounds
Amine Resins
Cellulose Acetate Butyrate
Cellulose Acetate Propionate
Cellulose Butyrate
Cellulose Nitrate
Cellulose Propionate
Chlorinated Polyethers
Chlorinated Polyethylene
Diallyl Phthalate Compounds
DuPont Nitrile Barrier Resins  (NR-16)
Ethyl Cellulose
Ethylene-Vinyl Acetate
Fluorocarbons
    CTFE  (Kel-F) Chlorotrifluoroethylene
    FEP
    TFE - Teflon Polytetrafluoroethylene
    PVDF - Polyvinyldifluoride
lonomers. Acrylics - Surlyn
LOPAC (Monsanto) + BAREX  (Sohio)   (Nitrile Barrier Resin)
Methyl Cellulose
Parylene  (U.C.)
Phenoxy Resins
Phosphonitrilic Resins
Polyallomer (PE/PP Copolymer)
Poly-alpha-methyl Styrene
Polyamides
Polyaryl Ether  (Arylon)
Polybenzimidazoles
Polybenzothiazoles'
Polybutene
Polycarbonate
Polyethylene Imines
Polymethacrylonitrile Resins
Polymethylaerylate
Polymethyl Pentene (ICI«s TPX)
Polyphenylene Oxides (Noryl)
Polyphenylene Sulfide  (Ryton-Phillips)
Polypropylene Fibers
Polysulfones
Polyvinyl Butyral
Polyvinyl Carbazoles
Polyvinyl Ethers
Polyvinyl Pyrrolidone
Silicones
Unsaturated Polyesters
                          17

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The  basis  for  selecting  products  from  this  segment  of the
industry for the development of effluent  limitations  guidelines
was  set  as  follows:   at  least  454 kg  (1 million Ibs) of the
material must be produced at a  single  manufacturing  site,  and
three  or  more  manufacturers  must produce the material.  These
criteria were chosen because location  or  production  facilities
for  lesser  quantities would be very difficult to establish, and
developing guidelines for products manufactured in  only  one  or
two  plants  would be tantamount to writing the permits under the
National Pollution Discharge Elimination System for  the  one  or
two  plants,  which  is  not within the scope of this work.  With
these  prerequisites,  an  extensive  survey  of  the   following
literature  sources  was  made  to determine names and numbers of
manufacturers, and production rates.

    Chemical Economics Handbook, Stanford Research
    Institute.

    Directgryr gf Chemical_Producers , 1973, USA,
    Chemical Information Services, S.R.K.

    Modern_Plastics_Encyclopj5dia, 1972-1973,
    Suppliers-Resins and Molding Compounds.
    Elasticsjtorld, 1972-1973, Directory of the Plastics
    Industry.

    Chemical_Hor izons_Fj.leJL_Predica^t , including
    updates to July 1973  (this includes references
    to journals such as Chemical_week) .

    Qhemical_Marketing_Regorter, "Chemical Profile"
    SectlonT from June 26, 1972, through July 23, 1973.

An exhaustive review of this information indicated it  was  often
impossible  to delineate between basic producers and distributors
of compounds or products, and many discrepancies  were  found  in
reported  production  capacities.   Consequently,  the literature
sources  were  supplemented  with  information  from   both   the
contractor's  files and direct contact with companies in order to
establish that there  were  three  or  more  plants  producing  a
specific  product  or  that there were two or less producers.  In
those product categories where only two producers were listed  in
the  original searches, the companies were contacted to ascertain
whether or not there were  other  producers.   Where  only  three
producers  were  found  originally, we contacted any companies we
were  uncertain  of  to  confirm  that  they  were  indeed  basic
producers  and  not  distributors.   Products  selected  for  the
development of effluent  limitations  guidelines  are  listed  in
Table  III-2.   These  include 13 from the original list of Table
III-l plus the following three additional  products,  which  were
found   to  meet  the  selection  criteria  and  which  were  not
considered in the Phase I work of this contract or by  other  EPA
contractors:
                          18

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    Polyamides  (other than Nylon 6 and 66)

    Thermoplastic polyesters

    Spandex fibers

Therefore,  29  products  were  eliminated between the two  lists.
The principal reasons for elimination of these   29   products   are
summarized below.

    1.  Misnomer or duplicates                4

    2.  Families cf compounds or further      5
          generic groupings

    3.  Insufficient nurrber of production   20
          sites                            ____

          TOTAL ELIMINATED                  29

A  short  discussion  of  the  rationale for  eliminating  the  nine
products in categories  (1) and  (2) above follows.

    (1)  Misnomers or duplicates

    Ajnine_rej3ins - not a meaningful designation  for
    a specific or generic group of products.

                       - not an article of commerce  -
    probably meant to apply to cellulose acetate
    butyrate.

    £2li2!§£hacrylcnitrile_res_inis - combined with the
    more general category of nitrile barrier resins.

    M.§thy.l_p.entene - another name for polymethyl
    pentene.

    (2)  Families of compounds or further generic
         groupings.

The product  category  "cellulose  derivatives"  was  created   by
combining    methyl   cellulose,   ethyl   cellulose,    cellulose
propionate, cellulose acetate prcpionate, and cellulose  acetate.
                         19

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        TABLE III-2

PRODUCTS TO BE CONSIDERED FOR DEVELOPMENT OF
EFFLUENT GUIDELINE LIMITATIONS
Acrylic resins
Alkyd molding compounds
Cellulose derivatives
Cellulose nitrate
Ethylene-vinyl acetate copolymers
Fluorocarbons
Nitrile barrier resins
Polyamides (other than Nylon 6 and 66)
Polyester resins  (thermoplastic)
Polyester resins  (unsaturated)
Polypropylene fibers
Polyvinyl butyral
Polyvinyl ethers
Polyvinylidene chloride and copolymers
Silicones
Spandex fibers
                        20

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butyrate from the original list  plus  two  additional  materials,
hydroxymethyl cellulose and  carboxy methyl cellulose  (CMC).   This
category  was   established   because the total  production of these
cellulose  derivatives  was   judged  to  be  important  for   the
development  of effluent  limitations guidelines,  although  none  of
the individual  products is   made by  more  than  two  companies.
These products  are regrouped below into general processes  and the
specific products are shown.

Derivative

Alkali Processes

     (a)  methyl cellulose,
     (b)  ethyl  cellulose,
     (c)  carbomethyl cellulose,
     (d)  hydroxyethyl cellulose

    Acid_Processes

     (e)  cellulose acetate butyrate,
     (f)  cellulose acetate propionate,
     (g)  cellulose propionate

Items  (a)  through  (d)  are made  by dissolving cellulose in alkali
and reacting with CH3C1,  C2H5C1, C1CH2COOH or C   C  respectively
NaCl  being in  most cases the biggest by-product.  The esters (e)
through  (f) are synthesized  in acid medium, rather  than   alkali,
using acetic, propionic and/or butyric acids.

Nitrile  barrier  resins  were chosen as the generic grouping for
the following products:

    DuPont's NR-16  (R)

    Monsanto's Lopac (R)

    Sohio's Barex (R)

Although these products are only produced in  limited  quantities
at  the  present  time, they  are believed to be potentially large
volume products.

    (3) Insufficient number  of production sites.

The remaining 20  products  were  eliminated  from  consideration
because  no  more than two manufacturing plants could be found or
because they are manufactured in less than one million pounds per
year quantities at a plant.    The products  are  listed  in  Table
III-3.
                       21

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                           TABLE III-3

             PRODUCTS ELIMINATED FRCW CONSIDERATION
       FOR ESTABLISHMENT OF EFFLUENT GUIDELINE LIMITATIONS
     Produc^

Chlorinated Polyethers
Chlorinated Polyethylene
Diallyl Phthalate Compounds
lonomers
Parylene
Phenoxy Resins
Phosphonitrilic Resins
Polyallomer
Poly-alpha-Methyl Styrene
Polyaryl Ethers
Polybenzimidazoles
Polybenzothiazoles
Polybutylene  (called polybutene
  in Table I)
Polycarbonate s
Polyethylene  Imine
Polymethyl Pentene
Polyphenylene Oxides
Polysulfone
Polyvinyl Carbazole
Polyvinyl Pyrrolidone
Urethane Prepolymers
                       22

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In  addition,  three  of the original product names were changed,
i.e., (1)  polybutenes are more correctly listed as  polybutylenes
(in the plastics and synthetics field polybutenes are tars where-
as polybutylene is a specific isomer of polybutylene used in film
and  pipe formation) , (2) poly (vinyl and vinylidene)  chloride was
reinterpreted to  mean  polyvinylidene  chloride  since  effluent
limitations  guidelines  for polyvinyl chloride were developed in
the Phase I study, and (3)   polymethyl  methacrylate  was  placed
into the more generic category "acrylic resins. "

Those  companies  which  were determined to be manufacturers (not
suppliers or distributors' only)   of  the  products  selected  for
consideration  in  the development of effluent limitations guide-
lines are shown in Table III-4.
Brief descriptions of the chemical nature of the products and the
manufacturing process technology are presented  in  this  section
with  special  emphasis  on  indicating  those process operations
which generate waste waters.  These descriptions are presented in
alphabetical  order  for  the  products  regardless  of   whether
guidelines  are  established  or not.  In some instances the only
available information was from patents and the  literature  since
manufacturing  processes remain proprietary; in some instances no
information was available.
                             23

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                                      TABLE III-4


MANUFACTURERS OF PRODUCTS TO BE CONSIDERED FOR DEVELOPMENT OF EFFLUENT LIMITATION GUIDELINES
                 &
                    o
                    CJ
01
n

X «|
O) ™
P. <"
g g
Cellulose Nitrate
Nitrile Barrier Resins
Fluorocarbon Polymers
Ethylene-Vlnyl Acetate
Polypropylene Fibers
Polyvlnyl Butyral
Polyvinyl Ethers
Polyvinylidene Chloride
Alkyd Molding Compounds
Polyester Resins (Unsat.)
Polyester Resins (Thermoplastic)
Acrylic Resins
Silicones
Polyamides (Except Nylpn 6 and 66)
Cellulose Derivatives
Spandex Fibers



X



X






X













X











X

X





X
X
X
X

X





X

X



X



X







X



X
















X
X




X
X





















X


X




























X


X
















X

X
X




X
X
X
X




X












X



X









X
X




X















X














X


X















X
















X

X













X
X















X

















X

X












X















X














X




















X













X















X
















X














X







X






















X



X


-------
 Acrylic Resins

 Polymers have been produced commercially from a wide  variety  of
 different  esters  of  both  acrylic  acid  and methacrylic acid.
 Specialty plastics have been produced from  2-haloacrylic  esters
 and  2-cyanoacrylic  esters.   In  recent years the production of
 methacrylate  polymers  has  exceeded   production   of   acrylic
 polymers.     Since   production   methods   are  similar,  methyl
 methacrylate polymers will be discussed here as representative of
 the aerylate resins.

 Methacrylic acid, CH2 C(CH3)COOH, can be considered as the parent
 substance from which  methyl methacrylate monomer and  poly (methyl
 methacrylate)   and all other methacrylate compounds are derived.
 In one  process,   methyl  methacrylate  monomer  is  manufactured
 starting  with  acetone cyanohydrin and 98 percent sulfuric acid.
 The methacrylamide sulfate  formed  as  an  intermediate  is  not
 isolated but reacts with methanol to produce methyl methacrylate.
 Both  steps  are  carried out continuously.   The reaction sequence
 is shown in Figure III-l,  Equation 1.

 Polymerization  of methyl  methacrylate   produces   poly(methyl
 methacrylate).    The   clarity,   outstanding  weather  resistance,
 light   weight,    formability,    and   strength    of   poly(methyl
 methacrylate)   have  led  to extensive use of acrylic plastics in
 aircraft glazing,  signs,  lighting,  construction,   transportation,
 appliances,   and  merchandizing.   Because of excellent suspending,
 rheological,  and  durability  characteristics,   acrylic  emulsions
 have wide  use  in  paints for exterior and interior  applications on
 wood,  masonry,  metals,  etc.

 Manufacture    -    Monomer   is   delivered  to  the   polymerization
 manufacturer usually  in tank car  quantities.    Low  concentration
 (5-15   ppm)  of inhibitor  is often  adequate for safe handling  and
 storage  of  methyl  methacrylate.   Low  inhibitor  content    is
 desirable,  since  subsequent polymerization  without first  removing
 the  inhibitor  is  possible.

 The  polymerization of  methyl methacrylate  shown in Figure III-l,
 Equation 2, may be  conducted in a variety of ways.   In commercial
 casting of sheets  of  poly (methyl  methacrylate)  each sheet  is cast
 in  a mold  assembled from two sheets  of  plate glass   spaced  apart
 at  the edges by  a  gasket  (see Figure III-2).   The  mold is filled
 by pouring in a charge  of  monomer with  exact amounts  of catalyst
 colorant if desired,  or other additives  for special  effects.  The
closed mold then  goes through  a  controlled  temperature  cycle
 generally  between  40  and  75°C  (113 and 158°F).  Annealing often
 follows the casting process.

Homo- and copolymers  can also  be  conveniently  prepared  by  an
 emulsion  technique.   in  a  representative  procedure  shown in
Figure III-3, methyl methacrylate is emulsified with  an  anionic
emulsifier  and  deionized  water  containing  a  little  ferrous
sulfate and ammonium peroxysulfate.  The emulsion is flushed with
nitrogen and then treated at 20°C  (68°F) with small quantities of
                            25

-------
(1)
      (CH3)2C(OH)(CN)  + H2SO4	 CH2 = C(CH2)CONH2 • H2S04
      CH2 =C(CH2)CONH2 • H2SO4 + CH2OH — CH2 = C(CH2)COOCH3  + NH4HS04
(2)    n
CH2 = C COOCH3

     CH3
      COOCH3

. CH2 - C 	
                                        CH3
                                     (where n is 500 to 3000)
     FIGURE  111-1  TYPICAL REACTIONS TO FORM POLY (METHYL METHACRYLATE)
                 INCLUDING MONOMER MANUFACTURE
                                  26

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                                                                REUSED  MOLDS
to
-j
MONOMER

CATALYST
ADDITIVES
PARTING
AGENT

MIXING



i

MOLD
FILLING




POLYMERIZATION
BATH OR
OVEN
t
i



PARTING
\



t
I
MOLD
CLEANING
1

                                                           AIR OR
                                                           WATER
                                                        (CONTROLLED
                                                       TEMPERATURE)
  CAST
 SHEET
PRODUCT
WASTE
WATER
                       FIGURE 111-2 ACRYLIC RESIN PRODUCTION - BULK POLYMERIZATION PROCESS

-------
sodium metabisulfite and t-butyl hydroperoxide.   The  temperature
rises  spontaneously  to  70°C  (158°F)  and the  polymerization is
completed at this temperature in about  15  minutes.   After  the
batch  is  cooled  to  room  temperature,   the  product typically
contains 35 percent total solids with a viscosity of about  6  cp
and a pH of 2.5.

In  suspension  as  well  as in emulsion polymerization, water is
used as a heat transfer medium in  the  reaction  zone,  but  the
methods  differ  in  the  state in which the polymer is obtained.
Suspension polymerization   (see  Figure  III-4)   yields  discrete
beads,  granules, or particles ranging in size from a few microns
to a fraction of an inch in diameter.

With water as the reaction medium, the following factors have  to
be controlled for successful suspension polymerization methods:

    1.   The  initiator  should  be  soluble  in  the monomer and
         insoluble in water.  This  prevents  the  polymerization
         from  occurring  in  the aqueous phase  and is especially
         necessary when the monomer  is  appreciably  soluble  in
         water.

    2.   Suspending agents may be used to prevent droplet contact
         and merging and to aid in the suspension of polymerizing
         droplets.  Such agents may be soluble products  such  as
         cellulose  derivatives,  starches,  gums,  and  salts of
         acrylic polymers; polyvinyl  alcohol,  or  they  may  be
         insoluble  materials  such  as clay or talc.  Thickeners
         such as polyoxyalkylene derivatives may also be  present
         to prevent droplet contact.

    3.   Inorganic  salts are often added to increase the density
         of the aqueous medium, to reduce the water solubility of
         the monomers, and to increase the interfacial tension of
         the system.

Waste Water Generation - The  primary  waste  water  streams  are
obvious  from   inspection cf the process schematic diagram.  Upon
cooling, the  polymer  product  is  washed,  usually  within  the
cooling  vessel,  and the water or brine leaving this vessel will
be contaminated with soire monomer, some polymer, and the  various
stabilizing,  emulsifying,  and chain-regulating agents as well as
the catalyst.   Final dewatering occurs in the centrifuge, and the
waste water stream from this equipment will contain the same type
of contaminants listed above.

If the monomer  is assumed to be present at  its  saturation  con-
centration  in  the wash water, it will comprise approximately 1.5
percent in the  waste stream.  If two volumes of water per  volume
polymer  are used to wash the product beads, then 1335 mass units
of water will be released per 1000 mass units of polymer  product
 (spec. gr. = 1.5).
                            28

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                  VENT
MONOMER
           HOLD

           TANK
           MIX

           TANK
AIR POLLUTION
  DEVICES
   WATER
  SCRUBBER
                                 ADDITIVES
                                          REACTION
                                           KETTLE
                    WASTE
                    WATER
                                                 FILTER
                                                WASHING
                                                                                     VENT
                                                                                            DRIED
                                                                                        *• MOLDING
                                                                                           POWDER
                                                                                      EMULSION
                                                                                      PRODUCTS
          FIGURE 111-3 ACRYLIC RESIN PRODUCTION - EMULSION POLYMERIZATION PROCESS

-------
                                ACRYLIC
                              MONOMERS
                                                      .COOLING  WATER
                                                      •RIVER
    INITIATOR,
GRANULATING AGENT,-
  MISC. ADDITIVES
      WATER
               WATER
               WATER
POLYMERIZATION
                                                      •DEMIN. WATER
                                            RECYCLE
                           COOLING  WATER* STEAM
                                      TO EXTRUDERS
                                RIVER
                              CENTRIFUGE
                           DEMIN WATER
                                 DRYING
                                                      •COOLING WATER'
                                                    -DRIVER
                                                -^-ACRYLIC BEAD POLYMER
                               EXTRUSION

                           'WATER
                         ACRYLIC MOLDING POWDER


       "* NON-CONTACT WATER


            FIGURE 111-4 ACRYLIC RESIN PRODUCTION - SUSPENSION
                       POLYMERISATION PROCESS
                                  30

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There  is  no  water of reaction for the polymerization of methyl
methacrylate (25) .

Other Pollutants

Oil and grease are due to the presence of lubricants used for the
extrusion  process.   Depending  on  the  specific  waste   water
chemical conditions and the analytical methods used, cyanides may
be  detected  due  to  the  presence  of  cyanoacrylic esters and
acetone cyanohydrin.
                          31

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Alkyd Molding Compounds

Alkyd molding compounds are mixtures of unsaturated polyester  or
polyalkyd  resins  with  various  fillers and additives which are
incorporated to  obtain  the  specific  physical  characteristics
required  for  the compression molding of parts.  The terms alkyd
and polyester are often used interchangeably, and  indeed  alkyds
are  chemically  very  sindlar  to  unsaturated  polyesters  (see
Unsaturated Polyester Resin section of this report).   The primary
difference is that in alkyds the acid component  is  supplied  by
long  chain unsaturated acids rather than the phthalic and maleic
anhydrides which are used in unsaturated polyesters.   The primary
use of alkyd resins is for paint formulations, but they are  also
used  in molding compounds.  The alkyds used for paints are often
made in the same plant as unsaturated polyesters.  When used  for
paints, the alkyds are diluted with the appropriate paint solvent
and  sold  as  a  liquid  in drums.  In this form they contain no
monomeric reactive diluent.

Manufacture - Alkyd molding compounds are sold  in  the  form  of
free flowing powder, gunk, and pastes.  They are usually prepared
in  two steps.  The resin producer carries out the polymerization
and sometimes adds a reactive diluent, such as diallyl  phthalate
or  styrene,  and sells the resin to a compounder in liquid form.
The compounder then adds the appropriate fillers such  as  glass,
fiber, asbestos, clay, calcium carbonate or alumina,  and packages
the  alkyd molding compound in a form appropriate to be sold to a
molder.  The process description and guidelines developed for the
resin manufacturer should be applicable to the manufacture of the
liquid alkyd resins which are used to make molding  compounds  as
well  as  for  alkyds  for  paints  (which are not covered by this
study) and unsaturated polyester resin manufacture.,

Waste Water Generation - Waste  water  production  in  the  poly-
merization process is similar to that described in the section on
Polyester  Resins.   The compounding steps are all mechanical and
do not generate liquid waste  (41).
                             32

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Cellulose Derivatives

This  group  of  materials  includes  ethyl   cellulose,   methyl
cellulose,  carboxymethyl  cellulose, and hydroxyethyl cellulose.
All are ethers of cellulose.

The first three of these derivatives are made by reaction  of  an
alkyl   chloride   —   ethyl   chloride,  methyl  chloride,  and
chloracetic acid — with cellulose.   Hydroxyethyl  cellulose  is
made  by  reaction  of ethylene oxide with cellulose.  Several of
the commercial grades of methyl cellulose are mixed ethers,  made
by  reaction  of  propylene oxide as well as methyl chloride with
cellulose. Equations  (1) through  (4) in Figure III-5 express  the
general reactions involved.

All  of the reactions are run using alkali cellulose — a mixture
of cellulose  with  sodium  hydroxide.   In  the  course  of  the
reactions  involving alkyl halides ±(1), (2), (3)1, the alkali is
neutralized by formation of  sodium  chloride.   This  salt,  and
excess  alkali,  must  be  removed  from  some of the products to
provide materials that are usable.

Manufacture - Figure III-6 on the following page  shows  a  block
flow  diagram  for  production of cellulose ethers.  The use of a
solvent in the process maintains the cellulose  as  a  relatively
easy-tO'handle  slurry.   Depending  on  the cellulose derivative
involved, the solvent may be either an alcohol or a hydrocarbon.

Proprietary processes appear to be widely used in  production  of
cellulose  ethers.  Manufacturers refuse to discuss the processes
in any detail.

Uses of the cellulose ethers are varied.  Ethyl  cellulose  is  a
plastic.     Methyl   cellulose,   carboxymethyl   cellulose,  and
hydroxyethyl cellulose are water soluble and are  generally  used
in   applications   involving  water  solubility.   Carboxymethyl
cellulose may be used as a suspending agent.  Methyl cellulose is
used as a film former.  All three  ethers  are  used  in  certain
foodstuffs.

Waste  Water  Generation  -  Wastes  generated  in  production of
cellulose derivatives constitute alkali, salt, solvent  residues,
pulp,  and treatment chemicals.  These wastes indicate relatively
high  BOD,  COD,  and  dissolved  solids  levels  (41).   Organic
nitrogen  may  be present in the waste waters of facilities where
nitrogen containing cellulose derivatives (other  than  cellulose
nitrate)  are produced.
                            33

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(1)   (C6H1005)n  +  CH3CI  +  NaOH 	-methyl cellulose + NaCI  + H2 O



(2)   (C6Hi005)n  +  C2HSCI + NaOH	 ethyl cellulose  +  NaCI +H20



(3)   (C6H1005)n  +  CIC2H302Na+NaOH	«-carboxymethyl cellulose + NaCI + H2O
(4)   (C6H10Os)n  + H2C-CH2	 hydroxyethyl cellulose
                     \  /
                      0
  FIGURE  III-5  TYPICAL REACTIONS TO FORM CELLULOSE DERIVATIVES
                                 34

-------
                         CELLUOSE     ALKALI
                               REACTION
 FRESH
SOLVENT
                       REACTANT
                     (ETHYL CHLORIDE,
                   -METHYL CHLORIDE,
                    CHLORACETIC ACID,
                     ETHYLENE OXIDE)
PURIFICATION
•*-WASTE
       I
SOLVENT
RECOVERY
   DRYING
  .WASTE
  WASTE
                                PACKING
          FIGURE 111-6 CELLULOSE ETHERS PRODUCTION
                             35

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Cellulose Nitrate

Cellulose  nitrate  is  produced ty reaction of fibrous cellulose
with a mixture of nitric and sulfuric  acids.   The  equation  of
reaction is shown in Figure III-7.

Manufacture - From the equation in Figure III-7 one may calculate
that  cellulose  nitrate  contains  14.1  percent  nitrogen.  The
commercial product contains about 12 percent nitrogen; this level
is attained by using  mixtures  containing  carefully  controlled
amounts  of  nitric acid, sulfuric acid and water.  These liquids
are present in the mix in the approximate proportion 1:3:0.75.

The fibrous nature  of  the  original  cellulose  is  essentially
unaltered  by  the  reaction.  In order to provide a commercially
useful product, the initially obtained nitrate is  taken  through
the following processes:

    1.   Washing with water to remove all acid.

    2.   Stabilization by boiling  with  water  to  remove  small
         amounts of combined sulfuric acid.

    3.   Digestion (heating in the presence of water)   to  reduce
         viscosity of the product to a useful level.

    4.   Dehydration or exchange of the water, by alcohol.

The steps listed above are shown  in  Figure  III-8,  which  also
indicates waste water streams.

Waste  Water  Generation  - Aqueous wastes generated in the manu-
facture of nitrocellulose constitute primarily acids (both nitric
and sulfuric)  and alcohol lost in the dehydration process.  Spent
acids are recovered as far as possible, but some  are  inevitably
lost.   Alcohol  is  recovered and recycled.  Suspended solids in
the wastes include a small amount of  cellulosic  material.   The
strongly  acidic  wastes are handled by neutralization with lime.
The calcium sulfate which is formed may be  removed  by  settling
                            36

-------
(C6H1005)n  +  3HN03  +  H2S04^=^:(C6H702 (N03)3)n  + H20  + H2S04
     FIGURE 111-7  TYPICAL REACTION TO FORM CELLULOSE NITRATE
                                37

-------



NITRICACID 	 - AC|D M|X
TANKS *
OLEUM >
f
SPENT <-
ACID
WATTI7 ^^^^— _


T T fl M -






t

SPENT
ALCOHOL
RECOVERY
STILLS "*
1
1
WASTE
WATER
DRYFR

1
NITRATING
POTS
I
rFNTRlFllftF


i r

BOILING TUBS
(STABILIZATION)

\
DIGESTER
(VISCOSITY
CONTROL)
1
BLENDING

\
i

DEHYDRATING
PRESS

I
PACKAGING
(ALCOHOL
WET)











	 ^.WASTE
WATER













FIGURE 111-8 CELLULOSE NITRATE PRODUCTION
                 38

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Chlorinated Polyethylene

Polyethylene  may  be  chlorinated  either  in  solution  or more
commonly as a suspension in  an  inert  diluent  such  as  water,
acetic  acid,  or cold carbon tetrachloride.  When water is used,
reaction temperatures between 50-65°C  (122-149°F) are used, and a
suitable catalyst is necessary  to  establish  economic  reaction
rates  at  atmospheric  pressure.  Artificial light of wavelength
below  4785  A  and  certain  azo  compounds  are  effective  for
accelerating  the  reaction.   No catalyst is needed, however, at
reaction  temperatures  when  pressures  are   greater   than   7
atmospheres  (100  psig)   or  greater.   The reaction equation is
given in Figure III-9.

The chlorinated polyethylenes are currently used commercially  to
improve   the   iirpact   strength  and  processibility  of  poly-
vinylchloride,  as an elastomer having good  chemical  resistance,
as  a  blending  agent with PVC in the manufacture of floor tile,
and  as  a  blending  agent  in  other  multi-component   plastic
compositions.

Manufacture - A flow chart for a typical chlorination is shown in
Figure  111-10.   Feed  materials  are polyethylene in hot carbon
tetrachloride solution and chlorine.  These are fed into a liquid
phase tubular reactor.  The reaction temperature is  between  50-
150°C  (122-302°F)  at  pressures  as high as 20 atmospheres (300
psig).  The reaction time for the exothermic reaction is about  5
minutes    (44).   After  reaction,  the  polymerized  product  is
separated from HCl, a ty-product of the reaction.

Waste Generation - The primary waste generated is the  by-product
hydrogen  chloride.   Recovery  or  ether  disposal  of  hydrogen
chloride (or hydrochloric acid vapor or solution)  would  be  the
primary  environmental concern.  About 590 mass units of HCl (dry
basis)  would be generated per 1000 mass units of product (5,  10,
11, 40, 44, 45).
                           39

-------
           CH2 — CH2-h   +   CI2—--(- CHCI— CH2 -b  +  HC1
FIGURE 111-9  TYPICAL REACTION TO FORM CHLORINATED POLYETHYLENE
                              40

-------
         POLYOLEFIN
          SOLUTION
CHLORINE
                SEPARATOR
                                PRODUCT
                                SOLUTION
                                                        CONDENSER
     FEED MATERIALS
         POLYETHYLENE
         CHLORINE
                           kg/1000 kg PRODUCT

                                  450
                                 1140
SOURCE; us. PATENT 2,954,509 BYD.M.HURT (TODUPONT)
       (DECEMBER 13, 1960).
         FIGURE 111-10 CHLORINATED POLYETHYLENE PRODUCTION
                                41

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Diallyl Phthalate Resins

Diallyl  phthalate  was one of the earliest unsaturated polyester
resins.  It is a member of the allyl family of resins.  The basis
for this family  of  resins  is  allyl  alcohol  (Figure  III-ll,
Equation  1) .    The vinyl group in the allyl alcohol provides the
unsaturation through  which  subsequent  free  radical  initiated
crosslinking  or  chain extension can take place in order to cure
the  resin.   When  allyl  alcohol  is  reacted   with   phthalic
anhydride,  the  resulting  product  is diallyl phthalate (Figure
III-ll, Equation 2).  This product is manufactured in the  United
States by the FMC Corporation, Princeton, New Jersey.

The  allyl alcohol can be condensed with either the orthophthalic
anhydride to produce diallyl orthophthalate  (trademark Dapon  35,
FMC Corp.) or with the isophthalate acid.  The isophthalate ester
is identified as Dapon M, FMC Corporation.

The product can be used as either a low viscosity monomer or as a
higher  molecular  weight  thermoplastic  prepolymer.   The allyl
monomers and,  in some cases,  the  prepolymers  find  utility  as
crosslinking  agents  for  other  unsaturated  polyester  resins,
either in conjunction with or as a substitute for styrene monomer
which is  the  conventional  reactive  diluent.   The  low  vapor
pressure  at  molding temperatures (2.4 mm of mercury at 1<49°C or
300°F)  favors  the  use  of  diallyl  phthalate  over   styrene,
particularly  for  larger  parts.   This  low  volaitility permits
aHylic polyesters to  be  molded  at  higher  temperatures  than
styrene polyester, and, as a result, faster molding cycles can be
achieved   (30).   Another advantage of using the allylic monomers
or prepolymers as the reactive diluent in unsaturated  polyesters
is  that  they result in formulations with lower volume shrinkage
on curing.

A major use of the  diallyl  phthalate  compounds  when  used  by
themselves  is  critical electrical/electronic applications which
require a high degree of  reliability  under  long-term,  adverse
environmental  conditions.   Examples  are  electrical connectors
used in communications, computer, aerospace, and  other  systems,
as well as insulators, potentiometers, and circuit boards.

Diallyl  phthalate  prepolymer is also used as a surfacing medium
for decorative laminates and in combination with polyester  resin
systems  to  meet the growing demand for economical, low pressure
laminates.

Manufacture - Conventional polycondensation  batch  reactor  type
technology  is  used to form the diallyl phthalate.  Conventional
free radical methods are used in extending the  molecular  weight
of the monomeric diallyl phthalate  (30).
                           42

-------
          (1)
CH, = CH - CH2 - OH
          (2)
            -COOCH2 CH = CH2



            - COO CH2 CH = CH2
FIGURE 111-11  TYPICAL REACTIONS TO FORM DIALLYL PHTHALATE
                          43

-------
Ethylene-Vinyl Acetate Copolymers

Manufacture  - Ethylene-vinyl acetate (EVA)  copolymers with vinyl
acetate contents in the range of about 7-40 percent by weight are
manufactured in the same facilities as low  density  polyethylene
(LDPE)  and  often  with  high  density  polyethylene  (HOPE).  A
process flow  diagram  is  shewn  in  Figure  111-12.   The  same
equipment  is  used  for  EVA  copolymers  as for LDPE except for
additional facilities needed  for  recovery  of  unreacted  vinyl
acetate  and  ethylene.   This  equipment consists of a separator
downstream from the polymerization autoclave, where the solid EVA
particles are sent to the pelletizing operation  and  the  liquid
phase  is  distilled  to recover ethylene and vinyl acetate.  The
distillate wastes consist cf a waxy residue that  is  incinerated
or used as fuel.

In the overall process, shown in Figure 111-12, vinyl acetate and
ethylene  monomers  are  fed  to  a  compressor  to  build up the
pressure necessary for polymerization.  Polymerization is carried
out in an autoclave using a peroxide type  initiator.   Following
polymerization,  the  pressure  is  reduced  and  the  mixture of
unreacted  vinyl  acetate  and  ethylene,   together   with   EVA
copolymer,  is  sent to a separator.  The separated EVA copolymer
is fed to an extruder  (where residual ethylene gas is removed and
returned to the compressor)  which  extrudes  continuous  strands
into  a  water  chill  bath  where they are mechanically cut into
pellets.  The polymer pellets are screened  from  the  water  and
spin dried.

The  liquid phase from the separator is distilled for recovery of
monomers, and the final residue incinerated as described above.

As the final process step, the EVA pellets are remelted, combined
with additives  and  repelletized.   Examples  of  aidditives  are
diatomaceous   earth,  amides,  butylated  hydroxy  toluene,  and
various cyclic organic compounds.  Since many of the; end uses for
the product involve direct contact with foods, it is produced  to
meet FDA requirements.

An  EVA  copolymer with distinctly different characteristics from
those described above is produced by an  emulsion  polymerization
process.   The  emulsion  copolymer has a very high vinyl acetate
content.  It is made at only one plant,  which  is  unrelated  to
those plants using the LDPE process.  The emulsion polymerization
process and associated waste water loads are essentially the same
as  those  reported for polyvinyl acetate homopolymer emulsion in
EPA Development Document No. EPA 440/1-73/010  (61).

Waste Water Generation - In plants using LDPE equipment  for  EVA
production,   the   pelletizer   cooling   water   is   generally
recirculated  through  the  refrigeration  cooling   system.    A
continuous  purge  is  maintained  to  control  vinyl acetate and
polymer fines contamination in  the  recirculated  water.   Vinyl
acetate  which  enters  the waste waters from the purge stream is
                           44

-------
                                                PEROXIDE
                                                INITIATOR
           VINYL
         ACETATE.
         ETHYLENE-
                         COMPRESSOR
                              I
                                                  I
                                                          VINYL ACETATE
                                                            RECYCLE
                            ETHYLENE
                            RECYCLE
                       AUTOCLAVE
SEPARATOR
                        OIL LEAKAGE AND
                           SPILLS TO
                        PROCESS SEWER
Ul
 EVA POLYMER
 a 450-500°C
PLUS ENTRAINED
    GASES
MONOMER
RECOVERY
                                                                             OILS & WAXES
                                                                            - TO BOILER
                                                                               AS FUEL
                                          ETHYLENE
                                          RECYCLE
                                      WET PELLETS
                                   DRIED
                                EVA PELLETS
                               (7-40% VA by Wt.)
                                                                                                  MAKE-UP WATER



REFRIGERATION
COOLING


                                                                                        PURGE TO PROCESS SEWER
                                                                                          (VINYL  ACETATE AND
                                                                                            POLYMER FINES
                                                                                            CONTAMINATION)
                             FIGURE 111-12  ETHYLENE-VINYL ACETATE COPOLYMER PRODUCTION

-------
biodegradable both as the intact compound and in the form of  its
hydrolysis products, acetaldehyde,  and acetic acid.

Other  waste  sources are oil leakage and spills from compressors
and pumps  which  enter  area  surface  water  drainage  ditches.
Washdown  water  from  processing and loading areas also flows to
the drainage ditches and  is  another  source  of  vinyl  acetate
contamination.   The  waste stream from the ditches is skimmed to
recover oil and EVA particles.   The oil is  incinerated  and  the
EVA is either land-filled or sold to scrap reprocessors (16, 25).
                           46

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Fluorocarbon Polymers

The term "fluorocarbon polymers" as used in this report refers to
addition type polymers in which all, or a significant portion, of
the  substituent  groups on the carbon atoms in the polymer chain
are fluorine.  Typically, the balance  of  the  substituents  are
chlorine   and/or  hydrogen.   The  fluorocarbcn  polymer  family
encompasses a range of  homopolymer,  copolymer,  and  terpolymer
compositions as indicated by the list shown in Table III-5.  Most
of the products are in the plastics category, but elastomer grade
polymers have also been included.

Polytetrafluoroethylene  (PTFE)   is  by  far  the  most important
commercial polymer in this group and accounts for an estimated 75
percent or more of the total production.  PTFE is produced in two
dry product forms (granular and fine powder) and  as  an  aqueous
dispersion.   It  is  the  only  fluorocarbon polymer produced in
three different plants.  In view of the relative significance  of
PTFE,  the  process  descriptions  below  have  been  divided  to
separate PTFE from the other fluorocarbon polymers.

Practice varies widely from plant  to  plant  in  this  industry.
Some plants produce only one type; more commonly several types of
fluorocarbon polymers are made at the same plant.  However, since
most  of  the  polymers  are proprietary, the product mix differs
from plant to plant.  All  existing  plants  are  located  within
larger   chemical   complexes.   The  practice  with  respect  to
production of monomer and monomer feedstock varies.  TFE  monomer
is  produced  on-site in all cases.  Production of other monomers
and monomer feedstocks (chlorodifluoromethane in the case of TFE)
may  or  may  not  be  carried  out  at  the  same  plant.   From
examination of available waste load data related to production of
the  various polymers and in view of the widely varying practices
from  plant  to  plant,  we  have  concluded  that  waste   water
guidelines  should be limited to the dominant products - granular
and fine powder grades of PTFE  -  and  that  aqueous  dispersion
grade  and  all other fluorocarbon polymers must be considered as
unique products.

It is also characteristic of this  industry  that  process  tech-
nology   is   considered   highly   confidential.    The  process
descriptions that follow, therefore, are necessarily  general  in
nature.

A.  Polytetrafluoroethylene (PTFE)

1.  TFE Monomer Process

Since  TFE  monomer  is  produced  on-site  in all cases, we have
included  monomer  synthesis  as  part  of  the  overall  polymer
process.

Manufacture - TFE monomer is produced by continuous process based
on   pyrolysis   of   chlorodifluromethane  (Refrigerant  22)   as
indicated by the flowsheet shown  in  Figure  111-13.    The  main
                            47

-------
reaction  involved is shown at the top of Figure III-1U.  Various
other fluorinated side products  may  also  be  forrr^d  in  minor
amounts.

The  process  stream  from the reaction furnace is scrubbed first
with water, then with  dilute  caustic  solution  to  remove  by-
product  HCl  and  other  soluble  components.  After the caustic
scrub, the gas stream is dried either with concentrated  sulfuric
acid  or  with ethylene glycol.  The dry gas stream is compressed
and distilled to recover purified TFE  monomer.   Extremely  pure
monomer is required for subsequent polymerization.

Waste  Water  Generation  - The sources of waste water generation
from the TFE monomer process are indicated in Figure 111-13.  The
effluent from the water scrubber is a  dilute  solution  of  HCl.
This  stream is the only significant source of fluoride discharge
from the process.  In general, waste waters from TFE monomer  and
polymer processes do not contain appreciable amounts of fluoride.
(However,  greater  amounts  of  fluoride  are  generated  in the
production  of  the  monomer  precursor.  Refrigerant  22.)   The
effluent  from the caustic scrubbers contains very dilute caustic
and dissolved salts.  In those cases where sulfuric acid is  used
for drying the gas stream, strong acid solution is recovered from
the  drying  tower.  Where ethylene glycol is used for the drying
step, a small amount of glycol is  lost  in  the  glycol  recycle
operation  and  contributes  a  minor BOD load in the waste water
stream.

2.  PTFE Polymerization

Manufacture - Polymerization of TFE  to  the  homopolymer,  PTFE,
proceeds  by  free-radical  addition  polymerization  typical  of
olefins.  The polymerization is carried  out  under  pressure  in
aqueous   media  in  batch  reactors.   The  literature  suggests
initiators such as sodium or potassium  peroxydisulfates  may  be
employed.   The  polymerization  reaction  is indicated in Figure
111-14 and a generalized flowsheet of the  process  is  shown  in
Figure 111-15.

PTFE is produced for sale in several forms:  a granular or pellet
form,  a  fine  powder,  and aqueous dispersion.  The dry product
forms, granular and fine powder, account for the major portion of
PTFE production.  Guidelines have been  proposed  for  these  dry
product  forms only.  Dispersion grade is made by only two of the
three plants presently producing PTFE.

Waste water Generation - Water  is  used  as  the  polymerization
medium  in  producing  all  forms of PTFE, but subsequent process
water use and waste water discharge varies with  the  form  being
produced.   High  purity, demineralized process water is required
in all cases.

For granular or pellet grades, process water use in  addition  to
polymerization  medium  includes  polymer  wash  water  and,  for
pellets, chill water for extrusion/pelletizing  operations.   The
                            48

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                                       ALTERNATIVE
                                         DRYING
                                        METHODS
                                   GLYCOL LOSS
                                  AQUEOUS WASTE
DISTILLATION
                                                                                    PURE
                                                                                    TFE
FIGURE 111-13 POLYTETRAFLUOROETHYLENE (PTFE) PRODUCTION - TFE MONOMER PROCESS

-------
       Feedstock
                                Monomer
                                                                      Polymers
  2CHF2CI	>-2HCI
           heat

(chlorodifluoromethane)
  CF2 =CF2
     (TFE)


  + CH2 =CH2
     (ethylene)
         CF3
  CF2  =  CF
     (HFP)
  CF2CI-CH3  	«
              heat
(chlorodifluoroethane)
                     HCI
   CF2CI-CFCI2
               Metal Cat.
 (trichlorotrifluoroethane)
CF2  =  CH2
     (VDF)
+ CF2 = CFCI
     (CTFE)
                                CH2 =CH2
                                (ethylene)
                                                                 (PTFE)

                                                              ~(CH2-CH2-CFj-CF2-)-n
                                                                 (ETFE)
                                                                              CF3
                                                              -fCF2-CF2-CF2-CF-)-n
                                                                 (FEP)
                                                                               CF3
                                                              H-CF2-CH2-CF2-CF-)-n
                                                                  (VDF-HFP)
                                                              -fCF2 -CHj-)-n
                                                                  (PVDF)
                                                               —fCF2-CH2-CF2-CFCI-^
                                                                   (CTFE-VDF)
                                                              -tCF2-CFCIt-n
                                                                  (PCTFE)
                                  -4CH2-CH2-CF2-CFCI4-n
                                      (ECTFE)
HC = CH    +    HF  —
(acetylene)      (hydrogen
              fluoride)
                              CH2  =  CHF
                                 VF
                                   -f-CH2-CHF-hn
                                      (PVF)
 Source:  Chemical Economics Handbook, Stanford Research Institute.
    FIGURE 111-14  TYPICAL REACTIONS TO FORM FLUOROCARBON POLYMERS
                                       50

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          WATER
        INITIATORS
        STABILIZERS
TFE
    BATCH
POLYMERIZATION
              SURFACTANT-
   POLYMER
RECOVERY/WASH
                                               I
                                             WASH
                                             WATER
                           DISPERSION
                             GRADE
                          AQUEOUS WASTE
                         (SUPERNATE LIQUOR)
                                                                        GRANULE
                                                             EXTRUSION/
                                                            PELLETIZING
                                                                 T
                                                             CHILL WATER
                                                                          FINE
                                                                         POWDER
            FIGURE 111-15 POLYTETRAFLUOROETHYLENE (PTFE) PRODUCTION -
                        PTFE POLYMER PROCESS

-------
process water discharged from these operations is very clean.  In
one  plant,  all  the  process  water  is  collected and recycled
through a purification system.  In the production of fine  powder
grade  PTFE,  wash  water  is  required  to  purify  the  polymer
particles.  The conditions required to produce fine powder  grade
are  such  that  the water discharged from the polymerization and
washing steps  may  contain  a  higher  level  of  suspended  and
dissolved solids than in the case of granular product.

In   the   production   of  the  dispersion  form  of  PTFE,  the
polymerization  batch  is  concentrated  after  addition   of   a
surfactant  to  stabilize  the  dispersion.  The supernate liquor
from the concentrating step is  discharged  as  a  waste  stream.
This stream has a BOD load due to presence of the surfactant.

    B.  Other Fluorocarbon Polymers

    The   nature  of  other  fluorocarbon  polymers  produced  is
    indicated by the list presented in Table III-5.   Since  most
    of  these  polymers are proprietary and process technology is
    considered highly confidential, it is not  possible  to  give
    detailed  process  descriptions.   Reactions  taken  from the
    literature, indicating the routes to most of these  polymers,
    are given in Figure 111-14.

    The  polymerization  step is comparable to that used for PTFE
    in  that  the  polymerization  is  carried  out  in   aqueous
    (purified  water)   medium in batch kettles.  Subsequent steps
    may vary significantly with the type of polymer arid  form  of
    product  made.   These  steps  may  include concentration and
    stabilization of a dispersion form of the product;  filtration
    or coagulation to recover polymer particles; polymer  washing
    with  water  or  solvent; conversion to final product form by
    drying granules or powder, extrusion of pellet or film forms,
    or solvent-casting.  Recovery operations to  recover  organic
    solvents   or   other   proprietary  additives  may  also  be
    associated with seme of the polymer processes  (6, 29, 30).
                           52

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                           TABLE III-5

                COMMERCIAL FLUORCCARBON POLYMERS


             Polymer                             Abbreviation


Polytetrafluoroethylene                               PTFE
Fluorinated Ethylene - Propylene                      FEP
Poly(ethylene - tetrafluoroethylene)                  ETFE
Chlorotrifluoroethylene                               CTFE
Poly(ethylene - chlorotrifluoroethylene}              ECTFE
Poly (chlorotrifluorothylene - vinylidene fluoride)     CTFE-VDF
Polyvinyl Fluoride                                    PVF
Polyvinylidene Fluoride                               PVDF
Poly (vinylidene fluoride - hexafluoropropylene)       VDF-HFP
                           53

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Nitrile Barrier Resins

This class of resins has  assumed  importance  primarily  because
nitrile   tarrier  resins  are  transparent  polymers  with  good
resistance to passage of gases and solvents.    They  are  in  the
early  stages  of  being  utilized  for beverage containers.  The
nitrile group is the source of  these  good  barrier  properties.
The   nitrile  group  originates  from  the  presence  of  either
acrylonitrile  or  methacrylonitrile  in  the   final   polymeric
structure.   The  nitrile  content  vias  previously restricted to
below 30 percent in  order  to  produce  resins  with  acceptable
processibility.   At  this level, the barrier properties were not
exceptional.  Recent developments have been in the  direction  of
producing  resins  which  have higher nitrile content while still
retaining adequate processibility by  conventional  thermoplastic
methods   (i.e.,  extrusion,  injection  molding,  blow  molding,
thermoforming).

The exact details of resin composition are considered proprietary
by the resin manufacturers.  The general structure however may be
viewed  as  a  butadiene   backbone   to   which   acrylonitrile/
methylacrylate  or  acrylonitrile/styrene copolymers are attached
by grafting.

The  exact  nature  of  the  technical  developments  which  have
resulted   in  this  breakthrough  is  closely  held  proprietary
knowledge by the three U.S. resin  suppliers  competing  in  this
field.

Any  of the generally known polymerization methods  (such as bulk,
solution, or emulsion) could be used  to.  prepare  these  resins.
Emulsion polymerization is undoubtedly the preferred method.  The
final  composition  may  result  from  a  two-step polymerization
scheme in which a copolymer (such as  acrylonitrile/acrylate)  is
polymerized   by   eirulsion  techniques  in  the  presence  of   a
previously  formed  graft  copolymer   (such   as   acrylonitrile/
butadiene) .

The  polymerization  scheme described below is speculative and is
based  on  a  review  of  in-house  information   and   published
literature.   It  is  believed,  however, that it is a reasonable
representation of a typical polymerization process.

A typical  polymerization  procedure  would  involve  a  two-step
process  in  which the acrylonitrile butadiene graft copolymer is
made by batchwise emulsion polymerization of  a  recipe  such  as
that listed below  (48).
                            54

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     Typi cal^Late x^Recipe               Parts

     Acrylonitrile                       40

     1,3-butadiene                       60

     Emulsifier                           2.4

     Azodiisobutyronitrile                0.3

     t-dodecyl mercaptan                  0.5

     Water                              200

Before  starting  the  reaction,  pH is adjusted to about 8 using
potassium hydroxide.  Conversion of 92 percent can be obtained in
22-1/2 hours at 45°C  (113°F)  giving a  total  solids  content  of
33.1 percent.

The final resin is then prepared by mixing the following:

     Latex  (from reaction above)         31.9

     Acrylonitrile  (or methacrylonitrile) 70

     Ethyl acrylate                      30

     Potassium persulfate                 0.06

     Emulsifier                           3.0

     n-dodecyl mercaptan                  1.0

     Ethylene diamine tetracetic acid     0.5

     Water                              200

Adjust   to   pH7   using   potassium  hydroxide.   Twenty  hours
polymerization time  (absence of oxygen) at 60°C   (140°F)  results
in 97 percent conversion to 33 percent solids.

The polymer is then coagulated using aluminum sulfate, washed and
dried.   At  this point the dried polymer chips are then probably
densified and passed to an extruder for processing into pellets.

Manufacture -  The  generalized  batch  process  description  for
emulsion polymerization shewn below is taken from EPA.
Development   Document   No.   440/1-73/010   (16)  along  with  a
generalized flowsheet shown as Figure 111-16.

A batch process, as shown in Figure  111-16,  is  commonly  used.
Typical  reactor  size  is  19 cu m  (5000 gal.).  The batch cycle
consists  of  the  continuous  introduction  of  a  water-monomer
emulsion  to the stirred reactor.  Polymerization occurs at about
the rate of monomer addition; the heat of reaction is removed  to


                            55

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cooling  tower  water circulated through the jacket.   The reactor
is vented through a  condenser  for  monomer  recovery;  and  the
condensate,  including  any  water,  is  returned directly to the
vessel.  On completion of the batch, a short  "soaking"  time  is
allowed  for  completion of the reaction, and water is then added
to dilute to the desired end composition.  The batch is drawn off
through a screen to product storage.  Oversize screenings (a very
small amount)  are disposed of to landfill.

Monomers, the principal raw materials, are often protected during
shipping and storage by an inhibitor, such as catechol, which may
be removed prior to polymerization by washing.  This  contributes
to the waste water load.

Waste  Water  Generation  - sources of waste water from a typical
emulsion polymerization include the following:

     o  Reactor cooling w.ater

     o  Cooling tower and boiler blowdown

     o  Monomer washing

     o  Liquid or solid waste from monomer stripping
        or recovery operations

     o  Discarded Latex batches

     o  Coagulant wastes

     o  Startup, spills, etc.

     o  Demineralizer wastes

     o  Possible liquid wastes from rronomer scrubbing
         (16, 51, 48).

Other Pollutants

Organic nitrogen occurs as a result of losses from
dissolution and emulsification of  reactants.
Cyanides will be detectable by analytical
methods due to the presence of acrylonitrile.
                            56

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Ul
           EMULSIFIER
      PROCESS
       WATER
CATALYST
L"DOLING
                        WATER
        MONOMERS'
        WASH WATER	
                               BATCH
                              REACTOR
                               CYCLE
                                                  COAGULATION
                                                    AGENT
                                                 SOLID
                                                 WASTE
                                          COAGULATION
                                             TANK
                                                                            WASTE
                                                                            WATER
                                                                                    DRY
                                                                                   PRODUC1
              FIGURE 111-16  NITRILE BARRIER RESIN PRODUCTION - EMULSION POLYMERIZATION PROCESS

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Parylene Polymers

Parylene is produced by vapor-phase polymerization and deposition
of paraxylylene  (or its substituted derivatives) .    The  polymers
are highly crystalline, straight-chain compounds with a molecular
weight  of  approximately  500,000.  It is extremely resistant to
chemical attack, exceptionally low in trace metal  contamination,
and compatible with all organic solvents used in the cleaning and
processing of electronic circuits and systems.  Although parylene
is insoluble in most materials, it will soften in solvents having
boiling points in excess of 150°C  (302°F).  It is also being used
for  moisture  barrier  coatings  on  discrete components such as
resistors, thermistors, thermocouples,  fast  responding  sensing
probes, and photocells.

Unlike  most  plastics,  parylene  is  not produced and sold as a
polymer.  It is not practical to melt, extrude, mold or  calender
it  as  with other thermoplastics.  Further, it cannot be applied
from solvent  systems  since  it  is  insoluble  in  conventional
solvents.

Parylene polymers are prepared from di-p-xylylene and dichlorodi-
p-xylylene,  through  a process called pyrolytic vapor deposition
polymerization.   Di-p-xylylene   and   the   chloro   derivative
dichlorodi-p-xylylene are white, high melting crystalline solids.
Di-p-xylylene  has a melting point of 284°C  (543°F) and a density
of 1.22 g/cm3.  Dichlorodi-p-xylylene has a melting point of 140-
160°C  (28U-320°F) and a density of 1.3.  Both  are  insoluble  in
water.   The reactions are illustrated in Figure 111-17, Equation
1.

Unsubstituted di-p-xylylene can be readily  purified  by  recrys-
tallization  from  xylene.  Dichlorodi-p-xylylene  is a mixture of
isomers as prepared by chlcrination of di-p-xylylene.  It is  not
necessary  to separate these isomers  since, after  pyrolysis, only
chloro-p-xylylene results regardless  of which isomeric  dimer  is
used as starting material.

The  polymerization process is exceptional  in that it takes  place
in  two   completely  distinct  and  separate  steps.   The   first
involves  the cleavage  of the two-methylene-methylene bonds  in di-
p-xylylene  by   pyrolysis  to  form two molecules  of the reactive
intermediate, p-xylylene.  This  latter molecule is stable in the
vapor   phase  but,  in the second  step, spontaneously polymerizes
upon condensation to form high molecular-weight poly(p-xylylene).

The polymerization  step  proceeds  by a free-radical mechanism  in
which,  as a  first  step,  two molecules of  p-xylylene condense on  a
surface and react  to  form  a diradical intermediate.

The   first   step  is   probably   reversible.   However,  subsequent
reaction  with   p-xylylene  by   addition   to  either  end  of the
reactive   diradical  of  the intermediate  results  in the  formation
of  stable species  (Figure  111-17,  Equation  2)  in  which  n  is 1,  2,


                             58

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(1)
          CH,
          CH,
          CH2
                            •*• 2CH,
                                CH7
          CH2
          X = H
            or
          X = Cl
r\CH,_CH,/n
                                 CH2'  +  CH,
(2)
         CH,
                    CH2-|— CH2.
                       n
                                                 CH,
           FIGURE 111-17 TYPICAL REACTIONS TO FORM PARYLENE POLYMERS
                              59

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or 3.  Growth then progresses by addition of p-xylylene  to  each
end  of  the  radical.   Growth  is terminated by reaction of the
radical end groups with reactive sites in other  growing  polymer
chains, by reaction of the free-radical sites with chain transfer
agents  (e.g.,  oxygen  or  mercaptans), or by the reactive sites
becoming buried in the polymer matrix.

This proposed method of polymerizing p-xylylene suggests that the
rate of polymerization should be markedly increased  by  lowering
the temperature of the deposition surface to increase the rate of
condensation and, therefore, the concentration of molecules of p-
xylylene  in the condensed phase.  This has also been shown to be
the case,  and relative polymerization rates of  1,  10,  and  100
were observed for p-xylylene on surfaces maintained at 30, 0, and
-40°C   (86,  32,  and  -40°F),  respectively,  and  at equivalent
monomer concentrations in the vapor phase.   These  data  provide
strong   evidence   that   the   rate  determining  step  in  the
polymerization is condensation of a p-xylylene  molecule  in  the
vicinity  cf  a  growing  free  radical, and that addition of the
condensed molecules  to  the  reactive  site  is  very  rapid  in
comparison.

Manufacture  -  Manufacture  is  accomplished  in a batch process
requiring relatively simple equipment  (see Figure  111-18).   For
example,  the  reactions  may  be carried out in a 61 cm  (24 in.)
section of 28 cm  (11 in.)  I.D. Vycor tubing.  The first 15 cm  (6
in.) of the tube serves as a distillation zone, and the following
46 cm  (18 in.) section as the pyrolysis zone.  The pyrolysis tube
is  connected  to  a  glass deposition chamber.  System operating
pressure is in the range of 1 Torr.   The  distillation  zone  is
maintained  at  temperatures  ranging from 140-220°C  (284-428°F),
depending upon the derivative.  The pyrolysis zone is  heated  to
600°C  (1112°F) and the deposition chamber is usually held at room
temperature.   With  seme  derivatives,  it  is heated as high as
160°C  (320°F) to permit deposition of polymer over a fairly broad
area.

Deposition chambers of virtually any  size  can  be  constructed.
Those   currently  in use range from 0.0082-0.459 cu m  (500-28,000
cu  in.).  Large parts up to 1.5 m  (5 ft) long and 46 cm  (18  in.)
high  can be processed in this equipment.  The versatility of the
process also enables the simultaneous coating of many small parts
of  varying configurations.

Waste Water Generation - The  waste  water  generation  from  the
manufacture of parylene is minimal since it requires no catalysts
or  solvents.   Any  waste  water generated will be that  from the
washing  and  cleaning  of  processing  equipment,   which   with
housekeeping  and  operational procedures can be contained in the
process area.  Provided the cold trap is efficient, air pollution
would  be minimal  (27,  34).
                             60

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Dl-P-XYLYLENE
VAPORIZER
                                PYROLYSIS
                               DEPOSITION
                                CHAMBER
                               COLD TRAP
      FIGURE 111-18 PARYLENE PRODUCTION
                   61

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Poly-Alpha-Methyl Styrene

The  poly(alpha-methyl  styrene)   homopolymer  is  apparently  of
little  commercial importance.  The homopolymer has a low ceiling
temperature (61°C or  141.8°F),  and  thus  depolymerization  can
occur easily during fabrication.   In addition, the hcinopolymer is
difficult to fabricate because of its high melt viscosity.

Radical polymerization of the pure monomer, alpha-methyl styrene,
proceeds  very  slowly  and  is  not  a  practical  technique for
production of this product.  Homopolymers are instead prepared by
anionic catalysis of the monomer.  Polymerizations by free alkali
metals are  included  in  this  category  since  a  free  radical
propagation  is  apparently  not involved.  The polymerization of
alpha-methyl styrene is readily catalyzed by metallic  potassium.
The polymerization proceeds as shown in Figure 111-19,.

Recent   literature  articles  report  additional  polymerization
techniques,  including:  radiation-   and   photo-induced   poly-
merization of pure alpha-methyl styrene; increased polymerization
rate  and  slightly  increased  degree of polymerization upon the
application of an- electric field for pure  alpha-methyl  styrene;
and  grafting  by  irradiation  of  alpha-methyl styrene to other
polymers for the purposes of  physical property modification.   It
is  doubtful  that  these  techniques  have yet been applied on a
commercial scale,  however.   Those  copolymerizations  utilizing
alpha-methyl  styrene  which  are carried out on commercial scale
are  accomplished  by   radical   polymerization.    In   styrene
copolymers  or  terpolymers   the presence of alpha-methyl styrene
results in a stiffening of the polymer  chain.   Usually,  higher
polymer    fabrication  temperatures  are  required   (and  can  be
tolerated) for these materials.

Manufacture - Adequate information is not available on commercial
methods used, if any.  Presumably, small batch processing may  be
employed  (25) .
                              62

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          CfiHc 	 C ~ CH?
CH2
C6HS



C 	
FIGURE 111-19   TYPICAL REACTION TO FORM ALPHA-WIETHYL STYRENE
                               63

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Polyamides

Materials  considered  to  fall  in  this category include nylons
other than Nylon 66 or 6, which were covered in  EPA  Development
Document  No.  EPA  440/1-73/010   (16).  Thus, the category would
include Nylon 6/12, Nylon 11, and other polyamides having special
structures.  Among resins produced in the U.S.A. are  Nylon  6/12
(DuPont)  and Nylon 11 (Rilsan, Inc.).

Manufacture  and  Waste Water Generation - Nylon 6/12 is produced
in equipment used regularly for production  of  Nylon  6/6.   The
product is based on sebacic acid rather than adipic.  The process
is  operated  under slightly different conditions than those used
for Nylon 6/6.  Wastes from the two processes are similar.

Nylon 11 is produced by  polymerization  of  11-amino  undecanoic
acid  in  a  process that is comparable to that used for Nylon 6.
In the production of Nylon 11, the reaction  is  such  that  very
little  free  monomer  remains  when  polymerization is complete.
Wastes developed in the process are negligible  (41).
                              64

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 Polyaryl Ether  (Arylon)

 The polyaryl ethers,  also  known   as  the   polyphenyl  ethers   or
 polyphenylene   oxides are a  new class of polymers.  They have the
 structure  shown in Figure III-20,  Equation   1,  where  Ar   is   an
 aromatic   radical  and R may be  aromatic or aliphatic.  The best
 known examples  of this type  of   polymer  are  the  thermosetting
 epoxy resins.   Recently, several  new polymeric  ethers have  become
 commercially  important  as  thermoplastics.  These polymers have
 outstanding  hydrolytic  resistance,  and   most  of   them  are
 unaffected by corrosive environments.

 The  polyaryl   ether  resins  are made by the oxidative coupling  of
 hindered phenols.  The reaction of  2,6-dimethyl phenol to produce
 polyphenylene oxide is illustrated  in Figure 111-20, Equation   2.
 The  di-substituted phenol,  copper  salt, and amine are dissolved,
 and  oxygen  is passed  through   the  solution  producing  the
 polyphenylene   ethers and   a  minor  amount of diphenyl quinone
 (Figure  111-20,  Equation   3).    The  polymer  obtained  is    an
 extremely   high   molecular   weight   material,  has  a   useful
 temperature of  -170°C to  +190°C   (-27<4°F   to  +374°F) ,  and   is
 chemically inert.

 An  alternative method  of  producing the polyphenylene ethers  is
 the oxidation of p-bromophenol.  A  solution of  2,6-dimethyl-4-
 bromophenol  in aqueous  potassium  hydroxide  is  reacted with
 potassium-ferricyanide, producing  poly-2,6-dimethyl-l,4-phenylene
 ether.

 One manufacturer produces  poly-2,6-dimethyl-l,4-phenylene  ether
 by another method, the copper-catalyzed oxidation of 2,6-xylenol.
 The  polymer  product is  marketed under the trademark PPO.  The
 commercial polyphenylene ether  is  a  linear   polymer  having  a
 molecular  weight of  25,000 to 30,000.  The  electrical properties
 of PPO  (R)  are  such that the material has been  used  extensively
 for  high-frequency   insulation of electrical equipment.  Because
 PPO (R)  can be  autoclaved in medical sterilizers, it is  used   to
 replace  glass  and   stainless  steel in a  variety of medical and
 surgical instruments  in hospital utensils.    It  is  also  employed
 in  household   appliances,   in  food  processing equipment  and  in
 plumbing fittings.

 A modified form of polyphenylene oxide resins has been introduced
 under the  trademark   NORYL,  also  by  General  Electric.   This
 material is based on  polyphenylene technology and is intended for
 applications  not  requiring  performance of polyphenylene  oxide.
 The properties  of PPO  (R)  and NORYL (R)  are  given in Table  III-6.

 A typical synthesis from the literature is   as  follows.     Oxygen
 was  passed for 10 minutes into a reaction mixture containing 5 g
 of 2,6-dimethyl phenol, 1 g of Cu2Cl2 and  100  ml  of  pyridine.
 During  the  course   of  the  reaction,  the temperature rose to a
 maximum of 70°C (158°F) and no water was  removed.    The  product
was  precipitated  by  pouring the reaction mixture into about 500
ml of dilute hydrochloric acid and was separated  by  filtration.
                              65

-------
(1)
-fArO-R-04-n
(2)
                            02, R3N
                              Cu+
(3)
                                       O =
                                                                 = O
            FIGURE 111-20  TYPICAL REACTIONS TO FORM POLYARYL ETHER
                                        66

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                         TABLE III-6

                PROPERTIES OF POLYARYL ETHERS
Density                             1.06          1.06

Tensile strength, psi         111,000         9,600
 kg/sq cm                         7UO           675

Elongation, %                      80            20

Tensile modulus, psi x 10s          3.8           3.55
 kg/sq cm x 10                      0.27          0.25

Impact strength notch, ft-lb/in.    1.5           1.3
 Joules/cm                          0.8           0.7

Heat deflection temp. , °F at
 264 psi fiber stress             375           265

Heat deflection temp., °C at
 18.6 kg/sq cm                    190.5         129.5

Dielectric constant, 60 cycles      2.58          2.64
                            67

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The  product, poly-2,6-dimethyl-l,4-phenylene ether, was produced
in substantially quantitative yields.

This product had a molecular weight in the range  of  300,000  to
700,000  and  did not melt at 300°C  (572°F).   The powder produced
on precipitation could be molded, calendered, or  extruded  under
pressure.

Manufacture  -  Manufacturing  processes for polyaryl ethers have
not been discussed in the literature.  By analogy to  the  bench-
scale  syntheses,  solution  polymerization  in water is probably
practiced for polyphenylene oxides.

Waste Water Generation - Waste water effluents will contain small
fractions of all components of the  reaction  mixture,  including
monomers,  catalysts  (copper-salts),  and amine and possibly the
by-product diphenyl quinone, or  other  reactants  and  catalysts
depending upon the process of interest.  In general, there is one
mole  of water of reaction produced per mole of oxide linkage or,
for poly-2,6-dimethyl-l,4-phenylene  ether,  159  mass  units  of
water per 1000 mass units of polymer product (23).
                              68

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Polybenzimidazoles

The  polybenzimidazoles  are  polymers  incorporating  the benzi-
midazole ring into the polymer backbone as shown in Equation 1 of
Figure 111-21.  These polymers are notable for their stability to
oxidative attack at high temperatures.  They have high  molecular
weights  and  excellent resistance to hydrolytic attack in acidic
or basic media.

Essentially, the benzimidazole is formed by  the  reaction  of  a
1,2-aromatic  diamine with a carboxyl group.  The reaction may be
written as shown in Equation 2 of Figure III-21.

The first polybenzimidazoles, described in a patent in 1959, were
synthesized  by  condensation  of  aromatic  bis-o-diamines  with
aliphatic  dicarboxylic  acids  in  a  manner  analogous  to  the
preparation of benzimidazoles.  This polymer, which  incorporated
an  aliphatic  linkage,  gave  the  first  indication  that  high
temperature resistance might be  achievable  in  these  polymers.
This  synthesis  was  followed  by  that  of  completely aromatic
polybenzimidazoles in the belief, later justified,  that  thermal
and  oxidative properties would be improved in a totally aromatic
system.

The initial work with the  aromatic  polybenzimidazoles  involved
reaction  of  an  aromatic tetraamine with a diphenyl ester of an
aromatic dicarboxylic acid —  in  particular,  the  reaction  of
3,3'-diaminobenzidine  and  the phenyl ester of isophthalic acid.
The reaction is illustrated  in  Equation  3  of  Figure  111-21.
Subsequent work extended to the synthesis of a number of polymers
from other acid derivatives.  From this initial exploratory work,
3,3'-diaminobenzidine  and  isophthalic  or blends of isophthalic
and terephthalic derivatives were  selected  as  most  promising.
These acids are illustrated in Table III-7.

Polybenzimidazoles have been synthesized to high molecular weight
by  solution,  melt,  or  solid  state  polymerization.  Solution
condensation can take place in either an organic solvent having a
boiling point sufficiently high for the reaction to  proceed,  or
in  polyphosphoric  acid.  A typical high-boiling organic solvent
is either phenol or m-cresol.  Phenol has the ability to  provide
an  easier,  more complete polymerization than most solvents.  It
is necessary to conduct all condensations under inert  atmosphere
to  prevent oxidation of the tetraamine.  Condensations have been
reported in which solvents such as  dimethylacetamide,   dimethyl-
formamide,  dimethylsulfoxide,  N-methylpyrrolidone,  phenol, and
cresol were used.   Polyphosphoric  acid  has  been  investigated
because  the  oxidation  sensitivity  of the tetraamines could be
circumvented by use of the tetrahydrochloride salt.   Upon heating
in an inert atmosphere,  hydrogen chloride  is  evolved   at  about
140-150°C  (28U-302°F),   giving  a  solution  of  tetraamine  and
polyphosphoric acid.
                              69

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                                                                       (Equation 1)
                                                N
                                                H

                                       benzimidazole
                        NH,
                        NH2
                              HCO2H
                                                           HNOCH
                              H20    (Equation 2)
            o-Phenylenediamine  Formic acid
                     NH2
         Amide intermediate    Water
                       HNOCH
                      .NH2

            Amide intermediate
                                              NH
                                                      + H20
Benzimidazole     Water
H, N
                     Generalized Synthesis of Polybenzimidazole
   H2N                     NH2

        3,3'-Diaminobenzidine
   Diphenyl isophthalate
                                            Polybenzimidazole
                                      (Equation 3)
                                                                               -00H
                                        Phenol
              FIGURE 111-21    TYPICAL REACTIONS TO FORM POLYBENZIMIDAZOLES
                                              70

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                                                   0
                                                   II
                                                 HOC
COM
           Isophthalic Acid
           Terephthalic Acid
TABLE 111-7   ACIDS WHOSE DERIVATIVES ARE USED IN POLYBENZIMIDAZOLE SYNTHESIS
                                        71

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Melt condensation for preparation of polybenzimidazoles has  been
investigated  in  some  detail.    Upon  application  of heat, the
mixture of monomers melts, and shortly thereafter  the  evolution
of  phenol  becomes  noticeable  and  rapid.   Continued  heating
results  in  increasing  viscosity  until  the  reaction  mixture
solidifies.   At  this  point vacuum is applied to remove as much
evolved phenol as possible.  After the polymer has been cooled to
room   temperature,   it   is   pulverized,   replaced   in   the
polymerization  tube,  and  the  polymerization  is  completed by
slowly heating to 350-400°C   (662-752°F)   in  vacuo.    Thus,  the
critical  phase  of  the  polymerization, in which high molecular
weight is achieved, takes place as a solid state reaction.

Many polybenzimidazoles have been synthesized since the  original
disclosures.   The  greatest  impetus  was  provided  by the work
involving the fully aromatic systems.

In general, if equimolar quantities of  reactants  are  employed,
the  polymerization  will  continue  with heating to produce high
molecular weight polymers soluble  only  in  formic  or  sulfuric
acids.    These   cannot   conveniently   be  processed  further.
Accordingly, the reaction may be interrupted at some intermediate
stage to produce soluble,  low-melting  compounds  which  can  be
applied  in  the liquid phase.  Alternatively, through the use of
an  excess  of  amine,  an  amine-terminated  prepolymer  may  be
produced,   which   is  then  combined  with  an  acid-terminated
prepolymer,  with  the  remainder  of  the  polymerization  being
subsequently  conducted  either  from  solution or as a hot melt.
During the final polymerization, there will be the  evolution  of
considerable volumes of volatiles, which must be removed from the
polymerizing  structure.   Thus, at high pressures, low molecular
weight polymers  may  be  developed  as  a  result  of  entrapped
volatiles.    For   some   purposes,  high  volatile  content  is
desirable.  For example, porous laminates provide better strength
properties  than  do  the  more  dense  structures.   For   other
purposes, systems with low volatile contents have been developed.
The  envisioned  applications  for polybenzimidazoles are as high
temperature adhesives and laminating  resins  for  the  aerospace
industry.   They  may be employed as secondary structural members
in supersonic aircraft, and as adhesives  for  honeycomb  bonding
and  similar applications.  Among the civilian potential of these
materials are their use as  ultrafiltration  and  hyperfiltration
membranes.

Manufacture  -  Specific  process information on this subject has
not been reported in  the  literature.   However,  processes  are
probably  scale-ups  of  the original laboratory synthesis, i.e.,
solution polymerization in high-boiling organic  solvents  or  in
polyphosphoric  acid.  Melt condensation is practiced for several
of the products, wherein processing may proceed only to  the  low
molecular  weight,  low-melting, soluble compounds which are used
in the liquid state.  Alternatively, prepolymers may be  produced
for later polymerization in solution or in bulk.
                              72

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Waste  Water  Generation  - Process wastes will include the water
and the phenol evclved in polybenzimidazole synthesis:   2  moles
of  each  per  mole of benzimidazole group.  For the condensation
with the isophthalic or terephthalic ester, this  corresponds  to
120  mass units water and 610 mass units of phenol per 1,000 mass
units of polymer product.  In the solution polymerization process
in polyphosphoric acid, hydrogen chloride is evolved  during  the
condensation.

The  quality of water effluent will depend upon pretreatment, but
some dissolved phenol and/or HCl and some monomer  reactant  will
likely be present  (29).
                              73

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Polybenzothiazoles

Similar  to  the  polybenzimidazoles  are the polybenzothiazoles.
These polymers are prepared from 3,3'-dimercaptobenzidine  and  a
diacid,  a  diphenyl ester, a diacid chloride, etc.  The reaction
sequence is as shown in Equation 1 of Figure 111-22  for  use  in
diphenyl  esters.   Typical of the structures synthesized by this
procedure are those shown in  Figure  111-23.   The  hydrochloric
acid salt of 3,3'-dimercaptobenzidine may also be used along with
the diacid chloride, overcoming the problem of sensitivity to air
oxidation  of  the  parent mercaptoamine.  This is illustrated in
Equation 2 of Figure 111-22.  Many  other  syntheses  of  various
polybenzothiazoles  have  also been attempted, some with success.
Many of  the  problems  associated  with  the  synthesis  of  the
polybenzimidazoles   are   common   to   the   synthesis  of  the
polybenzothiazoles and thus synthesis approaches  are  frequently
similar.

Typical  reaction  conditions  for  the  polymerization  to poly-
benzothiazoles are  temperatures  of  160-250°C   (320-482°F)  and
times of one to  25 hours.

Waste  Water  Generation  -  As  with the polybenzimidazoles, the
polymerization leads to the release of 2 moles of water per  mole
of  benzothiazole  group  and  2  moles of phenol if the diphenyl
ester is used.   For the condensation of  the  isophthalic  ester,
this  corresponds  to  110  mass  units  water and 550 mass units
phenol per 1000  mass units of polymer product  (29).
                              74

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(1)
                          SH
                                                                    Polybenzothiazole
       HCI • H2N
(2)
NH2 •  HCI + CIOC
                    HS                SH
             3,3'-Dimercaptobenzidine dihydrochloride
                                                                            -HCI
                   --HIM
                                            NH 	 OC
                                                                                            	I n
                   FIGURE 111-22   TYPICAL REACTIONS TO FORM POLYBENZOTHIAZOLES
                                              75

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                                                      HO2C         C02H
                                              NH2 +
                       HS                SH

                       3,3'-Dimercaptobenzidine
             Isophthalic acid
H,N
                              Poly-2,2'-(m-phenylene)-6,6'-bibenzothiazole
               H2N
NH2   HO2C-
                     HS                    SH
                     3,3'-Dimercaptobenzidine
                                                                       O
                   p-Oxydibenzoic acid
C02H
                                   Poly-2,2'-[p,p'-oxybis(phenylene)]-6,6'-bibenzothiazole
                       Poly-2,2'-[p,p'-oxybis(phenylene)-6,6'-bibenzothiazolyl]-2,2'-(3,5-pyridinediyl)-
                                                 6,6'-bibenzothiazole
    FIGURE 111-23   TYPICAL STRUCTURES PRODUCED IN THE SYNTHESIS OF POLYBENZOTHIAZOLES
                                                     76

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Polybutene

Polybutene  can be produced by the polymerization of  1-butene  in
the  presence  of catalysts as shown in Equation 1 of Figure III-
24.  Usually Ziegler-type catalysts are employed.

Manufacture -  Polybutene  or  polybutylene  is  currently  being
produced by either of two processes.  In the United States, Mobil
Chemical  Company uses a polymerization process which starts when
fresh feed  and recycle monomer are combined and passed through  a
distillation  and  drying  step to remove volatile impurities and
water prior to polymerization.  The reaction is  carried  out  in
the  presence  of Ziegler-Natta catalysts, and the product stream
from the reactor is  contacted  with  water  to  remove  catalyst
residues.   Water  is then separated, the polymer phase is heated
and flashed to  remove  1-butene  for  recycle,  and  the  molten
polymer is  cooled and extruded into pellets.  Another process for
polymerization of polybutene is utilized by Chemische Werke Huels
AG  and  is also based on the use of Ziegler-type catalysts.  In
this process, a C-4 feed stream along with recycled butenes  from
the  process  is  fed  to  the monomer purification section where
butadiene is removed.  The resultant 50 percent  1-butene  stream
(with only  trace quantities of butadiene and isobutylene)  is then
passed  to  the  first  of two distillation towers where the high
boiling components are removed as bottoms.  In the second  column
low  boilers  are  removed  at  the  top,  and  the reactants are
recovered at the bottom.

The monomer stream next goes to two  stainless  steel  continuous
polymerization  reactors.   Catalyst and solvent are added in the
first reactor.

The polymer/solvent slurry from the second step  is  then  washed
with water  to remove catalyst.  The wash water is directed to the
waste treatment facility, while the remaining slurry is sent to a
centrifuge  as  a first step in removing the atactic isomer which
is produced in the Huels process.    Liquid  from  the  centrifuge
goes  to  a  distillation  column where a waxy substance,  atactic
polybutylene, is removed as bottoms.  (This atactic  polybutylene
is  often   used as a carpetbacking material.)  The overhead liquid
butene stream is cooled and sent to monomer purification and then
recycled to the process.

Solid polymer is recovered from the centrifuge, dried,   and  sent
to  bins  where  additives  are  added  prior  to  extrusion  and
pelletizing.  A flow chart is shown in Figure 111-25.

There are several important differences  between  the  Mobil  and
Huels  processes.    The  Mobil  process,   which  is  based  on  a
relatively pure 1-butene monomer stream,  is carried  out  in  the
presence  of excess butene monomer.   This enables the reaction to
be carried out without the need for solvent.   The  Huels  process
is  based  on a raw C-4 cut,  which requires purification prior to
polymerization.   The  Mobil  process  does  not  produce  atactic
                              77

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  n QcHs CH2 - CH = CH^j-
CH—CH2--

CH2
I
CH3
FIGURE 111-24  TYPICAL REACTION TO FORM POLYBUTENE
                            78

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DISTILLATION
 COLUMNS  t LIGHT-
             ENDS
                                                                                EXTRACTION    EXTRACTOR
                                                                    SOLVENT       AGENT
                                                                                        WATER
FRESH BUTENE
  (C4 CUT)
                                                                  POLYMERIZATION REACTORS
                              ATACTIC
                           POLYBUTYLENE
                                                  BAGGING



                                                 PRODUCT POLYBUTENE
                      FIGURE 111-25 POLYBUTENE PRODUCTION - HUELS PROCESS

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isomer, a portion of the polybutene produced by the Huels process
is atactic.

Waste  Water  Generation - The major aqueous wastes are likely to
be minimal in  both  processes,  and  especially  so  in  Mobil's
process.   In the Huels process, liquid residues from columns and
some aqueous wastes from C-U washing are likely (25).
                              80

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Polycarbonate s

Polycarbonates are a  special  variety  of  linear  thermoplastic
polyesters  in which a derivative of carbonic acid is substituted
for the acid and  a  diphenol  is  substituted  for  the  glycol.
Polycarbonates   are   end  products  in  themselves,  undergoing
thermoplastic processing utilizing the conventional equipment  of
the  plastic  industry.  By far the most important polycarbonates
from the commercial point of  view  are  aromatic  polycarbonates
derived  exclusively  from  the  reaction  of  bisphenol  A  with
phosgene.    In   addition,   aliphatic   or   aliphatic-aromatic
polycarbonates may te derived, but indications are that they find
little industrial usage.  Thus they will not be discussed.

Phosgene  is  a  liquefied gas, boiling at 7.6°C  (45.7°F) , and is
only very slightly soluble in water.   Bisphenol  A  is  a  solid
melting at 152°C (305°F) and is soluble in water to the extent of
3000 mg/liter at 85°C  (185°F).  The polymerization may be carried
by  means of the following mechanisms: condensation, interfacial,
and  transesterification.   Of   the   three,   condensation   is
preferred.   Interfacial  polymerization is seldom used for it is
inconvenient and slow, and in order to achieve sufficiently  high
rates  of transesterificaticn, the reaction conditions must be so
drastic that a portion of the polycarbonate is decomposed.

The reaction between the two  raw  materials  takes  place  under
alkaline  conditions  in the presence of catalyst and pyridine as
shown by Equations 1 and 2 in Figure 111-26.

In contrast to base-free condensation,  which  proceeds  only  at
high temperatures in the presence of special catalysts and yields
polymers with insufficient molecular weights, condensation in the
presence  of  basic  substances  proceeds  at  high rates at room
temperature to give high  molecular  weight  polycarbonates.   As
shown  in  the above equation, two moles of hydrochloric acid are
formed  per  mole  of  phosgene  consumed.   To  maintain   basic
conditions  in  the reactant mix, the hydrochloric must be either
neutralized or consumed.  Pyridine is added, usually  in  excess,
to   act   as   an  acid  acceptor  and  so  that  the  resulting
polycarbonate  forms   a   more   or   less   viscous   solution.
Alternatively,  a good portion of the pyridine may be replaced by
an organic solvent in which the polycarbonate  is  soluble.    The
reactant  is  strongly  catalyzed by Lewis acids such as aluminum
chloride, aluminum isopropoxide, stannic  chloride  and  titanium
tetrachloride.    Suitable   reaction   media  solvents  are  the
chlorinated  aromatic  hydrocarbons,   such   as   chlorobenzene,
methylene  chloride, or o-dichlorobenzene.  A typical catalyst is
benzyl triethyl  ammonium  chloride.   It  is  important  to  use
equimolar  quantities  of  phosgene  and  bisphenol  A, since the
molecular weight of the product will depend on the ratio  of  the
starting  materials.   It is also important to avoid the presence
of substances such as monofunctional alcohols  or  phenols  which
act   as   chain  terminators.    The  molecular  weight  is   also
indirectly dependent on possible concurrent side reactions,  which
in turn depend on the usual parameters such as temperature,  time,


                              81

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(1)
       C5 Hs N + (CH3)2 + C(C6H4OH)2 +  COCI2
                                               Solvent
          Pyridine         BisphenolA    Phosgene
       C5H5N  + -K>C6H4C(CH3)j C6H40
-------
and  reactants.   In  choosing  the  solvent,  chlorobenzene   is
preferable  since  the pyridine hydrochloride formed is insoluble
in this medium  and  may  be  readily  separated  by  filtration.
Traces  of  the hydrochloride that are in solution may be removed
by distillation.

Manufacture - The process scheme is shown in Figure 111-27.   The
bisphenol A is charged with excess pyridine and a solvent such as
methylene  chloride  into the vessel.  Phosgene is vaporized in a
still, and then bubbled  through  the  reaction  mixture„   Total
moles  of  phosgene  fed  are  in  slight  excess of the moles of
bisphenol A charged.  Phosgene and bisphenol react  to  form  the
carbonate  monomer,  which in turn polymerizes.  Reacting mixture
is kept under UO°C  (104°F); residence time in the vessel is 1  to
3  hours.   The reaction can be controlled through any of several
variables, including residence time, temperature, and proportions
of the components introduced.  Component purity  also  has  great
effect on the reaction.

Reacted  mixture,  consisting  of  the  polymer,  pyridine hydro-
chloride, and unreacted pyridine in solvent, is fed to water wash
tanks.  Wash water and hydrochloric acid are added here, the acid
reacting with residual pyridine.  Additional solvent may also  be
introduced at this stage to lower the viscosity of the mixture.

The  next step is the removal of water and pyridine hydrochloride
by decantation or the equivalent.   The  aqueous  phase  goes  to
pyridine  recovery;  the  solvent phase, containing the dissolved
polymer, goes to an agitated precipitation tank.

Here the polymer  is  precipitated  by  addition  of  an  organic
"antisolvent"  such  as  an  aliphatic hydrocarbon.  This forms a
solution with the carrier  solvent  and  causes  the  polymer  to
precipitate.    The resulting slurry goes to a rotary filter, and
the separated polymer goes to a hot air dryer where the remaining
solvent is removed.  The polymer leaves the dryer as a powder and
is  sent  to  blending,  extrusion,  and  pelletizing.    Aqueous
pyridine hydrochloride solution is combined with caustic solution
in  a  mix  tank for removal of chloride ions as sodium chloride.
The stream then goes from the mix tank to a fractionating  column
where steam strips out any solvent present.

The  stripped solution goes to an azeotropic distillation column,
and the sodium  chloride  solution  is  removed  as  bottoms  and
discarded.   The  overhead  stream  is an azeotrope consisting of
about 43 percent water, 57 percent pyridine.

The azeotrope is condensed and  then  combined  with  a  breaking
agent.   The mixture goes to a pyridine distillation column where
water-free pyridine is removed overhead.  The bottoms are treated
to recover the breaking agent.

Waste Water Generation - The waste  water  originating  from  the
process  is  principally  due  to  polymer  washing.   The  major
substance present in  the  waste  water  stream  will  be  sodium
                            83

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                                                    HYDROCHLORIC
                                                        ACID
                                   POLYCONDENSATION
                                                        WATER
           PYRIDINE
           RECOVERY
              I
            SODIUM
           CHLORIDE
           SOLUTION
                                      SEPARATION
                                            ORGANIC PHASE
                                     PRECIPITATION
                                                    PRECIPITANT
                                      FILTRATION
  I
DRYING
                                          I
                                     PELLETIZING
FIGURE 111-27 POLYCARBONATE PRODUCTION - SEMI-CONTINUOUS PROCESS
                             84

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chloride.   The  amount and concentration of sodium chloride will
depend upon the excess of  pyridine  required  and  the  dilution
necessary  to  effect  adequate washing.  It is expected that the
waste waters will be alkaline from excess sodium  hydroxide  used
in  the recovery of pyridine.  Also, the waste water stream would
be expected to contain traces  of  pyridine,  solvents,  breaking
agents, bisphenol, polycarbonate, and side reaction products (25,
28, 36, 40, 46).
                           85

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Polyester Resins (Thermoplastic)

The  most  common  polyester  is derived from the linear polymer,
poly(ethylene terephthalate).   The other homopolymer  to  achieve
this  polymer,  the  dihydric  alcohol  is butanediol rather than
ethylene glycol.

The term thermoplastic polyester resin as  used  in  this  report
refers   to  the  saturated  polyester  polymers  based  on  poly
(ethylene terephthalate)  or poly (butylene terephthalate).   These
polymers are quite different in method of manufacture, chemistry,
and areas of application from the unsaturated polyester resins in
which  a  site  of  unsaturation is incorporated into the polymer
chain for subsequent reaction to form a crosslinked structure.

The saturated polyester resins comprise a rapidly growing  market
of  molding  materials.   These  resins  are produced by the same
polymerization  process  used  to  polymerize  resin  for   fiber
production.   Resin  chips  are often taken as a side stream from
integrated polyester fiber plants.  There are, however, some U.S.
polyester resin facilities which produce resin alone and are  not
integrated to fiber production.  In addition, there are polyester
film facilities which are integrated back to resin production.

The  dihydric  alcohol  most  frequently  used  in  the polyester
condensation reaction is ethylene glycol.  Specific  requirements
for   the  dihydric  alcohol  are  that  it  be  quite:  pure  and
particularly free from color-forming  impurities  and  traces  of
strong acids and bases.

The other component can be either dimethyl terephthalate (DMT) or
terephthalic  acid   (TPA).   The  use  of  DMT as a polyester raw
material is more common.  There is a difference in waste products
generated during polymerization depending on whether DMT  or  TPA
is  used.   The  use  of  DMT results in the generation of methyl
alcohol either as a waste or by-product stream, whereas the  TPA-
based  polymerization  process  does not.  In either case a waste
stream containing unreacted glycol is generated.

The exact nature of the  catalysts  used  in  the  polymerization
process  varies  somewhat  and  is regarded as proprietary infor-
mation.  They are, however, known to include acetates of  cobalt,
manganese, and cadmium.

Manufacture  -  Many  plants  still  use the batch polymerization
process.  A typica^. continuous polymerization  process  based  on
DMT  consists of a DMT melter, ester exchange vessel, and a poly-
merization reactor (s).  This process is  shown  schematically  in
Figure  III-28.   The  alternative system based on TPA involves a
direct esterification rather than ester interchange.

In the case of plants producing both resin and fiber, the  molten
polymer  stream  from  the  final  reactor  is  divided.  Polymer
destined to become resin is chilled by once-through cooling water
during a band casting operation and broken up into chip form  for
                           86

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shipping.   The  figure  shows  polyester  resin  production from
ethylene glycol or fcutanediol.

Waste Water Generation - Liquid wastes result  from  the  conden-
sation  of  steam  ejector  vapors (suction and discharge sides).
Process materials present  in  these  streams  are  methanol  and
ethylene  glycol  when  ethylene  glycol  is  the  diol feed, and
methanol and tetrahydrofuran in the case of butanediol feed.   In
the  latter  case,  when unreacted (excess)  butanediol is removed
from the process under vacuum,  it  spontaneously  dehydrates  to
produce tetrahydrofuran  (25) .
                           87

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                                                    EJECTOR
                                         STEAM
            DMT - DIMETHYLTEREPHTHALATE
              EG-ETHYLENE GLYCOL
            TMG-TETRAMETHYLENE GLYCOL
                 (BUTANEDIOL)
            THF-TETRAHYDROFURAN

            MATERIALS DENOTED (  )
            RELATE TO PROCESS WHERE
            DIOL IS BUTANEDIOL (TMG).
                                         STEAM
oo
00
       DMT-
 DIRECT
  OR
INDIRECT
COOLING
 WATER
CATALYST
  AND
ADDITIVES
                                                                                               COMBINED
                                                                                             WASTEWATER
                                                                RESIN PRODUCT
                                                                  TO BANDING
                  METHANOL
                   RECYCLE
                              FIGURE 111-28 THERMOPLASTIC POLYESTER RESIN PRODUCTION

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 Polyester Resins (Unsaturated)

 Unsaturated  polyester  resins   are  made  by  an  esterification
 reaction involving  a glycol and both an aromatic dibasic  acid and
 an Unsaturated dibasic acid.  The  Unsaturated  dibasic  acid  is
 used  to incorporate an ethylenic linkage into the polymer  and is
 a compound such as  maleic acid  or  fumaric  acid.    The  aromatic
 dibasic  acid can be phthalic acid, isophthalic acid or the like.
 The glycol is commonly propylene  glycol.    The  basic  polyester
 resin  is  made  typically  by   a  batchwise  reaction  process in
 stirred,  glass-lined,  or stainless steel  vessels   and  is   later
 dissolved  in  a reactive  monomer  such  as  styrene  which can
 crosslink with the  ethylenic bonds  in  the  main  polymer.    The
 resultant  viscous   liquid,  diluted with styrene,  is the current
 item of commerce known as polyester resin.

 The chemical  structure  of  the  various  materials  involved  in
 polyester  resin fabrication   are  shown in Figure III-29,  along
 with a representation  of the basic reactions involved.

 All of the starting materials for polyester resin  manufacture are
 derived from  petroleum fractions.   The aromatic  acids  are   made
 from  xylenes,  and  the Unsaturated acids are made  from  benzene by
 oxidation.  The most common  glycol,   propylene  glycol,   is   made
 from  propylene  via oxidation.   Styrene is made from benzene and
 ethylene.

 Phthalic  acid and maleic acid are both easily dehydrated  and  are
 therefore   used in  the form of  anhydrides rather than as  acids in
 order  to  avoid the  costs associated with shipping water.

 The  major use  for  Unsaturated   polyester   resins  is  in  the
 manufacture  of  reinforced  plastics.   They  constitute  about 80
 percent  of  all  the   materials   used  for  reinforced   plastic
 applications.   Glass  fiber is the  most  common  reinforcing agent,
 although other  reinforcements such  as  metallic  fibers and natural
 fibers  are  occasionally  used.   Typically,   glass  fiber   averages
 about   35   percent   of   the  weight  of  the reinforced polyester.
 Nonreinforced   applications  for  Unsaturated    polyester    resin
 include  molded  plastic  and   resins  used for  castings, surface
 coatings,   and  putty-like  compounds  used  as  body  solder  on
 automobiles.

 Manufacture  -  There  are  two somewhat different procedures  for
 carrying   out   the   polyester   polymerization   reaction.     The
 differences  are  related  to  the  manner  in which the water of
reaction is removed.  The fusion process  removes  the  water  by
 passing  an  inert  gas,  usually  nitrogen, through the reaction
mixture.   In the second  technique, which is referred  to  as  the
 solvent  or  azeotropic  process,  a  solvent   (usually xylene or
toluene) is added to the reaction mixture and  forms  a  constant
boiling  azeotrope with the water of reaction.  This azeotrope is
distilled off during the esterification reaction and the  solvent
is recovered.
                            89

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 HYDROCARBON STARTING MATERIALS
  I      II
HC^    CH


     H


ACIDS
             Benzene
                             COOH
                        COOH-


 Ortho-phthalic Acid   Iso Phthalic Acid (IPA)
                                         Toluene
                Ortho-xylene
    CH3

Meta-xylene
      HC - COOH           HC - COOH

       II                    II
      HC - COOH      HOOC -CH




       Maleic Acid      Fumaric Acid (FA)
           CO



Phthalic Anhydride (PA)

 GLYCOLS


    HOCH (CH3)CH2 OH


     Propylene Glycol (PG)


 REACTIVE SOLVENT

           CH =CH2
   Styrene (S)


  POLYESTERS

      HOOC - R-COOH + HO - R' - OH •
                                                      HCCO

                                                       II  >
                                                      HCCO
         Maleic Anhydride (MA)




         HOCH2 C(CH3)2 CH2 OH


           Neopentyl Glycol (NPG)
(- OOC - R - COOR' -)n + H2O
  Note: Some of the R groups contain the reactive ethylenic linkage.




  RESIN


      PA + MA + PG = Base Resin (Solid)


      Base Resin + Styrene = Polyester Resin (liquid)
         FIGURE 111-29   TYPICAL REACTION AND RAW MATERIALS USED TO FORM

                         UNSATURATED POLYESTER RESIN
                                           90

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After   carrying  the  polymerization  reaction  to  the  desired
molecular weight and removing the water of reaction, the  polymer
is  transferred to another vessel containing the reactive monomer
which is typically  styrene,  although  methyl  methacrylate  and
vinyl  toluene  are sometimes used.  After mixing in the thinning
tank, the final composition containing reactive monomer is either
discharged to a filtration press prior to being loaded into 208.2
1.  (55 gal.) drums or bulk tanks.  Discharge  from  the  thinning
tank  is  sometimes  carried  directly  to  drums or bulk without
filtration.  The  concentration  of  reactive  monomer  can  vary
considerably   (from 20 to about 55 percent by weight).  A typical
formulation contains about 35 percent styrene.

Although the vast majority of polyester reactions are carried out
in batch reactors, there are several plants in  the  U.S.    which
have  continuous esterification reactors.  This mode of operation
can usually only be justified when a large quantity of a specific
type of polyester  resin  is  desired.   The  continuous  reactor
undoubtedly generates less waste per pound of product as compared
to  batchwise  production  due  to more infrequent cleanout, more
efficient  operation,  and  more  careful  control  of  operating
parameters.

Waste  Water Generation - In addition to boiler and cooling tower
blowdown, the sources of effluent are as follows:

    Water of Reaction

    The water  of  reaction  which  is  passed  out  overhead  is
    condensed  by  some means and is either removed directly from
    the condenser,  or more typically from the decanter  following
    the  condenser.    This  condenser  also serves as  a means  for
    separating the solvents used in azeotropic  distillation  and
    sending  them back to the reactor.   The water  of reaction  may
    contain a variety of contaminants,  including glycols,   acids,
    and minor quantities of dissolved solvent.

    Scrubber Waste

    Scrubbers  are  used  on the overheads leaving the reactor in
    order to reduce  the concentration of  entrained  liquids  and
    solids.    Both  recirculating  and  once-through scrubbers  are
    used.   The scrubber operation usually consists of  passing  the
    gaseous  stream leaving the  top  of  the   reactor   through  a
    column  into which water is  sprayed.   The scrubber may  either
    use  a recirculating water stream or once-through  water.    In
    the   latter  case,   although the water use  is  quite high,  the
    effluent  concentration  in   the water  stream leaving  the
    scrubber  is  not  high and the stream can therefore be  passed
    to a  treatment   system.    In  the  case  of  a  recirculating
    scrubber,  however,  the BOD and COD  concentration can often be
    200,000  to 400,000  ppm.   Such  high  concentrations  could  upset
    the   operation   of  conventional biological or  municipal  waste
    treatment plants,  and therefore  it  is  common practice in  the
                           91

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    industry  to either discharge such concentrated recirculating
    scrubber wastes to a landfill or to incinerate the wastes.

    Caustic Cleanout of Reactors

    Concentrated caustic solution is typically used to clean  out
    the   polymerization  reactors.    The  frequency  of  reactor
    cleanout is highly variable depending on the grades and types
    of resin produced  by  the  manufacturer.    Cleanout  periods
    ranging  from  once  every  three  weeks  to once a year were
    encountered during our interviews.  The caustic  solution  is
    a]so used to clean out tank cars and tank trucks.  Generally,
    some  form of recycling is practiced on this caustic cleanout
    solution.

Alkyd Resins - Although there are some notable  exceptions,  most
polyester  resin  plants  also manufacture the alkyd resins which
are used in paint manufacture.  These resins are quite similar to
polyester resins with the exception that the acid portion of  the
polymerization  recipe  contains a significant quantity of a long
chain of  unsaturated  fatty  acid,  and  the  polymerized  resin
instead  of being diluted with a reactive monomer such as styrene
is diluted with a solvent such as xylene or naptha.

With these two exceptions,  the  processes  used  to  manufacture
alkyd  resins  are  quite similar to those used for manufacturing
unsaturated polyester resins.  Both azeotropic  and  fusion  cook
processes  are  used  for manufacturing alkyd resins and, in many
cases, identical reactors are used.

The nature of  the  effluents  in  alkyd  resin  and  unsaturated
polyester  resin  manufacture  is  also  quite  similar, with the
notable exception of  an increased  amount  of  an  oily  material
which  originates   from  the  long chain, unsaturated fatty acids
used in the  alkyd recipe.  The presence of  this  material  often
appears as a high "oil and grease" analysis in the discharge.  It
is also worthy to note that although  a typical polyester reaction
gives  off   about   12  percent   of  the  original  weight  of the
reactants  as water  of reaction,  the alkyds, because  of  the  high
molecular  weight of the reactant, typically give off  5 percent of
the weight of the original reactants  as water of reaction.

Litharge   (lead  oxide)  and  other   catalysts  such  as   lithium
compounds  are often used as alcoholysis catalysts  in  the reaction
vessel in  concentrations of   a   few   ppm.   Occasionally   benzene
sulfonic   acid   is  used   as  an  esterification catalyst.   Most of
these catalysts  go  out with the  polymer or  are  trapped   in  the
filtration step.

Various  additives  are  often  mixed with the resin  in the thinning
tank.  These are color  stabilizers such as  triphenyl  phosphate,
amines,  fire retardants  such as chlorophthalic anhydride,  curing
accelerators such  as  cobalt naphthenate,  and  thixotropic   agents
such  as Cab-o-Sil (R).   All these components appear to go out with
the  resin.
                            92

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Discharge  to  municipal  waste  is  the  waste  treatment method
utilized by 90 percent of  the  polyester/alkyd  resin  industry.
There  are  some notable exceptions, however, who carry out their
own biological treatment or who truck all  of  the  wastes  to  a
large,  centralized  municipal treatment plant.  The exact nature
of the wastes can be highly variable depending  on  such  factors
as:

    o The use of once-through vs. recirculating scrubbers.
    o The extent to which cooling water is recycled.
    o The frequency of reactor washout.
    o The product mix (polyesters vs. alkyds).
    o Whether or not polymerization catalysts are used.
    o Whether or not wastes are incinerated (41).
                          93

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Polyimides

The  development  of thermally-stable polymers has for many years
been one of the important tasks in the chemistry  of  high  mole-
cular compounds.  Such polymers ideally combine the properties of
heat  resistance  and  thermal  stability.  One  of  the greatest
successes in this direction was the synthesis  of  polyimides  —
cyclic  chain polymers with the structure shown in Figure 111-30,
Equation 1.  The greatest heat resistance and  thermal  stability
was obtained by the production of completely cyclic polymers with
no aliphatic units in the chain.

Polyimides  may  be  divided  into  two broad groups according to
their structure and method of preparation:   (1)  polyimides  with
aliphatic  units  in  the  main  chain;  and   (2) polyimides with
aromatic  units  in  the  main  chain.    Polyimides   containing
aliphatic units in their main chains of the general formula shown
in  Figure  111-30,  Equation  2,  are  obtained by thermal poly-
condensation by heating salts of aromatic  tetracarboxylic  acids
and   aliphatic   diamines.   The  preparation  of  an  aliphatic
polyimide in this manner is that illustrated  in  Figure  111-30,
Equation   3.    After   heating  at  110-138°C   (230-280°F),  an
intermediate low rrolecular weight product  (salt) is formed.  This
is converted into the polyimide by  additional  heating  at  250-
300°C  (482-572°F) for several hours.

The  melt  polycondensation  method  for the preparation of poly-
imides  has limited applicability.   The  melting  points  of  the
polyimides  obtained  must  be  below the reaction temperature so
that the reaction mixture will be in the fused  state  during  the
polycondensation  process.   Only  in this case  is it possible to
achieve a  high  molecular  weight.   Melt   polycondensation  can
therefore  be   used   successfully  only   for  aliphatic  diamines
containing at  least  7 methylene groups.  Aromatic polyimides  are
generally  infusable,  so that when aromatic diamines are used, the
reaction   mixture solidifies too early to permit the  formation of
a  high  molecular weight product.  Furthermore,  aromatic  diamines
are  not basic  enough to form salts with  carboxylic  acid.

Polyimides  with  aromatic  units  in the main  chain  (of the  general
formula  shown  in   Equation   4,  Figure  111-30)   are  generally
synthesized  by a  two-stage pcly-condensation method.   This method
has   recently   found  very widespread  use, since soluble  products
are  obtainable in the first stage of  the  reaction.    This  first
stage,   carried out  in  a  polar solvent,  consists of  the  acylation
of a diamine by a  dianhydride  of  a tetracarboxylic acid,   leading
to  the  formation   of  a  polyamic  acid according to Equation 5  of
 Figure  II1-30.   The  second   stage  of  the  reaction  —   the
 dehydrocyclization  of the polyamic  acid  (imidization)  —  proceeds
 according  to   Equation  6,  and  is  carried  out  thermally  or
 chemically.

 The first stage of  the synthesis of  polyimides — the preparation
 of polyamic acid — is effected as  follows.   To a solution of  an
 aromatic  diamine  in  a suitable solvent there is added in small
                            94

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(1)
                           CO.    CO
                           CO
                            \N-R'-
                            /
(2)
                    CO     CO
(3)
         HOOC  /^.  COOH
                               sl-(CH2)m-NH2-
CH3OOC
     HOOC
                       COONH3-(CH2)m-NH2
                                             A
          CH3OOC  ^  COOCH3
                   x. s^ ,CO.
              -N <
                 \
                          >N-(CH2]
                    CO  ^  ,C
(4)
           ).    CO.      ~~|
            \R/  \IM-R'-   ,whereR' =
           X  NCOX     J n
(5)
              /
                     .co
             ^^^
    0 <(   >R<(  ^>0 +H2N-R'-NH2
              HOOC^  ^ CO-NH-R'-
           -NH-CO^
(6)
                        COOH
                                     .2nH2Q
                       CO     CO
          FIGURE 111-30  TYPICAL REACTIONS TO FORM POLYIMIDES
                                95

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portions, with agitation,   an  equimolar  quantity  or  a  slight
excess  of  the dry tetracarboxylic dianhydride.   The reaction is
carried out at temperatures  of  -20-70°C  (-4-158°F),  with  the
optimum  reaction  temperature  in  most cases being 15-20°C (59-
68°F).  The reaction is carried out in polar solvents,  the  best
of   which   are   N,Ndimethylacetamide/   N,N-dimethylformamide,
dimethylsulfoxide,  and  N-methyl-2-pyrrolidone.    The   polyamic
acids  as  a  rule  apparently have a low molecular weight  (below
100,000)  and a low degree of polymerization (140 or lower).

The conversion of  polyamic  acids  to  polyimides,  imidization,
consists  of  the  intramolecular  evolution  of  water  from the
polyamic acid  to  form  a  cyclic  polyimide.   The  imidization
reaction can be carried out in two ways, thermally or chemically.
The  thermal  imidization generally consists of heating the dried
polyamic  acid  with  a  continuous  or  stepwise   increase   of
temperature.  Thermal treatment at high temperatures  (above 2CO°C
or 392°F) is carried out in vacuum or an inert medium.

The  chemical  imidization  method  consists  of  a  treatment of
polyamic acid film or powder  with  dehydrating  agents.   Acetic
anhydride  or  anhydrides of other lower aliphatic acids,  such as
propionic acid, can be used for this purpose.

Most  polyimides,  particularly  the  thermally  stable  aromatic
polyimides  which  are of great practical significance, are inert
toward organic solvents and oils.  They are also little  affected
by  dilute  acids,  but  dissolve  in strong acids such as  fuming
nitric   or  concentrated  sulfuric  acid.   Polyimides   have    a
relatively  low   stability  toward alkalis and superheated steam,
and under the action of both they are hydrolyzed.


Polyimides have been used as  electrical  insulating  films,  for
wire  enamel, for testing compounds, and for adhesives.  They are
being produced for the most part on a semi-industrial scale.

Polyimide Films - The  compounds  of  primary  industrial   signi-
ficance  are the  aromatic polyimides.  The DuPont  Company  started
the  production of polyimide film in  experimental  quantities  in
1962.  At the present time this company is producing  two types of
film under  the  general trademark Kapton:   H-Film made  from the
pure  polyimide, and H-F-Film made from the polyimide  and   coated
on one or  both sides with Teflon.

The   main   area for application of polyimide  film  at  this  time is
as a heat  resistant insulating, gasketing, and   winding   material
for   electric machines,  and  also  for electric cables.  The use of
polyimide   films  for   flexible   printed   circuits  is   of  great
interest.     Thin  polyimide   film   can  be   used   for   condenser
insulation  for operating temperatures  up to  250°C  (482°F).

Polyimide  Plastics  - Production of polyimide  plastics,   in  which
all    advantages   of   these   polymers   are  completely   realized,
involves greater  technological problems than  the   production  of
                           96

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films.   The  difficulties  are caused primarily by the necessity
for the removal of  large  quantities  of  salt.   Polyamic  acid
solutions  generally  contain  no  more than 20-30 percent of dry
material.  In addition, the water of imidization must be removed.
The direct conversion of a concentrated  polyamic  acid  solution
into a polyimide block in a manner similar to that used for epoxy
resins has not been achieved so far.  The preparation of polyamic
plastics, therefore, generally requires isolation of the polyamic
acid  from  solution in the form of thin films, powders, coatings
on glass, tape, or the like,  followed  by  complete  or  partial
imidization  of  these  intermediate  products  by  a chemical or
thermal method.  Processing into articles by molding,  sintering,
or other methods then follows.

Actual  consumption  of  polyimides for the period since 1970 are
not known.  However, prior  to  1970  one  estimate  predicted  a
meteoric  rise  in consumption of pclyimides rising to 50 million
pounds per year by 1972 or 1973.

Manufacture - Specific information on manufacturing processes has
not been reported in the  literature,  probably  for  proprietary
reasons  in  this relatively new field.  Patents largely refer to
bench-scale syntheses, as described previously.

Waste Water Generation - The generation of  water  wastes  during
polyimide  manufacture  is not documented.  The general synthesis
of interest, that represented by Equations 5 and 6 in Figure III-
30, leads to the generation of two moles of  water  per  mole  of
imide  linkages.   If  R and R1 refer to phenyl groups, then this
corresponds to generation of 125 mass units  of  water  per  1000
mass units of polymer products.

In  this  two-stage  polycondensation  reaction,  water is either
removed thermally in the vapor state under vacuum, or  chemically
through  the  use of dehydrating agents.  In the former case, the
water may be quite pure when condensed.  In the latter case,  the
condition  of  the  effluent water will depend upon the method of
regeneration of the dehydrating agent.

The  melt  polycondensation  method  is  now  obsolete  for  most
purposes.   However,  it is worth noting that this polymerization
and related polymerization methods lead to  the  release  of  two
moles of methanol per mole of imide linkage (25) .
                           97

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Polymethyl Pentene

Methyl  pentene  (or  U-methyl-1-pentene)   is  made by the alkali
metal catalyzed dimerizaticn of propylene as shown in Equation  1
of  Figure  111-31.   The polymerization of 4-methyl-l-pentene to
produce poly(methyl pentene)  can be carried out with ZieglerNatta
catalysts in inert  hydrocarbon  diluents  such  as  cyclohexane,
heptane,   and   commercial   saturated   aliphatic   hydrocarbon
fractions.   It  can  also  be  hcmopolymerized  in  bulk.    The
polymerization  reaction is shown in Equation 2 of Figure 111-31.
The typical polymerization product  contains  a  mixture  of  the
crystalline  isotactic polymer (which is almost insoluble in warm
aliphatic hydrocarbons)  and an amorphous,  atactic  polymer  which
is  soluble in the diluent.  The relative proportion of these two
products in the polymer mix depends on such factors as  the  type
of transition metal-halide catalyst plus organometallic activator
used  and  the  temperature  of polymerization (high temperatures
favor the formation  of  atactic  polymer).   The  catalyst  most
frequently  used  is  based  on titanium trichloride activated by
diethyl aluminum chloride.

In a typical polymerization, the diluent serves as a solvent  for
monomer,  activator, and the atactic product which is carried out
in the temperature range of  20-80°C   (68-176°F).   The  titanium
trichloride  and  the  isotactic polymer remain insoluble.  Thus,
the  monomer  polymerizes  at  the  titanium   trichloride-liquid
interface,  and  the  isotactic  polymer  precipitates out on the
TiCl# crystals forming a slurry of catalyst-polymer particles  in
the  diluent.   To  isolate  the isotactic polymer, the slurry of
catalyst-isotactic polymer particles in the  diluent  is  treated
with  agents  which kill the catalyst activity and solubilize the
catalyst residues so that they can be washed out.  An alcohol  is
usually employed for this purpose.  The polymer is separated from
the  wash  liquors  by  filtration  or  centrifugation.  Residual
liquor held in the polymer particles can then be removed by steam
distillation and/or drying.   An  important  feature  of  the  U-
methyl-1-pentene polymer is its optical clarity which can only be
attained by the almost complete removal of catalyst residues.  In
order  to  obtain  this  high degree of catalyst residue removal,
aqueous washings   (as  used  in  polypropylene  manufacture)  are
inadequate,  and  more  complex  systems  involving  washing with
hydrocarbons or with alcohols are required.

Waste Water Generation - The waste water generation occurs during
washing, and solid/liquid separations  since  the  polymerization
reaction  does  not  produce water.  The polymer washing step may
use water or, in some  cases,  hydrocarbon  or  alcohol.   Conse-
quently,  the  wash  liquids  may  contain dissolved mertals.  The
volume of waste waters per unit of production is expected to vary
widely depending upon the  specific  operations,  and  the  waste
waters  may  also  contain  hydrocarbons  or  alcohols from other
washing operations  (25).
                           98

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(1)     CH2 = CH - CH3	•- CH3 - CH - CH2 - HC = CH2

                             CH3
(2)    n  CH3 -CH -CH2 - CH = CH2

              CH3
--CH-CH2- —
   I        n
  'CH2
   I
   CH
   A
 CH3  CH3
  FIGURE 111-31  TYPICAL REACTIONS TO FORM POLYMETHYL PENTENE
                               99

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Polyphenylene Sulfide

Polyphenylene sulfide polymers possess recurring units of  sulfur
which  provide  linkage  for  aromatic  compounds.  Polyphenylene
sulfide (PPS) is a finely divided  light-colored  powder  and  is
insoluble  in  any known solvent below 190°C (375°F).   Above this
temperature it  has  limited  solubility  in  some  aromatic  and
chlorinated aromatic solvents and certain heterocyclic compounds.
It is highly crystalline with a melting point near 285°C (550°F).
Although  curing  in  air at elevated temperatures is required to
effect  chain  extension  and  crosslinking,  the  resin  remains
thermoplastic   in   nature.    It   can   be  processed  through
conventional equipment for compression and injection molding.

Polyphenylene sulfide is a recent thermoplastic  on  the  market;
therefore  only a small amount of information on its synthesis is
available in the literature.  It is  believed  that  the  process
employs  p-dichlorobenzene,  sodium  sulfide,  and  polar organic
material such as n-methyl pyrrclidone to yield PPS which  may  or
may not have crosslinking agents added to the reaction medium.

P-dichlorobenzene  is  solid  with  a  melting  point  of  53.1°C
(127.5°F) , a specific gravity of 1.46, and is insoluble in water.
Sodium sulfide in the hydrated form contains 9 moles of water and
is very soluble in water.  N-methyl pyrrolidone is a liquid which
boils at 197°C  (387°F) and is soluble in water.

The reaction between the two raw materials  takes  place  in  the
presence of a polar organic solvent as shown in Figure 111-32.

The reaction is carried out at a temperature in the range of 130-
175°C (266-347°F).  The mole ratio of p-dichlorobenzene to sodium
sulfide  should  be  in  the  range of 0.9:1 to 1.3:1.  If ratios
above  this  range  are  employed,  the   amount   of   unreacted
dichlorobenzene  will  be  increased,  requiring  separation  and
recycle.   Larger  excess  of  either  reagent  leads  to   lower
molecular   weight  polymers,  and  still  shorter  polymers  are
produced by an increase in the reaction temperature.

In general, the synthesis reaction is carried out by  reacting  a
polyhalo-substituted  compound with an alkali metal sulfide which
has been partially dehydrated by the polar organic compound  that
also serves as the solvent for the reactants.  The solvent should
be  stable  at  the  elevated temperatures for the reaction.  The
polymer formed may be heat treated in the absence  of  oyxgen  to
yield  a  higher  molecular  weight  polymer.   Molecular  weight
control may be achieved  by  introducing  a  monohalo-substituted
aromatic   compound   to   the   reaction  medium,  which  causes
termination of the chain growth.  Yields of finished polymer  are
higher if a catalyst such as copper or a copper compound is added
to the reaction medium.

It  is possible to obtain a cross-linked polymer through addition
of  a  polyhalo-substituted  aromatic  compound  which   contains
                           100

-------
  Cl
        + Na2S
                 C5H9NO
-+2NaCI
FIGURE 111-32   TYPICAL REACTION TO FORM POLYPHENYLENE SULFIDE
                           101

-------
substituents  through  which  crosslinking  can  be  effected  by
further reaction.

Manufacture - A typical process scheme is shown in Figure 111-33.

The hydrated sodium sulfide in n-methyl-pyrrolidone is charged to
a stainless steel autoclave.  The temperature is  brought  up  to
190°C  (374°F)  while flushing with nitrogen to remove the water of
hydration.   Upon  removal  of  water,  the  p-dichlorobenzene is
charged  to  the  autoclave  and  the   temperature   raised   to
approximately  250°C   (482°F)  for the desired reaction time after
which the polymer and reaction medium is dropped to  a  stainless
steel  tank.   The  contents  are washed with water and then with
acetone, which  carries  along  unreacted  reaction  media.   The
finished polymer is dried and packaged.

Waste  water  Generation - Aqueous wastes would be generated from
two sources:

    1.   Water of hydration.

    2.   Process wash water.  The primary  contaminant  would  be
         sodium  chloride,  of which two moles would be generated
         per mole of feedstock.

The water of hydration is associated with the water bound to  the
sodium  sulfide  which  is  removed  in  a  pre-reaction  step by
heating.  It is likely that the water removal would  carry  along
traces  of  sodium  sulfide and n-methyl pyrrolidone which may or
may not be recovered.  Process wash water is used to wash  sodium
chloride  from  the reaction mass.  Due to the high solubility of
n-methyl-pyrrolidone and  sodium  sulfide  in  water,  the  waste
generated  from  this source is most apt to contain a large waste
loading.  It is likely that  solvent  extraction  and  subsequent
further  recovery  operations  will  be applied to this stream to
recover the raw materials for recycle.

If it is assumed that the sodium chloride is removed in  a  water
solution  at  a concentration of about 10 percent by weight, then
about 10,000 mass units of water per 1,000 mass units of  product
would be required  (24, 47).
                          102

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 N-METHYL
PYRROLIDONE
                       LLf
 P-DICHLORO-
 BENZENE
RECOVERY
                                      SEPARATION
                                                       WATER
                AQUEOUS
                WASTES
          FIGURE 111-33 POLYPHENYLENE SULFIDE PRODUCTION
                             103

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Polypropylene Fibers

Manufacture  -  The polymerization of polypropylene was described
previously in EPA Development Document No. EPA 440/1-73/010 ±161.
Polypropylene fibers are made  by  melt  spinning.   The  general
process,  shown  in  Figure III-34, consists of coloring polypro-
pylene flake by some type of  dry  blending  of  the  flake  with
pigments  followed  by  a  melting  and  extrusion  process  that
regenerates the colored polypropylene as  pellets.   The  pellets
are  then  extruded  through  a  spinnerette into a column of air
which solidifies the molten filaments.  The  filaments  are  sub-
sequently  stretched  or  spun  and  crimped,  depending  on  the
applications of the final fiber.

As in most melt-spun fibers, drawing  is  the  critical  step  in
fiber  manufacture.   The quenched filaments are heated and drawn
to develop  molecular  orientation  along  the  fiber  axis.   To
relieve  internal stresses and provide dimensional stability, the
filaments are heat set.  This last step also aids in  development
of  a  higher  degree  of  crystallinity.  Fibers with degrees of
crystallinity of about 70 percent can be obtained  under  optimum
quenching and annealing conditions.

There  are  three  basic types of polypropylene filamemts.  These
include monofilaments, which may be round or flat or have special
cross-section; fibers; and fibrillated or slit film.

    Monofilaments

    A typical extrusion and  orientation  arrangement  for  mono-
    filament is shown in Figure 111-35, in which can be seen that
    extruded  filaments  coming from the spinnerette are quenched
    in a water bath (quench  tank)   and  then  hot  stretched  to
    several  times  their  original  length  between  a series of
    heated Godet rolls and ovens.  The source of heat can be  hot
    water, steam or hot air.  After leaving the orientation oven,
    the  filaments must then be annealed by heating tc> a specific
    temperature  (heat  set  temperature)  while  maintaining  an
    essentially  constant  length but permitting a limited amount
    of  retraction.   This  procedure  stabilizes  the   filament
    against shrinkage up to the heat set temperature.

    Fibers

    Polypropylene  fibers  are  produced  from 1-1/2 denier up to
    about 15 denier by a technique basically resembling that used
    for  nylon  and  polyester  fibers.   After   extruding   the
    filaments  downward  and  quenching  by  air  under carefully
    controlled  conditions,  the  new   undrawn   filaments   are
    collected  on  bobbins  in  bundles  and  then  passed to the
    stretching operation.  There are  two  different  methods  of
    stretching  depending  on  the  desired end product:  one for
    continuous multifilament yarn and another for  staple  fiber.
    For  continuous  multifilament  yarn, the bundles are removed
    from the individual bobbins and are drawn under heat to  four
                          104

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     DRY PIGMENT OR
   "COLOR MASTERBATCH
                                QUENCH
                                  WASTE
                                SKIMMED
                                SOLID
                                WASTE
PELLETIZE



COLORED
PELLET
STORAGE


i
PP FIBER PRODUCTS
   IN BALES OR
    ON TUBES
          FIGURE 111-34 POLYPROPYLENE FIBER PRODUCTION

-------
EXTRUDER
                       QUENCH TANK
       PULL-OUT
        ROLLS
        DRAW OVEN
             WIND-UP
RELAX
ROLLS
RELAX  OVEN
 DRAW
ROLLS
SOURCE: POLYPROPYLENE FIBERS AND FILMS.  A. U. GALANTI  and C.C.MANTELL,
       PLENUM PRESS, NEW YORK (1965).
                    FIGURE 111-35  POLYPROPYLENE MONOFILAMENT PRODUCTION

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    to  eight  times their original length (stretch ratios of 1:4
    to 1:8).  Typical drawing equipment consists of heated  metal
    shoe  over  which  the bundles are run; occasionally steam or
    hot air heating is used.

    In many cases the multifilament is used  in  the  form  of  a
    twisted yarn.  This is made in a draw twister, which combines
    a twisting motion with the stretching operation.

    Staple  fiber is produced from tow containing several hundred
    thousand filaments which are  combined  from  creels.   These
    tows  are  usually  stretched  in successive steps to stretch
    ratios of 1:3 or 1:4.  After drawing,  the  tow  is  normally
    crimped  (or deformed) by heat using specially shaped rollers
    to give bulk to the fiber (approximately that  of  wool,  for
    example).   The  crimped  tow  is then cut to staple fiber in
    lengths ranging from 1.3-12.7 cm (1/2-5 in.).

    Fibrillated or Slit Film

    This  product  is  made   by   extruding   or   casting   the
    polypropylene  into  a  thin film, which is then stretched to
    obtain a  high  degree  of  orientation  of  the  crystalline
    structure.    This highly-oriented film is then fibrillated by
    applying various kinds of forces perpendicular to the machine
    direction.   The fibrillation splits  the  sheet  into  fibers
    which are then processed into the final product.

    Slit film is made in a similar manner with the exception that
    the  extruded  film  is  slit  into  thin widths prior to the
    stretching step.  In making slit film, lower  stretch  ratios
    are used in order to avoid fibrillating the film.

The  applications  of  polypropylene  fiber  include  carpet face
yarns, carpet backing, and various industrial yarn applications.

Waste Water Generation - Water is used as a heat exchange  medium
in the extruders and in the air conditioning system of the plant.
Water  is also used as a rinsing medium for various equipment and
kettles associated with the blending step.

Sources of waste include rinse  water  from  the  blending  step,
extensive  quantities  cf cooling and air conditioning water, and
the spin and crimping finish waste.  These  are  lubricants  that
will  contribute  to  an  oil  and grease analysis.  The crimping
finish wastes are sometimes directly drummed and sent to landfill
rather than being put into the  waste  water  stream  because  of
their  high  BOD's.   Some  dissolved solids are generated by the
rinsing of gear pump parts that  are  periodically  removed  from
service  and cleaned in a molten salt bath.  In common with other
fiber production plants, polypropylene plants have a large number
of employees due to the number of hand operations associated with
the handling  of  the  product,   and  therefore  sanitary  wastes
account for a significant portion of the total effluent load from
                          107

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the  plants  (41).  Phosphate can be present in the wastes due to
phosphate containing surfactants.
                          108

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 Polysulfone Resins

 Polysulfones  are   high-molecular-weight   polymers   containing
 sulfone  groups  and  aromatic  nuclei in the main polymer chain.
 The term "polysulfone" is  also  used  to  denote  the  class  of
 polymers prepared by radical-induced co-polymerization of olefins
 and   sulfur   dioxide.     The  latter  do  not  have  commercial
 significance,  and will not be discussed.

 Among the  aromatic  polysulfones  synthesized,  the  polysulfone
 derived  from   dihydric   phenols (bisphenol A)  and 4,U«-dichloro-
 diphenyl sulfone have achieved commercial application  under  the
 trade  name of  Bakelite  polysulfone.    This is a rigid, strong
 thermoplastic  which can  be molded,  extruded, or thermoformed into
 a variety of shapes.   It is both stable  and self-extinguishing in
 its natural form.   Bakelite (R)  polysulfone is prepared from  the
 two  raw  materials  under  alkaline  conditions according to the
 equations listed in Figure 111-36,  Equations 1 and 2.

 The disodium salt  is prepared in_situ by reaction of bisphenol  A
 with exactly two moles"of aqueous sodium hydroxide.   A solvent is
 required  for   this  polymerization, dimethyl sulfoxide being the
 most suitable.   Very few others  are effective.   The reaction must
 be carried out  at  130-160°C (266-320°F), primarily because of the
 poor solubility of  the   disodium  salt   at  lower  temperatures.
 Polymerization   is,   however,  very  rapid  at these temperatures,
 leading to molecular  weights  as  high  as  250,000  in  an  hour's
 time.    As  these   molecular   weights are too high for commercial
 processing,  chain  growth must  be regulated   by  the  addition  of
 terminators.     A   variety   of monohydric  phenolic  salts  or
 monohalogen compounds have been  fourd to be effective.

 In the  polymerization, the highest  molecular   weights   will  be
 obtained  when   the   mole  ratio of co-monomers  approaches unity.
 Since the co-monomers contain  two functional groups per  molecule,
 as is required  for this  type of  polycondensation,  addition  of  a
 compound containing one  functional  group per molecule  will  result
 in  an   overall  imbalance in  functionality,   terminating chain
 growth.

 All  but  traces of  water  must be  removed  from the reaction  mixture
 before polymerization.   Hydrolysis  of the   dihydric  phenol   salt
 occurs otherwise,  resulting in the  formation of  sodium hydroxide,
 which  reacts  very   rapidly   with   the  dichlorodiphenyl  sulfone,
 forming   the  monosodium  salt    of    4-chloro-4'-hydroxydiphenvl
 sulfone  (Figure  111-36,  Equation  3).

 Two  moles  of   caustic   soda  (from  2  moles  of disodium salt)  are
 used per  mole  of  dichlorodiphenyl   sulfone,  which   creates  an
 imbalance  in  functionality   between  the   co-monomers.   Conse-
 quently,  it becomes in-possible to obtain high molecular weight.

Another,  somewhat less important,  side  reaction  may  occur  if
 caustic  soda  is  present  during   polymerization.   Cleavage of
 polymer chains  para to the sulfone groups  results  in  the  for-
                          109

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          HO
  CH3

   C
   I
  CH3
                             OH + 2NaOH
(1)
             NaO
                      CH
                      CH3
              ONa + 2H20
      NaO
CH3
I
C-
I
CH3
o-m
                            ONa + Cl
(2)
                  CH
                                                        .+2NaCI
(3)     Cl Ca H* S02 C6 H4 CI + 2 NaOH—Cl C6 H4 S02 C6 H40 Na + NaCI + H2O
         CH3
                                               CH
(4)
                                S02 	 +OH"
                                               CH
                                 HO
                     O
                                   S02
              FIGURE 111-36  TYPICAL REACTIONS TO FORM POLYSULFONE RESINS
                              110

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nation  of two phenoxides, as shown in Figure 111-36, Equation 4,
for polysulfone.

Other bisphenol A-derived  polysulfones  are  prepared  by  using
various combinations of dihydric phenol sodium or potassium salts
and  dichlorodiphenyl  sulfone.   Use  of  certain other aromatic
dihalides  besides  dichlcrodiphenyl  sulfone  expands  the  list
considerably.

Manufacture - A typical process scheme is shown in Figure 111-37.
Polymerization  of  bisphenol A and 4,4'-dichlorodiphenyl sulfone
 (DCDPS) is carried out batch-wise by first forming  the  disodium
salt of bisphenol A.  This is done by charging bisphenol A and an
excess  of  dimethyl  sulfoxide   (DMSO)  to  a  reactor where the
temperature  is  brought  up  to  60-80°C  (140-176°F).    Sodium
hydroxide as a 50 percent solution is added stoichiometrically to
the  mixture over a period of about 10 minutes.  Water is removed
from  the  system,  the  DMSO  that  co-distills  being  returned
continuously.  In so doing, the temperature of the contents rises
from  about  120°C   (248°F)  initially  to  140°C   (284°F) at the
conclusion of this step.  When this point is reached, most of the
water originally present has distilled, and the disodium salt  of
bisphenol A appears as a precipitate.

Excess  azeotrope  solvent is distilled from the system until the
temperature of the contents reaches  155-160°C  (311-320°F).   At
this  point the precipitate will redissolve with the formation of
a very viscous solution.  It is assumed that at this  point  only
traces of water remain.

A 50 percent solution of 4,4'-dicholordiphenyl sulfone (DCDPS)  in
DMSO maintained at 110°C (230°F) is fed stoichicmetrically to the
polymerizer.   The  temperature  must  not drop below about 150°c
 (302°F) until the polymerization is  well  along,   since  sodium-
ended  low  polymer  may precipitate on the walls of the reactor.
Too high  a  temperature  during  addition  of  the  sulfone  and
subsequent  polymerization  is  to be avoided, as the reaction is
mildly  exothermic,  extremely  rapid  over  160°C  (320°F),  and
excessive  solvent  decomposition  and/or  discoloration  or even
gelation of the reaction mass may occur.

The polymerization may be terminated in a variety of ways, one of
which is to pass methylene chloride into the polymerizing mixture
when the desired degree of polymerization is reached.

Additional DMSO is added to the reactant mixture  to  reduce  the
viscosity  to  a  workable  level.   The  mixture  is then passed
through a rotary drum filter  to  remove  sodium  chloride.    The
process  stream  is  fed to a coagulation vessel where an alcohol
such as ethanol is  added  to  coagulate  the  polysulfone.    The
solvent  and  unreacted  feed  materials  are  separated from the
polymer and sent to recovery.   The  polymer  is  then  dried  and
pelletized while the vented solvent is recovered and recycled.
                          Ill

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BISPHENOL A
  SODIUM
 HYDROXIDE
   (50%)
 DIMETHYL
 SULFOXIDE
 DICHLORO
 DIPHENYL
  SULFONE
TERMINATORS
COAGULANTS
                TO
             RECOVERY
   REACTION
          DISODIUM
          SALT
POLYMERIZATION
                                       I
  FILTRATION
                                       I
 COAGULATION
                                   SEPARATION
                                         SOLIDS
                                     DRYING
                                       i
                                   PELLETIZING
                       WATER
                        I
            FIGURE 111-37 POLYSULFONE RESINS PRODUCTION
                             112

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Waste  Water  Generation - The reaction products include 810 mass
units of water per 1000 mass units of the disodium salt,  and  an
estimated  1800  mass  units  of  water  is added with the sodium
hydroxide for a total of 2610.  The waste water  from  the  azeo-
tropic  distillation  are  likely  to  contain DMSO and traces of
bisphenol.  In addition,  appreciable  concentrations  of  sodium
chloride are expected to occur.  The waste waters are expected to
be  alkaline  because of the excess sodium hydroxide required for
pH control.  The  volume  of  waste  water  generated  is  highly
dependent  upon operating conditions, especially those associated
with the washing operations (25, 27).
                          113

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Polyvinyl Butyral

Polyvinyl butyral is formed by condensation of polyvinyl  alcohol
with  butyraldehyde  in  the presence of an acid catalyst (Figure
111-38) .

Manufacture - Two processes, shown in Figures 111-39 and  III-UO,
are used for production of polyvinyl butyral.

The  process  shown  in  Figure  111-39,  which  is used, by E. I.
DuPont de Nemours and Company, Inc., Fayetteville,  N.C.,  starts
with  powdered  polyvinyl  alcohol.   The alcohol is dissolved in
water and reacted with butyraldehyde according to the equation in
Figure 111-38.  The butyral is washed and slurried in water.  The
slurry is treated with a plasticizer  (triethylene  glycol  di-2-
ethyl  butyrate  is  one), and the mixture is sheeted to give the
product that is sandwiched and  heat  sealed  between  pieces  of
glass to produce safety glass.

The  process shown in Figure 111-40 is practiced by Monsanto Co.,
Indian Orchard, Mass., and Trenton, Michigan.  At  these  plants,
vinyl  acetate  monomer  is  polymerized  in  suspension  to give
polyvinyl acetate.  This polymer is separated, dissolved in ethyl
alcohol and hydrolyzed in the presence of a  mineral  acid.   The
polyvinyl alcohol is centrifuged and condensed with butyraldehyde
in  the presence of ethyl alcohol and acid.  The butyral solution
is filtered, precipitated with water, washed and dried.

The dry product may be sold as such, or  transferred  to  another
area  of the Monsanto plant for sheeting.  In this operation, the
polymer is combined with plasticizer and sheeted on  rolls.   The
sheeting   process   uses  very  little  water,  and  wastes  are
negligible.

Waste Water Generation - Wastes generated in the  DuPont  process
are indicated  in Figure 111-39.  The acid catalyst, small amounts
of the reaction components, and a small amount of the plasticizer
are anticipated wastes.

Wastes generated by the Monsanto process, shown in Figure III-UO,
are  considerably more complex than those generated by the DuPont
process.  The Monsanto process requires  ethanol,  which  is  not
needed  in  the  DuPont process; the ethanol combines with acetic
acid which is  liberated in the  hydrolysis   step  to  give  ethyl
acetate, which is recovered  (31, Ul).
                           114

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                          x
[CH2CHOHCH2CHOH]n  +  C3H7C ^	 [CH2CH CH2CH] n + H20
                           H
                                       0     O
                                        \  /
                                          c
                                        /  \
                                          7   H
  FIGURE 111-38  TYPICAL REACTION TO FORM POLYVINYL BUTYRAL
                              115

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                 DEMIN WATER & STREAM
 PVA
          1
   CATALYST
                                       BUTYRALDEHYDE
                                            DEMIN. WATER
PLASTICIZER
 I
          POLY  VINYL
        ALCOHOL (PVA)
          DISSOLVING
BIOTREATMENT
                                                               EXTRUSION
                                                                SHEETING
   FINISHED
   PRODUCT
                                    5%  BOD      30% OF BOD
                                 (MISC. SOURCES)
                   POWDERED  ROLLS
                               I
REFRIGERATED ROLLS
                               I
                     TINTED ROLLS
                                                                        DEMIN. WATER
                FIGURE 111-39 POLYVINYL BUTYRAL PRODUCTION - DU PONT INC. PROCESS

-------
    VINYL
  ACETATE-
  SUSPENDING AGENT

 i	 WATER


       CATALYST
                             LIME _
                            SLURRY
         POLYMERIZATION
  ETHYL
 ALCOHOL
MINERAL
CATALYST
 ETHYL
ALCOHOL
               I
          CENTRIFUGE
           DISSOLVING
  PV
ACETATE
          HYDROLYSIS
                  PV
                ALCOHOL
          CENTRIFUGE
                                                   WASTE WATER TREATMENT
                                     NEUTRALIZING
                                       FACILITY
                            0.9% FLOW
                                 WATER-
                                        OTHER
                                       • PLANT
                                        WASTE
                                                    STORAGE
                                      30.6% FLOW
                                        MISC.
                                                                   DRYING
                             68.5% FLOW
                                                  CENTRIFUGE
                                                       STEAM
                                                                WATER
                          SOLVENT

                         RECOVERY

                          SYSTEM
                     BUTYRALDEHYDE


                       WATER
                   r
                                                                    WASHING
                                                           WATER
                                                 PRECIPITATION
                               BUTYRALDEHYDE
            ACETAL
           REACTION
                                                  FILTRATION
                                       PV BUTYRAL
      FIGURE 111-40 POLYVINYL BUTYRAL PRODUCTION - MONSANTO INC. PROCESS
                                    117

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Polyvinyl Carbazole

Polyvinyl  carbazole  is  a  thermoplastic which can be molded at
temperatures of 210-270°C (410-518°F)  into sheets which are clear
and  stiff,  resenrbling  mica.   The  polymer   is   soluble   in
chloroform,   trichloroethylene,   aromatic   hydrocarbons,  etc.
Despite its excellent dielectric properties, the polymer has  not
been  used  to any great extent for electrical insulation, mainly
because of the high cost of the monomer.

Poly(N-vinyl carbazole)  can be prepared via the use  of  a  Lewis
acid  catalyst.  The polymerization is illustrated in Figure III-
41.

Substitution of other solvents such  as  toluene,  carbon  tetra-
chloride, etc., or the use of higher polymerization temperatures,
all lead to lower molecular weight products.

Alternatively,  very highly purified monomer may be heated in the
absence of catalyst at temperatures of 85-120°C  (185-248°F),  to
give  a  nearly  colorless clear product similar in appearance to
polystyrene.  Even  small  amounts  of  impurities  lead  to  low
molecular weight products, however.

The   literature  reports  successful  polymerization  with  zinc
bromide initiated by passing an  electric  current.   The  yields
increased  with  increased  applied current density and were high
after short times.  Molecular weights were low   (2000  to  5000),
but  the  distribution was very narrow.  It is doubtful that this
technique will reach commercialization in the near future.

Manufacture - It is presumed that batch processing  is  employed.
Further information is unavailable in published literature.

Waste  Water - While the reaction itself does not produce wastes,
washing of the  product  polymer  would  produce  aqueous  wastes
containing  the  catalyst   (such  as boron trifluoride) and small
amounts of the solvent.  Adequate information is  unavailable  to
make projections of quantities involved  (25, 29).
                           118

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FIGURE 111-41   TYPICAL REACTION TO FORM POLYVINYL CARBAZOLE
                               119

-------
Polyvinyl Ethers

The  various  vinyl  alkyl  ether  monomers  (the  reactants)  are
normally colorless liquids or low melting  solids.    All  readily
add  halogens  across  their double bonds.   The lower alkyl vinyl
ethers are sparingly soluble  in  water.   These  monomer  ethers
hydrolyze  slowly  in water at room temperature (and more rapidly
in the presence of irineral acids) ,  producing  acetalydehyde,   as
shown in Figure III-42, Equation 1.

Hydrolysis   of  the  monomers  is  avoided  by  adding  alkaline
stabilizers (for example 0.1 percent of triethanolamine)   to  the
stored vinyl ethers.  Stabilizers and impurities such as alcohol,
acetaldehyde,  and acetals are then removed before polymerization
by washing with water or very dilute KOH.  Vinyl  ethers  produce
high  molecular  weight homopolymers when reacted in the presence
of Lewis acid catalysts.   The  catalysts  used  are  related  to
Zeigler  catalysts,  for  example,  diethyl  aluminum chloride or
Grignard reagents.

The propagation step proceeds as shown in Figure 111-42, Equation
2, thereby producing a head-to-tail structure.   The  more  highly
branched  the  alkyl  groups  are,  the greater the reaictivity of
monomer.  Long chain alkyl ethers  are  generally  less  reactive
than  the  short  chain  hcmologs.   Aromatic vinyl ethers do not
polymerize readily and are susceptible to side reactions such  as
rearrangements and condensations.

Vinyl ethers do not copolymerize readily with other vinyl ethers,
but  they  readily  form  copolymers with a wide variety of ether
monomers including dibutyl maleate, iraleic  anhydride,  acryloni-
trile,  vinylidene  chloride,  vinyl chloride,  vinyl acetate,  and
methyl acrylate.

Polyalkyl vinyl ethers are utilized primarily for  their  ability
to  serve  as  plasticizers  for  coatings,  or  because of their
tackiness for use in adhesives.  The methyl homopolymer  is  used
as  a  plasticizer  for  coatings  and  is  an  aqueous  adhesive
tackifier.  The vinyl methyl ether-maleic anhydride copolymer  is
used  as  a  water  thickening  agent,  suspending  agent, and an
adhesive.

Manufacture - Commercial processes are typical  for  the  various
polymerization  techniques.   Solution  or  bulk  techniques  are
presently used in the  U.S.   Typical  flow  diagrams  for  these
processes  are  shown  in  Figures  111-43  and  III-4U.   In the
solution polymerization process, when a solvent-free  product  is
desired,  it  is  dried  by  heating  under  vacuum.  In the bulk
process, aqueous or organic solvent is  sometimes  added  to  the
product depending on desired properties.

Waste  Water Generation - Sources of waste water will depend upon
the polymerization process employed.  In solution polymerization,
when no drying step is employed,  there  are  no  direct  contact
                           120

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                         H+              H+
 (1)    CH2=CHOR + H20	 [CH2 = CHOH]	 CH3CHO
 (2)
VW-CH2-CH
         I
         O
         I
         R
=CH-OR-
      H     H
      I       I
-AVCH2-C-CH2-C
      I       I
      O     0
      II      I
      R     R
FIGURE 111-42  TYPICAL REACTIONS TO FORM POLYVINYL ETHERS
             INCLUDING MONOMER MANUFACTURE
                          121

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                                                                     COOLING WATER
                                                                    OR REFRIGERATED
                                                                     BRINE (INDIRECT)
                                                                                  STEAM
                     COOLING WATER
                       (INDIRECT)
NJ
to
MONOMERS

CATALYST •

SOLVENT
(ORGANIC)
                                                                              VACUUM
                                                                                              STEAM
                                                                                             EJECTOR
                     POLYMERIZER
STEAM FOR
 INDIRECT
 HEATING
                                                                                                   COOLING
                                                                                                   WATER
                                                                                              BAROMETRIC
                                                                                               CONDENSER
                                                                                         WASTE
                                                                                         WATER
                                           SOLUTION
                                           PRODUCTS
                                                    SOLVENT-FREE
                                                      PRODUCTS
                 FIGURE 111-43 POLYVINYL ETHER PRODUCTION - SOLUTION POLYMERIZATION PROCESS

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                                                                                STEAM
                                                                     VACUUM
                                                                   FOR AQUEOUS
                                                                    OPERATION
MONOMER
CATALYST
 ORGANIC
OR  AQUEOUS
 SOLVENT
   POLYMERIZER
  ORGANIC
OR AQUEOUS
  SOLVENT
                     FINAL
                  REACTOR
                                                                                    STEAM
                                                                                   EJECTOR
                                                                    BAROMETRIC
                                                                    CONDENSER
                          DILUTION
                        ADJUSTMENT
                                                                             .COOLING
                                                                              WATER
                                                                               WASTE
                                                                               WATER
                                                                                PRODUCT TO
                                                                                 PACKAGING
           FIGURE 111-44 POLYVINYL ETHER PRODUCTION - BULK POLYMERIZATION PROCESS

-------
waste waters.  When drying is employed, some contamination of the
water from the steam ejector barometric condenser results.

There  is no water of reaction in the polymerization of polyalkyl
vinyl ethers (25) .
                             124

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Polyvinylidene Chlorides

Polyyinylidene chloride latex is commonly used for paper and film
coatings.  The latex is produced by  emulsion  polymerization  of
vinylidene  chloride,  frequently  in  the  presence  of  another
monomer.  The equation in Figure 111-45  expresses  the  reaction
involved.

Manufacture  -  The polymerization is performed in water using an
emulsifier, a peroxide, and  a  reducing  agent  such  as  sodium
bisulfite.  The reaction is conducted in an inert atmosphere, and
after several hours it is complete.

Following  the  polymerization,  the  emulsion may be heated with
steam to destroy components in the mixture  that  might  generate
odors on standing or in use, and is then ready for sale.

Waste  Water Generation - Wastes developed in the process consist
of tank washings.  These wastes include a low level of all of the
ingredients used,  and  suspended  solids  corresponding  to  the
polymer produced (41) .
                            125

-------
                      CCJI]
-*(CH2-CCI2)n
FIGURE 111-45  TYPICAL REACTION TO FORM POLYVINYLIDENE CHLORIDE
                          126

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Polyvinyl Fyrrolidone

Polyvinyl pyrrolidone is a water soluble polymer characterized by
unusual  ccmplexing and colloidal properties.  It is available in
pharmaceutical grades, a beverage grade, and in a grade  suitable
for textile leveling and stripping.

The  monomer  reactant  is N-vinyl-2-pyrrolidone, shown in Figure
III-46, Equation 1.  This is a colorless liquid with  a  freezing
point of 13.6°C (56.5°F), a boiling point of 96°C (204.8°F) at 50
mm,  and  123°C  (253.4°F)  at 114 mm.  It is completely miscible
with  water  and  most  organic   solvents.    The   monomer   is
manufactured by the vinylation of 2-pyrrolidone with acetylene in
the presence of alkali metal salts of pyrrolidone.

The  polymerization  to the product polymer  (shown in Figure III-
46, Equation 2) is accomplished by ionic  catalysis  using  boron
trifluoride  or  potassium amide.  The polymerization may also be
catalyzed with free radical catalysts such as hydrogen  peroxide,
benzoyl   peroxide,   or  azobisisobutyronitrile.   Also,  highly
purified vinyl pyrrolidone combines with  atmospheric  oxygen  to
give    peroxide-type   compounds   which   themselves   act   as
polymerization catalysts.  Since the vinyl amides are  hydrolyzed
under  acidic conditions, polymerizations are best carried out at
neutral or basic pH in water.  The polymerization reaction is  as
shown in Equation 3 of Figure 111-46.

A typical batch solution process for homopolymerization which was
applied  on a semi-industrial scale is as follows.  One-half of a
30 percent solution of purified vinyl pyrrolidone  in  water  was
added  to  the  reaction  vessel.  The remainder was added slowly
during the reaction.  Catalysis was accomplished by  addition  of
0.2  percent  hydrogen  peroxide  and  0.1  percent ammonia.  The
reaction was complete in  2  to  3  hours.   It  was  found  that
molecular  weight  increases  with  ammonia  concentration and is
directly proportional to monomer concentration  up  to  about  30
percent.   Above  30  percent,  molecular  weight was found to be
inversely proportional to catalyst concentration.

Copolymerization of N-vinyl-2-pyrrolidone has  been  successfully
accomplished  with  a  number  of  co-monomers.   Among these are
ethylene glycol monovinyl ether, ethylene, laurylacrylamide,  CJJ!
to  CJJ3   methacrylate,  divinyl  carbonate,  cinnamic  acid, and
crotonaldehyde.  A typical  process  utilizes  solvents  such  as
alcohol  or  benzene,  a  reaction  temperature  of 50-75°C  (122-
167°F), and catalyst at concentrations 0.1 to 1 percent.  Typical
catalysts   are   benzoyl   peroxide,   lauroyl   peroxide,   and
azobisisobutyronitrile.

Graft  polymerization  has  also  been  readily accomplished in a
number of cases.

The homopolymer  polyvinyl  pyrrolidones  are  produced  in  four
viscosity   grades  corresponding  to  average  number  molecular
weights:  10,000, 40,000, 160,000, and  360,000.   Pharmaceutical
                            127

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 (1)
       Monomer
       N-Vinyl-2-Pyrrolidone
CH2 - CH2

 I        I
CH2      C = 0
                                   CH = CH2
 (2)    Polymer
Cii2 ~~~ •"
1
CH2
\NX
1
PM

CH2
C = 0
PH«

                                         —I    n
                              NH4OH
                          H202      "2HO-
                   HO-  + CH2= CH—^HO-CH2-C-
                              I               I
         H
HO-CH2~C-  +  nCH2=CH-
 (3)
  HO-CH2- C — (CH2 - CH) , -CH2-  CH-
           I             I            I
   FIGURE 111-46  TYPICAL REACTIONS TO FORM POLYVINYL PYRROLIDONE
                                 128

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grades,  beverage  grades,  and  textile  leveling  and stripping
grades are produced domestically.  Copolymers with vinyl  acetate
of varying proportions are also marketed domestically.

Manufacture  -  Polyvinyl  pyrrolidone  is produced on commercial
scale by polymerization in water at 20-60 percent  concentration,
depending  upon  the  desired  product  viscosity.   Reaction  is
carried out with catalysis by hydrogen peroxide  and  ammonia  in
the  temperature range 50-80°C (122-176°F).  The product is spray
dried.  An alternative commercial process  is  polymerization  in
water using azobisisobutyronitrile at 50-60°C (122-140°F).

Waste  Water  Generation - The typical solution polymerization in
water would yield only a  small  waste  water  stream  since  the
solvent  is  recycled  whenever possible.  The polymer product is
probably washed, depending upon its end use, and the  wash  water
would  contain  small fractions of all agents in the reaction mix
including some catalyst.  There is no water of reaction (25).
                             129

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Silicones

Manufacture - Plants producing silicones typically produce a wide
variety of chemicals incorporating silicone.  Silicone  chemistry
is  complex, and the discussion here is limited to indicating the
processes conducted and the types and scope of wastes  generated.
Figures III-U7 and 111-48 are simplified flowsheets which suggest
the   complexity   of  silicones  plants.   Figure  III-U7  shows
processes used for production of several different  chlorosilanes
and  hydrolysis  of  dimethyl dichlorosilane to dimethyl silicone
fluid.   Figure  III-48  shows  transformation  of  the  dimethyl
silicone  fluid  to  finished fluids, greases, emulsions, rubber,
and resins.  These  figures  dc  not  include  several  processes
conducted at the plants.

All  of  the  plants  we have examined purchase silicon metal and
react it with a wide range of chemicals, used in  several  steps.
The following processes may be conducted at a silicone plant:

    1.   Production of methyl chloride, generally by reaction  of
         methanol  and hydrogen chloride. Figure 111-49, Equation
         1.

         Methyl chloride is  used  in  production  of  methylated
         chlorosilanes.   Other organic chlorides, alkyl or aryl,
         are used also; e.g., phenyl chloride.

         Methyl chloride may be purchased by  a  silicones  plant
         rather  than being manufactured there.  As far as we are
         aware, other organic halides are always purchcised.

    2.   Chlorosilane production.  For the methyl fluids,  methyl
         chlorosilanes  are  produced  by  the  reaction shown in
         Figure 111-49, Equation 2.

    other organic chlorides  (see above) would be used to generate
    other chlorosilanes.  The mixture of products produced in the
    direct process are separated by  fractional  distillation  to
    provide  each  component; dimethyldichlorosilane must be very
    pure for use in subsequent syntheses (see  below).   Some  of
    the  chlorosilanes   (probably  methyl  trichlorosilane)  have
    limited use, and are wasted.

    The above equation represents the "direct" process for making
    chlorosilanes; it is widely used for  the  methyl  compounds,
    the  phenyl compounds, and perhaps others.  Chlorosilanes may
    also be made by a Grignard process, represented by  Equations
    3 and 4 in Figure III-U9.  The Grignard process finds limited
    use,  in  part because large amounts of solvent are required,
    and the metal salts go into a waste stream.  We believe  that
    it is used only for special chlorosilanes.

    Trichlorosilane   (HSiCl3)  is  produced  by reacting directly
    silicon and hydrogen chloride.  For production of still other
                             130

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V
£
(j
. Transistor-grade silicon
Benzene,
olefms,
acetylene, and
other reagents
                                  T
                                 Fluids,
                                 rubber
              FIGURE 111-47 PRODUCTION OF SI LANE MONOMERS, OLIGOMERS AND
                                    DIMETHYL SILICONE FLUID

-------
Co
NJ
Dimethyl silicone fluid

Hexamethyldisiloxane
from Me3SiCI

n
i
Depolymerizef
                      Phenyl oligomers
                       Vinyl oligomers*
                    Fluoropropyl oligomers*
                    Catalyze
                    and use
 Blends of
chlorosilanes
s


| Water
'+ y

"7


Catalysts
,
i /
/
~~ /
Hydrolysis
  kettle "
                                                                            Bodying
                                                                            ' kettle
                                                   Hydrochloric
                                                      acid
                                                                                .Silicone
                                                                                 resins
                                                                                                 Room temperature
                                                                                                  • curing rubber
                                                                                  Silicone
                                                                                  emulsions
                                 FIGURE 111-48  PRODUCTION OF SILICONE FLUIDS, GREASES, COMPOUNDS,
                                                        EMULSIONS, RESINS AND RUBBER

-------
(1)     CH3OH  +  HCI	-CH3CI +  H20
                           Cu
(2)     CH3CI +  Si  +  HCI	    SiCI4 + CH3SiHCI2  + CH3SiCI3 + (CH3)2SiCI2
                          300°C
(3)     CH3CI + Mg	-CH3MgCI
                                            C1
                                             i
(4)     2CH3MgCI  +  SiCI4	-2MgCI2  + CH3-Si-CH3
                                             i
                                            Cl
(5)     (CH3)2SiCI2  +  H20	-~(CH3)2 Si(OH)2  +  2 HCI
(6)     (CH3)2Si(OH)2	-(CH3)2  Si-0-Si(CH3)2
                                  I        i
                                  0      0

                           (CH3)2  Si-0-Si(CH3)2
                         and   HO [Si (CH3)2 0]nH
             FIGURE 111-49  TYPICAL REACTIONS TO FORM SILICONES
                                    133

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chlorosilanes, olefins  or  acetylene  may  be  reacted  with
appropriate silane ironomers.

3.    Hydrolysis.   For  production  of  the  methyl  fluids,
dimethyl dichlorosilane is hydrolyzed with water as shown  in
Figure 111-49, Equations 5 and 6.

The  cyclic  siloxane  may be further processed to the linear
polymer.  The linear products are  manufactured  in  a  broad
viscosity range to give the well-known fluids.

Silicone  fluids  are  often  sold  as  emulsions  in  water;
production of these mixtures involves use of emulsifiers  and
special  equipment.   In  addition,  the viscosity of certain
fluids may be substantially  increased,  probably  by  cross-
linking, to provide silicone greases.

4.   Silicone  resin  production.   The  resin  products  are
branched and cross-linked siloxane polymers,  generally  sold
as solutions in organic solvents.

The  resins  are  manufactured  by  hydrolysis of mixtures of
chlorosilanes in solvents.   The  mixtures  may  be  complex,
including  mono-,  di- and trichloro-silanes having different
organic radicals, alkoxysilanes, and  other  silane;s  bearing
special  functional  groups.   After  hydrolysis, the aqueous
layer is separated and the organic phase is  neutralized.   A
catalyst  may  be  added  to  the  organic  solution, and the
mixture may be heated to polymerize the dissolved chemicals.

5.  Elastomer production.  Silicone elastomers  are  produced
from  high  molecular  weight  fluids,  fillers,  and  curing
agents.  The mixtures are often called compounds.

Two types of  polymer-filler  mixtures  are  produced,  those
which  cure  to rubber by application of heat and those which
are cured at room temperature.  Catalysts used  for  products
cured at room temperature may be tin or organotin salts.

6.   Specialties  production.   For our purposes, specialties
constitute  materials  which  are  produced  in   significant
amounts  at a single silicones plant but in minor amounts, if
at all, at others.  We have  included  surfactants,  coupling
agents and fluorosilicones as specialties, but other products
may  also  be classified in this group.  It is characteristic
of silicones plants that new products  are  constantly  being
developed and offered commercially.

Surfactants  are produced by reaction of silicone fluids with
polyethylene  oxide,  or   polyethylene   oxide-polypropylene
oxide.  The products are water soluble.

Coupling  agents  are  monomeric silanes which serve as glass
surface primers to increase the adhering strength of a  resin
subsequently  applied.   The  typical  final  composition  is
                         134

-------
    glass-silane-resin.   The  resin  may  be  epoxy,  polyester,
    melamine,  or  ether.  One coupling agent which has been used
    is  aminopropyl  triethoxy  silane.    Production   of   such
    chemicals  generally involves reaction of a chlorosilane with
    an appropriate organic compound, followed by exchange of  the
    halogen atoms with alcohol groups.

Waste  Water  Generation - Resin production generates significant
amounts of acid wastes due to the liberation of hydrogen chloride
in the hydrolysis step.  The acid may be recycled, for example in
the production of irethyl  chloride,  but  in  many  cases  it  is
impractical  to  recover  it.   Organic  solvent  wastes, such as
naphtha or toluene, are also produced.  Most of the solvents  are
recovered,  but  trace  quantities may appear in the waste water.
Quantitative information on the waste water generated in silicone
polymerization processes is not documented in the literature (25,
Multi-Product Plants

Coupling agents are produced in  significant  quantities  at  one
manufacturing  location.   These  resins  require  a vacuum to be
applied  to  the  batch  reactor  kettle  during  the  hydrolysis
reaction   (5)  in Figure 49.  Existing plants employ once- through
barometric   condensers  to  achieve  the  vacuum;  use  of   such
condensers   increases the process water flow from the vicinity of
17,000 to 27,000 gallons per 1000 pounds of product.  These extra
waters cannot be recycled until concentrated, as is practiced  in
the manufacture of polyesters and alkyds, for instance, since the
materials  of  construction  of  the  process  equipment will not
withstand the more concentrated hydrochloric acid.   New  plants,
however,  could  incorporate such a change without undue penalty.
On existing  plants, this additional condenser water may  be  used
as  scrubber  water  for  incineration, thereby not adding to the
total hydraulic load by the addition  of  incineration.   Surface
condensers   of  current  design  are  very  expensive  for  this
application  due to the need for hastalloy  type  alloys  for  the
metal  parts  in  contact  with  the process waters, and are also
subject to frequent plugging from the products of reaction.

F luid Pr oduc t.,Plant s

By  virtue   of  being  both  newer  plants  and  because  of  the
inherently   more controllable process from the viewpoint of water
recycling and less product variation, the  fluid  product  plants
have been able to achieve considerably lower levels of unit water
use.

Source   of   heavy   metals  -  copper  catalyst  used  for  the
chlorosilane production process enters the waste water during the
hydrolysis step and in  subsequent  water  of  reaction  produced
during  polymerization.   Fluorides  may  be present in the waste
water where  f luorosilicones are being manufactured.
                             135

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Spandex Fibers

Spandex fibers are made  from  conventional  polyurethane  ingre-
dients.   Textile  Organon  (43)   defines spandex fibers as being
composed of "at  least  85  percent  by  weight  of  a  segmented
polyurethane."   In ccmmon with ether fiber processing reactions,
extremely careful control must be  maintained  in  raw  materials
specifications and reaction techniques to insure adequate quality
of fiber.

The  rubber-like  qualities of the spandex fibers result from the
formation of a polyurethane composed of alternating  sections  of
soft  and  hard segments.  The hard segments are considered to be
rigid and impart elasticity by limiting the  viscous  flow  which
results  from  the  soft  segments.   The soft segments are long-
chained  molecules  terminated  with  hydroxyl  groups.    Common
examples  are polyadipate which is the reaction product of adipic
acid and a glycol (Figure III-50, Equation 1), polytetramethylene
glycol  (Equation 2), and polycaprolactone  (Equation  3).   These
soft   segments  are  then  reacted  with  a  diisocyanate,  most
generally toluene diisocyanate (TDI)  (Equation 4) ,  or  methylene
bis(4-phenol   isocyanate)     (MDI)   (Equation  5),  to  give  an
isocyanate-terminated prepolymer  containing  urethane  linkages.
The  structure of a typical MDI-terminated polyadipate prepolymer
is shown in Figure 111-50, Equation 6.   This prepolymer  is  then
reacted  with  either  a  diamine  (such  as ethylene diamine) or
hydrazine to form the final spandex fiber; the reaction is  shown
in   Figure  111-50,  Equation  7.   Various  additives  such  as
delusterants  (titanium  dioxide),  ultraviolet  absorbers,   and
antioxidants are also added to obtain various properties.

Manufacture  -  Spandex  fiber  can  be  produced  by  wet or dry
solution spinning processes, reaction spinning, or melt spinning.

One major U.S. fiber producer, uses the dry spinning process.  In
this the heated polymer, dissolved in a solvent such as  dimethyl
formamide,  is  extruded  through  a spinnerette into a column of
circulating hot air which serves to  evaporate  the  solvent  and
thereby  solidify  the filaments.  A schematic diagram of the dry
spinning process is shown in Figure 111-51.

Another U.S. producer produces spandex fibers by the wet spinning
process.  This process is similar to that employed by  DuPont  in
that  a spinning solution is used, but instead of spinning into a
column of circulating hot air, the spinning solution is spun into
a water bath which serves to extract the solvent and  coalesce  a
multifilament  yarn.   A  schematic  of  the  process  based on a
discussion with Ameliotex is shown in Figure 111-52.

Another U.S. producer produces spandex fibers by a  variation  of
wet  spinning  which  is  known as reaction or chemical spinning.
The isocyanate-terminated prepolymer  is  extruded  into  a  bath
containing toluene and a diamine  (ethylene diamine).  The diamine
reacts  with the prepolymer by crosslinking or chain extending to
convert it to a solid  elastomeric  fiber.   Although  individual
                             136

-------
 (1)
                  H(OROCO CH2 CH2 CH2 CH2 CO)nOROH
(2)
                          H [0(CH2)3CH]nOH
(3)
                          H [0(CH2)5CO]nOROH
(4)
                           H3C  ((    )}  NCO


                             NCO
(5)
                 OCN-<      >— CH2-(     )>— NCO
                -0-IM-C-
(6)   OCN-0-CH2 -0-N-C-OCH2CH20
                      H
      ,L
-(CH2)4C-OCH2CH2O -C -N -0-CH2 -0IMCO
                       H
(7)    OCN- R -
      Prepolymer
                    H2NCH2CH2NH2
0            O
C-N-R-N-C-N-CH2-CH2 - N - -
   H      H     H             H
            FIGURE 111-50   TYPICAL REACTIONS TO FORM SPANDEX FIBERS
                                    137

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00
00
          MAKE  UP
                                     DIISOCYANATE
                                            DIAMINE
POLYMER-
 IZATION
 VESSEL
                                BLOW-DOWN
                                                            RECYCLE
                                 SOLVENT
                               PURIFICATION
                                                       (N- DtMETHYLFORMAMIDE)
                                                            SOLVENTS
                                                           WASTE  SOLUTION
                                                           TO  INCINERATION
                                                                                           WASTE TO INCINERATION
                                                     SOLVENT +
                                                      HOT AIR
SPINNING


       SPINNING WASTE
       TO INCINERATION

   HOT AIR



     LUBRICANT
                                                                       o
             SOURCE: BASED ON DISCUSSION
                    WITH DUPONT.
                                                            \
           HOUSEKEEPING WASTE WATER
           TO  BIOLOGICAL TREATMENT
                             FIGURE 111-51 SPANDEX FIBER PRODUCTION - DRY SPINNING PROCESS

-------
U)
VD
                          TOLUENE
                        DlISOCYANATE
         POLYTETRAMETHYLENE
              GLYCOL
                                                                                         LUBRICANT
          COOLING
         WATER FROM
            CITY
                         POLYMER-
                           Z AT I ON
                          VESSEL
                                                WELL WATER
                                                  COOLANT
                      TO
                    SEWER
           SOURCE: ADL, BASED ON DISCUSSIONS
                  WITH AMELIOTEX, INC.
                                                                  TO
                                                                 STORM
                                                                 SEWER
                                                                                        REGENERATION
                                                                                          WASTES
PRODUCT
                                                                                                         CITY
                                                                                                        WATER
                           FIGURE 111-52 SPANDEX FIBER PRODUCTION - WET SPINNING PROCESS

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filaments are produced in this way, usually the individual fibers
are  brought  together  to  form a coalesced, multifilament yarn.
After  leaving  the  ethylene  diamine/toluene  spin  bath,   the
coalesced  yarn is washed with water, dried, and lubricated prior
to winding.  A schematic of the process based on discussions  and
communications with Globe is shown in Figure III-53.

Waste  Water Generation - In addition to cooling water discharge,
the producer which uses the dry  spinning  process,  reports  the
following sources of wastes and corresponding handling methods:

    1.   Waste polymer — incinerated.

    2.   Waste solution from the  solution  preparation  step  —
         incinerated.

    3.   Spinning waste — incinerated.

    4.   Normal  housekeeping  water  and  equipment  washout  —
         biological treatment.

    5.   Waste from the solvent purification and recycle step  —
         biological treatment.

In  the  wet spinning process there are cooling water discharges,
regeneration  wastes  from  the  water   deionizing   unit,    and
occasional  wastes  resulting  from  cleanout  of lubricant  (spin
finish) tanks.  Note that the  solvent  water  mixture  from   the
spinning  bath  is transferred to  a recovery unit from which both
solvent and water are recycled to  the spinning bath.  The  company
states that  the  only  water  loss  is  by  evaporation   to   the
atmosphere.

The primary  source of waste  from the other  producers' reaction or
chemical   spinning process originates from  the washing step which
follows the  spinning bath.  This stream  containing  wash  water,
toluene,   and ethylene  diamine is  passed to  a continuous decanter
which allows separation of toluene and water by  gravity.   Toluene
is removed and purified by distillation prior to being  recycled
to  the  spin bath,  solid dregs remaining  after distillation  are
drummed  and  hauled to  a landfill.  In the  method used  by  Globe,
the   continuous   decanter  has  a  retention time of 160 minutes.
This  is  said to be sufficient to   give  a   water effluent  (con-
taining  a  faint odor  of toluene) which is  subsequently discharged
to a  municipal  sewage  system (41,  43).

Other Pollutants

Depending  on   the particular waste  water  chemical  conditions  and
the  analytical  methods used,  cyanides  may  be detected due  to  the
presence  of  isocyanates.    Oil   and grease   presence  is due to
 lubricants used in the spandex  fiber  after  extrusion.    Organic
 nitrogen derives  frcm the presence of ethylene diamine.
                             140

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   POLYESTER
               MDI
           •ISOCYANATE
                                                            RECYCLE-
TOLUENE
   I
DIAMINE
COOLING
WATER "
POLYMER-
 IZATION
 VESSEL
                                               DECANTED
                                                WASTE
                                                 H20
                                                STREAM
                                                                       DRUMMED AND
                                                                      HAULED TO DUMP
                                                           _^.WASTE WATER TO
                                                                MUNICIPAL
                FIGURE 111-53  SPANDEX FIBER PRODUCTION - REACTION SPINNING PROCESS

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Urethane Prepolymers

The reaction of a compound containing a hydroxyl (-OH)  group with
a  compound  containing  an  isocyanate  (-NCO)   group produces a
urethane linkage as indicated in Figure III-5U,  Equation 1.

Polyurethane resins are  produced  by  the  reaction  of  polyols
(which are compounds containing two or more hydroxyl groups) with
polyisocyanates  (which  are  compounds  containing  two  or more
isocyanate groups)  to form a polymer network with  many  urethane
linkages.   In  the polyurethane there may also be other types of
chemical linkages.   For instance, if  water  is  present  in  the
reaction  mixture either as a result of intentional addition of a
minor amount of water or accidental  presence  as  humidity,  the
-NCO  group  can  react with a water molecule to produce an amine
plus  carbon  dioxide   (Figure  111-54,  Equation  2).    Another
isocyanate  group  can  then  react  with  the amine to produce a
fciuret linkage.  Additional -NCO groups can  also  react  with  a
hydrogen  of  the urethane linkage  (Equation 1, Figure 111-54) to
produce an allophanate linkage.  However, as long as the  primary
linkages  in  the  polymer  network  are urethane, the product is
known as a  polyurethane.   There  is  a  wide  range   (literally
hundreds)  of  polyols  and  several  polyisocyanates that can be
utilized to make polyurethanes with a wide range of properties.

In some cases, prepolymers are utilized to make the  polyurethane
resin.   A  prepolymer  in the ccmmcn commercial form is a  liquid
reaction product of a polyol with  an  excess  of  isocyanate  to
produce  a  low  molecular  weight  polymer  containing  reactive
isocyanate end groups as exemplified by Equation 3 in Figure  III-
54.  This low molecular weight polymer normally becomes one   part
of  a  two-component  system  in  which  the  second component is
additional polyol with which the prepolymer can react to  form   a
cross-linked cured  urethane.

There  are a number of reasons for using the prepolymer technique
rather than  the  one-shot   approach   in  which  the  isocyanate,
polyol,  and   other  components  of  a formulation are  simply mixed
together and allowed to react.   The   prepolymer   approach   often
provides   tetter   central   of   rate   of  reaction  and  improved
compatibility  and  mixing   characteristics  in  the  components.
 Improved   product   properties  can  often  be obtained  both through
 better control of the  reaction and through the use  of   different
 polyols   in  making the   prepolymer   and for  the  final curing.
Another  important reason  for using the prepolymer  technique in
 polyurethanes  which   utilize   relatively low  molecular   weight
 polyisocyanates  such   as   toleuene   diisocyanate   (TDI)  is  that
 prereaction  of  the   polyol  with   the   isocyanate   reduces  the
 isocyanate  vapor pressure and  therefore  lowers  the   toxicity of
 the  formulation.

 Most  large volume  polyurethane   products   such  as flexible and
 rigid foams  are  produced primarily  by  the one-shot  technique in
 which  all  components  are blended together  with  no prereaction.
 The  one-shot approach  is used  for  large  volume  products  because
                             142

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                                  0
                                  II
   (1)     R-OH + R'-NCO	-R-0-C-N-R'
                                     I
                                     H
   (2)     R'-NCO + H20—-R'-NH2  + C02
   (3)     3R (NCO)2 + HO R'-OH	-



                 OCN - R (NHCOO - R' - OCO NHR)2 NCO
FIGURE 111-54  TYPICAL REACTIONS TO FORM URETHANE PREPOLYMERS
                             143

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it   is   the  most  economical  method  to  make  polyurethanes.
Prepolymers are generally used where  smaller  volumes  and  more
specialized  applications  of  pclyurethanes  are  involved.   For
instance, foam systems that  are  sold  as  two-component  liquid
formulations  for  field  spraying  or cast-in-place applications
frequently utilize prepolymers.  Similarly, for other high  value
products  where  maximum  control  of  the reaction is necessary,
prepolymers are frequently used.  Such applications include  cast
elastomers,  sealants,  adhesives, and two-component and air cure
polyurethane coatings.

Manufacture - Prepolymers are commonly made by  batch  procedures
although  continuous  processing  techniques have been developed.
In batch processing, a reactor jacketed  for  steam  heating  and
water  cooling  is  the only basic equipment required.  Auxiliary
equipment includes a  feed  system  to  place  materials  in  the
reactor  and,  frequently,  a  holding  tank to which two or more
batches of prepolymer can be transferred  from  the  reactor  and
blended  as  necessary prior to transfer to a shipping container.
The prepolymerization reaction is a simple addition reaction with
no water or by-products produced.  Throughout  the  process,  the
raw  materials  and  the  prepclymer  must be stored or processed
under a blanket of dry nitrogen or other inert  gas  because  the
isocyanate  will react rapidly with any moisture present and will
thus be converted to an amine and deactivated.

The continuous processes involve primarily  the  use  of  scraped
film  heat exchangers as the primary processing equipment but are
analogous  to  the  batch  operation  in  other  ways   including
maintenance  of a nitrogen blanket over the raw materials and the
prepolymer to eliminate any exposure to atmospheric moisture.

Waste Water Generation - Basically there is no water involved  in
the  prepolymer  production  except  for  minor amounts which may
purposely be added to the mix to produce  some  biuret  linkages.
In  fact,  every effort is made to assure that all unwanted water
is excluded both from the feed materials and the product  because
the  isocyanate  will  rapidly  react  with  any water to form an
unwanted amine.  Even a minor amount of such  unplanned  reaction
drastically changes the properties of the prepolymer and may even
cause  it  to gel  in the reactor or drum.  The only wat€;r used is
in the cooling jacket of the  reactor,  and  this  is  completely
separated  from  the  reaction  mixture.  It is unlikely that any
water would be  used  for  cleaning  a  reactor  between  batches
because  the  water  would produce a rapid cure of the prepolymer
and make the cleaning operation more difficult.  In addition, the
reactor would have to be thoroughly dried before processing of  a
new  batch  could  begin.   There is a remote possibility that in
some instances a water ndscible  solvent might be  used  to  clean
the  reactor  and  the solvent-prepolymer solution then mixed with
water in order to  react  with  the  prepolymer,  and  that  such
contaminated  water might be discharged.  We are not aware of any
such  operations,  and  the  possibility  of  such  contamination
occurring  on  any  significant   scale  is  remote because of the
significant  loss of raw materials that would be involved  (25).
                             144

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                            SECTION IV

                      INDUSTRY  CATEGORIZATION


The  most effective  means  of categorizing the  resin  segment  of  the
synthetics  and  plastics industry  was  to determine if  the  two most
relevant characteristics  of the waste waters  (i.e.,   raw  waste
loads   expressed  as   kg   of  pollutant  per   kkg of  product*  and
attainable  BOD5   concentrations   in  treated   waste  waters from
plants  using   technologies taken as  the basis of  BPCTCA) were
comparable  to the  subcategories   established  for  the  polymers
segment of the  industry.  The  data obtained on raw waste loads
and  treated waste water characteristics from  the plants  observed
and  from discussions  with industry representatives  indicated that
four major subcategories would also  represent the  resins segment
of the  industry.

     Major Subcategory I -  Lew raw  waste  load  (less  than  10
     units/1000    units    of   product);   attainable    low   BODS
     concentration (less than 20 ing/liter) .

     Major Subcategory II  -  High raw waste load (greater  than  10
     units/1000    units    of   product);   attainable    low   BOD5
     concentration.

     Major   Subcategory  III  -  High  or  low  raw  waste  load;
     attainable  medium  BOD5 concentration  (in the  30-75  mg/liter
     range) .

     Major Subcategory  IV  -  High or  low raw waste load;  attainable
     high BOD5 concentration  (over  75  mg/liter).

The  attainable BOD5 concentration  in  the effluent   is   influenced
by   both  treatability  and, for a  specific waste water treatment
plant design, by  variations in the  influent concentrations.

In Major Subcategory  I where reported BODS raw waste   loads  are
less  than  10  units/1000  units   of product  and where hydraulic
flows ranged from 0.4 to  153 cu m/kkg (55 to  18,300 gal/1000 Ib),
the  influent concentrations ranged  from 8 to  720 mg/liter.  While
the  influent concentrations varied  over  a   90-fold  range,  the
effluent concentrations varied over a 3-fold range,  i.e., 8 to 25
mg/liter.    This  indicates that practicable waste water treatment
plants  should be capable  of retaining effluent concentrations  in
the vicinity of 15 mg/liter when using properly designed and well
operated biological systems.


*   Production basis for establishing the unit effluent guidelines
has been on the basis of  actual production,  not rated capacity of
a  plant.
                            145

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The plants in Major Subcategory II are characterized by high  raw
waste  loads,  but  the  waste  waters  can  be  treated  to  low
attainable BODS concentrations.  Hydraulic flows varied from 14.2
to 116  cu  m/kkg  (1700  to  14,000  gal./lOOO  Ibs).    Influent
concentrations  of  froir approximately 600 to 4,300 mg/liter were
reported.   Although  only  one  treatment  plant  was   found  in
Category  II  and  this  was producing effluent concentrations of
approximately 25 mg/liter, it is known that the waste waters from
the other processes are readily treated by biological methods.

Major Sufccategory III plants are characterized by high raw  waste
loads  and  observed  flows  from  0 to 170 cu m/kkg (0 to 20,400
gal./lOCO Ibs) .  Influent BOD5 concentrations from  0  to  45,000
mg/liter  were  found, and effluent concentrations varied from 15
to 80 mg/liter indicating intermediate treatability of the  waste
waters.   One  of the waste water treatment facilities attained a
BOD5_ removal of abcut 97 percent in a four-stage  aeration  basin
indicating that ir.ediurr BOD5 concentrations are achievable.

Major  Subcategory  IV  facilities have high raw waste loads with
concentrations reported to be 2,200 mg/liter at flows of  from  7
to 40 cu m/kkg  (900 to 4,800 gal./lOOO Ibs).

Estimates  of  BOD5  concentrations  from  a one-stage biological
system were in the vicinity of 225 mg/liter.  The supposition  is
made  that  practicable  waste  water treatment technology, e.g.,
two-stage  biological  treatment,  might  reduce   the   effluent
concentration  of Category IV processes to levels comparable with
the  plants   appearing  in  Major   Subcategory   III;   however,
attainable  BOD5  concentrations below these levels have not been
documented.   Table VII-3 summarizes the performance  of  observed
waste water treatment plants.

Additional subcategorization within the above major subcategories
was  necessary to account for the waste water generation which is
specific to the individual products and their various  processing
methods.  The separation of each individual product into separate
subcategories  simplifies   the   application  of  the  effluent
limitations  guidelines  and standards of performance by  providing
a  clearly  defined  context  for  application  of  the numerical
values.  The  advantages  of  this  subcategorization  appear  to
outweigh  technical  advantages  that  might  be  connected  with
product  group  characterization  alone.   The  resulting   major
subcategories  and component product subcategories are ssummarized
in Table IV-1.

Several other  methods  for  subcategorizing  the  industry  were
considered.   These  included plant  size,  plant  age, raw materials
and  products, and air pollution and solid waste generation.   The
utilization   of  municipal  systems was considered as a method of
characterization for the  alkyd molding and unsaturated polyesters
category, however, since  the waste waters are generally  accepted
into  municipal  systems and since pretreatment  standards would be
applicable,  it  was decided to  establish a guidelines  limitation
as   though the  plants were treating waste waters  in private waste
                             146

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                             TABLE IV-1
                      INDUSTRY SUBCATEGORIZATION
       Major
   Subcategory I
      Major            Major            Major
  Subcategory II  Subcategory III   Subcategory IV
Ethylene-vinyl
 acetate
 copolymers
Fluorocarbons
Polypropylene
 fibers
Polyvinylidene
 chloride
Acrylic resins
Cellulose
 derivatives
Alkyds and un-    Nitrile barrier
 saturated poly-   resins
 ester resins     Spandex fibers
 Cellulose nitrate
 Polyamids
  (Nylon  6/12)
 Polyesters (therm-
 plastic)
 Polyvinyl-
 butyral
 Silicones
                                 147

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water treating  facilities.   The  age  of  the  plants  in  this
industry  are  determined  largely ty obsolescence due to size or
process changes and not physical age.  Similar raw materials  are
often  used  to  make  dissimilar  products.   The  impact of air
pollution control systems using water scrubbing and the  disposal
of  solid  wastes are not sufficient to warrant segmentation. For
these reasons none of the aforementioned factors  was  judged  to
have  sufficient  relationships with raw waste load generation or
effluent  compositions  to  warrant  their  use  as  a  basis  of
categorization.
                            148

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                             SECTION V

                      WASTE CHARACTERIZATION


 The  general  process  flow  diagrams in Section III indicate the
 major waste water  generation  points  for  individual  processes
 where information could be obtained.  Flow rates and compositions
 of  process  waste  water  streams  at  points of origin were not
 available since the  companies  surveyed  have  rarely  monitored
 these  streams  except  where  excessive  losses  of a particular
 component have been of concern, such as in the waste waters  from
 a  distillation  unit.   Not  only do waste water streams emanate
 from  direct  process  operations,  from  chemical  reaction  by-
 products  and  other  contacts, but also a significant portion of
 waste waters may come from the  washdown  of  process  vessels  -
 especially  where  batch  operations  are  preeminent  as  in the
 synthetic polymers industry - from area  housekeeping,   utilities
 blowdown and other sources such as laboratories and so on.

 Raw Waste_Loads

 Raw  waste  water  flow  ranges are shown in Table V-l,  and waste
 loads of BOD5,  COD,  and suspended solids are shown in Table  V-2.
 These  data  are  based  on information provided by the  companies
 contacted during the course of this study.   Much of the  data  was
 provided as units per unit of production by the manufacturers and
 was  not  obtained  from  daily  production rates and waste water
 flows and concentrations.   Furthermore,  it is  known that much  of
 the  data  on  waste  water  flows  and  raw waste loads has been
 derived from limited numbers  of samples over short time   periods.
 Because  the  synthetic  polymers  industry is  based to a large
 extent on batch production methods and  often  on  the commercial
 need   to  produce  a  large  number  of  product types of a basic
 polymeric material,  the waste water flows  and  raw waste  loads per
 unit  of production were reported  to vary   from  essentially  no
 water  use   (water  leaves  with  product   or  no water is used in
 manufacture)  to nearly 300  cu meters/kkg (36,000  gal./lOOO   Ibs).
 The  major   pollutant  parameters for which  data were  obtained are
 BOD5,  COD,   and  suspended  solids.   Inspection   of  the  ranges
 recorded  in Table  V-2  shows that these  pollutants  vary by factors
 of  up to  30 from low to high  values  for  an  individual polymer.

 Other   pollutants  which may occur  in  the waste  water  from various
 polymer manufacturing  processes  are  listed  in Table  V-3.    These
 elements,   compounds,   and  characteristics  were  developed  from
 information obtained  from industrial  representatives,  literature
 sources,  Corps  of  Engineers Permit  Applications  for a  number of
 plants in the plastics  and   synthetics  industry,  reviews  with
 personnel   in  Regional  EPA  offices,  and  internal  industrial
 consultants.

Note also that in  some  instances, insufficient operating data  on
raw   wastes   and   treatment   were   available   to  establish
variabilities;  as a result those chemical products  that  employ


                            149

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                              TABLE V-l

         WASTEWATER LOADING FOR SYNTHETIC POLYMERS  PRODUCTION
                                     Observed or Reported Ranges  of
                                           Wastewater Loading
Acrylic resins

Alkyd molding compounds and
unsaturated polyester resins

Cellulose derivatives

Cellulose nitrate

Ethylene-vinyl acetate copolymers

Fluorocarbon polymers

Nitrile barrier resins

Polyamides

Polyester resins (thermoplastic)

Polypropylene fibers

Polyvinyl butyral

Polyvinyl ethers

Polyvinylidene chlorides

Silicones

Spandex fibers
 (gal/1000#)

 1700 - 5600

   38 - 1440


 1700 - 14000

13300 - 20400

  275  -  300

 2200 - 18300

  900 - 4700

     N.A.

  260 - 770

  160 - 3700

 7800 - 14200

    0 - 6250

  500(E)

 1000 - 33500

 1000 - 1700
  (cu m/kkg)

 14.2 - 46.7

  0.3 - 12.0


 14.2 -116.8

110.9 -170.2

  2.3  - 2.5

 18.4 -152.7

  7.5 - 39.2

     N.A.

  2.2 -  6.4

  1.3 - 30.9

 65.1 -118.5

  0   - 52.2

  4.2(E)

  8.3 -279.5

  8.3 - 14.2
NA = Not available

E  = Estimated
                                150

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G
M
                                                     TABLE V-2
                                    SYNTHETIC POLYMERS PRODUCTION RAW WASTE LOADS
                             (All units expressed  as  kg/kkg (lb/1000 Ibs of production)
                                                             Observed, Reported, or Estimated (E)  Ranges  of
                                                                           Average Waste Loads	
Acrylic resins
Alkyd molding compounds and  unsaturated
polyester resins
Cellulose derivatives
Cellulose nitrate
Ethylene vinyl acetate copolymers
Fluorocarbon polymers
Nitrile barrier resins
Polyamides
Polyester resins (thermoplastic)
Polypropylene fibers
Polyvinyl butyral
Polyvinyl ethers
Polyvinylidene chlorides
Silicones
Spandex fibers
         E = Estimated
        NA «• Not available
                                                                  BODC
                                                                        COD
                              SS
                                                                  2 - 30

                                                                  9-25
                                                                140 - 220
                                                                 55 -  110(E)
                                                                0.44 -  4.4(E)
               3-55

              15 -  80
             340 -  950
             75  -  275(E)
              0.2  - 54(E)
5-10

1-2
1-42
 35(E)
0 -  4.1
0 -  6.6(E)  4.4  -  44(E)  2.2  - 6.6(E)
                                                                  5 - 10(E)
                                                                   NA
                                                                  0-10
                                                                0.4 -  l.l(E)
                                                                 30 - 200
                                                                   NA
                                                                   0(E)
                                                                  5 - 110
                                                                  20(E)
              10  -  30(E)
               NA
               1-30
3 - 10(E)
 NA
 NA
             1.8  -  2.6(E)  0.2  - 2.2(E)
              40 -  400
           10(E) -  40(E)
               8(E)
              15 -  200
               40(E)
 NA
 NA
0.2(E)
50(E)
 NA

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primary -treatment only for treatment of plant wastes may show raw
waste  loads  lower  than guideline limits; it was announced that
their variabilities were the same as those of other  products  in
the same major sutcategory.
                             152

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                        TABLE  V-3
        OTHER ELEMENTS,  COMPOUNDS  AND  PARAMETERS

 pH
 Color
 Turbidity
 Alkalinity
 Temperature
 Nitrogenous Compounds(organic, ammonia  and nitrates)
 Oils and Greases
 Dissolved Solids - principally inorganic chemicals
 Phosphates
 Phenolic Compounds
 Sulfides
 Cyanides
 Fluorides
 Mercury
 Chromium
 Copper
 Lead
 Zinc
 Iron
 Cobalt
 Cadmium
Manganese
Aluminum
Magnesium
Molybdenum
Nickel
Vanadium
Antimony
Numerous Organic Chemicals
                       153

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                            SECTION VI

                 SELECTION OF POLLUTANT PARAMETERS
 The selection of pollutant parameters for the purpose of effluent
 limitations  guidelines and standards of performance was based on
 the following general criteria:

     a.    Sufficient data on a parameter known to have deleterious
          effects in the environment were available for all of the
          product sufccategories with regard to the raw waste  load
          and  the  observed  degree  of removal  with demonstrated
          technology.

     b.    The parameter is present in the raw waste  load  for  an
          individual product sufccategory in sufficient quantity to
          cause  known  deleterious effects in the environment and
          there is demonstrated technology available to remove the
          parameter.

 Selected_Parameters

 The following parameters have been selected  for   the  purpose  of
 establishing  recommended  effluent  limitations   guidelines   and
 standards of performance based on the criteria discussed  above.

 BOD5

 Biochemical  oxygen  demand  (BOD)    is   a  measure   of  the   oxygen
 consuming capabilities   of   organic  matter.  The  BOD  does  not  in
 itself cause direct harm to a  water system,  but it  does exert   an
 indirect   effect  by   depressing  the  oxygen  content  of the  water.
 Sewage and other  organic effluents  during   their   processes   of
 decomposition exert   a  BOD, which  can  have  a catastrophic  effect
 on  the ecosystem  by depleting  the  oxygen  supply.  Conditions  are
 reached   frequently   where  all   of   the  oxygen  is used and the
 continuing decay  process  causes the production of  noxious  gases
 such  as   hydrogen  sulfide  and  methane.   Water with a high BOD
 indicates  the  presence  of   decomposing  organic   matter   and
 subsequent   high  bacterial  counts  that degrade its quality and
 potential  uses.

 Dissolved  oxygen  (DO)  is  a water  quality  constituent  that,   in
 appropriate   concentrations,  is  essential  not  only  to  keep
 organisms  living but  also to sustain species reproduction, vigor,
 and the development of populations.  Organisms undergo stress  at
 reduced  DO  concentrations  that  irake them less competitive and
 able to sustain their species  within  the  aquatic  environment.
 For  example,  reduced  DO  concentrations  have  been  shown  to
 interfere with fish population through delayed hatching of  eggs
reduced  size  and vigor of embryos, production of deformities in
young, interference with food digestion,  acceleration  of  blood
clotting,  decreased tolerance to certain toxicants, reduced food
                           155

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efficiency  and  growth  rate,  and  reduced  maximum   sustained
swimming  speed.   Fish  food  organisms  are  likewise  affected
adversely in conditions with suppressed DO.   Since  all  aerobic
aquatic   organisms   need   a  certain  amount  of  oxygen,  the
consequences of total lacfc of dissolved oxygen due to a. high  BOD
can kill all inhabitants of the affected area.

If  a  high  BOD  is present, the quality of the water is usually
visually degraded by the presence of  decomposing  materials  and
algae  blooms  due  to the uptake of degraded materials that form
the foodstuffs of the algal populations.

COD

Chemical oxygen demand  (COD) provides a measure of the equivalent
oxygen required to oxidize the materials present in a waste water
sample under acid conditions with the aid of  a  strong  chemical
oxidant,  such  as  potassium dischromate, and a catalyst (silver
sulfa-te) .  One major advantage  of  the  COD  test  is  that  the
results  are  available normally in less than three hours.  Thus,
the COD test is a faster test by which to  estimate  the  maximum
oxygen  exertion  demand  a waste can make on a stream.  However,
one  major  disadvantage  is  that  the   COD   test   does   not
differentiate  between biodegradable and nonbiodegradable organic
material.   In  addition,  the  presence  of  inorganic  reducing
chemicals  (sulfides, reducible metallic ions, etc.) and chlorides
may interfere with the COD test.

The  slow  accumulation  of  refractory   (resistant to biological
decomposition) compounds in watercourses has caused concern among
various  environmentalists  and  regulatory  agencies.   However,
until  these  compounds  are  identified,  analytical  procedures
developed to quantify them, and their effects on  aquatic  plants
and  animals  are  documented,  it  may  be premature  (as well as
economically questionable) to require their  removal  from  waste
water  sources.

Total  Suspended Solids

Suspended  solids  include  both organic and  inorganic materials.
The inorganic components  include   sand,   silt,  and  clay.   The
organic  fraction  includes   such   materials as grease, oil, tar,
animal and vegetable fats, various  fibers,   sawdust,  hair,  and
various  materials  from  sewers.   These  solids  may settle out
rapidly  and bottom deposits are often a mixture of  both  organic
and    inorganic  solids.   They  adversely  affect  fisheries  by
covering the bottom of  the stream   or   lake  with  a  blanket  of
material   that  destroys the fishfood bottom fauna or the spawning
ground  of  fish.   Deposits  containing   organic  materials  may
deplete  bottom oxygen   supplies   and  produce hydrogen sulfide,
carbon dioxide, methane,  and  other  noxious gases.

In raw  water   sources  for   domestic   use,   state  and  regional
agencies generally specify that suspended  solids in streams shall
not be present  in sufficient  concentration to be objectionable or
                            156

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 to  interfere  with normal treatment processes.  Suspended solids
 in water may interfere with many industrial processes  and  cause
 foaming  in  boilers,  or  encrustations  on equipment exposed to
 water, especially as the temperature rises.  Suspended solids are
 undesirable in water for  textile  industries;  paper  and  pulp-
 beverages;   dairy   products;  laundries;  dyeing;  photography;
 cooling systems; and  power  plants.   Suspended  particles  also
 serve   as   a  transport  mechanisir,  for  pesticides  and  other
 substances which are readily sorbed into or onto clay particles.

 Solids may be suspended in water for a time, and then  settle  to
 the   bed  of  the  stream  or  lake.   These  settleable  solids
 discharged with man's wastes may be inert,  slowly  biodegradable
 materials,   or   rapidly   decomposable  substances.    While  in
 suspension, they increase the  turbidity  of  the  water,  reduce
 light  penetration,   and  impair  the  photosynthetic activity of
 aquatic plants.                                              J

 Solids in suspension are aesthetically  displeasing.    When  they
 settle  to  form  sludge deposits  on the stream or lake bed,  they
 are often much  more  damaging to the  life  in  water,   and  they
 retain  the  capacity  to  displease  the  senses.    Solids,  when
 transformed to  sludge deposits, may  do  a  variety  of  damacrina
 things,   including  blanketing the stream or lake bed  and thereby
 destroying the  living spaces for  those  benthic  organisms  that
 "2"™  otherwise  °ccupy  the  habitat.    When  of an  organic and
 therefore decomposable nature,  solids use a portion or all of the
 dissolved oxygen available in the  area.   Organic  materials  also
 serve  as  a seemingly inexhaustible food source for  sludgeworms
 and associated  organisms.

 Turbidity  is   principally  a   measure   of  the   light   absorbing
 properties   of   suspended   solids.    it   is  frequently used  as  I
 substitute  method of   quickly   estimating  the   total   suspended
 solids when the concentration is relatively low.

 P.H,  Acidity, and Alkalinity

 Acidity  and alkalinity  are reciprocal terms.  Acidity is  produced
 by   substances   that   yield  hydrogen  ions  upon  hydrolysis and
 alkalinity  is produced  by  substances that   yield  hydroxyl  ions.
 The  terms   "total acidity" and "total alkalinity" are  often used
 to express  the  buffering capacity  of  a   solution.   Acidity  in
 natural waters  is caused by carbon dioxide, mineral acids, weakly
 AtK?faJ   ' aClds' a"d the salts <»« strong acids and weak bases!
 Alkalinity  is caused by strong bases  and  the  salts  of  strong
 alkalies and weak acids.                                        y

 The  term   pH is a logarithmic expression of the concentration of
 hydrogen ions.  At a pH of  7,  the  hydrogen  and  hydroxyl  ion
 concentrations  are  essentially  equal and the water is neutraU
 £lE?l3Valuesj;ndicatf acidity  while  higher  values  indicate
 alkalinity.    The   relationship   between  pH  and  acidity  or
alkalinity is not necessarily linear or direct.
                           157

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Waters  with  a  pH  below  6.0  are  corrosive  to  water  works
structures,  distribution  lines, and household plumbing fixtures
and can thus add such constituents to  drinking  water  as  iron,
copper,  zinc, cadmium, and lead.  The hydrogen ion concentration
can affect the "taste" of the water.  At a low  pH  water  tastes
"sour." The bactericidal effect of chlorine is weakened as the pH
increases,  and  it  is  advantageous  to keep the pH close to 7.
This is very significant for providing safe drinking water.

Extremes of pH or rapid pH changes can exert stress conditions or
kill aquatic life outright.  Dead fish, associated algal  blooms,
and  foul  stenches  are  aesthetic  liabilities of any waterway.
Even moderate changes from "acceptable" criteria limits of pH are
deleterious to some species.  The relative  toxicity  to  aquatic
life  of  many materials is increased by changes in the water pH.
Metalocyanide complexes can increase a thousand-fold in  toxicity
with  a  drop of 1.5 pH units.  The availability of many nutrient
substances varies with the alkalinity and  acidity.   Ammonia  is
more lethal with a higher pH.

The lacrimal fluid of the human eye has a pH of approximately 7.0
and  a  deviation  of 0.1 pH unit from the norm may result in eye
irritation for the swimmer.  Appreciable  irritation  will  cause
severe pain.

Other,gollutant_Parameters

The   quantitative   identification   of  other  pollutants  from
analytical  data  was   impossible  to  establish.   However,  the
following  are  identified  as  the  major  other  pollutants  or
parameters which may  have  to  be  considered  in  the  National
Pollution Discharge Elimination System permits.

Phenolic ggmpounds

Phenols and phenolic wastes are derived from petroleum, coke, and
chemical  industries;  wood distillation; and domestic and animal
wastes.  Many phenolic  compounds are more toxic than pure phenol;
their toxicity varies with the combinations and general nature of
total wastes.  The effect of combinations of  different  phenolic
compounds is cumulative.

Phenols  and  phenolic  compounds are both acutely and chronically
toxic to fish and other  aquatic  animals.   Also,  chlorophenols
produce  an  unpleasant  taste   in  fish flesh that destroys their
recreational and commercial value.

It  is necessary to limit phenolic compounds in raw water used for
drinking water supplies, as conventional treatment  methods  used
by  water supply facilities do not  remove phenols.  The ingestion
of  concentrated solutions of phenols will result in severe  pain,
renal  irritation, shock, and possibly  death.
                            158

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 Phenols  also  reduce the utility of water for certain industrial
 uses,  notatly food and  beverage  processing,   where  it  creates
 unpleasant tastes and odors in the product.

 N i tr ogenou s_ConjEg unds

 Nitrogenous  compounds  can  occur  as  a  result  of  biological
 activity in the waste water treatment  and  can  also  come  from
 manufacturing  processes  such as urea,  melamine,  nylon,  ABS/SAN,
 cellulose nitrate,  cellulose derivatives, nitrile barrier resins,
 and  acrylics.   Ammonia is a common product of   the  decomposition
 of  organic  matter.    Dead and decaying animals  and plants along
 with human and animal body wastes account for  much of the ammonia
 entering the aquatic   ecosystem.    Ammonia  exists  in  its  non-
 ionized  fcrm  only  at higher pH levels and is the most toxic  in
 this state.  The lower the pH,  the more  ionized ammonia is formed
 and  its  toxicity decreases.    Ammonia,   in   the  presence   of
 dissolved  oxygen,  is  converted  to nitrate  (N03)  by nitrifying
 bacteria.    Nitrite  (NO2),   which  is  an  intermediate  product
 between  ammonia  and  nitrate,  sometimes occurs  in quantity when
 depressed oxygen conditions permit.   Ammonia can  exist in several
 other  chemical combinations including ammonium chloride and other
 salts.

 Nitrates are considered to be among the  poisonous  ingredients  of
 mineralized  waters,   with potassium nitrate being more poisonous
 than sodium nitrate.   Excess  nitrates cause  irritation   of the
 mucous linings of  the gastrointestinal tract and the bladder; the
 symptoms  are   diarrhea  and   diuresis,  and  drinking one  liter  of
 water  containing 500  mg/1 of  nitrate can cause such symptoms.

 Infant methemoglobinemia,   a   disease characterized  by   certain
 specific  blood changes  and  cyanosis,   may   be   caused by high
 nitrate concentrations in the water  used  for   preparing   feeding
 formulae.    While  it  is  still   impossible   to   state   precise
 concentration  limits,  it has  been  widely recommended  that  water
 containing   more than 10  mg/1  of  nitrate  nitrogen (NO3-N)  should
 not  be used   for  infants.    Nitrates  are  also   harmful    in
 fermentation processes  and  can  cause disagreeable  tastes  in  beer.
 In   most  natural   water the pH range is  such that  ammonium  ions
 (NH4+)    predominate.     in    alkaline    waters,    however,    high
 concentrations   of  un-ionized  ammonia  in undissociated  ammonium
 hydroxide  increase  the  toxicity of  ammonia solutions.   In streams
 polluted with  sewage,   up to   one-half  of  the  nitrogen   in  the
 sewage   may  be  in  the  form of  free  ammonia, and sewage may  carry
 up to  35 mg/1  of total  nitrogen.   It has been   shown  that  at  a
 level   of   1.0 mg/1 un-ionized ammonia,  the  ability  of hemoglobin
 to combine with  oxygen   is   impaired  and   fish   may  suffocate.
 Evidence   indicates   that  ammonia   exerts   a  considerable toxic
 effect  on all  aquatic  life within  a range of less than  1.0  mg/1
to   25   mg/1,  depending  on  the  pH  and dissolved oxygen level
 present.

Ammonia  can add to the  problem  of  eutrophication  by  supplying
nitrogen  through   its  breakdown products.  Some lakes in warmer
                           159

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climates, and others that are aging quickly are sometimes limited
by the nitrogen available.  Any increase will speed up the  plant
growth and decay process.

Fluorides

As  the  most reactive non-metal, fluorine is never found free in
nature but as a constituent of  fluorite  or  fluorspar,  calcium
fluoride,  in  sedimentary  rocks  and  also  of cryolite, sodium
aluminum fluoride, in igneous rocks.  Owing to their origin  only
in certain types of rocks and only in a few regions, fluorides in
high  concentrations  are  not  a  common  constituent of natural
surface waters, but they may occur in detrimental  concentrations
in ground waters.

Fluorides  are  used  as  insecticides,  for disinfecting brewery
apparatus, as a flux in the manufacture of steel, for  preserving
wood  and mucilages, for the manufacture of glass and enamels, in
chemical industries, for water treatment, and for other uses.

Fluorides in sufficient quantity are toxic to humans, with  doses
of 250 to 450 mg giving severe symptoms or causing death.

There  are  numerous articles describing the effects of fluoride-
bearing waters on dental enamel of children; these  studies  lead
to  the generalization that water containing less than 0.9 to 1.0
mg/1 of fluoride will seldom cause mottled  enamel  in  children,
and  for  adults,  concentrations  less  than 3 or 4 mg/1 are not
likely  to  cause  endemic  cumulative  fluorosis  and   skeletal
effects.   Abundant  literature  is also available describing the
advantages of maintaining 0.8 to 1.5  mg/1  of  fluoride  ion  in
drinking   water  to  aid  in  the  reduction  of  dental  decay,
especially among children.

Chronic fluoride poisoning of  livestock  has  been  observed  in
areas   where   water   contained   10   to   15  mg/1  fluoride.
Concentrations of 30 - 50 mg/1 of fluoride in the total ration of
dairy cows is considered the upper  safe  limit.   Fluoride  from
waters  apparently  does  not  accumulate  in  soft  tissue  to a
significant degree and it is transferred to a very  small  extent
into  the  milk and to a somewhat greater degree into eggs.  Data
for fresh water indicate that fluorides  are  toxic  to  fish  at
concentrations higher than 1.5 mg/1.

Phosphates

Surfactants  may  be  used  in  the proprietary formulations of a
number of manufacturing processes such as  polypropylene  fibers,
acrylic resins, nitrile barrier resins, thermoplastic polyesters,
polyvinylidene  chloride, and so on.  During the past 30 years, a
formidable case has developed  for  the  belief  that  increasing
standing  crops  of  aquatic plant growths, which often interfere
with water uses and are nuisances to man, frequently  are  caused
by   increasing  supplies  of  phosphorus.   Such  phenomena  are
associated with a  condition  of  accelerated  eutrophication  or
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 aging  of  waters.  It is generally recognized that phosphorus is
 not the sole cause of eutrophication, but there  is  evidence  to
 substantiate  that it is frequently the key element in all of the
 elements required by fresh water plants and is generally  present
 in  the least amount relative to need.  Therefore, an increase in
 phosphorus allows use of other, already  present,  nutrients  for
 plant growths.  Phosphorus is usually described, for this reason
 as a "limiting factor."

 When a plant population is stimulated in production and attains a
 nuisance  status,  a  large  number of associated liabilities are
 immediately apparent.    Dense  populations  of  pond  weeds  make
 swimming  dangerous.    Boating  and  water  skiing  and sometimes
 fishing may be eliminated because of the mass of vegetation  that
 serves  as  an  physical  impediment  to  such activities.   Plant
 populations have been associated with  stunted  fish  populations
 and  with  poor  fishing.    Plant  nuisances  emit vile stenches,
 impart tastes and odors to water supplies,  reduce the  efficiency
 of  industrial  and  municipal  water treatment,  impair aesthetic
 beauty,   reduce  or  restrict  resort  trade,   lower   waterfront
 property  values,  cause skin rashes to man during water contact
 and serve as a desired substrate and breeding ground for flies.

 Phosphorus in the  elemental  form   is  particularly  toxic,   and
 subject   to  bioaccumulation  in much  the  same way as mercury.
 Colloidal elemental phosphorus will poison  marine  fish  (causing
 skin  tissue  breakdown  and discoloration).   Also,  phosphorus  is
 capable  of being concentrated and will accumulate in  organs   and
 soft  tissues.    Experiments  have   shown   that  marine  fish  will
 concentrate phosphorus  from  water containing as little  as 1 ug/1.

 Oils and Greases

 Although  oils  and greases are most  frequently  found  to   occur as
 the  result of  equipment leaks  and so on,  and are not  usually of
 significant concern  to  this    industry,   some   manufacturing
 processes   such   as are used  to  produce  silicones, polypropylene!
 and  spandex fibers may require that oil  and grease be  considered
 a  parameter.

 °*i  anf   Crease  exhibit  an  oxygen  demand,  oil emulsions may
 adhere to the gills of fish cr coat and  destroy   algae  or  other
 plankton.  Deposition of oil  in the  bottom sediments can  serve to
 exhibit  normal   benthic  growths,   thus interrupting the aquatic
 food chain.  Soluble and emulsified material ingested by  fish may
 taint the flavor of the fish  flesh.   water soluble components may
 exert toxic action on fish.  Floating  oil  may  reduce  the  re-
 aeration  of the water surface and  in conjunction with emulsified
 oil  may  interfere   with   photosynthesis.    Water   insoluble
 components  damage  the  plumage  and  coats of water animals and
fowls.  Oil and grease in a water can result in the formation  of
objectionable   surface  slicks  preventing  the  full  aesthetic
enjoyment of the water.
                           161

-------
Oil spills can damage the surface of boats and  can  destroy  the
aesthetic characteristics of beaches and shorelines.

Dissolved solids

Dissolved  inorganic  salts are an integral part of the operation
of many processes.  Although no  effluent  guidelines  have  been
established  for dissolved solids, receiving stream water quality
standards  should  determine  if   limitations   are   necessary.
Manufacturing  processes  for the following products are believed
to produce the greatest loads of dissolved solids:

    Acrylic resins
    Cellulose derivatives
    Cellulose nitrate
    Fluorocarbons
    Silicones

In  natural  waters  the  dissolved  solids  consist  mainly   of
carbonates,   chlorides,   sulfates,   phosphates,  and  possibly
nitrates of  calcium,  magnesium,  sodium,  and  potassium,  with
traces of iron, manganese, and other substances.

Many  communities in the United  States and in other countries use
water supplies containing 2000 to 4000 mg/1 of  dissolved   salts,
when   no  better  water  is  available.   Such  waters  are  not
palatable, may not quench thirst, and may have a laxative   action
on  new  users.   Waters  containing more than 4000 mg/1 of total
salts are generally considered unfit for human use,  although  in
hot  climates  such  higher   salt concentrations can be tolerated
whereas  they  could   not  be in  temperate  climates.     Waters
containing 5000 mg/1 or  mere  are reported to be bitter and  act as
bladder  and  intestinal irritants.  It is generally agreed that
the  salt concentration of good,  palatable water should riot  exceed
500 mg/1.

Limiting concentrations  of dissolved solids for   freshwater  fish
may  range   from  5,000  to  10,000 mg/1, according to  species and
prior acclimatization.   Some  fish are adapted to  living  in  more
saline  waters,   and   a  few  species of  freshwater  forms have  been
found in natural  waters  with  a  salt concentration  of  15,000  to
 20,000  mg/1.    Fish   can   slowly become  acclimatized to  higher
 salinities,  but  fish  in  waters  of  low   salinity   cannot  survive
 sudden   exposure  to high salinities, such  as those resulting  from
 discharges of oil-well hrines.   Dissolved   solids  may influence
the   toxicity   of  heavy metals  and organic compounds  to fish and
 other aquatic life,  primarily because of the  antagonistic   effect
 of hardness  on  metals.

 Waters   with total  dissolved solids over 500  mg/1 have decreasing
 utility as  irrigation water.   At 5,000  mg/1 water has   little  or
 no value for irrigation.

 Dissolved  solids  in  industrial  waters  can  cause   foaming  in
 boilers and cause interference with cleanliness,  color,  or  taste
                            162

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of  many  finished  products.   High contents of dissolved solids
also tend to accelerate corrosion.

Specific conductance is a measure of the  capacity  of  water  to
convey  an  electric  current.   This  property is related to the
total concentration of ionized  substances  in  water  and  water
temperature.   This  property  is frequently used as a substitute
method of quickly estimating the dissolved solids concentration.

Toxic and Hazardous Chemicals

The industry uses a large number of accelerators  and  inhibitors
which   are   considered   proprietary   and,   consequently,  no
information  could  be  obtained.   Some  of   these   compounds,
especially  cyanide,  cadmium,  and mercuric compounds, may be on
EPA's recently proposed list of toxic substances as published  in
the Federal Register of December 27, 1973.

Alkalinity, Color, Turbidity, and the Metals Listed in Table V-3

These  pollutants  may  be  present in waste waters from selected
processes in varying amounts; however,  no data could be  obtained
which  would  permit  establishing  raw  or  treated waste loads.
Therefore, they are listed so that appropriate cognizance can  be
taken  to  determine  whether  cr not they are present in amounts
requiring effluent limitation because of receiving water  quality
standards.   Where  appropriate  the  particular  parameters  are
summarized in Table VI-1.
                          163

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                           TABLE VI-1

          OTHER ELEMENTS AND COMPOUNDS SPECIFIC TO THE
       RESINS SEGMENT OF PLASTICS AND SYNTHETICS INDUSTRY
Alkyd Compounds and
Ester Resins

Fluorocarbons

Spandex Fiters



Acrylic Resins

Polypropylene Fibers


Nitrile Barrier Resins


Polyamides

Cellulose Derivatives

Cellulose Nitrate

Silicones
 Polyvinylidene  Chloride
 Polyester Resins (Thermoplastic)
Lead
Cobalt

Fluorides

Cyanides
Oils and Grease
Organic Nitrogen

Oils and Grease

Oils and Grease
Phosphates

Organic Nitrogen
Cyanides

Organic Nitrogen

Inorganic Nitrogen

Inorganic Nitrogen

Polychlor inated
  Organics
Copper
Fluorides

Polychlorinated
  Organics

Cobalt
Manganese
Cadmium
                            164

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                            SECTION VII

                 CONTROL AND TREATMENT TECHNOLOGY
 Technology for the control and treatment  of  waste  waters  from
 this  segment  of  the  plastics  and  synthetics industry is not
 specifxc to the  industry  but  can  utilize  any  of  the  broad
 spectrum  of  technologies found in waste water treatment.  These
 technologies can be divided into the same three broad  categories
 found in the rest of the synthetics and plastics industry.  These


     1.  Presently used waste water treatment technology.

     2.  Potentially usable waste water treatment technology.

     3.   Control  of  waterborne  pollutants  by  in-plant or in-
          process practices.

 The application of presently or potentially  usable  waste water
 treatment  technologies  may  be  applied  on  selected  bases  to
 segregated streams or may  be  incorporated  into  a  centralized
 waste  water treatment plant.   Although categories 1 and 2 often
 denoted as end-of-pipe treatment,  may be  applied  regardless  of
 the   manufacturing   process,    in-process  control  to  prevent
 pollutants from entering water  streams has a great potential  for
 reducing the load of pollutants as well as the waste water flows.
 The  application  of  in-plant   control technology falls into two
 broad  categories:    (1)   process   requirements  and  (2)   plant
 practices.    Process requirements  for water usage depend upon the
 types of reactions  being carried out,  the  amounts  of   unreacted
 raw  materials   or   undesired by-products that must  be  removed  by
 water washing to attain product specifications,   the removal   of
 catalyst  activators  or other  additives  necessary to control the
 reaction or  create  the appropriate  chemical characteristics,  and
 the  use  of  water  for quenching,   creating  vacuum,   or other
 operations  that  contact   process  streams.    The  emission    of
 pollutants   into  waste  streams  outside  of   the direct  process
 operations may  come frcm poor housekeeping practices  or  from  the
 excessive  usage  of   water  for  cleaning  up spills,  leaks, and
 accidental occurrences  due  to   equipment  failure   or   personnel
 error.   Water used  to  control accidental  occurrences  or  hazardous
 conditions,  such   as  fires, etc., is  employed very occasionally,
 and usually is not  considered as contributing  to  the   pollution
 loads  in the waste waters.

As  indicated  earlier, the survey found no waste water treatment
technologies unique to  this segment  of  the   plastics  and  syn-
thetics  industry.   The  waste  water  treatment  technology  is
similar to that found during the survey of the first  segment  of
the   industry   and  is  generally  similar   to  that  of  other
industries.   Obviously,   application   of   basically   similar
technology,  e.g.,  activated  sludge biological treatment, often


                           165

-------
requires unique conditions for specific waste water  and  results
in  considerable variation in performance characteristics such as
efficiency of pollutant removal.

Presently Used Waste Water Treatment Technology

This segment of the plastics and synthetics industry was found to
have relatively few waste water treatment plants  devoted  solely
to  the  treatment of the waste waters from a particular product.
A major portion of the individual manufacturing plants,, except in
the  alkyd  and  polyester  resins  categories,  was  visited  or
otherwise  contacted  to  determine if water treatment facilities
were installed. It was found that a large portion  of  the  waste
waters   from  the  various  products  enter  either  centralized
treatment  facilities  for  multi-plant  chemical  complexes   or
municipal  sewage systems.  The major portion of the waste waters
from the manufacture of silicones is treated or will  be  treated
in  their  own  waste  water treatment plants.  Typical operating
data or design information  on  silicone  waste  water  treatment
plants  are included in Tables VII-1 and VII-2; however, one-half
of the companies requested  confidential  handling  of  the  data
provided  and,  therefore,  those  data  are  not  included.   In
addition, confidentiality was requested by a fluorocarbon  and  a
nitrile  barrier  resin  manufacturer.   Although  a  significant
portion of the design and operating data shown  in  Tables  VII-1
and  VII-2  are from waste water treatment plants receiving waste
waters  from  a  number  of  different   chemical   manufacturing
processes,  the  inclusion of data from multi-process waste water
treatment plants was made to indicate  the  operating  conditions
and  efficiencies  found  even though the load of pollutants from
the particular process was a small portion of the total  load  on
the  waste water treatment plant.  It must be recognized that the
efficiency of pollutant  removal  from  waste  waters  would  not
necessarily be the same as that demonstrated by the multi-process
treatment  plant  unless  the  waste waters represented the major
portion of the hydraulic and pollutant load.  Because of the many
variables  that  can  influence  performance  of  a  waste  water
treatment  plant,  the performance of a multi-process weiste water
treatment plant can only be taken as a qualitative  indicator  of
the  removal  efficiency  that  might  be achieved when operating
exclusively on the waste  waters  from  a  single  process.   The
paucity  of data on waste water treatment facilities, as recorded
in Tables VII-1, VII-2, VII-3, and VII-4, for this segment of the
industry is  not  surprising  because  of  the  relatively  small
production  capacities  of  the products and the use of municipal
sewerage systems or multi-process waste water treatment plants.

Biological treatment of the waste waters from this segment of the
industry appears to be the method chosen for effecting removal of
soluble substances.  Pretreatment before  biological  systems  is
often  required  whether the biological system is operated by the
manufacturer or is a  municipal  sewage  treatment  plant.   This
treatment  is  predominantly neutralization for the control of pH
prior  to  biological  treatment.   Primary  treatment  such   as
required in municipal treatment plants is not routinely necessary
                           166

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                                                                                        TABLE VII-1

                                                                   OPERATIONAL PARAMETERS OF WASTEHATEB TREATMENT PLANTS
                                                                                       (Metric Units)

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Type of Plant
Type of Treatment
Hydraulic Load (cu m/day) 1]
Residence Time (hours) '
BODe (kg removed/ day / cu m)
COD ( kg removed/day/cu n)
Power (HP/cu m)
Suspended solids (mg/liter)
Clarifier overflow (m/day)
Biomass (mg/liter)
BODj (kg removed/day/ kg MLSS)
Typical Values NH,-N out (ag/liter)
Typical Values T1QI out (lag/liter)
BOD5 in (mg/llter)
BOD out (mg/liter)
COD BOD5 In
COD in (mg/liter)
COD out (mg/llter)
COD/BOD5 out
Eff. BODj Removal
Eff. COD Removal
Methyl*
Methacrylate

equalize,
cool, nutrient,
bio ox, clarify,
sludge aeration
& centrifuging
1,000(6800 actual)
19+
0.85+
-
0.106+
50+
24.5
3000+
-
-
-
800+
120+
-
-
-
-
85+
-
Polyvinyl Thermoplastic*
Butyral P/E

lagoon coag aer lagoons
add, clarif
1,135 43,906
34 120(2904)
0.36 0.009
0.46
0.06 0.018
135
7.7
2991
0.17
14.6
14.8
543 1,476
39.7 422
1.5
839
179
4.5
92.7+ 71+
79+
Acrylic*
(30-70% of wastes
due to acrylic
rafg) equal, 2
trickling filters
parallel or series
clarif 4 polish
lagoons (57 acres)
3,936
41.5(424)
0.109
-
-
42
24.4 & 57.0
-
-
1.89
8.33
1,946
11
-
-
16
1.45
99.4
-
Vinyl Acetate
EVA
ill* 42*
Skin, oil sep Skim, filter, Skim, oil sep
equal, bio-aer burn recovered clar, anaerob
clarif w/chem oil, recycle bio
add, bio-anaer-recovered
obic polymer
(primary only)
409 4,807 30,280
36
1.03
0.5?
0.007
28
0.20
1200-1800
-
-
-
1,562
17
0.6(TOC/BOD)
904 (TOC)
37 (TOC)
2.2(TOC/BOD)
99+
96+(TOC)
0.3 8760
(API type skimmer)
_ _
40.7
23
51
_
_ _
.1 to 1.5
— _
(154) +
13
(4.2) +
20, 000 (TOC)
47 800 (TOC)
3.6
-
96 (TOC)
Polypropylene Polyvinylldene*
Chloride
Skim before Aerated lagoon
discharge settling basin
(primary only)
1,890 4,650
_
_
„ „
_ _
33 35
_
_ _
_
_
_ _
59
22
13
776
27 251
11.4
63+
68+
Comments:
                                         + Design Values

                                         Submerged aerators
                                         horsepower
                                         calculated from
                                         size of blowers.
                                         * Indicates wastewater plant serves a chemical manufacturing

                                              First value is residence time in aerobic biological syste
                                              Values In ( ) is residence time in total system.

-------




Type of Plant
1 Type of Treatment <»•«'•>
" municipal
treatment


2 Hydraulic Load (cu tc/day) '•'
3 Residence Time (hours)
4 BOD, (/removed/day/ cu m) *
5 COD (fremoved/day/cu m)
6 Power (HP/cu m)
7 Suspended solids (mg/liter)

8 Ciarifier overflow (a/day)

9 Blomass (mg/liter)

10 'BOD, (kg removed/day/kg MLSS)
11 Typical Values NHj-N out (mg/liter)
12 Typical Values TKS out (mg/liter)
13 BODj indag/liter)
14 BOD, outtmg/llter)
15 COD BODj in
16 COD in (mg/liter)
17 COD out (mg/liter)
18 COD/BOD, out
:>
19 Eff. BODj Removal
in vff rnn Vc**™ral -


OPERATIONAL

Alkyd/Polyester Resins
Settling, bio- Municipal
aerobic (4 treatment
stage)clarify (neut) &
hold lagoon

1 in 1
170 *
252
0.28
0.36
0.034
64

12.7

4,000

0.7
(Nutrient* added) -
2,960
•\Q ..
£.0
1.36
3,890
146
5.2


99+
96.2+
TABLE VI1-1
(Continued)
PARAMETERS OF WASTEWATER TREATMENT PLANTS
(Metri: Units)
Silicones
Neut screen Neut . clarify Bio-aerobic,
sedimentation sludge dewater clarify
screen, , skim, basin
filtration
(primary only) (primary only) secondary)
1,022 25,740 25,740
1.3 3+
(Ciarifier)


20 100

43.2 24.4

6500+

0.04

1.12
276+
24 - 38+

688

13.9 - 205+
0.58 - 5-4+

86.2+
70.2+





Cellulose* Polyvinyl Ether Spandex
Nitrate
tl* »2*
Neut. sediment Equal, neut. Settle S, neut Biological Municipal
spray oxidation process wastes coagulation, treatment
chlorinate city centrifug-
wastes act . ation
aludge clarify

2.0 «.«20 34,440
8.4 - '-5 plant
^ city
•- 0.93
0.66
0.02 - -
40.6 60 208 120

- - 52.3
_
- - ~ ~


- 156 - -
16 - -
219 - 776 2,200 3,
30 1,100 104 225
3.05 2.1
2,370 4,440
123.4 1,800 640 li**0
4.1+ 1.6 6-2 6.4
or t 73 -
86 - 86-6 "
_ 73 65-70+

Conenu:
•fDesign Values
Submerged aerators
horsepower
calculated from
size of blowers.
* Indicates waatewater plant serves a
  chemical manufacturing complex,
(1) First value is  residence time in
    aerobic biological system.
    Values io  ( ) ifl  residence  tiae in
    total syeten.
Includes lagoon
separator -
skimmer, sump
& pU controller.

-------
                                                                                         TABLE VII-2
                                                                    OPERATIONAL PARAMETERS OF WASTEWATER TREATMENT PLANTS
                                                                                       (English Units)


1
2
3
4
5.
6
7
8
9
10
11
\~>
CTi ,2
kD 1-!
13
14
15
16
17
18
19
20
Type of Plant

Type of Treatment
Hydraulic Load (MGD)
Residence Time (hours) '
BOD5 (Cremoved/day/lOOO ft3)
COD (Jreaoved/day/1000 ft3)
Power (HP/1000 ft3)
Suspended solids (mg/liter)
Clarifier overflow (GPD/ft )
Blonass (mg/liter)
BOD5 (f removed/day/*MLSS)
Typical Values NH -s out (mg/liter)
Typical Values TKN out (me/liter)
EODj in (mg/liter)
BODj out (mg/liter)
COD/BOD5 in
COD in (mg/liter)
COD out (ing/liter)
COD/BOD out
Eff. BCD, Removal
Eff. COD Removal
Methyl*
Methacrylate

Neut, screen,
equalize,
cool, nutrient.
bio ox, clarify,
sludge aeration
& centrifuging
2.9+
(1.8 actual)
19+
53+
-
3.0
50+
600+
3,000+
0.23
-
-
800+
120+
-
-
-
-
85+
-
Polyvinyl
Butyral

Equal, aer
lagoon coag
add, clarif
0.3
34
22
29
1.7
135
189
2,991
0.17
14.6
14.8
543
39.7
1.5
839
179
4.5
92.7+
79+
Thermoplastic * Acrylic*
P/E

Equal & aeut, (30-707. of wastes
aer lagoons due to acrylic
fflfg) equal, 2
tricking filters
parallel or series
clarif 4 polishing
lagoonR (57 acres)
11.6 1.04
120(2904) 41.5(424)
0.54 6.8
_
0.5
42
600 & 1400
-
-
1.89
8.33
1,476 1,946
422 11
-
-
16
1.45
71+ 99.4
_
Vinyl Acetate EVA
#1 112
Skim, oil sep Skim, filter, Skim, oil sep
equal, bio-aer burn recoverd clar, anaerob
clarif w/chem oil, recycle bio
obic polymer
(primary only)
0.108 1.27 8
36 °-3 8,760
64 (API type skimmer)
36 (TOO
0.2
28 23
5 - 1,257
1200-1800
-
.1 to 1.5
-
(154)+
17 13
0.6(TOC/BOD) - (4.2)+
904 (TOC) - 20,000(TOC)
37(TOC) 47 800(TOC)
2.2(TOC/BOD) 3.6
Q04- _ _
96+(TOC) - 96 (TOC)
Polypropylene Poly% inylidene*
Chloride

Skim before Aerated lagoon
discharge settling basin
(prijaary only)
0.5 1.23 MGD
-
-
-
33 35
-
-
-
-
-
59
22
13
776
27 251
11.4
63+
68+
Comments:r
Notes;
+ Design value

Submerged aerators
horsepower
calculated from
size of blowers.
* Indicates wastewater plant serves a chemical
manufacturing complex.
(1) First value is residence time in aerobic biological syste
    Values in (  } is residence time in total system.

-------

T
1


2
3
4
5
6
7
8
9
10
11
i2
"
14
15
-Lo
17
18
19
20

ype of Plant
Type of Treatment (Neut.)


Hydraulic Load(MGD) 0.0015
Residence Time (hours)'1^
BOD (t removed/day/ 1000 cu ft)
COD (fraaoved/day/1000 cu ft)
Po'.er (HPAOOO cu ft)
Suspended solids (mg/liter) -
Clarifler overflow (m/day)
Biomass (mg/llter)
EOD5 ( t removed/day/ * MLSS)
Typical Values KU^-N out (mg/liter)
Typical Values TOf out (mg/llter)
BOD5 in (mg/liter)
BOD, out (mg/liter)
COD BOD in
C03 in teg/liter)
COO out (mg/liter)
COD/BOD5 out
Eff. BOD Removal
Eff. COD Removal
OPERATIONAL
Alkyd/Polyester Resins
Settling, Municipal
aerobic (4 treatment

0.045 0.00053
252
17.4
22.2
0.95
64
312.5
4,000
0.7
(Nutrients added)
-
2,960
28
1.36
3,890
146
5.2 '
99+
96.2+
TABLE VII-2
(Continued)
PARAMETERS OF WASTEWATER TREATMENT PLANTS
(English Units)
Silicones
Neut screen Neut. clarify Bio-aerobic,
sedimentation sludge dewater clarify
screen, skim, basin
(proposed
(prijoary only) (primary only) secondary)
0.27 6.6 6.8
1.3 3+
(clarifier)
-
-
20 100
1,060 600+
6,500+
0.04
-
1.12
276+
24 - 38+
2.5
688
13.9 - 205+
0.58 - 5.4+
86.2+
70.2+

Cellulose* Polyvinyl Spanie*
Nitrate Ether
H 12
chlorinate city centrifuga-
sludge clarify
2.0 1.3 9.1
8.4 - 7.5 plant
2 city
- 58 -
41 - -
0.6 - - -
40.6 60 208 120
1,283
.
-
- 156 - - -
- 16 - -
219 - 776 2,200 3,900
30 1,100 104 225
3.05 2.1
2,170 4,400
123.4 1,800 640 1,440
4.1+ 1.6 6.2 6.4
86 - 86.6 90+
- - 73 65-70+
^Design Values

Submerged aerators
horsepower
calculated irom
size of blowers.
•Indicates wastewater plane serves a chemical
 manufacturing complex.
(1) First value is residence time in aerobic
    biological system.
    Values 10 ( > is residence time in total
    system.
Includes lagoon
separator -
skimmer, sump
& pH controller.

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                                                  TABLE VI I-3

                              PERFORMANCE OF OBSERVED WASTEWATER TREATMENT PLANTS
                                               BODr
                                                                      COD
                                                                                     Suspended Solids
  Inlet      Outlet
mg/liter   mg/liter
                                                                 Inlet     Outlet       Inlet       Outlet
                                                                Eg/liter  mg/liter     mg/llter    mg/liter
 Major Subcategory  I

   Ethylene-Vinyl Acetate*


   Ethylene-Vinyl Acetate*


   Fluorocarbons


   Polypropylene Fibers


   Polyvinylidene Chloride*


 Major Subcategory  II

   Acrylic Resins*


   Acrylic Resins**


   Cellulose Derivatives


   Polyvinyl Butyral


 Major Subcategory III

   Alkyds & Unsat.  Polyesters


   Cellulose Nitrate


   Polyamids (Nylon 6/12 only)


   Polyesters (Thermoplastic)*


   Polyvinyl Ethers***


   Silicones**


Major Subcategory  IV

  Nitrile Barrier  Resins


  Spandex*
  59
 630


 666
 543
1476
 776
 276
             10
             22
             17
             66
             40
2960         28


 251         34
422


104


 38
                      20,000(TOC)  SOO(TOC)
                                      48
                                     27
                         776         251
                                     24
                        839
                       3890
                       2370


                        688
                                    179
                         146
                                    124
640


205
                                                            21
                                                           360
                                                42
                                                           135
                                                64
                                                           41
                                                          208
                                       2200        225
                                                               4400        1440
                                                                                                  120
*     Part °f a multi-plant wastewater treatment facility :  Polyester operations contribute app.  14Z of  the
**    Design values  -  facility not operable at time of visit

***   Combined industrial municipal treatment facility
                                                            171

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                                                                                                   TABLE VII-4


                                               OBSERVED  TREATMENT  AND AVERAGE  EFFLUENT LOADINGS  FROM HASTE WATER TREATMENT PLANT INSPECTIONS
Piodjct
Control and Treat-
ment Technology
Currently in Use
Acrylic Resine
Equalization,
Trickling Filters
Polishing Lagoons
Acrylic Resins
Neutralization,
- Equalization
Bio-oxidation
(design)
Alkyds and
Unsatucated
Polveeter
Settling. Four-
Stages of Bio-
oxidation
Cellulose
Nitrate*
Neutralization,
Sedimentation
Spray Oxidation
Ethylene-
Vinyl Acetate*
Skimming
B io-ox id a t ion
Polypropylene
Fibers
Skimming
Only
Polyvinyl
Butyral
Sludge
(Multi-Product)
Bio-oxidation
(design)
Siliconea
(Fluid Product)
£ds£««:
                                                                             Observed  or Reported  Effluent Loading
 Ug/kkg'(lb«/1000)
 of Product]
 BOD5


 £OD



"Suspended Solids
                            o.io
                                               3.1


                                              30.8
0.09


0.47


0.21
0.07


0.25


0.15
0.24


0.78


0.98
*Multi-plant vai
                                    cillty

-------
for these waste waters; however, when significant amounts of oils
or  solvents  do  occur, the use of oil separators, skimmers, and
settling basins or lagcons is used.

The  effectiveness  of  a  particular  operational  mode  of  the
biological  processes  for  removal  of  biologically  degradable
pollutants varies widely depending upon  the  characteristics  of
the  waste  waters being treated.  Consequently, it is impossible
to generalize  regarding  the  operating  conditions  applied  in
biological  treatment  other  than to say that these are based on
well  understood  principles.    The   design   and   operational
characteristics  of  the  biological waste water treatment plants
are paramount in determining  the  overall  success  in  removing
biologically degradable pollutants.  Operational parameters found
for  waste water treatment plants in this segment of the plastics
and synthetics industry were generally  within  the  range  found
earlier  and  reported  in EPA Document 440/1-73/010 (16).  These
are  recorded  in  Tables  VII-1  and  VII-2.   Similar   removal
efficiencies  for  COD were found and the ratios of COD/BOD5 were
within the earlier ranges.

The  applicability  and  limitation   of   biological   treatment
processes  as  well as physico-chemical processes to this segment
of the plastics and synthetics industry are the same as  outlined
for  the  first  segment  and will be found in Section VII of EPA
Document 440/1-73/010  (16).

Cop.p_er

The most widely accepted and  economically  feasible  method  for
the  removal  of  relatively low concentrations of soluble copper
from  waste  water   streams   is   precipitation   followed   by
sedimentation and filtration.

Under alkaline conditions, copper will tend to precipitate out of
solution and form solid particles composed of the various oxides,
hydroxides,  and  carbonates  of copper.  Alkaline conditions are
generally accomplished by the  addition  of  lime  to  the  waste
water.   Typically,  a solids-recirculation clarifier is employed
to promote  the  formation,  growth,  and  sedimentation  of  the
precipitated particles.  Coagulants were often added to the waste
water  in  order  to  encourage the agglomeration of precipitated
particles to such a size where they may readily settle.

The theoretical minimum solubility for copper  in  the  pH  range
employed  in  the  lime treatment process is on the order to 0.01
mg/liter, but this level is seldom attained due to slow  reaction
rates,   poor  separation  of  colloidal  precipitates,  and  the
influence of other ions  in  solution.   Most  reported  effluent
copper  concentrations from the lime precipitation process are on
the order to 0.5 to  1.0  mg/liter.   If  lime  precipitation  is
followed  by  filtration,  concentrations  on  the  order of 0.25
mg/liter are attainable.
                           173

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 Lower levels  can  be  achieved  by  subjecting  the  effluent  from  the
 lime  precipitation step  to carbon  adsorption.

 Ion   exchange  can   be   employed  as  an  alternative to the lime
 precipitation process.   While  ion  exchange  has  been  reported  to
 produce   lower effluent concentrations   (0.03 mg/1)   than that
 achievable  by lime precipitation,  it usually entails much  higher
 capital  and operating costs.   Ion  exchange  becomes more  practical
 when   the  waste  streams  are  relatively  small and contain high
 concentrations of copper.

 Lead

 The most  commonly employed process fcr  the  removal  of  soluble
 lead   from  waste water is precipitation under alkaline conditions
 followed  by sedimentation and  filtration.

 Under  alkaline  conditions (usually created  by  the  addition  of
 lime)  lead  will  precipitate  out  of  solution  and form solid
 particles of  lead carbonate and  lead  hydroxide.   As  with  the
 removal   of  copper, it  is often necessary to also add coagulants
 to  produce  precipitates  of  sufficient   size.    Precipitation
 followed  by   sedimentation has  been reported to produce effluent
 lead concentrations  on  the   order  of  0.5  mg/liter.   If  the
 sedimentation  step  is  followed by filtration, an effluent lead
 concentration of 0.03 mg/liter may be achieved.

 Ion    exchange,   while   reported   to   produce   lower    lead
 concentrations,   usually  entails  a  much  higher  capital  and
 operating cost than lime precipitation.
The most promising and  technically  proven  processes  currently
available  for  the  removal  of  low  concentrations  of soluble
mercury from large  waste  water  streams  are  ion  exchange  or
sulfide precipitation.

In the ion exchange process, the waste water, after sedimentation
for  the  removal  of  any  free  mercury,  is  passed  through a
proprietary ion  exchange  resin.   Mercury  is  removed  as  the
mercuric  chloride  complex  anion.   A second stage ion exchange
step  serves  as  a  polishing  step  and  reduces  the   mercury
concentration  down  to  very low levels.  Concentrations of less
than 0.005 mg/liter have been reported.

In  the  sulfide  precipitation  process  mercurous  and  organic
mercury  compounds  must  first  be oxidized to the mercuric ion.
Lime and sulfide are then added  along  with  coagulant  aids  in
order  to promote the formation of mercuric sulfide precipitates.
The precipitates are removed from the waste water stream by means
of sedimentation and  filtration,  as  in  the  copper  and  lead
removal  processes.  This process has been reported to be capable
of producing an effluent mercury  concentration  of  0.1  to  0.3
mg/liter.
                           174

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In addition to ion exchange and sulfide precipitate several newly
developed  organic  adsorbents  and  complexing agents have shown
promising results in laboratory tests.

The entire technology for the removal of  mercury  has  not  been
developed very far in terms of full scale actual plant operation.

Fluoride

Precipitation  with  lime  is  the  standard  technique  for  the
reduction  of  high  concentrations  of  soluble  fluoride.   The
fluoride   is   precipitated  as  calcium  fluoride.   While  the
theoretical   solubility   limit   for   calcium   fluoride    is
approximately 8 mg/liter at pHll, effluent concentrations of less
than  20  mg/liter  are  seldom achieved due to the slow reaction
rates, difficulty in separating colloidal  particles  of  calcium
fluoride,  and  the interference  of other ions.  The addition of
alum and other coagulants encourages the formation of larger  and
more readily removable precipitates.

Where effluents fluoride concentrations lower the 20 mg/liter are
required, various adsorptive techniques must, be used.

In such processes the fluoride containing water is passed through
contact beds of hydroxylapatite or activated alumina.  Adsorptive
on activated alumina has been reported to be capable of producing
effluent fluoride concentrations as low as 1.0 mg/liter.  The use
of  adsorptive  techniques  has  largely  been  confined  to  the
treatment of municipal drinking water containing undesirably high
concentrations of fluoride.
The process most frequently employed for the treatment  of  waste
water  containing  cyanide  is  destruction by chlorination under
alkaline  conditions.   In  this  process  the  cyanide  may   be
partially  oxidized  to  cyanate  or  totally  oxidized to carbon
dioxide and nitrogen, depending on the chlorine dosage.

Theoretically, if sufficient chlorine  is  added  and  sufficient
contact  time  provided,  complete oxidation of cyanide should be
achievable.  In reality, the  presence  of  small  quantities  of
soluble  iron  often  causes  the  formation  of extremely stable
ferrocyanide complexes which prevent the  complete  oxidation  of
cyanide.

In  recent years ozonation has shown to be effective in oxidizing
cyanides.  There are indications that ozonation is more effective
than alkaline chlorination in attacking  the  more  difficult  to
oxidize metal complexes of cyanide.

Both the alkaline chlorination and ozonation processes can become
prohibitively  expensive  if  the  cyanide containing waste water
also contains large quantities  of  oxidizable  organic  material
which will unavoidably be oxidized along with the cyanide.
                            175

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Oil_and_Grease

Oil  and  grease  are usually present in waste waters both in the
suspended and emulsified form,

Particles of suspended oil and grease are  generally  removed  by
means  of  gravity  separators.   Such  separators  can typically
remove 90-95 percent  of  the  suspended  oil,  but  are  totally
ineffective in removing emulsified oil.

To  remove  emulsified  oil, the emulsion must first be broken by
chemical  means  consisting  of  the  addition  of  acids  and/or
coagulant  salts  such as alum.  After so treated, the oil can be
removed by flotation or filtration.  The concentration of oil and
grease in the treated effluent depends largely on the  degree  of
success  in  breaking  the emulsion.  Generally an oil and grease
concentration of less than 30 mg/liter should  be  achievable  by
emulsion  breaking  and  gravity  separation.   If  filtration is
employed, a concentration of 10 mg/liter should be achievable.

Depending on conditions, varying amounts of emulsified oil may be
removed along  with  other  biodegradable  material  in  standard
biological treatment processes.
                            176

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                           SECTION VIII

            COST, ENEKGY, AND NONWATER QUALITY ASPECTS


 Approximately   160   company   operations   participate  in  the
 manufacture of the fifteen synthetic polymer products (see  Table
 VIII-1).    The actual number of plants is not known.  Some of the
 60 company operations include multi-plant  divisions;  many  more
 are part  of multiprcduct plants.

 Total production in the 1972-1973 time frame was estimated at 1.2
 million  kkg (2.6  billion Ibs)  per year or about one-tenth of the
 volume (26 billion Ibs)  represented by the  larger-volume  resins
 studies  earlier.   Together (i.e., these fifteen polymers and the
 earlier eighteen resins)  the products covered in the two  studies
 were estimated to  represent 99  percent of the total production of
 synthetic and plastic materials.

 Current  discharge  resulting  from  the  production of  synthetic
 polymers  was estimated at 90 thousand cubic meters   per   day  (24
 MGD).     Water   discharges  (at   current  hydraulic  loads)   was
 projected  to  increase   at  10   per  cent  through  1977,   while
 production  was projected  to  increase at 14 percent in the same
 period.   Approximately 25 percent of  current  discharge  by  the
 industry  was estimated to be treated in municipal plants.

 The   first  part  of  this  section  (Tables  VIII-1  to  VIII-4)
 summarizes the costs  (necessarily  generalized)  of  end^of-pipe
 treatment  systems  either  currently  in  use or recommended for
 future use in synthetic  polymers   production  facilities.    Costs
 have   been  estimated  for  all   fifteen  product categories  even
 though specific guidelines or  standards  were  not  recommended.
 Lacking    specific  effluent requirements,   appropriate  control
 technologies  were  assumed which   were  consistent  with   existing
 knowledge  of  waste composition.

 In order to reflect  the  different  treatment  economics  of existing
 versus  new   plants,   large  versus   small   plants,  free-standing
 versus  joint  treatment facilities,  or municipal  versus industrial
 facilities, costs  have been  developed typically  for  more than one
 plant  situation  in  each   product   subcategory.   These   product-
 specific analyses  are  presented in  Tables VIII-4/1 to VIII-4/30.

£°st_Modeis_of_Treatment_Technolo2ies

 Information  on  treatment cost experience was more scarce in the
 production of synthetic polymers  than   it  was   from  the  resin
facilities  studied  earlier.   in large part this was due to the
small number of free-standing plants  in  this industry.  There  is
also  much  greater dependence upon municipal treatment  for these
smaller-volume products than was true for resin production.  More
important, much of the wastes resulting  from these  products  are
treated in the central facilities of the large chemical complexes
                            177

-------
in  which  they  are  located.   Many times the main production in
these multi-product plants includes the resins covered earlier.

Consequently, the tasic data for estimating the costs of treating
the wastes from synthetic polymers  was  that  developed  in  the
first  study.   These  cost models were developed around standard
waste water treatment practice and compared to actual data from a
dozen resin  plants.   That  comparison  resulted  in  deviations
within +20 percent of model values.  For details on the basis of
the  cost  models  and their assumptions, see the cost section of
the development document for the resins industry segment  (16).

Cost-Effectiveness, Perspectives

Rough estimates were made of the existing degree of BOD5  removal
by  either industrial or municipal systems in the fifteen product
groups.  A 74  percent  weighted  average  removal  of  BOD5  was
calculated  for  these  synthetic  polymers  in  1972.   This  is
substantially higher  than  the  42  percent  removal  for  resin
products  because  of  the  higher  use  of municipal systems for
polymer wastes and the availability of larger central  industrial
treatment  systems  to  handle the lower volumes of these wastes.
By 1977, the average removal implicit in BPCTCA  requirements  is
estimated at 90 percent.  This is lower than the 95 percent to be
required  of  resin  production  because,  again,  of  the larger
proportion of municipal treatment - for which 85 percent  removal
is expected.

Annual Cost Perspectives

Annual  costs  for existing plants were roughly estimated at $1.8
million.   The  expected  annual  costs  for  existing  synthetic
polymers   plants   in  1977  consistent  with  best  practicable
technology was estimated at $5.0 million.  This  estimate   (Table
VIII-2)  was  the  result  of  the following considerations:  the
production volumes and  waste  loads  for  each  of  the  fifteen
product  groups;  the  average  costs  of treatment for different
plant sizes; or the costs to  be  expected  from  handling  these
wastes  as  part  of  a  larger  municipal  or industrial system.
Similarly, by  1983,  the  estimated  costs   (Table  VII1-2)   for
existing  plants  using  best  available  technology  were  $12.0
million.  It is noted that these costs were associated with  end-
of-pipe   treatment   only.   Costs  for  in-plant  additions  or
modifications were not included.

The above annual cost estimates for  existing  plants  for  1972,
1977,  and 1983 indicate average increases of 23 percent  per year
between 1972 and 1977, and 20 percent per year between  1977   and
1983.   Much  of the estimated increase  in costs between  1972  and
1977 was tied to the assumed full payment of charges for  the   use
of  municipal  facilities.   User  charges for treatment  services
beyond secondary biological treatment in municipal  systems  were
not  considered  appropriate  before  1983.    To  the  costs  for
existing plants must be  added  the  costs  associated  with   new
plants, governed by BADT-NSPS.  Assuming the production volume of
                             178

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 new  plants to be equal to the expected growth in production, the
 potential annual cost associated with  new  plants  in  1977  was
 estimated at $3.4 million (Table VIII-2).  Altogether, that means
 that  the  industry's  annual  costs  are expected to increase 36
 percent per year (from $1.8 million in 1972 to $8.3 million  (5.0
 +  3.3)   in 1977),  this supported by a sales growth of 14 percent
 per year.  A similar estimate for 1983 has been precluded by  the
 lack of a meaningful forecast of product growth.

 Cost_Per_Unit_Persp.ectives

 Another  measure by which to gauge the importance of the costs in
 Table VIII-2 is to  relate them tc the sales price of the products
 as is done in Table VIII-3.   The average range of water pollution
 control costs under EPCTCA was estimated at 0.3  percent  to  1.3
 percent  of current sales prices.  On average, the range of costs
 for applying EATEA  to existing plants was 0.6 to  3.3  percent  of
 sales  price.   The  cost of BADT-NSPS was estimated at 0.5 percent
 of sales price over the fifteen products.   These  cost impacts are
 lower on average than  those  for  the  eighteen   resin  products
 studied  earlier primarily   because  the  average price of these
 polymers is higher.

 Waste_Water_Treatment_Cgst_jEstimates

 The average range of water pollution control  costs (Table VIII-4)
 under BPCTCA,  BATEA, and  BADT-NSPS  technologies respectively were
 $0.16 ($0.63),  $0.40 ($1.52),  and $0.17  ($0.66) per  cubic  meter
 (per   thousand  gallons).     Table   VIII-4  and its 30  associated
 tables portray the  costs  of  major  treatment   steps  required to
 achieve   the   recommended technologies.    Where   municipal   user
 charges  are not considered directly,  the appropriate  charge  would
 be  $0.39 or $0.63 per thousand   gallons  depending  on   the   size
 economies of the representative  municipal system.

 In  each of the representative plant  cost analyses, typical  plant
 situations were identified  in   terms  of  production   capacity,
 hydraulic  load,  and  treatment  plant size.   Capital  costs  have
 been  assumed to be a constant percentage   (8   percent)   of   fixed
 investment.    Depreciation  costs have been calculated  consistent
 with  the faster write-off  (financial  life)   allowed   for  these
 facilities   (10  percent   per year) over 10 years  even though the
 physical life  is longer.

 Cost-effectiveness relationships  are implicit  in the  calculation
 of these costs  together with the  effluent levels achieved by each
 treatment step  in each major relevant pollutant dimension.  These
 effluent   levels    are    indicated   at   the   bottom  of  each
 representative  plant sheet.

l£^ustrial_Waste_Treatment_Model_Data

In Tables VIII-5/1 to VIII-5/3  the  total  discharges  for  each
product  sufccategory  are estimated for 1972 and 1977.  The quality
of  effluents  remaining  untreated  in 1977 is indicated as that
                             179

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consistent with the application of EPCTCA  technology.    Finally,
the  current  status  of  treatment  in  each  product  group  is
estimated in terms of the proportion utilizing primary  treatment
and  that  utilizing  a  form  of  biological  treatment, whether
industrial or municipal.
Each of the  representative  plant  analyses  in  the  30  tables
summarized  by  Table VIII-4 includes an estimate of energy costs
(of control) .   The basis for  these  energy  cost  estimates  was
explained   in   the  earlier  development  document  for  resins
production.  The most important assumption  therein  was  one  of
1972  energy  prices.   That  assumption  has  been retained, for
purposes c± comparison, in this analysis of polymers production.

Generally,  the  biological   treatment   systems   employed   by
industries  and municipalities are not large consumers of energy.
By the cost models employed in this report, the energy  costs  of
BPCTCA and BADT-NSPS technologies in this industry were estimated
at  about  2  percent  of  the total annual waste water treatment
costs  in  Table  VIII- 2.   The  add-on  technologies  for  BATEA
compliance, however, were estimated to raise that proportion to 7
percent by 1983.

Non-Water Quality Effects

The  nonwater  quality  aspects  of  the  treatment  and  control
technology found in the  synthetics  and  plastics  industry  are
related  to (1) the disposal of solids or slurries resulting from
waste water treatment and in-process plant control  methods,  (2)
the  generation of a by-product of commercial value, (3) disposal
of off-specification and scrap products, and (4) the creation  of
problems  of  air  pollution and land utilization.  These effects
were discussed in the development document for resins production.

Other nonwater quality aspects of treatment and pollution control
are minimal in this industry and largely depend upon the type  of
waste  water  treatment  technology  employed.   In general, noise
levels  from  typical  waste  water  treatment  plants  are   not
excessive.   If  incineration of waste sludges is employed, there
is potential for  air  pollution,  principally  particulates  and
possibly  nitrogen  oxides, although the latter should be minimal
because incineration of sludges does not normally take  place  at
temperature  levels  where the greatest amounts of nitrogen oxide
are generated.  There are no radioactive nuclides used within the
industry, other than in instrumentation,  so  that  no  radiation
problems  will  be  encountered.   Odors  from  the  waste  water
treatment plants may cause occasional problems since waste waters
are sometimes such that heavy, stable,  foams  occur  on  aerated
basins  and septicity is present.  But, in general, odors are not
expected to be a significant  problem  when  compared  with  odor
emissions possible from other plant sources.
                              180

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The  final  part  of  this  section reports on updated inputs for
EPA's Industrial Waste Treatment Model  (Tables Vlll-5/1 to  VIII-
5/3).   The estimated total volume of waste waters discharged for
product sutcategories has been estimated  for  1972-1977.   Also,
general estimates of the current level and source of treatment in
different industry segments have been made.

Alternative_Treatment_Technoloigies

The range of components used or needed to effect best practicable
control  technology  currently available  (EPCTCA) , best available
technology economically achievable (BATEA),  and  best  available
demonstrated  technology  for  new  source  performance standards
(BADT-NSPS)  in  this  portion  of  the  plastics  and  synthetics
industry  have  been  combined into eight alternative end-of-pipe
treatment steps.  These are as follows:

    A«    l2it.ial_Treatmenti  For removal of suspended solids  and
         heavy  metals.    Includes  equalization, neutralization,
         chemical coagulation or precipitation,  API  separators,
         and primary clarification.

    B«    Ii2l2aical_Treatment:.  Primarily  for  removal  of  BOD.
         Includes  activated  sludge  (or  aerated  stabilization
         basins), sludge disposal,  and final clarification.

    c-    Mai^iz§taa§_iiolocticali   For  further  removal  of  BOD
         loadings.   Either another  biological treatment system in
         series or  a long-residence-time polishing lagoon.

    D.    Granular	Media	Filtration.:    For  further  removal  of
         suspended   solids  (and  heavy  metals)   from biological
         treatment  effluents.   Includes some chemical coagulation
         as  well as granular media  filtration.

    E-    5jhysical-Chemical_Treatmentj.    For  further  removal  of
         COD,  primarily  that attributable to refractory organics,
         e.g.,  with activated  carbon adsorption.

    F-    £iauid_Waste_Incinerationi For  complete   treatment  of
         small  volume  wastes.

    G.    Municj.2al_Treatmentj.   Conventional  municipal  treatment
         of  industrial   discharge  into  sewer collection  systems.
         Primary settling   and  secondary  biological   stages
         assumed.
                              181

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                                            TABLE VIII-1
                        PERSPECTIVES ON THE PRODUCTION OF SYNTHETIC POLYMERS
                                             WATER USAGE
Guidelines Subcategory
Product
I
EVA Copolymers
Fluorocarbons
Polypropylene Fibers
Polyvinylidene Chloride
II
Acrylic Resins
Cellulose Derivatives
Subtotal - A&B
III
Alkyd and Unsaturated
Polyester Resins
Cellulose Nitrate
Polyamids
Polyesters (thermoplastic)
Polyvinyl Butyral
Polyvinyl Ethers
Silicones
IV
Nitrile Barrier Resins
Spandex Fibers
Subtotal - C&D
Total - 15 Products
Number of
Company
Operations (1)

5
5
3
4

>4
_3
>24
>14
2
3
3
2
2
4

3
_J.
>36
>60
Percent of
Total 15 Product
Production(2)

5.9
1.0
5.5
1.0

11.8
3.9
29.1
58.8
2.0
1.0
0.2
1.6
0.4
5.1

1.0
0.8
70.9
100.0
Percent of
Water Used
by 15 Products

0.8
4. 6
1. 7
0.4

14.6
17.6
39.7
7.5
10.9
0.8
0.4
5.9
0.4
33.2

0.8
0.4
60.3
100.0
Percent of Growth
In Water Usage of
15 Products:
1972-1977

0.7
2.6
1.3
0

34.4
8.6
47.6
11.9
0
0.6
0.6
2.6
0.6
32.9

3.2
0 	
52.4
100.0
(1)     Number of companies  producing  each  of  the  products;  the number  of  plants  is  greater because
       of  multiple sites  for any  one  company.

(2)     Estimated annual 15-product  production in  1972-73  period:  1.15B kkg  (2.55 B  Ibs) .

(3)     Result of projected  product  growth   at current  representative hydraulic loads.
                                                 182

-------
                                           TABLE VIII-2
                           PERSPECTIVES ON SYNTHETIC POLYMERS  PRODUCTION
                                      ANNUAL TREATMENT COSTS
        Guidelines Subcategory
III
IV
    Alkyds and Unsaturated
    Polyester Resins
    Cellulose Nitrate
    Polyamides
    Polyesters (thermoplastic)
    Polyvinyl Butyral
    Polyvinyl Ethers
    Silicones
    Nitrile Barrier Resins
    Spandex  Fibers

         Total
             Total Annual Costs, $MM
Product
I.
EVA Copolymers
Fluorocarbons
Polypropylene Fibers
Polyvinylidene Chloride
Acrylic Resins
Cellulose Derivatives
Existing Plants
1977

0.04
0.36
0.17
0,01
0.58
0.97

1983

0.12
0.36
0.17
0.04
0.64
2.84
New Plants
1983

0.02
0.13
0.08
0.00
0.86
0.34
0.45
                      0.59
                                          0.45
0.30
0.08
0.03
0.30
0.03
1.56
0.04
0.04
0.51
0.22
0.07
0.92
0.07
5.21
0.08
0.08
0.00
0.04
0.03
0.09
0.03
1.13
0.12
0.00
                                          4.96
                                                                11.92
                                                                                     3.32
                                                183

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                                     TABLE VIII-3

                     PERSPECTIVES  ON SYNTHETIC POLYMERS PRODUCTION
                                    COST1  HIP ACT
                                                  Control Cost Range as  % of Sales Price
Guideline Subcategory
Product
EVA Copolymers
Fluor ocarbons
Polypropylene Fibers
Polyvinylidene Chloride
Acrylic Resins
Cellulose Derivatives
III
Alkyd and Unsaturated
Polyester Resins
Cellulose Nitrate
Polyamids
Polyesters (thermoplastic)
Polyvinyl Butyral
Polyvinyl Ethers
Silicones
II
Nitrile Barrier Resins
Spandex Fibers
Price Level
C/lb
15
325
35
55
70
50
20
50
130
70
70
100
100

60
100
BPCTCA
0.2
0.1
0.7
0.1
0.1
1.1
0.4
0.8
0.1
0.1
0.4
0.2
0.6

0.1
0.1
- 2.0
- 0.6
- 1.4
- 0.2
- 0.4
- 2.0
- 1.9
- 1.7
- 0.9
- 2.9
- 2.1
- 0.7
- 1.2

- 0.6
- 0.3
BATEA
0.4
0.1
0.7
0.1
0.1
3.3
0.4
1.0
0.2
0.3
0.4
0.2
1.7

0.1
0.1
- 6.2
- 0.6
- 1.4
- 0.7
- 0.4
- 5.7
- 3.8
- 3.6
- 2.5
- 6.4
-10.7
- 1.8
- 3.5

- 1.3
- 0.5
BADT
0.2
0.1
0.7
0.1
0.1
1.2
0.8
0.9
0.2
0.2
0.8
0.3
0.7

0.3
0.2
    Unweighted Average
0.3- 1-3
0.6 - 3.3
                                                                                   0.5
-'-Low  end of  cost range generally based on  large plants with standard water
 usage  or municipal  treatment  charges.  High end of  range  based  on small
 plants with  high water usage.   BADT  costs  based on  mininum water  usage
 by larger plants.
                                         184

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                                       TABLE VIII-4

                          SUMMARY OF WATER EFFLUENT TREATMENT COSTS3
                                 COST PER UNIT VOLUME BASIS
  Guidelines Subcategory
                                  BPCTCA COSTS
                                                       BATEA  COSTS
                                                                             BADT COSTS'

EVA Copolymers
Fluorocarbons
Polypropylene Fibers
Polyvinylidene Chloride
II
Acrylic Resins
Cellulose Derivatives
III
Alkyd and Unsaturated
Polyester Resins
Cellulose Nitrate
Polyamids
Polyesters (thermoplastic)
Polyvinyl Butyral
Polyvinyl Ethers
Sillcones
IV
Nitrile Barrier Resins
Spandex Fibers
Average
$/cu m S/1000 gal
0.16
0.26
0.33
0.9 - 0.13

0.13
0.18


0.13 - 0.66
0.08 - 0.11
0.32
0.26
0.13 - 0.26
0.13 - 0.26
0.09 - 0.22

0.13 - 0.18
0.13 - 0.33
0.17
0'60
1.00
1.25
0.35 - 0.50

0.50
0.70


0.50 - 2.50
0.30 - 0.40
1.20
1.00
0.50 - 100
0.50 - 1.00
0.35 - 0.85

0.50 - 0.70
0.50 - 1.25
0.63
$/cu m S/1000 gal $/cu m $/1000 gal
0.49
0.26
0.33
0.13 - 0.53

0.15
0.54


0.13 - 1.32
0.11 - 0.22
0.87
0.59
0.13 - 1.32
0.13 - 0.66
0.26 - 0.66

0.13 - 0.40
0.13 - 0.66
0.40
1.85
1.00
1.25
0.50 - 2.00

0.55
2.05


0.50 - 5.00
0.40 - 0.85
3.30
2.25
0.50 - 5.00
0.50 - 2.50
1.00 - 2.50

0.50 - 1.50
0.50 - 2.50
1.52
0.16
0.26
0.33
0.12

0.13
0.21


0.20
0.11
0.32
0.26
0.18
0.24
0.18

0.18
0.33
0.17
0.60
1.00
1.25
0.45

0.50
0.80


0.75
0.40
1.20
1.00
0.70
0.90
0.70

0.70
1.25
0.66
Assume  330 day /year  operation.   Estimated  proportions  treated
municipal systems  factored  in  at $0.50/1000 gal.
Assume   new plants  are larger  facilities  with minimum flows.   New
plant production  assumed equivalent to  growth between 1972  and
                                            185

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                           TABLE VIII-4/1

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Ethylene Vinyl Acetate

Plant Description:  Small Plant - Large  Industrial  Complex

Representative Plant Capacity
    million kilograms (pounds) per year:    11.3         (25)

Hydraulic Load
    cubic meters/metric ton of product:       <••?         (.
    (gal/lb)

Treatment Plant Size
    thousand cubic meters per day  (MGD):      6.4         (1.7)*


Costs -  $1000                           Alternative Treatment  Steps
 Initial Investment                    7.6       18         3         24
 Annual Costs:

     Capital Costs (8%)                 0.6    1.4        0.3       2.0
     Depreciation (10%)                 0.8    1.8        0.3       2.4
     Operation and Maintenance         0.1    0.8        0.1       3.7
     Energy and Power                  0.1    0.1         -        1

             Total Annual Costs        1.6    4.1        0.7       9.1

 Effluent Quality (expressed in terms ot yearly averages)


                      Raw Waste Load       Resulting Effluent Levels
                                        (units per 1000 units of product)
                                        A       B_        J)       !
 B.O.D.                     1            -       °-03      -       0.03
 C.O.D.                     2                     0.2                0.1
 Suspended Solids         N/A          0.1       -        0.02


 *The EVA contribution is     thousand  cubic meters per  day  (    mgd).  This
  is  approximately i.g%  of the total flow  to be treated.
                                 186

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                            TABLE VIII-4/2


                     WATER EFFLUENT TREATMENT COSTS

                    PLASTICS AND SYNTHETICS INDUSTRY
 Industry Subcategory:  Ethylene Vinyl Acetate

 Plant Description:  Large Plant - Industrial Complex

 Representative Plant  Capacity
     million kilograms  (pounds)  per  year:     22.7

 Hydraulic Load
     cubic meters/metric  ton of  product:       2.9
     (gal/lb)

 Treatment Plant Size
     thousand  cubic meters per day (MGD):      6.8
                                (50)


                                (0.35).



                                (1.8)*
 Costs -  $1000
              Alternative Treatment Steps
Initial Investment
                                       14
                       33
                                                                  47
Annual Costs:
    Capital Costs (8%)
    Depreciation (10%)
    Operation and Maintenance
    Energy and Power
            Total Annual Costs         2.7       7.6     1.3

Effluent Quality (expressed in terms of yearly averages)
1.1
1.4
0.1
0.1
2.7
3.3
1.4
0.2
0.5
0.7
0.1

3.8
4.7
7.4
1.8
                                       17.7
B.O.D.
C.O.D.
Suspended Solids
                     Raw Waste Load
 1
 2
N/A
     Resulting Effluent Levels
  (units per 1000 units of product)
 A        E        L>        E
          0.03      -       0.03
          0.2       -       o.l
0.1        -       0.02
* The EVA contribution is thousand cubic meters per day.
  This is approximately 3% of the total flow to be treated.
                              187

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                           TABLE VIII-4/3


                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY



Industry Subcategory: Fluorocarbons

Plant Description:  Small  Plant  - Free Standing

Representative Plant Capacity
    million kilograms (pounds) per year:    1.4         (3)

Hydraulic Load
    cubic meters/metric ton of product:   125           (15.0)
    (gal/lb)

Treatment Plant Size
    thousand cubic meters per day  (MGD):    0.5         (0.14)


Costs -  $1000                           Alternative Treatment  Steps

                                       A
 Initial Investment
                                       44
 Annual Costs:
     Capital Costs (8%)                  3.5
     Depreciation (10%)                  4'^
     Operation and Maintenance          2-0
     Energy and Power                   ".1

             Total Annual Costs        ^

 Effluent Quality (expressed in terms of yearly averages)
                      Raw Waste Load       Resulting Effluent Levels
                                        (units per 1000 units of product)
 Suspended Solids
                                 188

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                            TABLE  VIII-4/4

                     WATER EFFLUENT TREATMENT COSTS
                    PLASTICS AND SYNTHETICS INDUSTRY


 Industry  Subcategory:   Fluorocarbons

 Plant Description:      Small Plant - Municipal Discharge

 Representative Plant Capacity
    million kilograms  (pounds)  per year:   1.4        (3)

 Hydraulic Load
    cubic meters/metric  ton of  product:  125          (15.0)
    (gal/lb)

 Treatment Plant Size
    thousand cubic  meters  per day (MGD):   0.5        (0.14)


 Costs - $1000                          Alternative Treatment  Steps

                                                  M         M
Initial Investment                     102


Annual Costs:

    Capital Costs (8%)                   8
    Depreciation (10%)                  10
    Operation and Maintenance            4        -
    Energy and Power                     1        -

            Total Annual Costs          23       18          29

Effluent Quality (expressed in terms of yearly averages)


                     Raw Waste Load       Resulting Effluent Levels
                                        (units per 1000 units of product)

B.O.D.                    3
C.O.D.                   20                   (municipal treatment)
Suspended Solids          5

* Neutralization of acids

tt^ is the municipal treatment charge associated with a 38 to 76 thousand cubic
   meters per day (10-20 mgd) treatment plant.  A charge of 39
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                           TABLE VIII-4/5
                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:  Fluorocarbons

Plant Description: Large Plant - Free Standing

Representative Plant Capacity
    million kilograms (pounds) per year:    6.8

Hydraulic Load
    cubic meters/metric ton of product:  125
    (gal/lb)

Treatment Plant Size
    thousand cubic meters per day (MGD):    2.6
                             (15)


                             (15.0)



                             (0.7)
Costs - $1000
              Alternative Treatment Steps

              A
Initial Investment
             145
Annual Costs:

    Capital Costs (8%)
    Depreciation (10%)
    Operation and Maintenance
    Energy and Power

            Total Annual Costs
              11.6
              14.5
               8.6
               0.3

              35
Effluent Quality (expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
                     Raw Waste Load
 3
20
 5
    Resulting Effluent Levels
 (units per 1000 units of product)
 A
 2
20
 5
                                 190

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                            TABLE VIII-4/6

                     WATER EFFLUENT TREATMENT COSTS
                    PLASTICS AND SYNTHETICS INDUSTRY


 Industry Subcategory:    Fluorocarbons

 Plant Description:   Large Plant - Municipal Discharge

 Representative Plant Capacity
     million kilograms  (pounds)  per year:    6.8        (15)

 Hydraulic Load
     cubic meters/metric  ton of  product:   125          (15.0)
     (gal/lb)

 Treatment Plant Size
     thousand cubic  meters  per day  (MGD):    2.6        (0.7)


 Costs -  $1000                         Alternative Treatment Steps


                                       -*        -1        ^2


 Initial  Investment                     285


 Annual Costs:

     Capital Costs (8%)                  23
     Depreciation (10%)                  29
     Operation and Maintenance            6        -
     Energy and Power                     1        -

            Total Annual Costs         59       88        142

 Effluent Quality (expressed in terms of yearly averages)


                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)

B.O.D.                     3
C.O.D.                   20                (Municipal treatment)
Suspended Solids          5


 * Neutralization of Acids
                               191

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                            TABLE VIII-4/7

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:     Polypropylene Fibers

Plant Description:        Free  Standing Treatment Plant

Representative Plant Capacity
    million kilograms (pounds) per year:      20.4          (45)

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                  8.3          (1.0)

Treatment Plant Size
    thousand cubic meters per day (MGD):      0.5          (0.14)


Costs -  $1000                          Alternative Treatment Steps

                                        A      D       E
Initial  Investment                      96    50    433


Annual Costs:

     Capital  Costs  (8%)                   8     4     35
     Depreciation  (10%)                  10     5     43
     Operation  and Maintenance            2     2    115
     Energy and Power                     0.5  -      10

             Total Annual  Costs          20.5  11    203

Effluent Quality  (expressed  in  terms  of yearly averages)


                      Raw  Waste  Load       Resulting Effluent Levels
                                        (units per 1000 units of product)
                                        A     P.      1
B.O.D.                     0.5          0.3   -      0.1
 C.O.D.                     1.5          1.3   -      0.2
 Suspended Solids           1.0          0.5   0.1
                                192

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                             TABLE  VIII-4/8

                     WATER EFFLUENT TREATMENT COSTS
                    PLASTICS AND SYNTHETICS  INDUSTRY


 Industry  Subcategory:      Polypropylene Fibers

 Plant  Description:         Municipal Discharge

 Representative Plant Capacity
    million  kilograms  (pounds)  per year:      20.4         (45)

 Hydraulic Load
    cubic meters/metric  ton of  product:
    (gal/lb)                                   8.3         (1.0)

 Treatment Plant Size
    thousand cubic  meters  per day  (MGD):       0.5         (0.14)


 Costs  - $1000                         Alternative  Treatment  Steps



                                       P*    Mj     M2

 Initial Investment                      89     -


 Annual Costs:

    Capital Costs (8%)                 7
    Depreciation (10%)                 9
    Operation and Maintenance         18     -      -
    Energy and Power                   i

            Total Annual Costs        35     13     29

 Effluent Quality (expressed in terms of yearly averages)
                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)

B.O.D.                    0.5
c-°-D.                    1-5          (Municipal Treatment)
Suspended Solids          1.0
*Air flotation for oil and grease removal.
                                 193

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                               TABLE VIII-4/9

                        WATER EFFLUENT  TREATMENT COSTS

                       PLASTICS AND SYNTHETICS  INDUSTRY



    Industry Subcategory:       Polyvinylidene Chloride

    Plant Description:          Small Plant - Industrial Complex

    Representative Plant Capacity
        million kilograms (pounds)  per  year:    2.3            (5)

    Hydraulic Load
        cubic meters/metric ton of product:
        (gal/lb)                               4.2            (0.5)

    Treatment Plant Size
        thousand cubic meters per day (MGD):    1.7            (0.45)*


    Costs - $1000                          Alternative Treatment Steps
                                                     D
    Initial Investment                      4        2        11
    Annual Costs:

        Capital Costs (8%)                  0.3      0.2      0.9
        Depreciation (10%)                  0.4      0.2      1.1
        Operation and Maintenance           0.06     0.1      1.8
        Energy and Power                    0.04     -        0.2

                Total Annual Costs          0.8      0.5      4.0

    Effluent Quality (expressed in terms of yearly averages)


                         Raw Waste Load       Resulting Effluent Levels
                                            (units per 1000 units of  product)

    B.O.D.                     0
    C.O.D.                     8              (No specific  guidelines)
    Suspended  Solids           0.2

*The PVC1 contribution  is  0.03  thousand cubic  meters  per day  (0.007 MGD);
 this  is approximately  1.5% of  the  total flow  to be treated.
                                    194

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                            TABLE VIII-4/10

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY


Industry Subcategory:      Polyvinylidene Chloride

Plant Description:         Large Plant - Industrial  Complex

Representative Plant Capacity
    million kilograms  (pounds) per year:   11.3            (25)

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                4.2            (0.5)

Treatment Plant Size
    thousand cubic meters per day (MGD):    1.7            (0.45)*


Costs - $1000                          Alternative Treatment Steps
Initial Investment                      21       11       55


Annual Costs:

    Capital Costs (8%)                  1.7      9        4.4
    Depreciation (10%)                  2.1      11       5.5
    Operation and Maintenance           0.2       0.1     9.4
    Energy and Power                    0.1      -        1.5

            Total Annual Costs          4        20.1    21

Effluent Quality (expressed in terms of yearly averages)
                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)

B.O.D.                    0             (No specific guidelines)
C.O.D.                    8
Suspended Solids          0.2

*The PVC1 contribution is 0.13 thousand cubic meters per day (0.035 MGD);
 this is approximately 20% of the total flow to be treated.
                               195

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                            TABLE  VIII-4/11

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY



Industry Subcategory:     Acrylic Resins

Plant Description:        Small Plant - Industrial Complex

Representative Plant Capacity
    million kilograms (pounds) per year:     9.1           (20)

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                 32             (3.8)

Treatment Plant Size
    thousand cubic meters per day (MGD):     17.4           (4.6)*


Costs -  $1000                          Alternative Treatment  Steps

                                        A     B       D
 Initial  Investment                      45    110    24


 Annual Costs:

     Capital  Costs  (8%)                   4      9     3.9
     Depreciation (10%)                   5     11     2.4
     Operation  and Maintenance            0-4    6.5   0.2
     Energy and Power                    0<1    0.5

             Total  Annual Costs          9.5   27     4.5

 Effluent Quality (expressed in terms of yearly averages)


                      Raw Waste Load       Resulting Effluent Levels
                                        (units per 1000 units of product)

 B.O.D.                     15
 C.O.D.                     30           (No specific guidelines)
 Suspended Solids           7.5

 *The acrylic  resin  contribution is 0.9 thousand cubic meters per day  (0.23 MGD),
  this is  approximately  5% of  the total flow to be treated.
                                196

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                             TABLE VIII-4/12

                     WATER EFFLUENT TREATMENT COSTS
                    PLASTICS  AND SYNTHETICS  INDUSTRY



 Industry  Subcategory:      Acrylic Resins

 Plant  Description:         Large Plant _ industrial  Complex

 Representative Plant Capacity
    million kilograms  (pounds)  per year:      54 4         Q20)

 Hydraulic Load
    cubic meters/metric  ton  of  product:
    (gal/lb)                                  32           (3i8)

 Treatment Plant Size
    thousand  cubic  meters  per day (MGD):      13.1         (3  46)*


 Costs  - $1000                         Alternative  Treatment  Steps

                                       A     B      D
Initial Investment                    296    724    156


Annual Costs:

    Capital Costs (8%)                 24    58     12
    Depreciation (10%)                 30    72     16
    Operation and Maintenance           3    36      1
    Energy and Power                    13-

            Total Annual Costs         58   169     29

Effluent Quality (expressed in terms of yearly averages)


                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)

B.O.D.                    15
C.O.D.                    30           (No specific guidelines)
Suspended Solids           7.5

*The acrylic resin contribution is 5.2 thousand cubic meters per day
 (1.38 MGD), this is approximately 40% of  the total flow to be  treated.
                                19?

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                           TABLE VIII-4/13
                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:

Plant Description:
 Cellulose Derivates

 Small Plant  - Industrial  Complex
Representative Plant Capacity
    million kilograms (pounds) per year:      4.5          (10)
Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)

Treatment Plant Size
    thousand cubic meters per day (MGD):
                 117
                (14)


                (2.1)*
Costs - $1000
            Alternative Treatment Steps

            A       B       D          E
Initial Investment
           104
   256
56
334
Annual Costs:

    Capital Costs (8%)
    Depreciation (10%)
    Operation and Maintenance
    Energy and Power

            Total Annual Costs
8
10
3
0.5
20
26
18
8
4.5
5.6
0.6
-
27
33
33
8
            21.5
    72
10.7
Effluent Quality  (expressed in terms of yearly averages)
101
B.O.D.
C.O.D.
Suspended Solids
                     Raw Waste Load
180
650
 20
               Resulting Effluent Levels
             (units per 1000 units of product)
(No specific guidelines)
*The cellulose derivative contribution is 1.6 thousand cubic meters per day
 (0.42 MGD); this is approximately 20% of the total flow to be treated.
                                198

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                             TABLE VIII-4/14
                     WATER EFFLUENT TREATMENT COSTS

                    PLASTICS AND SYNTHETICS INDUSTRY
 Industry Subcategory:

 Plant Description:
Cellulose Derivatives

Large Plant - Industrial Complex
 Representative Plant Capacity
     million kilograms (pounds) per year:   22.7

 Hydraulic Load
     cubic meters/metric ton of product:
     (gal/lb)                              117

 Treatment Plant Size
     thousand cubic meters per day (MGD):  151
                                (50)



                                (14)


                                (40)*
 Costs - $1000
             Alternative Treatment Steps

              A        B        D      E
 Initial Investment
              154
        376
220
636
 Annual Costs:

     Capital Costs (8%)
     Depreciation (10%)
     Operation and Maintenance
     Energy and Power
             Total Annual Costs           34     160       44

 Effluent Quality (expressed in terms of yearly averages)
12
15
5
2
30
38
54
38
18
22
4
-
51
64
200
50
                                      365
 B.O.D.
 C.O.D.
 Suspended Solids
                      Raw Waste Load
180
650
 20
                Resulting Effluent Levels
             (units per 1000 units of product)
(No specific guidelines)
*The cellulose derivatives contribution is 8.0 thousand cubic meters  per day
 (2.12 MGD);  this is approximately 5% of the total flow to be treated.
                                  199

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                            TABLE VIII-4/15

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:     Alkyds and Unsaturated Polyester Resins

Plant Description:        Large Plant - Once-thru Scrubber - Free Standing

Representative Plant Capacity
    million kilograms (pounds) per year:     15.9         (35)

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                  3-3         <°'4>

Treatment Plant Size
    thousand cubic meters per day  (MGD):      0.15        (0.04,1


Costs -  $1000                           Alternative  Treatment  Steps

                                        A     B*     C**
 Initial  Investment                     30    84     84
 Annual Costs:

     Capital Costs  (8%)                   2.4    6.7     6.7
     Depreciation (10%)                   3.0    8.4     8.4
     Operation and  Maintenance           2.4   15.3    10.4
     Energy and Power                    0.2    0.6     0.5

             Total  Annual Costs          8     31      26

 Effluent Quality (expressed in terms of yearly averages)


                      Raw Waste Load       Resulting Effluent Levels
                                        (units per 1000 units of product)
                                        A     B.      c_
 B.O.D.                    10           -      0.2     0.0?
 C.O.D.                    25                  1       0.3
 Suspended Solids           1            0.1   -       0.02

 *Two-stage biological treatment
**Two additional stages of biological treatment
                                200

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                             TABLE VIII-4/16


                     WATER EFFLUENT TREATMENT COSTS
                    PLASTICS AND SYNTHETICS INDUSTRY



 Industry Subcategory:      Alkyds and Unsaturated Polyester Resins

 Plant Description:         Small Plant - Recirculating Scrubber -
                           Municipal Discharge
 Representative Plant Capacity
     million kilograms  (pounds)  per year:      2.3          (5)

 Hydraulic Load
     cubic meters/metric ton  of  product:
     (gal/lb)                                  0.4          (0.05)

 Treatment Plant Size
     thousand  cubic  meters per day (MGD):      0.003        (0.001)


 Costs -  $1000                         Alternative Treatment  Steps


                                        P*    MJL     M2


 Initial  Investment                      5.0


Annual Costs:

     Capital Costs (8%)                 04-
     Depreciation (10%)                 0'5
     Operation and Maintenance          10-
     Energy and Power

            Total Annual Costs         i^   Q.I     Q 2

Effluent Quality (expressed in terms of yearly averages)


                     Raw Waste Load        Resulting Effluent Levels
                                       (units per 1000 units of product)

B.O.D.                    10
c-°-D-                    25           (Municipal Treatment)
Suspended Solids           1

*Pretreatment is Clarification or Filtration.
                            201

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                            TABLE VIII-4/17

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND  SYNTHETICS  INDUSTRY
 Industry  Subcategory:     Alkyds  and Unsaturated Polyester Resins

 Plant  Description:         Large Plant - Recirculating Scrubber-
                           Free Standing
 Representative Plant Capacity
     million kilograms (pounds)  per year:
                                              15.9         (35)
 Hydraulic Load
     cubic meters/metric  ton of product:
     (gal/lb)                                  0.4         (0.05)

 Treatment Plant Size
     thousand cubic meters per  day (MGD) :       0.15        (0.04)*


 Costs - $1000                          Alternative Treatment Steps


                                        A     15**    £***


 Initial Investment                     30    84     84


 Annual Costs:

     Capital Costs  (8%)                  2.4   6.7    6.7
     Depreciation (10%)                  3.0   8.4    8.4
     Operation and Maintenance           2.4  15.3   10.4
     Energy and Power                    0.2   0.6    0.5

             Total  Annual Costs          8    31     26

 Effluent  Quality (expressed in terms of yearly averages)


                      Raw Waste Load       Resulting Effluent  Levels
                                         (units per  1000 units  of product)
                                         A     B.      C_
 B.O.D.                     10            -     0-2    0.07
 C.O.D.                     25            -     1      0.3
 Suspended Solids            1            0.1   -      0.02

  *Dilution of 7:1  for effective operation  of  the biological  treatment has
   been allowed.
 **Two-stage biological treatment.
***Two additional stages  of biological treatment.

                                202

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                             TABLE VIII-4/18

                     WATER EFFLUENT TREATMENT COSTS
                    PLASTICS AND SYNTHETICS INDUSTRY


 Industry Subcategory:     Alkyds and Unsaturated Polyester Resins

 Plant Description:         Large Plant - Recirculating Scrubber -
                           Municipal Discharge
 Representative Plant Capacity
     million kilograms (pounds)  per year:      15.9         (35)

 Hydraulic Load
     cubic meters/metric ton  of  product:
     (gal/lb)                                   0.4         (0.05)

 Treatment Plant Size
     thousand  cubic  meters  per day  (MGD):       0.02        (0.005)


 Costs -  $1000                         Alternative Treatment  Steps


                                        P*    MI     M2


 Initial  Investment                      10    -


 Annual Costs:

     Capital Costs (8%)                 Q.8
     Depreciation  (10%)                 i.o
     Operation and Maintenance          1.0
     Energy and Power                   -

            Total Annual Costs         2.8   0.7     1.1

 Effluent Quality  (expressed in terms of yearly averages)


                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)

B.O.D.                     10
C.O.D.                     25           (Municipal Treatment)
Suspended Solids           1

 *Pretreatment is clarification or filtration.
                            203

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                            TABLE VIII-4/19


                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:

Plant Description:
  Cellulose Nitrate

  Plant in Industrial Complex
Representative Plant Capacity
    million kilograms (pounds) per year:   18.1           (40)
Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                              167

Treatment Plant Size
    thousand cubic meters per day (MGD):   43.1
                               (20.0)


                               (11.4)*
Costs - $1000
             Alternative  Treatment Steps

             A        B        D       E
Initial Investment
            334
779
179
968
Annual Costs:
    Capital Costs  (8%)
    Depreciation  (10%)
    Operation and Maintenance
    Energy and Power

            Total Annual Costs
27
33
6.4
0.6
62
78
43
9
14
18
2
-
77
97
79
22
                                        67
                     192
          34
Effluent  Quality  (expressed in  terms of yearly averages)
        275
 B.O.D.
 C.O.D.
 Suspended Solids
                     Raw Waste Load
35
75
85
                Resulting Effluent Levels
             (units.per 1000 units of product)
             A        B        D       E
 7
23
         2
        14
 *The cellulose nitrate contribution  is  9.2  thousand  cubic meters  per  day
  (2.43 MGD);  this  is  approximately 20%  of the  total  flow to be  treated.
                                 204

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                            TABLE VIII-4/20

                    WATER EFFLUENT TREATMENT COSTS
                   PLASTICS AND SYNTHETICS INDUSTRY



Industry Subcategory:      Cellulose  Nitrate

Plant Description:         Plant with Municipal  Discharge

Representative Plant Capacity
    million kilograms (pounds) per year:      18.1          (40)

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                 167           (20.0)

Treatment Plant Size
    thousand cubic meters per day (MGD):      9.1          (2.4)


Costs - $1000                          Alternative Treatment Steps

                                       P_    MI



Initial Investment                     260


Annual Costs:

    Capital Costs (8%)                 21
    Depreciation (10%)                 26
    Operation and Maintenance            5.5  -
    Energy and Power                     0.5

            Total Annual Costs         53    309

Effluent Quality (expressed in terms of yearly averages)
                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)

B.O.D.                    35
C.O.D.                    75           (Municipal Treatment)
Suspended Solids          35
                              205

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                            TABLE VIII-4/21
                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:

Plant Description:
 Polyamides  (Nylon  6/12)

 Production  in  a  Complex
Representative Plant Capacity
    million kilograms (pounds) per year:      4.5

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                 16.7

Treatment Plant Size
    thousand cubic meters per day (MGD):      4.8
                                 (10)



                                 (2.0)


                                 (1.26)*
Costs - $1000
             Alternative Treatment Steps

             A     B      C     D      E
Initial Investment
                                       18
                   42
             42
10
60
Annual Costs:

    Capital Costs (8%)
    Depreciation (10%)
    Operation and Maintenance
    Energy and Power
            Total Annual Costs          3.7  13     13     2

Effluent Quality (expressed in terms of yearly averages)
1.4
1.8
0.4
0.1
3.4
4.2
3.7
1.7
3.4
4.2
3.7
1.7
0.8
1.0
0.2
-
4.8
6.0
7.1
1.1
                                       19
B.O.D.
C.O.D.
Suspended Solids
                     Raw Waste Load
N/A
N/A
N/A
   Resulting Effluent Levels
(units per 1000 units of product)
A     IB      £     I)      E
             0.3   -      0.1
             3     -      1.2
0.2   -      -     0.07
*The polyamide contribution is 0.23 thousand cubic meters per day
 (0.06 MGD), this is approximately 5% of the total flow to be treated.
                             206

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                            TABLE VIII-4/22
                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:      Thermoplastic  Polyester  Resins

Plant Description:         Large  Plant  -  Industrial Complex
Representative Plant Capacity
    million kilograms (pounds) per year:    2.3

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                8.3

Treatment Plant Size
    thousand cubic meters per day (MGD):    2.2
                                 (5)



                                 (1.0)


                                 (0.58)*
Costs - $1000
              Alternative Treatment Steps

              A     B      C     D      E
Initial Investment
                   21
            20
24
Annual Costs:

    Capital Costs (8%)
    Depreciation (10%)
    Operation and Maintenance
    Energy and Power
            Total Annual Costs         1.6   6      5     0.8

Effluent Quality (expressed in terms of yearly averages)
0.7
0.8
0.1
0.03
1.7
2.1
2.0
0.2
1.6
2.0
1.2
0.2
0.3
0.4
0.1
-
1.9
2.4
3.4
0.3
B.O.D.
C.O.D.
Suspended Solids
                     Raw Waste Load
 5
15
N/A
   Resulting Effluent Levels
(units per 1000 units of product)
A     B_      C_     D_      E_
             0.4   -      (D.2
             5-1
0.2   -      -     0.08
*The thermoplastic resin contribution is 0.06 thousand cubic meters per day
 (0.015 MGD); this is approximately 3% of the total flow to be treated.
                              207

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                            TABLE  VIII-4/23

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY



Industry Subcategory:     Polyvinyl Butyral

Plant Description:        Free Standing Treatment Plant

Representative Plant Capacity              9.1           (20)
    million kilograms (pounds) per year:

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                              96             (11.5)

Treatment Plant Size
    thousand cubic meters per day (MGD):   2.6           (0.7)


Costs - $1000                          Alternative Treatment S teps

                                       A     1      D     E
Initial Investment                    285   725    135  1614


Annual Costs:

    Capital Costs (8%)                 23    58     11   129
    Depreciation (10%)                 29    73     14   161
    Operation and Maintenance           3    50      2   525
    Energy and Power                    0.5   4      -   155

            Total Annual Costs         55.5 185     27   970

Effluent Quality (expressed in terms of yearly averages)
                     Raw Waste Load       Resulting Effluent Levels
                                        (units per 1000 units of product)
                                       A     1      D     E
B.O.D.                    30           -     0.9    -
C.O.D.                    40                 9
Suspended Solids          N/A          -     -      0.5   -
                               208

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                            TABLE VIII-4/24

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY



Industry Subcategory:     Polyvinyl Ether

Plant Description:        Plant in Industrial Complex

Representative Plant Capacity
    million kilograms (pounds) per year:     1.8          (4)

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                12.5          (1.5)

Treatment Plant Size
    thousand cubic meters per day (MGD):     2.3          (0.6)*


Costs - $1000                          Alternative Treatment Steps

                                       A     B      D     E
Initial Investment                     8     21     4     25


Annual Costs:

    Capital Costs (8%)                 0.6   1.7    0.3   2.0
    Depreciation (10%)                 0.8   2.1    0.4   2.5
    Operation and Maintenance          0.1   1.1    0.1   4.0
    Energy and Power                   -     0.1    -     0.5

            Total Annual Costs         1.5   5      0.8   9

Effluent Quality (expressed in terms of yearly averages)
                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)
B.O.D.
C.O.D.                    25           (No specific guidelines)
Suspended Solids
*The polyvinyl ether contribution is 0.07 thousand cubic meters per day
 (0.018 MGD); this is approximately 3% of the total flow to be treated.
                               209

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                            TABLE VIII-4/25
                    WATER EFFLUENT TREATMENT COSTS
                   PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:     Silicones

Plant Description:        Fluids Only - Free Standing

Representative Plant Capacity
    million kilograms (pounds) per year:      22.7          (50)

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                 54            (6.5)

Treatment Plant Size
    thousand cubic meters per day (MGD):       3.8          (1.0)
Costs - $1000
             Alternative Treatment Steps

             A     B      D     E
Initial Investment
                                      305   745
                         232   1338
Annual Costs:
    Capital Costs (8%)
    Depreciation (10%)
    Operation and Maintenance
    Energy and Power
            Total Annual Costs       61.6   184     44    522

Effluent Quality (expressed in terms of yearly averages)
24
31
6
0.6
60
75
40
9
19
23
2
-
107
134
228
53
B.O.D.
C.O.D.
Suspended Solids
                     Raw Waste Load
N/A
15
N/A
   Resulting Effluent Levels
(units per 1000 units of product)
A     B_      D     E_
      1.5    -     0.6
      7.5    -     4.0
1.0   -      0.2
                              210

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                             TABLE VII1-4/26


                     WATER EFFLUENT  TREATMENT  COSTS

                    PLASTICS AND  SYNTHETICS  INDUSTRY
 Industry Subcategory:      Silicones
                            Fluids Only - Industrial Complex
 Plant Description:

 Representative Plant Capacity
     million kilograms  (pounds) per  year:      22.7          (50)

 Hydraulic Load
     cubic meters/metric ton of product:
     (gal/lb)                                  54            (6.5)

 Treatment Plant Size
     thousand cubic meters per day (MGD):      43.5          (11.5)*
 Costs - $1000                          Alternative Treatment Steps

                                        A    Jl     P_    E.



 Initial Investment                    143   334     77   435


 Annual Costs:

     Capital Costs (8%)                 n    27       6    35
     Depreciation (10%)                 14    33       8    44
     Operation and Maintenance            3    18       1    36
     Energy and Power                     0.3   4       -    10

             Total Annual Costs         28.3  82     15   125

 Effluent Quality (expressed in terms of yearly averages)
                      Raw Waste Load       Resulting Effluent Levels
                                        (units per 1000 units of product)
                                        A     I      5.     I
 B-°'D-                     N/A          -     1.5    -     0.6
 C'°-D-                     15           -     7.5    -     4.0
 Suspended Solids          jj/A          1 0
0.2
*The silicone contribution is 3.8 thousand cubic meters per day (1.0 MGD);  this is
 approximately 9% of the total flow to be treated.
                              211

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                            TABLE VIII-4/27

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:      Silicones
                           Multi-product - Free  Standing
Plant Description:

Representative Plant Capacity
    million kilograms (pounds) per year:      22.7          (50)

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                 142           (17.0)

Treatment Plant Size
    thousand cubic meters  per day  (MGD):      17.2          (4.55)


Costs -  $1000                          Alternative  Treatment  Steps

                                        A     1      &     Ji



Initial  Investment                      720    1760    441   3044


Annual  Costs:
     Capital Costs (8%)                   58     141     35    244
     Depreciation  (10%)                   72     176     44    304
     Operation and Maintenance           15      74      4    646
     Energy and Power                     2      14     -     200

             Total Annual Costs         147     405     83   1394

 Effluent Quality  (expressed in terms of yearly averages)


                      Raw Waste Load       Resulting Effluent Levels
                                        (units per 1000 units of product)
                                        A     I     2.     _E
 B.O.D.                    85           _     7      -     3
 C.O.D.                    115           -     35     -    18
 Suspended Solids          50           5     -     1     -
                               212

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                            TABLE VIII-4/28

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:      Silicones

Plant Description:         Multi-product  -  Industrial  Complex

Representative Plant Capacity
    million kilograms (pounds) per year:      22.7          (50)
Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)
                    142
Treatment Plant Size
    thousand cubic meters per day (MGD):      /~ i
                    (17.0)


                    (11.3)*
Costs - $1000
              Alternative Treatment Steps
Initial Investment
             509   1187   289   2191
Annual Costs:

    Capital Costs (8%)
    Depreciation (10%)
    Operation and Maintenance
    Energy and Power

            Total Annual Costs
 41
 51
  9
  1

102
                     95    23    175
                    119    29    219
                     66     2    622
                     13          194
                    293
                  1210
Effluent Quality (expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
                     Raw Waste Load
 85
115
 50
   Resulting Effluent Levels
(units per 1000 units of product)
A     B      D     E
~     1      ~     ~3
     35      _     15
5            1     -
*The silicone contribution is      thousand cubic meters per day
             this is approximately 20% of the total flow to be treated.
                               213

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                            TABLE VIII-4/29

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY



Industry Subcategory:     Nitrile Barrier Resins

Plant Description:        Plant  in Industrial Complex

Representative Plant Capacity
    million kilograms (pounds) per year:     4.5           (10)

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                25             (3.0)

Treatment Plant Size
    thousand cubic meters per day (MGD):     8.3           (2.2)*


Costs - $1000                          Alternative Treatment Steps
Initial Investment                      23     59      12     67


Annual Costs:

     Capital  Costs  (8%)                   25       15
     Depreciation  (10%)                   26       17
     Operation and Maintenance            0.3    5       0.1    6
     Energy and Power                     0.1    1       -      1

             Total Annual  Costs           4.4   17       2.1   19

Effluent  Quality  (expressed  in  terms  of yearly averages)


                      Raw  Waste  Load        Resulting Effluent  Levels
                                        (units per 1000  units  of product)

B.O.D.                     10
 C.O.D.                     30           (No specific guidelines)
 Suspended Solids            5

 *The nitrile barrier resin contribution is 0.34  thousand  cubic meters per day
  (0.09 MGD); this is approximately 40% of  the total flow  to be treated.
                                 214

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                             TABLE VIII-4/30

                     WATER EFFLUENT TREATMENT COSTS
                    PLASTICS AND SYNTHETICS INDUSTRY


 Industry Subcategory:      Spandex Fibers

 Plant Description:         Plant in Industrial Complex

 Representative Plant Capacity
     million kilograms  (pounds)  per year:      2.3          (5)

 Hydraulic Load
     cubic meters/metric  ton of  product:
     (gal/lb)                                  8.3          (1.0)

 Treatment Plant Size
     thousand cubic  meters  per day (MGD):      3.4          (0.9)*


 Costs -  $1000                         Alternative Treatment  Steps

                                        A     B       D     E
Initial Investment                      8     16       3     21


Annual Costs:

    Capital Costs (8%)                  0.6   1.3     0.2   1.7
    Depreciation (10%)                  0.8   1.6     0.3   2.1
    Operation and Maintenance           0.2   1.4     0.1   3.7
    Energy and Power                    -     0.2     -     0.5

            Total Annual Costs          1.6   4.5     0.6   8

Effluent Quality (expressed in terms of yearly averages)


                     Raw Waste Load       Resulting Effluent Levels
                                        (units per 1000 units of product)

B.O.D.                    20
C-°'D'                    40            (No specific guidelines)
Suspended Solids          N/A

*The Spandex contribution is 0.06 thousand cubic meters per  day (0.015 MGD);
 this is approximately 2% of the total flow to  be treated.
                                 215

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                                          TABLE VIII-5/1
                INDUSTRIAL WASTE TREATMENT MODEL  DATA SYNTHETIC POLYMERS PRODUCTION
                                 EVA      Fluorocarbons  Polypropylene Polyvinylidene  Acrylic
                              Copolymers	Fibers	Chloride.     Resins

Total Industry Discharge
 1000 cubic meters/day
(or million gallons/day)
    1972                         0.6(0.2)      4.2(1.1)     1.5(0.4)       0.4(0.1)    13.2(3.5)
    1977                         1.1(0.3)      5.7(1.5)     2.3(0.6)       0.4(0.1)    33.1(8.7)
Quality of Effluents in 1977
(Expressed in terms of yearly averages)
    Parameters:
     (in units/1000 units of product)
        BOD
        COD
 Suspended Solids
Hydraulic Load: 1972-1977
cu m/kkg  (or gal/lb)             8.3(1.0)     92   (18)      16.7(2.0)       NA          NA
Numbers of Companies             5             53              4           >4
Percent of Treatment  in 1972
(in  percent now treated)
     A.  Industrial  Pretreatment   100           100          0              100         80
     B.  Industrial  Biological       60              0          0                50         65
     C.  Municipal                   0           100          100              0         20
0.13
1.3
0.25
2.3
23
4.5
0.25
1.25
0.50
NA
NA
NA
NA
NA
NA
                                                   216

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                                           TABLE  VIII-5/2
                 INDUSTRIAL WASTE TREATMENT MODEL DATA  -  SYNTHETIC  POLYMERS  PRODUCTION
                               Cellulose
                              Derivatives
           Alkyds and
           Unsaturated
            Polyesters
Total Industry Discharge
 1000 cubic meters/day
(or million gallons/day)
    1972
    1977
15.9(4.2)
20.9(5.5)
 Quality of Effluents  in 1977
 (Expressed in terms of yearly averages)
    Parameters:
    (in units/1000 units of product)
        BOD5                     NA
        COD                      NA
 Suspended Solids                NA
Hydraulic Load: 1972-1977
 (cu m/kkg (or gal/lb)            NA
Numbers of Companies             3
Percent of Treatment in 1972
(in percent now treated)
    A.  Industrial Pretreatment   100
    B.  Industrial Biological     100
    C.  Municipal                   0
                                               0.4
                                               2.0
                                               0.1
             Cellulose   Polyamides    Polyesters
              Nitrate                Thermoplastic
 6.8(1.8)     9.8(2.6)
13.7(3.6)     9.8(2.6)
                           5.0
                          25
                           4.2
                                              3.2(0.4)    142(17)
                                              L4            2
               0.8(0.2)
               1.2(0.3)
10
10
90
100
 40
 60
                             0.3
                             3.0
                             0.2

                             6.7(0.8)
                             3
                                                                          100
                                                                           60
                                                                            0
                                                                                        0.4(0.1)
                                                                                        0.8(0.2)
                           0.35
                           5.3
                           0.24

                           2.2(0.95)
                           3
                                                     100
                                                      50
                                                       0
                                               217

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                                          TABLE VIII-5/3

                 INDUSTRIAL WASTE TREATMENT MODEL DAT£  - SYNTHETIC  POLYMERS  PRODUCTION
Polyvinyl
Butyral
Total Industry Discharge
1000 cubic meters/day
(or million gallons/day)
1972 5.3(1.4)
1977 6.7(1.8)
Quality of Effluents in 1977
Polyvinyl Silicones Nitrile Spandex
Ethers Barrier Resins Fibers

0.4(0.1) 29.9(7.9) 0.8(0.2) 0.4(0.1)
0.6(0.2) 48.5(12.8) 2.7(0.7) 0.4(0.1)

(Expressed in terms  of yearly averages)

    Parameters:
    (in units/1000 units of  product)
BOD
COD
Suspended Solids
Hydraulic Load: 1972-1977
cu m/kkg (or gal/lb)
Numbers of Companies
Percent of Treatment in 1972
(in percent now treated)
A. Industrial
B. Industrial Biological
C. Municipal
NA
NA
NA
NA
2
100
25
75
NA
NA
NA
NA
2
70
0
30
10.5
53
7.0
233(28)
4
100
20
0
NA
NA
NA
NA
3
100
70
30
NA
NA
NA
NA
3
100
60
10
                                                 218

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                            SECTION IX

      BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
                    GUIDELINES AND LIMITATIONS


 Definition	of	Best	Practicable^ Control  Technology  Currently
 Available_JBPCTCAl                                    	

 Based on the analysis of the information presented in Sections IV
 to   VIII,   the  basis  for  BPCTCA  is  defined  herein.    Best
 practicable control technology currently available  (BPCTCA)   for
 existing point sources is based on the application of end-of-pipe
 technology  such  as  biological  treatment for BOD5 reduction as
 typified by activated sludge,  aerated lagoons,  trickling filters,
 aerobic-anaerobic lagoons,  etc,,   with  appropriate  preliminary
 treatment  typified  by  equalization,  to dampen shock loadings,
 settling, clarification,  and chemical treatment,  for  removal  of
 suspended  solids,   oils,  other  elements,   and   pH control, and
 subsequent treatment  typified  by  clarification  and  polishing
 processes  for  additional  BOD5 and suspended  solids removal and
 dephenolizing  units  for  the  removal  of   phenolic  compounds.
 Application  of  in-plant  technology  and  changes  which  may be
 helpful  in meeting  BPCTCA include  segregation of  contact process
 waste from  noncontact waste  waters,  elimination of once-through
 barometric condensers,  control of  leaks,   and  good  housekeeping
 practices.

 The   best  practicable  control technology currently available has
 been  _found  to  be  capable  of  generally   effecting   removal
 efficiencies  of  upwards  to 85 percent in single-stage biological
 systems.   The design and  operating parameters of   the  biological
 treatment  system  may  vary from essentially  those of  a  municipal
 sewage treatment  plant  to those uniquely  tailored  to  a  specific
 plant waste.   The  acceptability of  many  of the waste  waters  into
 municipal sewage  systems  has been  established and  often  proves to
 be one of  the  best methods   of  waste  water  treatment  where
 suitable   pretreatment  can be effected and where  the  synergistic
 effects of  treating with   sewage  occur.   The  applicability  of
 biological   systems has been proven  regardless of  the  age or  size
 of the manufacturing plant.

 Because of  the  relatively  small  number of  single   product  waste
 water  treatment  plants  (much  of  the  industry uses  either multi-
 plant waste water treatment  or  municipal  treatment)  the amount of
 data  on which effluent limitations can be based is   limited,  and
 it  has been necessary to  rely  on  analogy and technology transfer
 for guidelines  in some instances.  Because of  the   variabilities
 inherent  in  the performance  characteristics of industrial waste
water treatment plants, especially those affecting the growth  of
microorganisms  such  as temperature and variable concentrations,
the guidelines  have taken  into consideration demonstrated  unique
properties  such  as high concentrations of COD that can exist in
the treated waste waters.  The parameters of primary concern  are
BOD5,   COD,  and  suspended solids.  Other parameters such as pH,
                               219

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metals, nitrogenous compounds  and  specific  chemicals  such  as
phenolics are also of concern to the industry.

In  Table  VII- 4  of  Section VII the effluent loadings which are
currently being attained by the product subcategories  for  BOD5,
COD,  and  suspended  solids are presented.  In some instances it
was  necessary  to  calculate  effluent  loadings  based  on  the
hydraulic  flows  emanating  from  the  production  plaint and the
concentrations of the particular parameters in the effluents from
a waste water treating plant handling waste water streams from  a
number  of  other  processes.  This procedure was adopted when it
was  known  that  a  significant  fraction  of  the  waste  water
treatment plant load came from the process under consideration or
where  the  treatability of the waste waters could be expected to
be analogous to those of the major product, e.g., the  similarity
of  ethylene- vinyl  acetate  wastes  to  low density polyethylene
wastes.  Using this approach, it was apparent from the results of
this work that practicable waste water treatment  plants  are  in
operation and that their operational parameters are comparable to
those  of  the  resins  segment  of this industry as well as with
biological  treatment  systems  in  other  industries.    It   is
apparent,   therefore,  that  the  most  significant  factors  in
establishing effluent limitations guidelines on a basis of  units
of  pollutants  per  unit  of  production are  (1) the waste water
generation rates  per  unit  of  production  established  for  an
exemplary  plant  and   (2)  the concentration levels in the waste
waters  from  the  best   practicable   waste   water   treatment
techniques .

The ^guidelines

The effluent limitations guidelines as kg of pollutant per kkg of
production    (lb/1000  Ibs)  are  based  on  attainable  effluent
concentrations  and  demonstrated  waste  water  flows  for  each
product  and  process  subcategory  where  a sufficient number of
similar products or processes could be identified.

Attainable Ef f luent_Cgncentrations

Based  on  the  definition  of  BPCTCA,  the  following  long-term
average  BOD5  and suspended solids concentrations were used as  a
basis  for the guidelines.


                                             SS
                               mg/liter   mg/liter

 Major  Subcategory  I                15          30
 Major  Subcategory  II               20          30
 Major  Subcategory  III              45          30
 Major  Subcategory  IV               75          30

 The BOD5  and  suspended   solids   concentrations   are   based   on
 observed  or  reported performance of water  treatment plants.   In
 many sufccategories of  this  segment of the plastics  and  synthetics
                              220

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 industry, the  in-place  waste  water  technology  and  treatment
 levels  are  inadequate.  By proper design and application of the
 defined technologies,  the  levels  proposed  are  attainable  as
 demonstrated  by  other  subcategories  within  this industry and
 other industries such as organics and petroleum refining.

 The COD characteristics of the polymer segment of the  synthetics
 and  plastics industry vary significantly from product to product
 and within an individual plant over time.  The ratio of  COD  and
 BOD5 in the raw waste water and treated waste waters are shown in
 Table  IX- 1 and range from a low of 1.0 to a high of 23.  The COD
 limits for BPCTCA guidelines are based on these values as well as
 by analogy with the bases used in establishing guidelines for the
 resins segment of the industry.  They are expressed as ratios  to
 the  BOD5  limit  for upper limits of the ratio of COC/BOD5 of 5,
 10, and 15.   Table IX-2 records the ratios corresponding  to  the
 individual  products.  where reasonable to do so,  actual COC/BOD5
 ratios that were observed were used.

 There is a real need for more data in all sections of the polymer
 segment of the plastics and  synthetics  industry   to  provide  a
 better  understanding  of the waste water loads, the treatability
 of the waste waters and,  in particular,  a better understanding of
 the nature of the COD component and methods   for   its  reduction
 In  the interim,  the purpose of the proposed BPCTCA guidelines is
 simply to reflect the removal of COD  to  be  expected  along  with
 best practicable  removal  of those pollutants measured by the BODS
 "   "                                                            —
 Although   guidelines   are   not   established   for  phenolics  in  the
 polymers  segment  of the  industry,  wherever phenolic  compounds  are
 identified their  removal should  remain the same as for the  resins
 portion of the  industry, i.e., an  attainable  concentration   level
    .   ^mg/1iter monthlv  limit as  demonstrated  by  deohenolizing
                               (13'   ^'  ^  39>  or 'biological
       ^1  H?  0±1   and greaS6  iS based on 30 mg/liter monthly
       attainable  concentrations  as  demonstrated  by   various
pnysical and chemical  processes in other industries  (35) .

The  removal of fluorides is based on an attainable concentration
of  20  mg/liter  by   lime  precipitation  as  used  in  effluent
th^eihne%n °r-,the ir°n and Steel i^ustry.  it should be noted
that the  fluoride  level  shewn  for  the  f luorocarbons  (PTFE)
?h?2^!°ry  a^ll€? t0 the fluoride content of the effluent from
the water scrubber in  the TFE monomer process only,  not  to  the
total  waste  water discharge from the overall PTFE process.   The
scrubber effluent, a dilute HC1 solution, is the only significant
source of fluoride discharge  from  the  PTFE  process?   At  all
present  PTFE manufacturing operations, this scrubber effluent is
segregated from other  waste waters and  disposed  of  by  various
^ahSA  an^udin
-------
                            TABLE  IX-1
                          COD/BOD  RATIOS
                                         Raw
Acrylic Resins

Alkyd and Unsaturated
Polyester Resins

Cellulose Derivatives

Cellulose Nitrate

Ethylene-Vinyl Acetate/
Polyethylene

Fluorocarbons

Nitrile Barrier Resins

Polyesters  (thermoplastic)

Polypropylene Fibers

Polyvinyl Butyral

Polyvinyl Ether

Polyvinylidene Chloride

Silicones
1.3 - 2.7


2   - 3.7

2.4 - 4.2

2.5 - 4.1


4.2

1.8

2.3 - 2.9



3.2 - 3.8

1   - 4.8
                  Treated
                                                      1.4 - 3.3
5.2
5.0
4.6 -  23
 2.5
                  5.1
                                    222

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                          TABLE IX-2

       COD/BOD5 RATIOS CORRESPONDING TO  INDIVIDUAL PRODUCTS
                     (TREATED WASTEWATER)
      Product                             COD/BOD
Alkyds and unsaturated polyesters,             5
cellulose nitrate, polyamides


 Ethylene-vinyl acetate, polypropylene

 fibers, silicones,  fluorocarbons


Polyesters  (Thermoplastic)                   15
                            223

-------
guideline for fluoride was  derived  on  the  basis  of  20  mg/1
attainable  concentration  and  a  scrubber effluent flow of 3500
gal/1000 Ibs product.

Cyanides, mercury, and cadmium limitations should  be  consistent
with the limitations cf toxic and hazardous chemicals prepared in
the Federal Register of December 27, 1973(38).

The  removal  of  copper  and  lead  is  based  on  an eittainable
concentration  of  0.5  mg/liter  as  demonstrated  by   alkaline
chemical precipitation  (35).

The copper limitations for both multi-product silicone and fluid-
product  silicone  production  facilities were established in the
following manner.

    1.   Precipitation  of  soluble  copper  by  means  of   lime
         treatment  was selected as the most applicable treatment
         technology.   It  has  been  shown  to  be  capable   of
         achieving  effluent  copper  concentrations of less than
         0.5 mg/liter.

    2.   It was assumed that no internal waste stream segregation
         would be employed and that the  total  volume  of  waste
         water  emanating from the production facilities would be
         subjected to the above lime treatment.

    3.   The average waste flows in terms of  gal/1000  Ibs  were
         calculated  for the fluid-product plants by averaging the
         values  of  the  reported range of waste  flows.  For the
         multi-product  plants an average was taken of  the  waste
         flows  of   the two plants having the more reliable data.
         In the case of the multi-product  plants,  estimates  of
         product  quantities  were  estimated  from  actual sales
         quantities.

    U.   The maximum average  for a  30-day period for   BPCTCA  was
         then developed using the  average waste flows  established
         in  (3) in  conjunction with the demonstrated 0.5 mg/liter
         copper   effluent  using   lime  treatment.   The  maximum
         average  daily  limitations  were  taken  as  twice  the
         average  30-day limitations.

         Since  the  lime treatment process theoretically  removes
         copper to  a fixed solubility  limit rather than  removing
         a   certain  percentage   of   the   influent  copper,  the
         quantity of copper  in the raw  waste  water   is   of  no
          consequence  with   respect to   the   attainable effluent
          copper  concentration.   Thus,  the  fact   that  different
          silicone  production facilities  may  produce waste  waters
         with vastly varying quantities  of  copper   is   irrelevant
         with   respect  to   the  established  limitations.   The net
          result  is  that the  limitations  on  copper, in  pounds/1000
          pounds  of   product,   are   dependent   on   hydraulic  load
          attainable.    In one respect, the  copper  limitations  are
                              224

-------
          actually conservative in favor of the industry,  because
          it  was  not  presumed that copper-bearing waste streams
          would  be  segregated  from  other  waste  streams   for
          treatment,  a  practice  which  would  reduce  the total
          quantity of copper in the effluent.

 Demonstrated_Waste_Water_Flows

 The waste water flow basis for EPCTCA is  based  on  demonstrated
 waste  water  flows  found  within  the industry.   Because of the
 small number of manufacturing plants in most  categories,  and/or
 the  limited  data base,  the demonstrated waste water flows shown
 in Table IX-3 were based  on  engineering  judgments  taking  into
 consideration  reported  flows  and other assessments such as the
 type  of  operation,  nature  of   housekeeping,    and   apparent
 operational  attention to good water conservation  practices.   The
 demonstrated waste water  flows  are  based  (where  possible)   on
 process  water  only  and  do  not include boiler  water blowdown,
 water treatment regeneration wastes, cooling water blowdown,   and
 any other waters deriving from utilities and supporting services.
 as  laboratories  and  so  on.    It  is  essential  to  take  into
 consideration the fact that waste water flow is often an integral
 part of the basic process design and operation of  the process and
 plant and,  therefore,  would be subject  to  significant  reduction
 only  at  considerable expense.    Although  generally  the  unit
 hydraulic loads are larger for older plants,  the availability  of
 water influences the design as does the designer's philosophy and
 the  company's  operating procedures.   No simple formula has  been
 found for relating hydraulic load to plant age, size or location.

 Statistical_Variability._of_a_Prop_erlv_Desi2ned and Operated Waste
 Treatment_Plant                    ~                 	

 The effluent  from a  properly  designed  and   operated  treatment
 plant  changes  continually due to a variety  of factors.   Changes
 in production mix,   production   rate,   climatic  conditions,   and
 reaction chemistry  influence   the  composition of raw waste  load
 and,  therefore,  its treatability.   Changes in  biological   factors
 influence   the   efficiency   of  the  treatment process.  A common
 indicator of  the  pollution  characteristics of  the  discharge   from
 a  plant  is  the  long-term  average  of  the  effluent load.   The long-
 term  (e.g., design  or  yearly) average is not a suitable  parameter
 on which   to  base  an enforcement standard.   However,  using data
 which show  the  variability   in  the  effluent  load,   statistical
 analyses  can  be   used  to compute  short-term limits  (monthly or
 daily) which  should  not be  exceeded, provided  that the   plant  is
 designed  and  run  in the proper way to achieve the desired long-
 term  average  load.   It is these short-term  limits  on  which  the
 effluent guidelines  are based.

 In  order  to  reflect the  variabilities associated with properly
 designed and  operated treatment plants  for  each  of  the  major
 subcategories as discussed  above, a statistical analysis was made
 of  plants where sufficient data was available to determine these
variances for  day-to-day   and  month-to-month  operations.   The
                              22f

-------
                           TABLE IX-3

                  DEMONSTRATED WASTEWATER FLOWS
Alkyd Molding Compounds  and
Unsaturated Polyester Resins

Cellulose Nitrate

Ethylene-Vinyl Acetate

Fluorocarbons

Polyamides  (Nylon 6/12 only)
                                   WASTEWATER FLOW RATES

                               cum/kkg           ^al/1000 Ibs
  3.3

142

  2.9

150

  6.7
Polyester Resins (Thermoplastic)     7.9
Polypropylene Fibers

Polyvinyl Butyral

Silicones

    Multi-products

    Fluid Products
  16.7

   _*



 233

  33
   400

17,000

 1,000

18,000

   800

   950

 2,000

   _*



 28,000

 4,000
 *See  footnoote  page 232b
                              226

-------
 standard  deviations for day-to-day and month-to-month  operations
 were   calculated.    For  the   purpose   of   determining    effluent
 limitation,  a variability factor was defined  as  follows:

          Standard  deviation          =  Q monthly,  Q  daily
          Long-term average (yearly  or design)  =  x
          Variability factor =  y  monthly, y  daily
          y monthly = x_+_22_monthly,
                        x
          y daily = x_+_3Q_daily_
                      x

 The  variability   factor  is   multiplied by  the long-term yearly
 average  to determine the effluent limitations guideline for  each
 product   subcategory.   The monthly  effluent limitations guideline
 is calculated by   use  of a   variability   factor  based  on  two
 standard  deviations and is  only  exceeded 2 to 3 percent of the
 time for a plant that is attaining  the   long-term  average.   The
 daily  effluent limitations guideline is calculated  by the use of
 a variability factor based on  three standard   deviations  and  is
 exceeded  only 0.0-0.5   percent  of the time for  a  plant that is
 attaining the long term  average.  Any plant designed to meet  the
 monthly   limits  should   never exceed the daily  limits.  The data
 used   for the variability  analysis   came   from  plants   under
 voluntary  operation.     By   the   application  of   mandatory
 requirements,  the  effluent limitations  guidelines as discussed in
 this paragraph should never be exceeded  by  a properly  designed
 and operated  waste treatment facility.

 The  variability   factors  in  Table  IX-4  are  based on the data
 obtained in the synthetic  resin segment  (16)  of  the  plastics  and
 synthetics industry.

 The variability factors  for suspended solids  removal are the same
 as  used  in   the  resins  segment  of  the  industry, i.e., a monthly
 variability of 2.2  and a daily variability of 4.0.

 The  variability   factors   recommended   for   total   chromium,
 phenolics,  copper,  lead,  and  oils and grease are based on the
 monthly  limits and a variability factor  of   2.0  for  the  daily
 maximum.

Based  on  the  factors  discussed  in this section,  the effluent
 limitations guidelines for BPCTCA are presented  in  Tables  IX-5
and IX-6.
                              227

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                            TABLE LX-4

                   VARIABILITY FACTORS FOR BODr
                                   BOD5       Variability Factors
                                 Monthly      	Daily	
Major subcategory I                1.6                3.1

  "        "      II               1.8                3.7

  "        "      III              2.2                4.0

  "        "      IV               2.2                4.0
                               228

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                                      TABLE IX-5

BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE EFFLUENT LIMITATIONS GUIDELINE"
                          [kg/kkg (lb/]000 lb) of production]

Foot-
note
So.
1
. 2
3
4
S
6
7
S

NJ »
NJ
VO 1C

u
13



14

15

Subcategory
Ethylene-Vinyl Ac-Cate Copolymari.
Fli-orocarbons
Polypropylene Fiber
PflyvinyllJene Chloride
Ar.yllc e.iins
Cellulose Derivatives
A->yds ann Unsaturated Polyester tasln*
O'.lulosc Nitrat/

Polyanidc* (Syloi 6/12 oi,ly)
Prlyeste,. Resins (then»"^laatic)

Pflyvlnyi Butyral
Pclyvlnyi Ethem
Slllconeo
Multi-Product Plants
Allucatlo.i for

Fluid Product Plants

Spandex Fibers
B*jQr
Maximum Average of Maximum for Any
Dally Values for Any One Day
Period of Thirty
Consecutive Days
0.07 0.14
3.6 7.0
0.40 0.78
Ho numerical guldellnea-aee discussion
in footnote
n tt
" M
0.33 0.60
14 26

0.66 1.20
0.78 1.4

Ho numerical guidelines-see discussion
in footnote

14 26

8.2 15
3.3 6.0
No numerical guidelines-see dis-
cussion ln footnot.
1* n
COD
Maximum Average of Maximum for Any
Dally Values for Any One Day
Period of Thirty
0.35 0.70
6.7 13
2.0 3.9
No numerical guidelines-see discussion
in footnote
n n
1.7 3.0

46 85
3.3 6.0

12 22
No numerical guidelines -see discussion
in footnote
« ii

70 127

41 75
17 30
No numerical guidelines-see dis-
cussion in footnote
n n
— 	 SUSPrKE'D SOLIDS 	 '
Maximun Average of Maxis'ir for \r.v
Dally Values for Any One r..y
Period of Thirty
Consecutive D-t-s
0.19 0.35
9.9 13.0
1.1 2.0
No numerical guidelines-see discussion
in footnote
» n
0.22 0.40

9.4 17
0.44 O.SO

0.52 0.95
No numerical guidelines-see discussion
In footnote

9.1 17

5.4 10
2.2 4.0
No numerical guidelines-see dl&-


-------
                                                            FOOTNOTES  FOR  TABLES     Ix~5
1.  Ethylene-Vinyl Ac«tsts (EVA)  Copolfner.  Two of  the  flw
    known producers were contacted.All plants sre located
    at polyethylene production facilities.   Hater use and
    vastewater characteristics for EVA are  essentially  Iden-
    tical" to those for low density polyethylene. However,
    an emulsion polymerization process Is known and produce!
    a distinctly different waste  load which Is essentially
    that of polyvlnyl acetate emulsion polymerization
    reported in EPA 440/1-73/010.  Both multi-plant and
    municipal sewage treatment is used.
2,  Fluorocarbons. Three of the seven manufacturing plants
    were visited.  A wide range of products are produced.
    The most Important la polytetrafluorethylene (PTFE) and
    these guidelines are recommended for PTFE granular  and
    fine povder grades only.  The wastewater discharges
    differ considerably depending upon the process  recovery
    schemes for hydrochloric acid and the disposal  of  selec-
    ted streams bv deep well,  ocean dumping or off-site
    contract methods.  The use of ethylene glycol In a  pro-
    cess can significantly affect the waste loads.  Fluoride
    concentrations In untreated wastewaters are generally
    below levels  attainable by alkaline precipitation.

3.  Polypropylene Fibers. Two of the three producers were
    contacted. The volumetric flow ranges per unit  of pro-
    duction vary  widely depending upon  the  type of cooling
    system used.  The waste loads are for plants where aelec-
    ted concentrated wastes are  segregated and  disposed  of
    by  landfllllng, etc. Primary treatment at  one plant slt«
    was observed  while the other plant discharges to a
    Municipal  sewage system.
4.  folyvinylidene Chloride, the two major manufacturers
    were contacted. Both plant sites send wastewaters  to
    multi-plant  treatment plants of which  the  polyvlnylidena
    chloride  is  a snail portion.  Consequently, there was
    insufficient  data  to develop reconnended  guidelines.

5.  Acrylic Resins. Three of  the four manufacturers were
    contacted.  Large  numbers  of  product  grades are produced
    by  bulk,  solution,  suspension and  emulsion polymeriza-
    tion.   The widely  varying hydraulic  loads  for  the  large
    number  of products  in addition  to  treatment of  the waste-
    waters  by multi-plant wastewater  treatment facilities
    prohibited obtaining  sufficient meaningful data to
    recommend effluent  limitation guidelines.

 6.  Cellulose Derivatives.  Cellulose  derlvates investigated
     Included  ethyl cellulose, hydroxyethyl cellulose,  methyl
    cellulose and carboxymethyl  cellulose.  Wide' variations
     In unit flow rates for  two plants producing the same
     product,  differences in manufacturing  techniques and th»
     availability of data prevented  recommending guidelines.
     The wastewaters from the three  manufacturers are being
     treated In multi-plant  wastewater treatment facilities
     or will enter municipal sewage  systems.
7,  AlkyJs and Unsaturated Polyester Resins.  Six carefully
    selected plants were visited to provide a cross-section
    of the industry for size of operation,  type of manufac-
    turing process and wastewater treatment methods.  Hydrau-
    lic loads vary widely depending upon the  process  designs.
    Similarly, raw waste loads vary widely  because some
    plants segragate wastes for disposal in other manners.
    Generally, the Industry discharges wastewaters into
    municipal sewage systems and should continue.  Also,  the
    type of air pollution control, e.g. combustion or scrub-
    bing, has a significant effect on the wastewater  loads.
    The recommended guidelines are for plants having  their
    own vastewater treatment system - a very  infrequent
    occurrence.
8.  Cellulose Nitrate. The two major manufacturers of the
    four manufacturers were contacted.  These wastes  require
    pH control and contain large amounts of nitrates. One
    plant discharges to a municipal sewage system while the
    other goes Into a multi-plant treatment complex.

9.  Polyaaides. Various polyamides are produced but only
    Nylon 6/12 produces significant amounts of wastewater,
    e.g. Nylon 11 uses no process water. Consequently, the
    guidelines are restricted  to Nylon 6/12 and were develop-
    ed on the basis of similarity with waste loads from
    Nylon 66 production.
10,  Polyester Thermoplastic Resins. There are three manu-
     facturers, two of which produce polyfethylene, terephtha-
     late) In quantities less  than 21 of their total thermo-
    plastic production. The guidelines are recommended for
     poly(ethylene  terephthalate) since the other  product
     poly(butylene  terephthalate) Is produced at only one
     plant and  the wastewater  goes Into a municipal sewage
     syst 'm,  so no  data  on performance  could be obtained.

11,   Polyvlnyl Sutyral.  Of three production sites,two have
     processes  beginning with  vinyl acetate monomer which
     generates much  larger wastewater volumes  than the  pro-
     cess  beginning with polyvinyl alcohol. Since  the manu-
     facturing  sites where production starts with  a monomer
     discharge  Into  municipal  sewage  systems,  there was no
     data available. Consequently,  the  recommended guide-
     lines are  only for NSPS-BADT when  starting with  poly-
     vinyl alcohol since any other  guidelines would be
     tantamount  to establishing a  permit  for  the  production
     site.
12.  Polyvlnyl  ethers.  The three present  plants use differ-
     ent processes each of which produces several grades of
     product.    The different  ctieaical  conpaoUiuns used in
     both bulk and solution  polymerization  processes  and the •
     lack of data on both  raw  and  treated wastewaters pre-
     vented establishing guidelines.  The wastewatera are
     presently sent to either  multi-plant treatment faclliti*
     or municipal sewage systems.
13. Silicones. Pour companies manufacture silicones at five
    locations.  Three plants vere visited and data were
    obtained from all plants. The major processing steps at
    the five plants are shown below.
           Ha'or Processes st Five Stlicone Plants
       Plant No.            12345*
    CH.C1                   x     *  »
    Chlorosilane prod.      x  x  x  x  x
    Hydrolysis              x  x  x  x  x
    Fluids, greases,        x  x  x  x  x
      emulsions  prod.
    Resin  production        x  x  x
    Elastomer production    x  x  x     x
    Specialties prod.*      x  x  x
    Fumed  silica prod.            x
    HC1  production                      x
    * e.g. surfactants, fluorinated silicones, coupling
       agents, and other materials.

    Based  on  the manufacturing process,  the  wastewater flows
    and  the raw waste loads,  the  plants  1, 2, 3 were  desig-
    nated  as  multir-product plants while  4 and 5 were  desig-
    nated  as  fluid  product plants.    Guideline   quantities
    based on  production  rates  that were estimated
     from  sales  volumes  for BPT.

 14. Nitrlle Barrier Resins.  Commercial scale production  and
     sale of these  resins  has not  yet  begun.  The companies
    expected  to have production  facilities were contacted,
    and  two provided estimates of raw waste  loads.  Because
    of the lack of  demonstrated  flows and  raw waste loads,
     It was impossible to  establish  effluent  guideline
    limitations.
 15. Spandex Fibers. Three manufacturers  each produce   '
    Spandex fibers  by significantly different processes.
    These  are dry,  wet  and reaction spinning methods.  '
    Because of  lij&ited  data on raw waste loads and
    because each plant  operates a different  process,
    it was impossible to  establiah meaningful guidelines.

-------
                                                       TABLE IX-6
                   BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE EFFLUENT LIMITATIONS  GUIDELINES
                                              (Other Elements and Compounds)
                       Product
                                           Parameter
                                               	kg/kkg (Ibs/lOQQ Ibs of production)
                                               Maximum average of  daily          Maximum
                                               values for any period of          For Any
                                               thirty consecutive  days           One Day
            Alkyds and unsaturated
            polyester resins
                                     Lead
                                                                     0.0017
                                                                               0.0034
U)
Fluorocarbons
Spandex fiber
Nitrile barrier  resins
Polypropylene  fibers
Silicones
   Multi-product
   Fluid-product
   Barometric
    allocation
 Polyester resins
 (Thermoplastic)
Fluorides
Cyanides
Cyanides
Oils & grease

Copper
Copper

Copper
Cadmium
            0.6                    1.2
Toxic and hazardous chemicals guidelines to apply
                                                                    0.5

                                                                      .071
                                                                    0.017

                                                                      .042
                                  1.0

                                   .14
                                  0.034

                                   .083
                                                          Toxic and  hazardous  chemicals guidelines
                                                          to  apply

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                             SECTION X

         BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE


                              Te chnolog2__EconomicallY__Achievable


        n + he *nalysjs of the information presented in Sections IV
        , the basis for BATEA is defined below.

 Best  available  technology  economically  achievable (BATEA)  for
 existing point sources is based on the best in-plant practices of

 as" t±fSiS "h1^ I"inimiZe the V°1Ume °f -Degenerating  "ter
 as  typified  by  segregation  of  contact  process  waters  from
 noncontact waste water,  maximum waste water  recycle  and  reuse
 !iaks   ano, °h  0nfe-thrOUgh  b*^tric  condensers,  cltroTof
 leaks   good  housekeeping  practices,   etc.,    and   end-of-pipe
 elemenisgY'tvnifiS "T^ ^T*1  °f susPend^ solids  and o?ner
 elements   typified   by   granular   media  filtration,   chemical
 treatment,  etc.,  and further  COD removal  as  typified  by  the
 adsorSivenflof adS°Jpti°n Processes such as activated carSn  and
 adsorptive  floes,  and incineration for  the  treatment of  highly
 concentrated   small  volume  wastes  and  additional biological
 treatment  for  further BOD5 removal when needed.          io-Logica±
 Best  available  technology  economically  achievable  can be  expected
 areaS/T  ^  ^  °f  th°Se  ^^^±e5   which  provSf the
 Historical fgrJ.' °H  P°llutant  ^ntrol  per  unit  expenditure?
 oollSSon  S'H?         een the  aPProach to ^e  solution  of  any
 ??ii££ ?  Frobiem,- as typified by the mechanical and biological
 treatment  used   for  removal  of  solids and biochemically activ-
 dissolved  substances, respectively.   At  the  present  stage  of
 development,  it  is technologically possible to achieve  complete
 imnaS  °ff P°lluta"ts from wa^e  water  streams.   The   economic
 impact  of doing this mist be assessed by computing cost  benefits
 to specific plants, entire industries, and the  overall   economy
 The application of best available technology will demand  Sat Se
 economic  achievability be determined, increasingly, on the basis
 of considering water for its true economic impact/  Snlikl  best
 practicable  technology,  which  is readily applicable across tSe
 industry  the selection of best available technology economically
achievable becomes uniquely specific to each proceS and ?n  each
plant.    Furthermore,    the   human   factors   associated  wiS
conscientious operation and meticulous attention to detai! become
                                         technology is to acMeve
                                                             froS
                             233

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The_Guidelines

Achievable_Effluent_Concentrations

Susp_ended_Solids

The  removal  of  suspended  solids  from waste water effluent is
based on well-understood technology  developed  in  the  chemical
process industries and water treatment practices.  Application of
filtration to the effluents from waste water treatment plants has
not  been  applied  often,  although  its  feasibility  has  been
demonstrated  in  projects   sponsored   by   the   Environmental
Protection  Agency.  The operation of filtration systems, such as
the in-depth granular media  filter  for  waste  waters,  is  not
usually  as straightforward as it is in water treatment.  This is
due, especially, to the  biological  activity  still  present  in
waste  waters   and  sometimes  to  the  nature  of  the colloidal
particles  from  the process.

Long residence  time lagoons with their low flow-through rates are
often  effective means   for  the  removal  of  suspended  solids,
although   the   vagaries  of  climatic conditions, which can cause
resuspension of settled  solids,  and  the   occurrence  of  algal
growth can  cause  wide  fluctuations  in   the  concentration of
suspended  solids   in  the effluent.   Although  technology   is
available  for  reducing  suspended solids in  effluents to very low
levels (approaching a  few  mg/ liter) , the  capital   and  operating
cost   for  this technology  adds   significantly  to  waste water
treatment  costs.   The  concentration  basis  for  BATEA  is  10
ing/liter for  all product and process subcategories  (1,  15, 35).
 Removal    of    biochemical-oxygen-demanding    substances  _  to
 concentration levels less than the range proposed  for  municipal
 sewage treatment plants will require the utilization of physical-
 chemical  processes.  It is expected, however,  that the chemical-
 oxygen-demanding substances will present a  far  greater  removal
 problem  than  BODS because the biochemically treated waste water
 will have proportionally much higher ratios of COD to  BOD|  than
 entered  the  waste  water treatment plant.  In the case of a tew
 polymer products, the waste waters may contain substances  giving
 a   significant   COD  concentration  while  being  resistant  to
 biological degradation under the  most  optimum  conditions.   To
 reduce the COD in a treated effluent, it will be necessary either
 to   alter  processes  so  that  ncnbiodegradable  fractions  are
 minimized or attempt to remove these substances by some method of
 waste  water  treatment.   Both  of  these  approaches   may   be
 difficult.   Alteration  of  processes  so that they produce less
 refractory wastes may not be possible within the  constraints  of
 the  required  chemical  reactions.   However,  reduction  in the
 quantities  of  wastes  generated   by  spills,  leaks,  and  poor
 housekeeping  practices  can contribute significantly to reducing
 the total COD discharges, especially where a  large  fraction  of
 the    pollutants    are   refractory to  biological  degradation.


                               234

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 Consequently  one of the  first   steps   in   a   program  to  reduce
 emissions   should  be  a thorough  evaluation  of  the  process
 operation alternatives and techniques for   preventing  pollutants
 from entering the waste water streams.                   -tiutdnxb
   sorno  m^h°ds  ,for  re*oval  of  oxygen demanding substance,
 adsorption  by  surface-active  materials,  especially  activated
 carbon,  has  gained  preeminence.  Although the effectiveness of
 activated  carbon  adsorption  has  teen  well  demonstrated  for
 removing   BOD5  and  COD  from  the  effluents  of  conventional
 municipal sewage treatment  plants,  its  effectiveness  for  the
 removal  of the complex chemical species found in the waste water
 of this industry can be expected to be highly specific.  Evidence
 of the low adsorption efficiency of activated carbon for a number
 ?^h   T^-f  I"1Cal sPecies  is  Beginning  to  appear  in  the
 ^nija^  ^erature.   However,  the  only  way to determine if
 activated carbon adsorption is an effective method  for  removing
 COD  is  to  make  direct determinations in the laboratory and in
 pilot plants,   in some instances, activated carbon adsorption may
 prior  tr° JTr S^tances ^lectively (for  example, Pphenolsf
 prior  to  treatment by other methods.   Although activated carbon
 adsorption is  proving to be a powerful tool for  the  removal  of
 many  chemical  oxygen demanding and carbonaceous substances from
 evSf»SSer- StrfamS'  1VS   not  a  Panacea.    Its  use  must  be
 H™  ??  ^    !rmS  °f the  high  caPital  a^ operating costs,
 especially for charcoal replacement and energy,  and the  benefit
        C    carb?nace°us  and  oxygen  demanding  substances can
sometimes be  achieved  through  oxidation  by  chlorine,  ozone
               ATChl?riteS'  etC'    H°Weve*'  not °n" must the
                  bf S be assessed but certain ancillary effects,
  n    »   ,i                                              y  e
 such  as  (1,  the  production of  chlorinated  by-products   which   may
 be  more  toxic than  the  substance  being  treated,  (2) the  addition
 of  inorganic salts,  and  (3) the  toxic  effects  of  the  Sxidan?s
 crr8'-/^   be  taken   int°   acc^t.   Consequnt, wen
 chemical  oxidation  is  employed for  removal  of  COD,  it  may  be

 SSuS ^£f0Jnr thVreaTnt Wlth an°ther SteP to ««^e tSe
 wafers?                chemicals  prior  to discharge to receiving


 Degradation of oxygen  demanding substances may take place  slowly
 If sn^°nS  lf.fu"icie»tly long residence time can be provided!
 »L P? f  X^ Available, this may be  an economic choice.  Also, the
 use of land irrigation, or the "living filter" approach to  water
 purification,  is receiving selected attention.  01?ra-f StrSiSn
 Spnre^rSe 0!rno^is' bcth of ^ich  are membrane techniques,  SvS
 species  bSt tL  hteChniCailY Capable °f rem°ving high molecular
 species, but they have not been shown  to  be  operationally  and

disSibuSon7 ofCtieVahle'   ,With  theSe techniquL, the moIecuSr
distribution of the chemical species determines the efficiency of
the separation.  They probably  have  limited  potential  in  the
of ^S , M  SYn^hetics industry,  due to the particular spectrum
of molecular weights occurring in the waste waters
                              235

-------
The concentration basis for BATEA for COD is either 130  mg/liter
as  demonstrated  in  an  activated  carbon  plant  (U)  or  that
concentration documented by plants  in  Table  VII-3.    The  BODJ
concentrations  which  are  attainable  by  biological  treatment
plants as expressed in the better waste water treatment plants as
presented in data from the synthetic resins segment (16) of  this
industry, are 15 mg/liter for Major Subcategory I and II products
and  25  mg/liter for Major Subcategory III and IV products.  The
removal of fluorides is on  the  same  basis  as  for  BPCTCA  as
outlined  in  Section IX.  Similarly, the limitations on mercury,
cadmium, and cyanides should be those prescribed  for  toxic  and
hazardous chemicals.

The  removal  of  oils  and  greases  to  a  concentration  of 10
mg/liter, copper to a concentration of 0.25 mg/liter,  and lead to
0.03 mg/liter is based on the concentrations attainable  (35) when
filtration is used for solids removal.

Waste_Load_Reduct ion_ Basis

The waste load  recommendation   for   BATEA  is   based   on  overall
loading   reduction  through  the   use   of  the  best  achievable
concentrations  and  the  reduction of waste water flows from  BPCTCA
to a  level between  the  EPCTCA waste water flows and the  verified
BADT   waste   water  flows  as described in Section XI.   These flows
are given  in Table  X-1.
                                236

-------
  BATEA_Waste_Water
TABLE X-1

        Flow gates
Alkyd Molding Compounds and
 Unsaturated Polyester Resins

Cellulose Nitrate

Ethylene-Vinyl Acetate

Fluorocarbons

Polyamides  (Nylon 6/12 only)

Polyester Eesins
 (Thermoplastic)

Polypropylene Fibers

Polyvinyl Butyral

Silicones
 multi-products
 fluid products

*See footnote page 212a
   121
    21.9
1.83
125
2.50
91.7
6.67
7.92
9.17
220
15,000
300
11,000
800
950
1,100
14,500
 2,625
                             237

-------
Increased efficiency in the utilization of  water  combined  with
closer  operational  control  to prevent pollutants from entering
waste water streams have the greatest promise  for  reducing  the
amounts  of  pollutants  discharged  from  waste  water treatment
plants.  While the reduction of water usage may  directly  reduce
the  total  emission  of  certain  pollutants,  it  may mean that
advanced waste water treatment systems become  more  economically
feasible.

Variability

The  variability  factor  for  BATEA  guidelines  is based on the
variability determined by data from BPCTCA.  Both the monthly and
daily variabilities are based on  two  standard  deviations.   As
technology  and  plant  operations  improve,  it is expected that
these variabilities will become more stringent.  The  BOD5,  COD,
and  TSS  variabilities  are  presented  in  Table  X-2.  The TSS
factors are based on data obtained from multi-media filters  used
    the  petroleum  refining  industry.  The other parameters are
in
based on the achievable- concentration for monthly maximum
variability factor of  2 to determine the daily maximum.

                            TABLE X-2
                                                           and
                    Variability Factors BATEA

                          BOD5 and COB
                       Monthly      Daily
                                                    TSS
                                             Monthly    Daily
 Major Subcategory I      1.6
 Major Subcategory II    1.8
 Major Subcategory III    2.2
 Major Subcategory IV    2.2
                                    2.4
                                    2.8
                                    3.0
                                    3.0
1.7
1.7
1.7
1.7
2.0
2.0
2.0
2.0
 Based  on  the  factors  discussed  in this  section,  the  Effluent
 Limitations Guidelines for Best Available  Technology  Economically
 Achievable, BATEA,  are presented in Tables X-3 and X-4.
                               238

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                                    TABLE  X-3

BiST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE EFFLUENT  LIMITATIONS GUIDELINES
                        [kg/kkg  (lb/1000 Ib) of production]

Fo;:-
r.^;e
Nj.
1
2

3
5
6
7
5
NO
$ 9

10
11
u


14
15
Subcategory
Ethylene -Vinyl Acetate Copolyseca
f luorocarbons

Po:>Trcf>lcne fiber
Pol>vinylldene Chloride
Acrylic Resins
Cellulose Derivatives
Alkyds and Unsaturated Polyester Realm
Cellulose Nitrate

?ol..aaiJ«s (Nylon 6/12 only)

Polyester Resins (theraoplastlc)
Polyvln; 1 Ejtyral
PclvvJi'yl Ethers
Sili.cor.ee
fluid Product Plants

N'itrile Barrier Kesins
Spandex Fibers
Maximum Average of Maximum for Any
Dally Values for Any One Day
Period of Thirty
	 Consecutive B... 	
0.06

2.2
0.22
Mo numerical guidelines-see
In footnote
..
0.10

6.9
0.37

0.44
Mo numerical guidelines-see
In footnote

6.7
1.2
No numerical guidelines-see
in footnote
0.09

3.3
0.33
dlacusaion
„
0.14

9.4
0.50

0.59
disrusslon

9.1
1.6
diacusaion
COD
Maximum Average of Maximum for Any
Dally Values for Any One Day
Period of Thirty
Consecutive Davs
0.19 0.29

4.0 5.9
0.40 0.59
No numerical guidelines-see discussion
In footnote
ti „

0.52 0.7«

34 47
1.9 2.6

2.3 3.1

In footnote

35 , *'
6.3 8.5
Mo numerical guidelines-see discussion
in footnote
S!T_: I £3' SCU35
Kaxir.uT Avcr.-.ge of Kaxi-ui fcr Av.
Daily V-.'.utf for Any G.i* 3iv
Period c: Tdirty
0.04 C.C5

1-6 :.S
0.16 ;';-
So numerical juiii-1 ;n< '-c«i li-."-. . .-
in frot.iclv

0.03 :. :

2.1 ; .

0.11 c.:;
0.14
,..,
in fo tr,ul<

2.0 2.4

0.37 ;.„
No nuaerical guidelinc5-%»,* iisr i\t ;-:.
In fCuCnoc*?

-------
                                                                  FOOTNOTES   FOR  TABLES     X-3
NJ
£»
O
1.  Ethvlene -Vinyl Acetate (EVA)  CopolTner.  Two of the five
    known producers were contacted.   All plants are located
    at polyethylene production facilities.  Water use and
    wastewater characteristics for EVA are essentially Iden-
    tical to those for low density polyethylene.  However,
    an e'mulsion polymerization process Is known and produce!
    a distinctly different waste load which Is essentially
    that of polyvinyl acetate emulsion polymerization
    reported In EPA 440/1-73/010.  Both multi-plant and
    municipal cewage treatment is used.

2.  Tluorocaibons . Three o{ the seven manufacturing plants
    were visited.  A wide range of products are produced.
    The most important la polytetraf luorethylene  (PTFE) and
    these guide] Ines are recommended for PTTE granular and
    fine powder  grades only.  The wastewater discharges
    differ  considerably depending upon the process recovery
    schenes for  hydrochloric acid and the disposal of selec-
    ted  streacs  by deep well,  ocean dumping or off-site
    contract methods.  The use of ethylene glycol  in a pro-
    cess can significantly affect the waste loads. Fluoride
    concentrations In untreated wastewaters are generally
    below levels attainable by alkaline  precipitation.

 3.  Polypropylene Fibers. Two of  the three producers were
    contacted. The volumetric flow  ranges per  unit of pro-
    duction vary widely depending upon  the  type of cooling
    system  used.   The waste loads are  for plants  where selec-
    ted  concentrated wastes are  segragated  and disposed   of
    by landfllling,  etc.  Primary  treatment  at  one plant  site
    was  observed while  the other  plant  discharges to  a
    lounicipal  sewage  system.

 *.  PolyvinyHdene Chloride.  The  two major  manufacturers
    were contacted.  Both plant  sites  send wastewaters to
    multi-plant  treatment plants  of which the  polyvinylidene
     chloride is  a small portion.   Consequently, there was
     Insufficient data to develop recommended  guidelines.

 5.   Acrylic Resins. Three of  the four  manufacturers were
     contacted. Large numbers  of product grades are produced
     by bulk, solution,  suspension and emulsion polymeriza-
     tion.  Ihe widely varying hydraulic loads for the large
     number of products in addition to treatment of the waste-
     waters by nulti-plant wastewater treatment facilities
     prohibited obtaining sufficient meaningful data to
     recommend effluent limitation guidelines.
7.  Alkyds and Unsaturated  Polyester  Resins. Six  carefully
    selected plants were visited to provide  a  cross-section
    of the industry for size of operation,  type of manufac-
    turing process and wastewater treatment  methods.  Hydrau-
    lic loads vary widely depending upon the process  designs.
    Similarly, raw waste loads vary widely  because some
    plants segragate wastes for disposal in other manners.
    Generally, the industry discharges  wastewaters into
    municipal sewage systems and should continue. Also,  the
    type of air pollution control, e.g. combustion or scrub-
    bing, has a significant effect on the wastewater  load's.
    The recommended guidelines are for  plants  having  their
    own wastewater treatment system - a very Infrequent
    occurrence.
g.  Cellulose Nitrate. The two major manufacturers  of the
    four manufacturers were contacted.   These wastes  require
    pH control and contain large amounts of nitrates. One
    plant discharges to a municipal sewage  system while the
    other goes into a multi-plant treatment complex.
       6.   Cellulose  Derivatives. Cellulose derlvates investigated
           Included ethyl  cellulose, hydroxyethyl cellulose, methyl
           cellulose  and carboxynethyl cellulose. Wide' variations
           in unit  flow rates  for two plants producing the same
           product, differences  in nanufacturlng  techniques and th«
           availability of data  prevented  recommending guidelines.
           The wastewaters from  the  three  manufacturers  are being
           treated  In multi-plant wastewater treatment facilities
           or will  enter municipal sewage  systems.
 9,   Polyamides. Various polyamides are produced but only
     Nylon  6/12 produces significant amounts of wastewater,
     e.g. Nylon 11 uses no process water. Consequently, the
     guidelines are restricted to Nylon 6/12 and were develop-
     ed on  the basis of similarity with waste loads from
     Nylon  66  production.
10.   Polyester Thermoplastic Resins. There are three manu-
     facturers, two of which produce poly(ethylene, terephtha—
     late)  in  quantities less than 2Z of their total thermo-
     plastic production. The guidelines are recommended for
     poly(ethylene terephthalate) since the other product
     polyibutylene terephthdlate) is produced at only one
     plant  and the wastewater goes into a municipal sewage
     system, so no data on performance could be obtained.
11.   Polyvlnyl Butyral. Of three production sites,two have
     processes beginning with vinyl acetate monomer which
     generates much  larger wastewater volumes than the pro-
     cess beginning with polyvinyl alcohol. Since the manu-
     facturing sites  where production starts with a monomer
     discharge into  municipal sewage systesrs, there was no
     data available.  Consequently, the recommended guide-
     lines are only  for NSPS-BADT when starting with poly-
     vinyl alcohol  since any  other guidelines would be
     tantamount to  establishing  a permit  for  the production
     site.
12.  Polyvlnyl ethers. The  three present  plants use differ-
     ent processes  each of which produces  several grades of
     product.   The different chemical compositions used In
     both bulk and  solution  polymerization processes and th«
     lack of data on both  raw and  treated  wastewaters  pre-
     vented establishing  guidelines.  The wastewaters  ate
     presently sent to either multi-plant  treatment  facllitle
     or municipal sewage  systems.
                                                                                                                                     13. Silicones. lour companies manufacture sillcones at five
                                                                                                                                         locations.  Three planta were visited and data were
                                                                                                                                         obtained from all planta. The major processing steps at
                                                                                                                                         the five plants are shown below.
                                                                                                                                                Ma^or Processes at Five Sllicone Plants

                                                                                                                                            Plant No.            12345'
   CH-C1                   *     x  *
   Chlorosilane prod.      x  X  x  x  X
   Hydrolysis              x  x  x  x  x
   «uid., greases,        x  x  x  x  x
     emulsions  prod.
   Resin  production        x  x  x
   Elastomer production    x  x  x     x
   Specialties prod.*      x  x  x
   Fumed  silica prod.            x
   BC1  production                     x
   * e.g. surfactants, fluorinated  sillcones, coupling
      agents, and  other materials.

   Based  on  the manufacturing process, the wastewater flows
    and  the raw waste loads,  the  plants 1, 2,  3 were  desig-
   nated  as  multi-product plants while 4  and  5 were  desig-
   nated  as  fluid product plants.    Guideline   quantities
   based on  production  rates  that were estlcated
    from  sales  vol
                                                                                                                                                                 fo
                                                                                                                                                                     BPT.
14. Hltrlle Barrier Resins. Commercial scale production and
    sale of these resins has not yet begun.  The companies
    expected to have production facilities were contacted,
    and two provided estimates of raw waste  loads.  Because
    of the lack of demonstrated flows and raw waste loads,
    it was Impossible to establish effluent  guideline
    limitations.
IS. Spandex Fibers. Three manufacturers each produce
    Spandex fibers by significantly different processes.
    These are dry, wet and reaction spinning methods.
    Because of limited data on raw waste loads ana
    because each plant operates a different  process,
    it was impossible to establish meaningful guidelines.

-------
NJ
*>.
                                                      TABLE  X-4
                    BEST AVAILABLE TECHNOLOGY  ECONOMICALLY ACHIEVABLE EFFLUENT LIMITATIONS GUIDELINES
                                            (Other  Elements and  Compounds)
                    Product
           Alkyds and unsaturated
           polyester resins
           Fluorocarbons

           Spandex fibers

           Nitrile barrier  resins

           Polypropylene fibers

           Silicones

              Multi-product

              Fluid-product

           Polyester  resins
           (thermoplastic)
                                          Parameter
Lead
Mercury

Fluorides

Cyanides

Cyanides

Oils and grease


Copper
Copper

Cadmium
                              kg/kkg (lbs/1000 Ibs of Production)
                                                          Maximum average of daily
                                                          values for any period of
                                                          thirty consecutive days
                                                        Maximum
                                                        For Any
                                                        One Day
           0.000055               0.00011

Toxic and hazardous chemicals  guidelines  to apply

            0.6                    1.2

Toxic and hazardous chemicals  guidelines  to apply
           0.092


           0.03
           0.011
0.18


0.06
0.0055
                     Toxic  and  hazardous chemicals guidelines to  apply

-------
                           SECTION XI

                NEVv SOURCE PERFORMANCE STANDARDS
             BEST AVAILABLE DEMONSTRATED TECHNOLOGY
Definition	of	New	Source	Performance^Standards Best Available
Demonstrated TechnologY^iNSPS-EADTj          ~~

Based on the analysis of the information presented in Sections IV
to VIII, the basis for NSPS-BADT is defined below.

Best available demonstrated  technology  (BADT)  for  new  source
performance  standards   (NSPS)   is  based  on BPCTCA, the maximum
possible reduction of process waste water generation  as  defined
in  BATEA along with the application of granular media filtration
and chemical treatment for additional suspended solids and  other
element  removal  as  well as additional biological treatment for
further BOE5 removal as needed.

The_Standards

Achievable Effluent Concentration

The concentration basis for NSPS-BADT is the  same  as  that  for
BATEA for all parameters except COD.  The COD concentration basis
for   NSPS-BADT   is  based  on  the  concentrations  which  were
attainable in observed plants as expressed in  Table  VII-3.   In
cases  where attainable concentrations were not available as long
term  data,  the  BPCTCA  ratios  of  COD/BOD5  were   used   for
determining  COD.   To  determine  limitations,  the  variability
factors  determined  from  BPCTCA  are   applied   to   the   COD
concentration  basis.   By  the application of these factors, the
COD limitations are liberal,  do  not  determine  the  technology
required,  but in effect require that COD wastes be treated along
with the BOD_5 wastes.

Waste Load Reduction Basig

The waste water flow basis for NSPS-EADT is based on  the  lowest
verified  flows  associated  with  each product.  The waste water
basis ranges from 0 to 50 percent of  the  BPCTCA  basis  and  is
product specific.  water flows are summarized in Table XI-1.

It  is  apparent  that  effluent  limitations standards requiring
significant reductions over that attainable by  best  practicable
control   technology   currently   available    (EPCTCA)   requires
considerable  attention  to  both  the  process   generation   of
waterborne  pollutants  as well as the water use practices of the
plant.

Variability

The variability factors for  BADT  standards  are  based  on  the
variability  factors determined for BPCTCA for BODS and COD.  The
                              243

-------
                            TABLE XI-1

               LOWEST DEMONSTRATED WASTEWATER FLOWS



Product Subcategory                 cu meter/kkg      gal/1000 Ibs


Alkyd molding compounds
and unsaturated polyester
resins                                     0.33              40

Cellulose nitrate                        108             13,000

Ethylene-vinyl acetate                     2.09            250

Fluorocarbons                             33              4,000

Polyamides (Nylon 6/12 only)               6.7              800

Polyester resins -  (thermoplastic)         7.9              950

Polypropylene fibers                       1.67             200

Polyvinyl butyral                         47              5,600

Silicones

   Multi-products                        100             12,000

   Fluid products                         10.4            1,250
                               244

-------
TSS  variability  factors  are   1.7  monthly  and  2.5  daily  as
demonstrated  by  multi-media  filtration  data obtained from the
petroleum industry.   The  other  parameters  are  based  on  the
achievable  concentration  for  monthly maximum and a variability
factor of 2 to determine the daily iraximum.
        nd Unsaturated_Poly_esters
In the manufacture of alkyds and   unsaturated  polyesters,  there
are three main sources of process-related waste water:
    1.   Water of reaction
    2.   Scrubber water
    3.   Reactor cleancut water
(Surface condensers are assumed to be used instead of  barometric
type.)

Minimum  discharge may be achieved by  (1) reducing in-plant water
usage through good housekeeping and water conservation practices,
(2)  recirculating scrubbing  water  until  the  concentration  of
organic  material in that water is sufficiently high to allow for
periodic  incineration.   If  the   organics   are   sufficiently
concentrated  the  combustion may be self-supporting,  (3)  reusing
reactor cleanout water to the maximuir permissible, then combining
it with  the  water  of  reaction,  concentrating  the  blend  by
evaporation and sending the resulting waste to contract disposal.

Based  on  the  factors discussed in this section, the New Source
Performance Standards for Best Available Demonstrated  Technology
(NSPS-BADT)  are presented in Tables XI-2 and XI-3.
                             245

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                               TABLE  XI-2

BEST AVAILABLE  DEMONSTRATED TECHNOLOGY NEW SOURCE  PERFORMANCE STANDARDS
                   [kg/kkg (lb/1000 Ib) of production]
Foot-
note
No.
1
2
3
4
5
.6
j ?
a>
9
10
11
12
13


14
15
Subcategory
Ethylene-Vinyl Acetate Copolymers
Fluorocarbons
Polypropylene fiber
Polyvinylidene Chloride
Acrylic Resins
Cellulose Derivatives
Alky da and Unsatursted Polyester Resins
Cellulose Nitrate
Jolyamides (Hylon 6/1? only)
Polyester Resins (thermoplastic)
Polyvinyl Butyral
Polyvinyl Ethers
Slllcones
Multi-Product Plants
Fluid Product Plant*
Hitrlls Barrier Resin*
Spandex Fibers
__ _
Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Days
0.05 0.10
0.80 1.60
0.04 0.08
No numerical guidelines-see discussion
in footnote.
n n
« ii
0.02 0.03
6.0 11
0.37 0.67
Q. 44 0.80

No numerical guidelines-sea discussion
in footnote

5.5 -0
0.57 1.0
Ho numerical guidelines-see discussion
in footnote.
n "
COD
Maximum Average of Manlmimi for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Days
0.22 0.40
1.4 2.9
0.07 0.14
Ho numerical guidelinea-sae discussion
in footnote
„
00.11 0.20
30 54
1.9 3'*
6.5 12

Ho numerical guidelines-see discussion
in footnote

46 82
4.7 6.5
Ho numerical guidelines-see discussion
In footnote.
Suspended Solids
Maximum Average of Mayimina for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Days
0.04
0.57
0.03
Ho numerical guidelines-see
In footnote
"
0.0 06
1.8
0.11
0.14

No numerical guidelines-see
in footnote

1.7
0.18
Ho numerical guidelines-see
In footnote
0.05
0.83
0.04
discussion
"
0.008
2.7
0.17
0.20

discussion

2.5
0.26
discussion

-------
FOOTNOTES  FOR  TABLE   XI-2
Ethylene-Vlnyl Acetate (EVA) Copolymer. Two of the fiv«     7.
known producers were contacted.  All plants are located
at polyethylene production facilities.  Water use and
wastewater characteristics for EVA are essentially Iden-
tical to those for low density polyethylene.  However,
an emulsion polymerization process is known and produces
a distinctly different waste load which is essentially
that of polyvlnyl acetate emulsion polymerization
reported in EPA WO/1-73/010.  Both multi-plant and
municipal sewage treatment is used.
Fluorocarbons. Three of the seven manufacturing plants
were visited.  A wide range of products are produced.
Tile most important is polytetrafluorethylene (PTFE) and
these guidelines are recommended for PTFE granular and
fine powder grades only.  The wastewater discharges
differ considerably depending upon the process recovery
scheaes for hydrochloric acid and the disposal of selec-
ted streams by deep well,  ocean dumping or off-site
contract methods.  The use of ethylene glycol in a pro-
cess can significantly affect the waste loads. Fluoride
concentrations in untreated wastewaters are generally
below levels attainable by alkaline precipitation.
Polypropylene Fibers. Two of the three producers were
contacted. The volumetric flow ranges per unit of pro-
duction vary widely depending upon the type of cooling
system used.  The waste loads are for plants where selec-
ted concentrated wastes are segregated and disposed  of
by landfllling, etc. Primary treatment at one plant sita
was observed while the other plant discharges to a
municipal sewage system.

Pplyvlnylidene Chloride. The two major manufacturers
were contacted. Both plant sites send uastewjters to
multi-plant treatment plants of which the polyvlnylldene
chloride Is a snail portion.  Consequently, there was
insufficient data to develop recommended guidelines.
Acrylic Resins. Three of the four manufacturers were
contacted. Large numbers of product grades are produced
by bulk, solution, suspension and emulsion polymeriza-
tion.  The widely varying hydraulic loads for the large
number of products in addition to treatment of the waste-
waters by nulti-plant wastewater treatment facilities
prohibited obtaining sufficient meaningful data to
reccnzzend effluent limitation guidelines.

Cellulose Derivatives. Cellulose derlvates investigated
Included ethyl cellulose, hydroxyethyl cellulose, methyl  12.
cellulose and carboxymethyl cellulose. Wide variations
in unit flow rates for two plants producing the same
product, differences in manufacturing techniques and the
availability of data prevented recommending guidelines.
The vastewjters from the three manufacturers are being
treated in multi-plant wastewater treatment facilities
or will enter municipal sewage systems.
 8.
 9.
10.
11,
       Alkyda and Unsaturated  Polyester  Resins. Six carefully
       selected plants were visited  to provide a  cross-section
       of the Industry for size  oi operation, type of manufac-
       turing process and vastewjter treatment methods. Hydrau-
       lic loads vary widely depending upon  the process designs.
       Similarly, raw waste loads vary widely because some
       plants segragate wastes foi disposal  In other manners.
       Generally, the industry di£ charges wastewaters Into
       municipal sewage systems  at-d  should continue.  Also, the
       type of air pollution control, e.g. combustion or scrub-
       bing, has a significant effect on the wastewater loads.
       The recommended guidelines are for plants  having their
       own wastewater treatment  system - a very Infrequent
       occurrence.

       Cellulose Nitrate.  The  two major  manufacturers of the
       four manufacturers were cortacted.  These  wastes require
       pH control and contain  large  amounts  of nitrates. One
       plant discharges to a municipal sewage system while the
       other goes into a  multi-plant treatment complex.
       Folyaroldes.  Various polyamides are produced but only
       Nylon 6/12 produces significant amounts of uastewater,
       e.g. Nylon 11  uses no process water.  Consequently, the
       guidelines are restricted to  Nylon 6/12 and were develop-
       ed on the basis of similarity with waste loads from
       Nylon 66 production.
       Polyester Thermoplastic Resins. There are  three manu-
       facturers, two of  which produce poly(ethylene, terephtha-
       late) in quantities less  than 2T  of their  total thermo-
       plastic production. The guidelines are recommended for
       poly(ethylene  terephthalate)  since the other product
       poly(butylene  terephthalate)  Is produced at only one
       plant and the  wastewater  goes into a  municipal sewage
       system, so no  data on performance could be obtained.
       Polyvlnyl Butyral.  Of three production sites, two have
       processes beginning with  vinyl -acetate monomer which
       generates much larger wastewater  volumes than the pro-
       cess beginning with polyvinyl alcohol. Since the manu-
       facturing sites where production  starts with a monomer
       discharge into municipal  sewage systems, there was no
       data available.  Consequently, the recommended guide-
       lines are only for NSPS-BADT  when starting with poly-
       vinyl alcohol  since any other guidelines would be
       tantamount to  establishing a  permit for the production
       site.

       Polyvinyl ethers.  The three present plants use differ-
       ent processes  each  of which produces  several grades of
       product.    The different  chemical compositions used in
       both bulk and  solution  polymerization processes and the .
       lack of data on both raw  and  treated  vastewaters pre-
       vented establishing guidelines.   The  vastewaters are
       presently sent to  either  multi-plant  treatment facilltie
       or municipal sewage systems.
13. Slllconea. Four companies manufacture  sillcones  at  five
    locations.  Three plants were visited  and  data were
    obtained from all plants. The major  processing steps  at
    the five plants are shown below.
           Major Processes at Five Slllcone Plants
       Plant No.            12345
    CH3C1                   x     xx
    Chlorosilane prod.      x  x  x  x  x
    Hydrolysis              x  x  x  x  x
    Fluids, greases,
     emulsions prod.
    Resin production        x  x  x
    Elastomer production    x  x  x     x
    Specialties prod.*      x  x  x
    Fumed silica prod.            x
    HC1 production                      x
    * e.g. surfactants, fluorlnated sllicones, coupling
      agents, and other materials.

    Based on the manufacturing process,  the wastewater  flows
    and the raw waste loads, the plants  1, 2,  3 were desig-
    nated as multi-product plants while  4  and  5 were desig-
    nated as fluid product plants.'   Guideline  quantities
    based on  production  rates that were esc in.-, re d
    from sales volumes  for  BPT.

l** Nltrlle Barrier Resins. Commercial scale production and
    sale of these resins has not yet begun. The companies
    expected to have production facilities were contacted,
    and two provided estimates of raw waste loads. Because
    of the lack of demonstrated flows and  raw  waste  loads,
    It was impossible to establish effluent guideline
    limitations.

t»V-Spandex Fibers. Three maciufacturers  each'produc.*-
    Spandex fibers by significantly different  processes.
    These are dry,  wet and reaction spinning methods.   '
    Because of limited data on raw waste loads- and
    because each plant operates a different process,
    it was Impossible to establish meaningful  guidelines.

-------
                                                     TABLE   XI-3

                      BEST AVAILABLE DEMONSTRATED TECHNOLOGY - NEW SOURCE PERFORMANCE STANDARDS
                                           (Other Elements and Compounds)
                 Product
     Parameter
         kg/kkg (lbs/1000 Ibs of Production)
K)
£*
00
        Alkyds and unsaturated
        polyester resins
        Fluorocarbons

        Spandex fibers

        Nitrile barrier resins

        Polypropylene fibers

        Silicones

           Multi-product

           Fluid-product

        Polyester resins
        (thermoplastic)
Ke.rcury

Fluorides

Cyanides

Cyanides

Oils and grease



Copper

Copper

Cadmium
                                                        Maximum average of daily-
                                                        values for any period of
                                                        thirty consecutive days
                                                        Maximum
                                                        For Any
                                                        One Day
Toxic and hazardous chemicals guidelines to apply

            0.6                    1.2

Toxic and hazardous chemicals guidelines to apply
            0.017


            0.025
            0.0026
0.034


0.050
0.0052
Toxic and hazardous chemicals guidelines to  apply

-------
                            SECTION  XII

                          ACKNOWLEDGMENTS


 The  preparation  of  the  initial  draft report was accomplished
 through a contract with Arthur D. Little, Inc., and  the  efforts
 of  their staff under the direction of Henry Haley, with James I.
 Stevens and  Terry  Rothermel  as  the  Principal  Investigators.
 Industry  subcategory  leaders  were Robert Eller, Charles Gozek,
 Edward  Icteress,  and  Richard  Tschirch.   J.  E.   Oberholtzer
 coordinated  the sampling and analytical work and Anne Witkos was
 Administrative Assistant.
       t* Decker, Project Officer, Effluent  Guidelines  Division,
 through  his assistance, leadership, advice, and reviews has made
 an invaluable contribution to the  overall  supervision  of  this
 study and the preparation of this report.

 Allen  Cywin, Director, Effluent Guidelines Division, Ernst Hall
 Assistant Director, Effluent Guidelines Division, and  Walter  j'
 Hunt, Chief, Effluent Guidelines Development Branch,  offered many
 helpful suggestions during the program.                         Y

 The   members   of   the  working  group/steering  committee  who
 coordinated the internal EPA review are:

     Walter J. Hunt - Effluent Guidelines  Division (Chairman)
     Allen Cywin -  Effluent Guidelines Division
     David Becker - Effluent Guidelines Division (Project Officer)
     William Frick  - office of General Counsel
     Judy Nelson -  Office of Planning and  Evaluation
     Robert Wooten  - Region IV
     Walter Lee  - Region III
     Frank Mayhue - Office cf Research and Monitoring  (Ada)
     Wayne Smith -  National Field Investigation Center (Denver)
     David Garrett,  Office of Categorical  Programs
     Paul  Des Rosiers  -  office of Research and  Monitoring
     Herbert Skovronek - office of Research  and Monitoring

Acknowledgment  and  appreciation  is  also given  to the  secretarial
staffs  of   both  the  Effluent  Guidelines  Division and  Arthur D.
Little, Inc., for   the   administrative  coordination,  typing  of
drafts,    necessary  revisions,   and  final preparation  of  the
effluent  guidelines  document.    The  following  individuals  are
acknowledged  for their  contributions.  Brenda  Holmone, Kay Starr?
and  Nancy   Zrubek  -   Effluent   Guidelines  Division.  Mary Jan4
Demarco and Martha  Hananian, Arthur D. Little, Inc.

Appreciation  is extended to  staff members from EPA's Regions  III
and IV offices  for  their assistance and cooperation.

Appreciation  is also extended to both the Manufacturing Chemists
Association and  the  Synthetic  Organic  Chemical  Manufacturers
Association  for the valuable assistance and cooperation given to
                             249

-------
this program.  Appreciation is also extended to  those  companies
which participated in this study:

    Air Products and Chemicals, Inc.
    Allied Chemical Corporation
    Ameliotex
    American Cyanamid
    Aquitaine Societe Nationale des Fetroles
    Ashland Chemical Company
    BASF Wyandotte
    Celanese Chemical Company
    Chemplex Company
    Cook Paint and Varnish Company
    Diamond - Shamrock
    Dow Chemical Company
    Dow-Corning Company
    E.I. duPont de Nemours and Co., Inc.
    Durez
    FMC Corporation
    Freeman Chemical Corporation
    GAF Corporation
    General Electric Corporation
    Globe Manufacturing Corporation
    Goodyear Tire and Rubber Conpany
    Hercules, Inc.
    ICI American, Inc.
    Koppers Company
    Monsanto Company
    Pennwalt Corporation
    Phillips Fibers Company
    Plastics Engineering Company
    Reichhold Chemicals, Inc.
    Rilsan Industrial, Inc.
    Rohm and Haas Company
    SCM-Gl'idden-Durkee
    SWS Silicones
    Sherwin-Williams Company
    Standard Oil Company
    Swedlow, Inc.
    Tennessee Eastman
    3  M Company
    Union Carbide Corporation
    U.S. Industrial Chemicals
    U.S. Polymeric Company
    W. R. Grace, Inc.
                              250

-------
                           SECTION XIII

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                             251

-------
13.  Conway, R. A., et al. , "Conclusions from Analyzing
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                             252

-------
     P^rt_Azl  (5),  2375-2398  (1967).

 24. Jones, R. Vernon,  "Newest  Thermoplastic  -  PPS,"
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 26. Labine, R. A., ed.r "Flexible Process Makes Silicone
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 33.  "National Pollutant Discharge Elimination System,  Proposed
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     |ed§£|l_Re3ister  37 (234) ,  25898-25906  (December
     ->,  1 972) .

 34.  "Parylene Conformal Coatings,"  brochure prepared by
     Union Carbide Corporation,  New  York,  New  York.

 35.  Paterson, James W.  and Roger  A.  Minear, Wastewater  Treat-
     ment .Technology,  2nd Ed., January 1973, fo7~thi --------
     State of  Illinois Institute for  Environmental
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36.  "Polycarbonates - General Electric Company," Hydro-
    car bon_Proc ess ing ,  p. 262  (November 1965)  .     ----

37"  "^°cedures/  Actions and Rationale for Establishing
    Effluent Levels and Compiling Effluent Limitation


                            253

-------
    Guidance for the Plastic Materials and Synthetics
    Industries," Unpublished report of the Environmental
    Protection Agency and the Manufacturing Chemists
    Association, Washington, B.C. (November 1972).

38.  "Proposed Environmental Protection Agency Regulations
    on Toxic Pollutant Standards," 38 FR 35388,
    Federal^Register, December 27, 1973.

39.  shumaker, T. P., "Granular Carbon Process Removes  99.0
    to 99.2% Phenols," Chemical  Processing  (May 1973) .

40.  Sittig, M . , Or g an i c_C hemic al_Pr oc e s s_Ency.c lop.edi a ,
    2nd Edition, Noyes Development Corp., Park
    Ridge, New Jersey  (1969) .

41.  supplement to this report, Detailed Record of  Data Base.

42.  "Supplement B -  Detailed Record  of Data Base," Develop-
    ment J^ument_f^_Pr£^seJ_EfJluent_I^itay^n£
    ^idelajies_and_Ne\^Source_Performance_Standards
           ______
    Ind_i£nthetic  Materials_Manufacturing_Point
    Source_Catigory,,  Report  No.  EPA 440/1-73/010,
    Effluent  Guidelines Division,  Office of Air and
    Water  Programs,  U.S.  EPA,  Washington,  D.C.
     (September  1973) .

 43. Textile Organ, Textile Economics Bureau, Inc., New
    YorkT  New York.

 44. U.S.  Patent 2,964,509 (December 13, 1960),  D.  M. Hurt
     (to DuPont) .

 45. U.S.  Patent 2,994,668 (August 1, 1961), Eugene D. Klug
     (to Hercules Powder Company) .

 46. U.S.  Patent 3,144,432 (August 11, 1964), Daniel W.
     Fox (to General Electric Company) .

 47.  U.S.  Patent 3,354,129 (November 21, 1967), James T.
     Edmonds,  Jr.,  and Harold Wayne Hill, Jr. (to
     Phillips Petroleum Company) .

 48.  U.S.  Patent 3,426,102  (February  4,  1969),  T.  A. Solak
     and J. T. Duke  (to Standard Oil Company) .

 49.  Weaver,  D. Gray, ed. , and O'Connors, Ralph J.,  "Manu-
     facture  of Basic Silicone Products," Modern
     Chemical_Processe§,  6,  7-11 (1961) .
                             254

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                            SECTION  XIV

                             GLOSSARY
Refers  to that portion of  a  molecular  structure  which  is  derived
from  acetic acid.

Additign_Polyjneri z at ion

Polymerization without formation  of  a by-product  (in contrast   to
condensation polymerization.)

Aerobic

A  living  or  active  biological system  in  the presence of  free,
dissolved oxygen.

Alky.1

A general term for  monovalent aliphatic hydrocarbons.
A derivative of an acid, NH2CONHCOOH,  which   is  only  known  in
derivative forms such as esters.

Alumina

The oxide of aluminum.

Amorphous

Without apparent crystalline form.

Anaerobic

Living or active in the absence of free oxygen.

Annealincj

A • process  to  reduce  strains  in  a  plastic  by  heating  and
subsequent cooling.

AryJ.

A  general  term  denoting  the  presence  of  unsaturated   ring
structures in the molecular structure of hydrocarbons.
A polymer in which the side chain groups are randomly distributed
en  one  side  or  the  other  of the polymer chain.   (An atactic
polymer can be molded at much  lower  temperatures  and  is  more
                            255

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soluble   in  most  solvents  than  the  corresponding  isotactic
polymer, g.q.)•

Autoclave

An enclosed vessel where various conditions  of  temperature  and
pressure can be controlled.

Azeotrpjoe

A  liquid  mixture that is characterized by a constant minimum or
maximum boiling point which is lower or higher than that  of  any
of   the   components   and   that  distills  without  change  in
composition.

Backer io_st at

An agent which inhibits the growth of bacteria.

Slowdown

Removal of a portion of a  circulating stream to  prevent  buildup
of dissolved solids, e.g., boiler and cooling tower blowdown.

BOD5

Biochemical  Oxygen Demand (5 days as determined by procedures in
Standard  Methods)  19th   Edition,   Water   Pollution   Control
Federation,  or ~EPA«s  Manual   16020-07/71, Methods  for  Chemical
Analysis of  Viater and Wastes.^

Catalyst

A substance  which initiates  primary  polymerization or   increases
the   rate  of cure or crosslinking when added  in  quantities which
are  minor  as compared with the  amount  of primary  reactants.

Caustic_Soda

A name for  sodium hydroxide.

Chain Terminator

 An agent which,  when added to the ccirponents of a  polymerization
 reaction,   will  stop  the  growth  of  a  polymer chain, thereby
 preventing the  addition of MER units.

 COD

 Chemical Oxygen Demand (determined by methods  explained  in  the
 references given under EOD5.)
                             256

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 The  polymer  obtained  when two or more monomers are  involved in
 the polymerization reaction.

 Crggs-link

 A comparatively short connecting unit  (such as a chemical bond or
 a chemically bonded atom or group)  between  neighboring  polymer
 chains.

 Crystalline

 Having  regular  arrangement  of  the atoms in a space lattice —
 opposed to amorphous.
 A compound (usually an inorganic mineral)  added to  reduce  gloss
 or surface reflectivity of plastic resins or fibers.

 Dialysis

 The  separation  of  substances  in  solution  by  means of their
 unequal dzffusion through semipermeable membranes.

 2i§t=.2!2.§c
-------
Filtration

The removal of particulates from liquids by membranes on in-depth
media.

Formalin

A solution of formaldehyde in water.

Free_Radical

An atom or a group of atoms, such as triphenyl methyl   (C6H5)3C«,
characterized  by  the presence of at least one upaired electron.
Free radicals are effective in initiating many polymerizations.

Godet_Roll

Glass or plastic rollers around  which  synthetic  filaments  are
passed under tension  fcr stretching.

GPD

Gallons per day.

GPM

Gallons per minute.

Halogen

The    chemical   group  containing  chlorine,   fluorine,  bromine,
iodine.

Isotactic_Politner

A polymer in which the side chain groups  are all located  on  one
 side of the polymer chain.  See also "Atactic Polymer. "

 Lewis Acid

 A  substance capable of accepting from a base an unshared pair of
 electrons which then form a covalent bond.   Examples  are  boron
 fluoride, aluminum chloride.
 A polymer containing only units of one single monomer.

 Humectant

 An  agent  which  absorbs  water.   It  is  often  added to resin
 formulations  in order to increase water  absorption   and  thereby
 minimize problems associated with electrostatic charge.

 Influent
                             258

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 The flow of waste waters into a treatment plant.

 M

 Thousands (e.g.,  thousands metric tons).

 MM

 Millions (e.g., million pounds).

 Monomer

 A relatively simple compound which can react to form a  polymer.

 El

 A  measure   of  the  relative acidity  or  alkalinity  of  water  on  a
 scale  of 0-14.  A pH of 7  indicates a neutral  condition,   less
 than 7 an acid condition,  greater than 7  an  alkaline condition.

 Phenol

 Class   of  cyclic  organic  derivatives  with  the basic  chemical
 formula C6H50H.
A chemical  added to polymers tc  impart   flexibility,  workability
or distensibility.

Poly_mer

A  high  molecular weight organic compound, natural or synthetic,
whose structure can be  represented  by  a  repeated  small  unit
 (MER) .
A  chemical  reaction  in  which  the  molecules of a monomer are
linked together to form large molecules whose molecular weight is
a multiple of that of the original substance,  when two  or  more
monomers are involved, the process is called copolymerization.

Pretreatment

Treatment  of waste waters prior to discharge to a publicly- owned
waste water treatment plant.

Primary Treatment

First stage in sequential treatment of waste waters - essentially
limited to removal of readily settlable solids.

Quenchincj
                           259

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Sudden cooling of a warm plastic, usually by air or water.
Reflux
Condensation of a vapor and return of the liquid to the zone from
which it was removed.
Resin
Any of a class of solid or semisolid organic products of  natural
or  synthetic  origin, generally of high molecular weight with no
definite melting point.  Most resins are polymers.
Scrubber
Equipment  for removing condensable vapors and  particulates  from
gas streams by contacting with water or other liquid.
Second ary,_Treatment
Removal  of  biologically active soluble substances by the growth
of microorganisms.
Slurry
Solid particles  dispersed in  a  liquid  medium.
Spj.nnerette
A type  of  extrusion  die  consisting  of  a  metal   plate  with   many
small  holes   through  which   a mclten plastic  resin  is forced to
make  fibers and  filaments.
 Stable
Textile fibers of short length, usually  one-half to three inches.
 Stoichiometric
 Characterized by being a proportion of substances  exactly  right
 for  a  specific chemical reaction with  no excess of  any reactant
 or product.
 TDS
 Total dissolved solids -  soluble  substances  as  determined  by
 procedures given in reference under BOD5.
 Thermoplastic
 Having  property  of  softening  or   fusing  when  heated  and of
 hardening to a  rigid form again when  cooled.
 Thermosetting
                            260

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Having the  property  of  becoming  permanently  hard  and  rigid   when
heated or cured.
 TOG
Total  Organic  Carbon  -   a  method   for determining the organic
carbon content of waste waters.

Tow

A large number of continuous filaments of long  length.   Tow  is
the  usual form of  fibers after  spinning and stretching and prior
to being chopped into short lengths cf staple.

JJIa n sester if icati on

A reaction in which one ester is converted into another.

Vacuum

A condition where the pressure is less than atmospheric.

Ziealer-Natta_Catal^st

A  catalyst  (such  as  a   transition   metal   halide   or   an
organometallic   compound)    that   promotes  an  ionic  type  of
polymerization  of  ethylene  or  other  olefins  at  atmospheric
pressure  with  the  resultant  formation  of  a relatively high-
melting polyethylene or similar product.
                          261

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                                    TABLE XIV-1

                                   METRIC TABLE

                                 CONVERSION TABLE

MULTIPLY (ENGLISH UNITS)                   by                TO OBTAIN (METRIC UNITS)

    ENGLISH UNIT      ABBREVIATION    CONVERSION   ABBREVIATION   METRIC UNIT
acre                    ac
acre - feet             ac ft
British Thermal
  Unit                  BTU
British Thermal
  Unit/pound            BTU/lb
cubic feet/minute       cfm
cubic feet/second       cfs
cubic feet              cu ft
cubic feet              cu ft
cubic inches            cu in
degree Fahrenheit       °F
feet                    ft
gallon                  gal
gallon/minute           gpm
horsepower              hp
inches                  in
inches of mercury       in Hg
pounds                  lb
million  gallons/day    mgd
mile                    mi
pound/square
   inch (gauge)          psig
square feet             sq  ft
square inches            sq  in
 ton (short)             ton
yard                    yd
      0.405
   1233.5

      0.252
ha
cu m

kg cal
0.555
0.028
1.7
0.028
28.32
16.39
0.555(°F-32)*
0.3048
3.785
0.0631
0.7457
2.54
0.03342
0.454
,785
1.609
kg cal/kg
cu m/min
cu m/min
cu m
1
cu cm
°C
m
1
I/sec
kw
cm
atm
kg
cu m/day
km
(0.06805  psig +1)*   atm
       0.0929       sq m
       6.452        sq cm
       0.907        kkg
       0.9144       m
hectares
cubic meters

kilogram - calories

kilogram calories/kilogra
cubic meters/minute
cubic meters/minute
cubic meters
liters
cubic centimeters
degree Centigrade
meters
liters
liters/second
killowatts
centimeters
atmospheres
kilograms
cubic meters/day
kilometer

atmospheres  (absolute)
square meters
square  centimeters
metric  ton (1000 kilograt
meter
 * Actual conversion, not a multiplier
                                            262

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                     Protection Agency
TT C   TT1— •«• n -d /•> n TTT '! ' L (i J- •*• A -
U . O .
                  st'eet, Boom 16*0

                60604

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