EPA
 Group I, Phase II
     Development Document for
  Effluent Limitations Guidelines and
  New Source Performance Standards
               for the


        SYNTHETIC POLYMERS

           Segment of the
    PLASTICS AND SYNTHETIC
  MATERIALS MANUFACTURING
        Point Source Category
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

              JANUARY 1975

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                    DEVELOPMENT  DOCUMENT

                             for

              EFFLUENT LIMITATIONS GUIDELINES

                             and

              NEW SOURCE PERFORMANCE STANDARDS

                          for  the

              SYNTHETIC POLYMER  SEGMENT OF THE
      PLASTICS AND SYNTHETIC  MATERIALS MANUFACTURING
                   POINT SOURCE  CATEGORY
                      Russell E.  Train
                       Administrator
                       James  L.  Agee
Assistant  Administrator for  Water and Hazardous Materials
                                 i
                                 a
                        Allen Cywin
           Director, Effluent Guidelines Division
                      David L.  Becker
                      Project Officer
                        January 1975
                Effluent  Guidelines Division
          Office of Water and Hazardous Materials
            U.S. Environmental Protection  Agency
                  Washington, D.C.  20460
           For sale by the Superintendent of Documents, U.S. Government Printing Office
                     Washington, D.C. 20402 - Price $3.55

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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
    Polytetrafluoroethylene
    Polypropylene Fiber
    Alkyds and Unsaturated Polyester Resins
    Cellulose Nitrate
    Poly amides  (Nylon 6/12)
    Polyester Resins  (thermoplastic)
    Silicones

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

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

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

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                     TABLE OF CONTENTS


Section                                              Page

   I     CONCLUSIONS                                   1

  II     RECOMMENDATIONS                               3

 III     INTRODUCTION                                 13

           Purpose rand Authority                      13
           Methodology                                14
           General Description of the Industry        16
           Product and Process Technology             25
             Acrylic Resins                           27
             Other Pollutants                         33
             Alkyd Molding Compounds                  34
             Cellulose Derivatives                    35
             Cellulose Nitrate                        38
             Chlorinated Polyethylene                 41
             Diallyl Phthalate Resins                 44
             Ethylene-Vinyl Acetate copolymers        47
             Fluorocarbon Polymers                    50
             Nitrile Barrier Resins                   58
             Parylene Polymers                        62
             Poly-Alpha-Methyl Styrene                67
             Polyamides                               69
             Polyaryl Ether  (Arylon)                  70
             Polybenzimidazoles                       74
             Polybenzothiazoles                       79
             Polybutene                               82
             Polycarbonates                           86
             Polyester Resins  (Thermoplastic)         91
             Polyester Resins  (Unsaturated)           94
             Polyimides                               99
             Polymethyl Pentene                      104
             Polyphenylene Sulfide                   107
             Polypropylene Fibers                    112
             Polysulfone Resins                      117
             Polyvinyl Butyral                       122
             Polyvinyl Carbazole                     126
             Polyvinyl Ethers                        128
             Polyvinylidene Chlorides                133
             Polyvinyl Pyrrolidone                   135
             Silicones                               138
             Spandex Fibers                          145
             Other Pollutants                        151
             Urethane Prepolymers                    152
                                111

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                  TABLE OF CONTENTS Contd

Section                                              Page

  IV     INDUSTRY CATEGORIZATION                     157

   V     WASTE CHARACTERIZATION                      161

           Raw Waste Loads                           161

  VI     SELECTION  OF POLLUTANT PARAMETERS           167
           Selected Parameters
              BODS                                     I67
              COD                                     168
              Total  Suspended Solids                  163
           Other Pollutant Parameters                170
              Phenolic Compounds                      171
              Nitrogenous compounds                   171
              Flour ides                               172
              Phosphates                              173
              Oil and Grease                          174
              Dissolved Solids                        175
              Toxic  and Hazardous Chemicals           176
              Alkalinity, Color, Turbidity, and  the   176
                Metals Listed in Table V-3

 VII     CONTROL AND TREATMENT TECHNOLOGY            i79

           Presently Used Waste ^Water^ Treatment     I80
           Technology
              Copper                                  188
              Lead                                     188
              Mercury                                 I89
              Flouride                                189
              Cyanide                                 190
              Oil and^ Grease                          191

VIII     COST,  ENERGY, AND NONWATER QUALITY          193
         ASPECTS

           Cost Models of Treatment Technologies     194
           CostrEf fectiveness Perspectives           194
           AJQQU£i_c.°.st_P.ei:s|2§c.£ive.§                  194
           Cost Per Unit Perspectives                195
           Waste Water Treatment „ Cost Estimates     195
           Industrial Waste Treatment Model  Data     196
           Energy  cost Perspectives                  196
           Non Water Auality Effects                 197
           Alternative Treatment Technologies        197
                                IV

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                  TABLE OF CONTENTS Contd

Section                                             Page

   IX   BEST PRACTICABLE CONTROL TECHNOLOGY           237
        CURRENTLY AVAILABLE GUIDELINES AND
        LIMITATIONS

           Definition of Best Practicable Control     237
           Technology Currently Available  (BPCTCA)
           The Guidelines                             238
           Attainable Effluent Concentrations         239
           Demonstrated Waste Water Flows             243
           Statistical Variability of a Properly
           Designed and Operated Waste Water          243
           Treatment Plant                            243

    X   BEST AVAILABLE TECHNOLOGY ECONOMICALLY        251
        ACHIEVABLE

          Definition of Best Available Technology     251
          Economically Achievable  (BATEA)
          The Guidelines                              252
          Achievable EfTluent Concentrations          252
          Suspended Solids'                            252
          Oxygen-Demanding Substances                 253
          Waste Load Reduction Basis                  255
          Variability                                 257

   XI   NEW SOURCE PERFORMANCE STANDARDS - BEST       261
        AVAILABLE DEMONSTRATED TECHNOLOGY

          Definition of New Source Performance        261
          Standards Best Available Demonstrated
          Technology  (NSPS BADT)
          The Standards"261
          Achievable Effluent Concentration           261
          Waste Load Reduction Basis                  261
          Variability                                 263
          Alkyds and Unsaturated Polyesters           263
  XII    ACKNOWLEDGMENTS                              267

 XIII    REFERENCES                                   271

  XIV    GLOSSARY                                     277
                          v

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                      LIST OF FIGURES
Figure No.                                         Page

 III-l   Typical Reactions to Form Poly(Methyl
         Methacrylate) Including Monomer
         Manufacture                                28

 III-2   Acrylic Resin Production - Bulk Poly-
         merization Process                         29

 III-3   Acrylic Resin Production - Emulsion
         Polymerization Process                     31

 III-4   Acrylic Resin Production - Suspension
         Polymerization Process                     32

 III-5   Typical Reactions to Form Cellulose
         Derivatives                                36

 III-6   Cellulose Ethers Production                37

 II1-7   Typical Reaction to Form Cellulose
         Nitrate                                    39

 III-8   Cellulose Nitrate Production               40

 III-9   Typical Reaction to Form Chlorinated
         Polyethylene                               42

 111-10  Chlorinated Polyethylene Production        43

 III-ll  Typical Reactions to Form Diallyl
         Phthalate                                  45

 111-12  Ethylene-Vinyl Acetate Copolymer
         Production                                 48

 III-l3  Polytetrafluoroethylene (PTFE) Pro-
         duction - TFE Monomer Process              52

 II1-14  Typical Reactions to Form Fluorocarbon
         Polymers                                   53

 111-15  Polytetrafluoroethylene (PTFE) Pro-
         duction - PTFE Polymer Process             54

 111-16  Nitrile Barrier Resin Production -            »
         Emulsion Polymerization Process            61
                             VI

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                   LIST OF FIGURES Contd
Figure No.                                           Page

III-17    Typical Reactions to Form Parylene
          Polymers                                    63

111-18    Parylene Production                         65

111-19    Typical Reaction to Form Alpha-Methyl
          Styrene                                     68

III-20    Typical Reactions to Form Polyaryl Ether    71

111-21    Typical Reactions to Form Polybenzimid-
          azoles                                      75

III-22    Typical Reactions to Form Polybenzo-
          thiazoles                                   80

III-23    Typical Structures Produced in the
          Synthesis of Polybenzothiazoles             81

III-24    Typical Reaction to Form Polybutene         83

111-25    Polybutene Production - Huels Process       84

III-26    Typical Reaction to Form Polycarbonate      87

111-27    Polycarbonate Production - Semi
          continuous Process                          89

III-28    Thermoplastic Polyester Resin Production    93

III-29    Typical Reaction and Raw Materials Used
          to Form Unsaturated Polyester Resins        95

III-30    Typical Reactions to Form Polyimides       100

111-31    Typical Reactions to Form Polymethyl
          Pentene                                    105

III-32    Typical Reaction to Form Polyphenylene
          Sulfide                                    108

III-33    Polyphenylene Sulfide Production           110
                               VI1

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                   LIST OF FIGURES Contd

Figure No.                                          Page

III-34   Polypropylene Fiber Production             113

III-35   Polypropylene Monofilament Production      114

III-36   Typical Reactions to Form Polysulfone
         Resins                                     118

III-37   Polysulfone Resins Production              120

111-38   Typical Reaction to Form Polyvinyl
         Butyral                                    123

III-39   Polyvinyl Butyral Production - DuPont,
         Inc. Process                               124

III-40   Polyvinyl Butyral Production Monsanto,
         Inc. Process                               125

III-41   Typical Reaction to Form Polyvinyl
         Carbazole                                  127

111-42   Typical Reactions to Form Polyvinyl
         Ethers - Including Monomer Manufacture     129

III-43   Polyvinyl Ether Production - Solution
         Polymerization Process                     130

III-44   Polyvinyl Ether Production - Bulk Poly-
         merization Process                         131

111-45   Typical Reaction to Form Polyvinylidene
         Chloride                                   134

111-46   Typical Reactions to Form Polyvinyl
         Pyrrolidone                                136

111-47   Production of Silane Monomers, Oligomers,
         and Dimethyl Silicone Fluid                139

111-48   Production of Silicone  Fluids, Greases,
         Compounds Emulsions, Resins, and Rubber    140

111-49   Typical Reactions to Form Silicones        141
                              vin

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                   LIST OF FIGURES Contd


Figure No.                                          Page

III-50   Typical Reactions to Form Spandex Fibers   146

III-51   Spandex Fiber Production - Dry Spinning    147
         Process

III-52   Spandex Fiber Production - Wet Spinning
         Process                                    148

III-53   Spandex Fiber Production - Reaction
         Spinning Process                           150

III-54   Typical Reactions to Form Urethane Pre-
         polymers                                  153

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                       LIST OF TABLES
Table No.                                             Page

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

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

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

  IT-H    Best Available Technology Economically
          Achievable Effluent Limitations Guide-
          lines (Other Elements and Compounds)          9

  II-5    Best Available Demonstrated Technology -
          New Source Performance Standards            10

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

 III-l    Plastics and Synthetics for Consideration   18

 III-2    Products to be considered for Development
          of Effluent Guideline Limitations           22

 III-3    Products Eliminated From Consideration for
          Establishment of Effluent Guideline
          Limitations                                 24

 III-U    Manufacturers of Products to be Considered
          for Development of Effluent Limitations
          Guidelines                                  26

 II1-5    Commercial Fluorocarbon Polymers            57

 III-6    Properties of Polyaryl Ethers               72

 II1-7    Acids Whose Derivatives Are Used in
          Polybenzimidazole Synthesis                 76

  IV-1    Industry Subcategorization                  159
                             x

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                    LIST OF TABLES Contd
Table No.                                            Page

  V-l     Waste Water Loading for Synthetic Polymers  162
          Production

  V-2     Synthetic Polymers Production Raw Waste
          Loads                                       163

  V-3     Other Elements, Compounds, and Parameters   165

 VI-1     Other Elements and compounds Specific to
          the Resins Segment of Plastics and
          Synthetics Industry                         177

VII-1     Operational Parameters of Waste Water
          Treatment Plants  (Metric Units)             181

VII-2     Operational Parameters of Waste Water
          Treatment Plants  (English Units)            183

VII-3     Performance of Observed Waste Water
          Treatment Plants                            185

VII-4     Observed Treatment and Average Effluent
          Loadings From Plant Inspections             186

VIII-1     Perspectives on the Production of Syn-
           thetic Polymers - Water Usage              199

VIII-2     Perspectives on Synthetic Polymers
           Production - Annual Treatment Costs        200

VIII-3     Perspectives on Synthetic Polymers
           Production - Cost Impact                   201

VIII-U     summary of Water Effluent Treatment
           Costs - Cost Per Unit Volume Basis         202

VIII-H/1   Water Effluent Treatment Costs: Ethylene
           Vinyl Acetate  (Small Plant - Large
           Industrial Complex)                        203

VIII-4/2   Water Effluent Treatment Costs:  Ethylene
           Vinyl Acetate  (Large Plant - Industrial
           Complex)                                   204
                              XI

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                   LIST OF TABLES Contd
Table No.

 VIII-4/3



 VIII-U/4



 VIII-4/5


 VIII-4/6


 VIII-4/7


 VIII-4/8


 VIII-a/9


 vin-a/io


 VIII-4/11


 VIII-U/12


 VIII-4/13


 VIII-U/14


 VIII-4/15



 VIII-4/16
                                         Page

Water Effluent Treatment Costs:
Fluorocarbons  (Small Plant - Free
Standing)                                 205

water Effluent Treatment Costs:
Fluorocarbons  (Small Plant - Municipal
Discharge)                                206

WETC:  Fluorocarbons  (Large Plant -
Free Standing)                            207

WETC:  Fluorocarbons  (Large Plant -
Municipal Discharge)                      208

WETC:  Polypropylene Fibers  (Free
Standing Treatment  Plant)                 209

WETC:  Polypropylene Fibers  (Municipal
Discharge)                                210

WETC:  Polyvinylidene Chloride  (Small
Plant -  Industrial  Complex)               211

WETC:  Polyvinylidene Chloride  (Large
Plant -  Industrial  Complex)               212

WETC:  Acrylic Resins  (Small Plant -
Industrial Complex)                       213

WETC:  Acrylic Resins  (Large Plant -
Industrial Complex)                       214

WETC:  Cellulose Derivatives  (Small
Plant -  Industrial  Complex)               215

WETC:  Cellulose Derivatives  (Large
Plant -  Industrial  Complex)               216

WETC:  Alkyds  and Unsaturated  Polyester
Resins  (Large  Plant - Once-Through
Scrubber - Free standing)                 217

WETC:  Alkyds  and Unsaturated  Polyester
Resins  (Small  Plant - Recirculating
Scrubber - Municipal  Discharge)           2.18
                            XII

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                    LIST OF TABLES Contd
Table No.

 VIII-4/17



 VHI-4/18



 VIII-4/19


 VIII-4/20


 VIII-4/21


 VIII-4/22


 VIII-4/23


 VIII-4/24


 VIII-U/25


 VIII-4/26


 VIII-4/27


 VIII-4/28


 VIII-U/29


 VIII-4/30
                                         Page

WETC:  Alkyds and Unsaturated Polyester
Resins (Large Plant - Recirculating
Scrubber - Free Standing)                 219

WETC:  Alkyds and Unsaturated Polyester
Resins (Large Plant - Recirculating
Scrubber - Municipal Discharge)           220

WETC:  cellulose Nitrate  (Plant in
Industrial Complex)                       221

WETC:  cellulose Nitrate  (Plant with
Municipal Discharge)                      222

WETC:  Polyamides  (Nylon  6/12) Pro-
duction in a complex                      223

WETC:  Thermoplastic Polyester Resins
 (Large Plant - Industrial Complex)        224

WETC:  Polyvinyl Butyral  (Free Standing
Treatment Plant)                          225

WETC:  Polyvinyl Ether  (Plant in
Industrial Complex)                       226

WETC:  silicones  (Fluids  Only - Free
Standing)                                 227

WETC:  Silicones  (Fluids  Only - Indus-
trial Complex)                            228

WETC:  Silicones  (Multi-product -
Free Standing)                            229

WETC:  Silicones  (Multi-product -
Industrial Complex)                       230

WETC:  Nitrile Barrier  Resins  (Plant
in  Industrial Complex)                    231

WETC:  spandex Fibers  (Plant in
Industrial Complex)                       232
                             Xlll

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                    LIST OF TABLES Contd

Table No.                                             Page

 VIII-5/1    Industrial Waste Treatment Model Data
             Synthetic Polymers Production             233

 VIII-5/2    Industrial Waste Treatment Model Data
             Synthetic Polymers Production             234

 VIII-5/3    Industrial Waste Treatment Model Data
             Synthetic Polymers Production             235

   IX-1      COD/BOD5 Ratios                           240

   IX-2      Demonstrated Waste Water  Flows            244

   IX-3      Variability Factors  for BOD5              247

   IX-U      Best Practicable Control  Technology
             Currently Available  Effluent Limita-
             tions Guidelines                          248

   IX-5      Best Practicable Control  Technology
             Currently Available  Effluent Limita-
             tions Guidelines  (Other Elements
             and Compounds)                            250

    X-1      BATEA Waste Water Flow Rates              256

    X-2      Variability Factors  BATEA                257

    X-3      Best Available Technology Economically
             Achievable Effluent  Limitations Guide-
             lines                                     258

    X-4      Best Available Technology Economically
             Achievable Effluent  Limitations
             Guidelines  (Other Elements and Compounds) 260

   XI-1      Lowest Demonstrated  Waste Water Flows     262

   XI-2      Best Available Demonstrated Technology
             New Source Performance Standards          264

   XI-3      Best Available Technology Economically
             Achievable Effluent  Limitations
             Guidelines                                266

  XIV-1      Metric Units Conversion Table             285
                              xiv

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                         SECTION I

                        CONCLUSIONS
In  this  segment  of  the plastics and synthetics industry,
approximately 160 company operations are responsible for the
manufacture of products which have been grouped into fifteen
product subcategories.  Annual production  for  the  fifteen
products  was  estimated  to be 1.2 million kkg (2,6 billion
Ibs)  per year or  about  one-tenth  of  the  volume  of  the
eighteen  larger-volume resins surveyed earlier.  The volume
of effluents currently discharged was  estimated  to  be  90
thousand  cu  m/day   (24  MGD) .   Water  usage  (at  current
hydraulic loads) was projected to increase at 10 percent per
year  through  1977,  while  production  was  projected   to
increase at 14 percent in the same period.

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

Based  on these two dimensions of categorization, four major
subcategories were defined.
    Major Subcategory I - low waste load, low attainable
    BOD5 concentration (4 products:  ethylene vinyl
    acetate, polytetrafluoroethylene, polypropylene fiber,
    and polyvinylidene chloride).

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

    Major Subcategory III - high or low waste load,
    medium attainable BOD5_ concentration (7 products:
    alkyd and unsaturated polyester resins, cellulose
    nitrate, polyamides, saturated thermoplastic
    polyesters, polyvinyl butyral, polyvinyl ethers,

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    and silicones).

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

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

Annual  costs of treatment for the synthetic polymer segment
of the plastics and synthetics industry  were  estimated  at
$1.8 million.  By 1977, under BPCTCA guidelines and assuming
full  payment of user charges by this industry for municipal
treatment, it was  estimated  that  the  synthetic  polymers
industry  segment should expect annual costs of $5.0 million
- an increase of 23 percent per year.  By 1983, under  BATEA
guidelines, existing plants would be expected to have annual
pollution control costs of $12.0 million - an increase of 20
percent  per  year  between  1977  and 1983.  By 1977, under
BADT-NSPS and projected product growth, the annual costs for
new plants are estimated at  $3.3  million.   The  estimated
average  cost  of  treatment  over  the industry for BPCTCA,
BATEA, and BADT-NSPS technologies respectively  was:   $0.16
($0.63),  $0.t»0   ($1.52),  and $0.17 ($0.66) per cubic meter
(per thousand gallons).

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

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                         SECTION II

                      RECOMMENDATION S
BOD!5r COD, and total suspended solids and pH are recommended
as the critical parameters  requiring  effluent  limitations
guidelines  and  standards.   Other pollutant parameters are
specific  to  product  subcategories  as  indicated  in  the
following  list.  Some of these pollutants are identified as
being of potential concern, and others  as  being  ones  for
which  effluent  limitations  guidelines  and  standards are
recommended.
Subcategory

Alkyd compounds and
unsaturated polyester
resins
 Pollutant
Parameters

lead
cobalt
                      Guidelines
                     Recommended
Polytetrafluoroethylene  fluorides

Spandex fibers
                          x

                          x
Acrylic resins

Polypropylene fibers


Nitrile barrier resins


Polyamides

Cellulose derivatives

Cellulose nitrate

Silicones
cyanides
oils and grease
organic nitrogen

oils and grease

oils and grease
phosphates

organic nitrogen
cyanides

organic nitrogen

inorganic nitrogen

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

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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 were insufficient
data available to determine the magnitude of the  raw  waste
loads  or  their  concentration  in  treated  waste  waters.
However in most cases where metals are used, the combination
of neutralization and biological waste  water  treatment  is
expected  to  reduce  or  remove  them to low concentrations
which are within the recommended guidelines.  In the case of
mercury, cyanides, and cadmium the standards for  toxic  and
hazardous chemicals should apply.

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

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

-------
results  in  small volume, highly concentrated streams which
can be treated selectively or incinerated.

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

The levels of technology considered above as BPCTCA,  BATEA,
and   BADT-NSPS  are  the  bases  for  effluent  limitations
guidelines and standards of performance.  (Tables II-l,  II-
2,  II-3,  II-4, II-5, and II-6) .  The tables are based upon
documented   effluent   concentrations   attained   by   the
techniques  outlined  above or upon the engineering judgment
that available technologies from  other  industries  can  be
transferred to this one.

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

-------
                                       TABLE II-I

BEST PRACTICABLE  CONTROL TECHNOLOGY CURRENTLY AVAILABLE EFFLUENT LIMITATIONS  GUIDELINES
                           [kg/kkg (lb/]000 Ib)  of  production]

Foot-
note
No.
1
. 2
3
4
5
6
7
8
9
10
ii
12
13




14

Sub category
Ethylene-Vinyl Acetate Copolymers
Folytetr£fluoroethylene
Polypropylene Fiber
yolyvinylldene Chloride
Acrylic Resins
Cellulose Derivatives
Alkyds and Unsaturated Polyester Eeains
Cellulose Nitrate
Polyanides (Nylon 6/12 only)
Polyester Resins (thermoplastic)
Polyvinyl Butyral
Polyvlnyl Ethers
Silicons
Fluid
Greases, Emulsions,
Rubbers, Resins
Coupling Agents
Ultrile Barrier Resina
BOD
Maximum Average of Maximum for Anv
Daily Values for Any One Day
Period of Thirty
Consecutive Days
0.20 0.39
3.6 7.0
0.40 0.78
No numerical guidelines-sec discussion
in footnote
ii ii
"
0.33 0.60
14 26
0.66 1.20
0.78 1.4
No numerical guidelines-sea discussion
in footnote
it t«

1.0 1.9

13.2 "
8.2 15
No numerical guidelines-see dia -
CUSSion in footnote
SUSPENDED SOUDS
Maximum Average of Kaxiffiun for Any
Daily Values for Any Otve Bay
Period of Thirty
Consecutive Davs
0.55 1.0
9.9 18.0
1.1 2.0
No numerical guidelines-see discussion
la footnote
..
0.22 0.40
9.4 17
0.44 0.30
0.52 0.95
No numerical guidelines-see discussion
in footnote
"

0.69 1-25

8.8 It
5.4 10
No numerical guidelines-see dis-
       15
           Spandex Fibers

-------
                                          TABLE II-2

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

                         Mercury

 Polytetrafluoroetbylene  Fluorides

Spandex fiber            Cyanides

Nitrile barrier resins   Cyanides

Polypropylene fibers      Oils & grease
Silicones

    Fluids
                    Toxic and hazardous chemicals  guidelines to apply

                                0.6                   1.2

                    Toxic and hazardous chemicals  guidelines to apply
Copper
                                0.5
 0.005
                        1.0
0.010
    Greases, Emulsions,
    Rubbers and Resins    Copper

    Coupling Agents       Copper

Polyester resins       Cadmium
(Thermoplasti c)
                               0.067

                               0.042
                         0.13

                         0.084
                    Toxic  and hazardous  chemicals  guidelines
                    to apply

-------
                                    TABLE II-3

BiST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE EFFLUENT LIMITATIONS  GUIDELINES
                       [kg/kkg (lb/1000 Ib) of production]
Foct-
r.ot«
So.
1
2
3
A

5
j
B
CO,
•°
12
13





14

15
Subcategory
Ethylene-Vinyl Acetate Copolyoers
Polytetr«fluoro«thylen«
Polypropylene Fiber
PMyvinylidere Chloride

Acrylic Resins

Colluiose Nitrate
?clyaai,!es (Nylon 6/12 only)
Polyester Resins (thermoplastic)
Pclyvinyl Ethers
SilLcones

Fluid
Greases, Euldons,
Rubbers, Resins, and
Coupling Agents
Nitrile Barrier Resins

Spaadex Fibers
	 gpj)

Maximum Average of Maximum for Any
Dally Values for Any One Day
Period of Thirty
Consecutive Davs
0.19
2.2
0.22
No numerical guidelines-see
in footnote


0. 10
6.9
0.37
0.44
in footnote


0.57

6.4

No nuaerical guidelines-see
in footnote
"
0.29
3.3
0.33
discussion



0.14
9.4
0.50
0.59
"


0.28

8.8

discussion

"

COD Sl'srEMiD' SOL;3S
Maximum Average of Maximum for Any Maxiaura Avernge of Maj:}-ui f:r A">
Dally Values for Any One Day Daily Vnluc? fcr Any Coe L'-;y
Period of Thirty Period of Thirty
Consecutiye Davs Crn^i'cut ivc IV.v~
1.65
4.0
0.40
No numerical


0.52
34
1.9
2.3
No numerical


3

33.4

No numerical


l.U °'1* 0.16
5-9 1.6 1.?
J-59 0.16 C':JV
gujdeliin-a-see discussion No nunerical gu: j*.-l i:> =-:-... •, - -
in footnote in ni't.'.- tv

0.74 0.03 <-••<:«
47 2.1 * f
2-6 o.n «->J
3.1 0.14 Cjt
guidelines-see discussion No numerical guid-'.-i i •:^-~ •'•<:• .. - :
in footnote in Is ir.i. tt

4 0.21 0.18


*5'5 2.0 2.3

guidelines-see discussion No numerical gu;dolir.cs-s*:t: J; ;•
in footnote in footnote
*l M "

-------
                                           TABLE  II-4

         BEST AVAILABLE TECHNOLOGY  ECONOMICALLY ACHIEVABLE  EFFLUENT  LIMITATIONS  GUIDELINES
                                 (Other Elements  and Compounds)
         Product
Spandex fibers

Nitrile barrier resins

Polypropylene fibers

Silicones

   Fluids

   Greases, ^mulsions,
   Rubbers, Resins and
   Coupling Agents

Polyester resins
(thermoplas tic)
     Parameter
Alkyds and unsaturated
polyester resins

                          Mercury

Polytetrafluoroethylene   Fluorides
Cyanides

Cyanides

Oils and grease



Copper



 Copper

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

            0.6                    1.2

Toxic and hazardous chemicals guidelines to apply
            0.092
              .0026
0.18
  .0052
              .029                     .058

Toxic and hazardous chemicals guidelines to apply

-------
                              TABLE  II-5

BEST AVAILABLE DEMONSTRATED TECHNOLOGY  NEW SOURCE PERFORMANCE STANDARDS
                  [kg/kkg  (lb/1000 Ib)  of  production]
Foot-
note
Bo.
1
2
3
4

5
6
7
£ 0

10
11
12
13




14

IS
Subcstegory
Ethylene-Vinyl Acetate Copolymers
Poly tetrafluoroethy lens
Polypropylene Fiber
Polyvlnylidene Chloride

Acrylic Resins
Cellulose Derivatives
Alkyds and Unsaturated Polyester Resins
Cellulose Nitrate
PoIysMides (Hrlon 6/13 only)
Polyester Resins (thermoplastic)
Polyvinyl Butyral
Polyvinyl Ethers
Silicon**
Fluid
Creases, Emulsions,
Rubbers, Resins, and
Coupling Agent*
Hltrlle Barrier Eeains

Spudex fibers
BOD,

Maximum Average of Maximum for Any
Dally Values for Any One Day
Period of Thirty
Consecutive Days
0,18
0.80
0.04
No numerical guldellaes-see
In footnote
**
»
0.02
6.0
0.37
0.44

No numerical guidelines-see

.57

e C
J « J
No nu-wrical guide lines- a e»
in footnote
n
0.35
1.60
0.08
discussion

"
"
0.03
11
0.67
0.80

discussion

1.0

10

di«cu«lon

n
COD
Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Pays
1.8 3.5
1.4 2.9
0.07 0.14
Mo numerical guidelines-see discussion
in footnote
M It
.,
00.11 0.20
30 54
1.9 3'*
6.5 12

No numerical guidelines-see discussion
In footnote
4.7 8.5

45 82

No numerical guidelines-see discussion
In footnote

Suspended Solids
Minimum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Days
0.13
0.57
0.03
No numerical guidelines-see
in footnote
"
"
0.0 06
1.8
0.11
0.14

No numerical guidelines-see

0.18

* 7
i. '
Ho numerical guidelines-see
In footnote
»
0.19
0.83
0.04
discussion

"
"
0.008
2.7
0.17
0.20

discussion

0.26

2 5

discussion

"

-------
                                             TABLE II-6

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

                          Mercury

Polytetrafluoroethylene   Fluorides

Spandex fibers

Nitrile barrier resins

Polypropylene fibers
Cyanides

Cyanides

Oils and grease
Silicones
   Fluids                 Copper

   Greases, Emulsions,
   Rubbers, Resins and
   Coupling Agents        Copper

Polyester resins          Cadmium
(thermoDlaPtic)
Toxic and hazardous chemicals guidelines to apply

            0.6                    1.2

Toxic and hazardous chemicals guidelines to apply
            0.017
                                 0.0026
0.034
                                   0.0052
                                 0.025                  0.050

                    Toxic and hazardous chemicals guidelines to apply

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

 2. Polytenrafluoroethylene.  Three of the seven manufacturing
    plants were visited. A wide range of products  are produced.
    The most  important is polytetrafluoroethylene  (PTFE) and
    these guidelines are recommended for PTFE granular and
    fine powder grades only.  The wastewater discharges differ
    considerably depending upon the  process recovery schemes
    for hydrochloric acid and the disposal of selected streams
    by deep well, ocean dumping or off-site contract methods.
    The use of ethylene glycol in a  process can  significantly
    affect the waste loads.  Fluoride concentrations in
    untreated wastewaters are generally below lev  Is attain-
    able by alkaline precipitation.

3-  Polypropylene Fibers. Tvo of the three producers were
    contacted.  The volumetric flow ranges per unit of pro-
    duction vary widely depending  upon the type of cooling
    system used.   The waste loads are for plants where  selec-
    ted concentrated wastes are segregated and disposed  of
    by iandfilling, etc. Primary treatment at one plant site
    was observed while the other plant discharges to a
    municipal sewage system.

*•  P-Ql^yJ-nxlldene Chloride. The two major manufacturers
    were contacted. Both plant sites send wastewaters to
    multi-plant treatment plants of which the polyvlnylidene
    chloride is a snail portion.  Consequently, there was
    insufficient data to develop recommended guidelines.

5.  Aery11^__Resj.ns^, Three of the four manufacturers were
    contacted.  Large numbers of product grades are produced
    by bulk,  solution, suspension and emulsion polymeriza-
    tion.  The  widely varying hydraulic loads for the large
    number of products In addition to treatment of the  waste-
    waters by multi-plant wastewater treatment facilities
    prohibited  obtaining sufficient meaningful data to
    recoamend effluent limitation guidelines.

6.  pellulose Pertvatlyes. Cellulose derivates Investigated
    included ethyl cellulose, hydroxyethyl cellulose, methyl
    cellulose and carboxymethyl cellulose. Wide variations
    in unit  flow rates for two plants producing the aame
    product,  differences In manufacturing techniques and  the
    availability of data prevented recommending guidelines.
    The wastewaters from the three manufacturers are being
    treated  in  multi-plant wastewater treatment facilities
    or will  enter municipal sewage systems*
 7.  Alkyda and Unsaturated Polyester Regjjia. Six carefully
     •elected plants were visited to provide a cross-section
     of the industry for size of operation, type of manufac-
     turing process and wastewater treatment methods. Hydrau-
     lic loads vary widely depending upon the process designs.
     Similarly, raw waste loads vary widely because some
     plants segragate wastes foi disposal in other manners.
     Generally, the industry discharges wastewaters into
     municipal sewage systems ard should continue.  Also, the
     type of air pollution contiol, e.g. combustion or scrub-
     bing, has a significant effect on the wastewater loads.
     The recommended guidelines are for plants having their
     own wastewater treatment system - a very infrequent
     occurrence.

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

 '•  jPolxajBijg3• Various polyamides are produced but only
     Nylon 6/12 produces significant amounts of wastewater,
     e.g. Nylon 11 uses no process water. Consequently, the
     guidelines are restricted to Nylon 6/12 and were develop-
     ed on the basis of similarity with waste loads from
     Nylon 66 production*
\Q.  Poji^^er The^                 There are three manu-
     facturers, two of which produce poly(ethylene, terephtha-
     late) in quantities less than 21 of their total thermo-
     plastic production. The guidelines are recommended for
     polyfethylene terephthalate) since the other product
     poly(butylene terephthalate) Is produced at only one
     plant and the wastewater goes into a municipal sewage
     system, so no data on performance could be obtained.
11.  Polyvinyl Butyral. Of three production sites,two have
     processes beginning with vinyl-acetate monomer which  ~~
     generates much larger wastewater volumes than the pro-
     cess beginning with polyvinyl alcohol. Since the manu-
     facturing sites where production starts with a monomer
     discharge into municipal sewage systems, there waa no
     data available*.  Consequently, there are no recommended
     guidelines since they would be tantamount  to establishing
     a permit  for the direct discharger production site.
12*  Po 1 yviny 1___gth
-------
                        SECTION III

                        INTRODUCTION

Purpose and Authority

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

Section  301(b)  of  the  Act  requires the Administrator to
publish within one year of enactment of the Act, regulations
providing guidelines for effluent limitations setting  forth
the  degree  of  effluent  reduction  attainable through the
application  of  the  best  practicable  control  technology
currently  available  and  the  degree of effluent reduction
attainable through  the  application  of  the  best  control
measures  and  procedure  innovations, operation methods and
other alternatives.  The  regulations  proposed  herein  set
forth  effluent  limitations  guidelines pursuant to Section
304 (b) of the Act for  the  lower  volume  products  of  the
plastics   and   synthetic  materials  manufacturing  source
category.

Section 306 of the Act requires  the  Administrator,  within
one  year  after a category of sources is included in a list
published pursuant to Section 306 (b)  (1) (A) of the Act,  to
propose   regulations   establishing  Federal  standards  of
performances for new sources within  such  categories.   The
                           13

-------
Administrator  published  in the Federal Register on January
16, 1973 (38 F.R. 1624), a list  of  27  source  categories.
Publication  of  the  list  constituted  announcement of the
Administrator's intention  of  establishing,  under  Section
306,  standards  of  performance  applicable  to new sources
within the plastic  and  synthetic  materials  manufacturing
source   category,   which  was  included  within  the  list
published January 16, 1973.

Methodology

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

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

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

The  types of waste water control and treatment technologies
existing in the industry were identified.  This includes  an
identification   of  each  distinct  control  and  treatment
technology for both in-process  and  end-of-process  techno-
logies which are existent or capable of being engineered for
each subcategory.  It also includes an identification of the
pollutants  in  terms  of chemical, physical, and biological
characteristics,  and  the  effluent  concentration   levels
resulting  from the application of each of the treatment and
                          14

-------
control  technologies.   The  problems,   limitations,   and
reliability  of  each treatment control technology were also
identified as well as the time required for  implementation.
In  addition,  certain  other nonwater environmental impacts
were discussed, such as the effects of control  technologies
on  other  pollution problem areas (e.g., air, solid wastes,
noise, and radioactivity) .  Energy demand  requirements  for
each   of   the  control  and  treatment  technologies  were
developed, and the cost  of  applying  such  technology  was
estimated.

The   information  outlined  above  was  then  evaluated  to
determine what levels of waste water treatment  technologies
constituted   the   "best   practicable  control  technology
currently   available   (BPCTCA),"   the   "best   available
technology  economically  achievable (BATEA)," and the "best
available  demonstrated   control   technology,   processes,
operating  methods,  or  other alternatives." In identifying
such technologies, various factors were  considered.   These
include  the  total  cost  of  applying  the  technology  in
relation to the age of both the equipment and  the  facility
involved, the processes employed, the engineering aspects of
applying various types of control techniques through process
changes,  nonwater  quality  environmental impact (including
energy requirements), the treatability of waste water, water
use practices, and other factors.

The data for identification of industry  segments,  analyses
of  waste  water  generation  rates,   evaluation  of process
control  technology  and  determination   of   waste   water
treatment  technologies  were  developed  from  a  number of
sources.  These sources included public information from the
U.S. EPA research and development efforts, data from permits
filed under the 1899 Refuse Act permit program,  records  of
selected  state  agencies,  published literature, surveys of
waste  water  treatment  practices  by   the   Manufacturing
Chemists  Association  and  by  EPA  contractors,  qualified
technical consultants, interviews with  industry  personnel,
and  on-site inspection of manufacturing processes and waste
water treatment facilities.  References used  in  developing
guidelines   for   effluent  limitations  and  standards  of
performance of new sources reported here for this segment of
the plastics and synthetics  industry  are  essentially  the
same  as  those  reported  in  EPA 4UO/1-73/010  (16) and are
listed in Section  XIII  of  this  document.   Because  this
segment of the industry represents generally less well known
and   smaller   volume   products,  significant  amounts  of
information on manufacturing processes  were  obtained  from
the companies and are included in files developed to support
this Development Document.
                         15

-------
General Description of the Industry

The  plastics  and  synthetics industry is composed of three
separate segments:  the manufacture of the raw materials  or
monomers,  the  conversion  of  these  monomers into a resin
plastic  material,  and  the  conversion  of   the   plastic
materials  into  products  such  as  toys,   synthetic fiber,
packaging  film,  adhesives, and  so  on.   The  development
document for the first group of plastics and synthetics  (EPA
440/l-73/010a)  was concerned primarily with the manufacture
of  the  basic  plastic  or  synthetic  resins  (SIC  2821);
however,  also  included  were  the  production of synthetic
fibers such as nylon (SIC 2824),  man-made  fibers  such  as
rayon   (SIC  2823),  and  cellulose  film or cellophane  (SIC
3074).  The first industry grouping dealt  with  16  of  the
major resins, most of the major synthetic fibers, and all of
the  cellulose  fibers and cellophane film, that is, over 90
percent of the total volume of the industry.   Consequently,
this group of plastics and synthetic products deals with the
remaining  less  than 10 percent of the industry.  The large
number of products  (45) encompassed in this segment  of  the
industry  is  indicated  in  Table  III-l,  which  lists the
plastics and synthetics  fibers  to  be  considered  in  the
second   phase  of  the  work  on  development  of  effluent
limitations guidelines and new source performance standards.

The total production of this  segment  of  the  industry  is
approximately  1.2  million  kkg  (2.6 billion Ibs)  of which
approximately 0.7 million kkg (1.5 billion Ibs) is accounted
for in the production of unsaturated polyesters by  over  40
producers.  The remaining products are generally produced by
less  than four manufacturers.  Because many of the products
are manufactured  to  end  use  specifications,  it  is  not
possible to categorize the industry commercially except in a
very general way, such as price range, size product, size of
market,  or  potential  growth.   From a commercial point of
view, this segment of the synthetics and  plastics  industry
can  be  divided  into  four generally distinct groups.  The
first group is the relatively  new,  high  performance,  low
volume and high priced materials, e.g., selling generally at
over  $6.60/kg   ($3.00/lb)r  such as chlorinated polyethers,
methyl pentene,  phenoxy  resins,  parylene  phosphonitrilic
resins,  polyaryl  ether,  polybenzothiazoles,  polyethylene
amines, polybenzimidazoles,  polyimides,  polymethyIpentene,
polyphenylene   sulfide,   poly  alpha-methyl  styrene,  and
polyvinyl carbazol.  A second group is the  older  materials
which  have  a  significant market and, being medium priced,
are generally produced by a  limited  number  of  companies.
These   are  the  cellulosics,  polyvinyl  butyral,  diallyl
phthalates,       polytetrafluoroethylene,        silicones,
                         16

-------
pyrrolidines, and vinylidene chloride.  A relatively new and
fast  growing  third  group  encompasses  ionomers,  nitrile
barrier resins, polyphenylene oxide, and  polybutenes.   The
fourth  group  is those relatively large volume resins which
can  anticipate   good   growth   such   as   methacrylates,
polyesters, polycarbonates, and ethylene-vinyl acetate.
                          17

-------
                        TABLE II1-1

         PLASTICS AND SYNTHETICS FOR CONSIDERATION

Alkyd Molding Compounds
Amine Resins
Cellulose Acetate Butyrate
Cellulose Acetate Propionate
Cellulose Butyrate
Cellulose Nitrate
Cellulose Propionate
Chlorinated Polyethers
Chlorinated Polyethylene
Diallyl Phthalate Compounds
DuPont Nitrile Barrier Resins  (NR-16)
Ethyl Cellulose
Ethylene-Vinyl Acetate
Fluorocarbons
    CTFE  (Kel-F) Chlorotrifluoroethylene
    FEP
    TFE - Teflon Polytetrafluoroethylene
    PVDF - Polyvinyldifluoride
lonomers. Acrylics - Surlyn
LOPAC (Monsanto) + BAREX  (Sohio)   (Nitrile Barrier Resin)
Methyl Cellulose
Parylene  (U.C.)
Phenoxy Resins
Phosphonitrilic Resins
Polyallomer (PE/PP Copolymer)
Poly-alpha-methyl Styrene
Polyamides
Polyaryl Ether  (Arylon)
Polybenzimidazoles
Polybenzothiazoles
Polybutene
Polycarbonate
Polyethylene Imines
Polymethacrylonitrile Resins
Polymethylacrylate
Polymethyl Pentene  (ICI's TPX)
Polyphenylene Oxides (Noryl)
Polyphenylene Sulfide  (Ryton-Phillips)
Polypropylene Fibers
Polysulfones
Polyvinyl Butyral
Polyvinyl carbazoles
Polyvinyl Ethers
Polyvinyl Pyrrolidone
Silicones
Unsaturated Polyesters
                         18

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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.

    Directory of Chemical Producers, 1973, USA,
    Chemical Information Services, S.R.K.

    Modern Plastics Encyclopedia, 1972-1973,
    Suppliers-Resins and Molding Compounds.

    Plastics World. 1972-1973, Directory of the Plastics
    Industry.

    Chemical Horizons File, Predjcast, including
    updates to July 1973 (this includes references
    to journals such as chemical Week) .

    Chemical Marketing Reporter, "Chemical Profile"
    Section, from June 26,  1972, through July 23, 1973.

An exhaustive review of this information  indicated  it  was
often  impossible  to  delineate between basic producers and
distributors   of   compounds   or   products,   and    many
discrepancies  were found in reported production capacities.
Consequently, the literature sources were supplemented  with
information  from  both  the  contractor's  files and direct
contact with companies in order to establish that there were
three or more plants producing a specific  product  or  that
there   were  two  or  less  producers.   In  those  product
categories where only  two  producers  were  listed  in  the
original searches, the companies were contacted to ascertain
whether or not there were other producers.  Where only three
producers  were found originally, we contacted any companies
we were uncertain of to confirm that they were indeed  basic
                         19

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producers  and  not distributors.  Products selected for the
development of effluent limitations guidelines are listed in
Table III-2.  These include 13 from  the  original  list  of
Table  III-l  plus  the following three additional products,
which were found to meet the selection  criteria  and  which
were  not considered in the Phase I work of this contract or
by other EPA contractors:

    Polyamides (other than Nylon 6 and 66)

    Thermoplastic polyesters

    Spandex fibers

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

    1.  Misnomer or duplicates               4

    2.  Families of compounds or further     5
          generic groupings

    3.  Insufficient number of production   20
          sites                            	

          TOTAL ELIMINATED                  29

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

    (1)   Misnomers or duplicates

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

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

    Polymethacrylonitrile resins - combined with the
    more general category of nitrile barrier resins.

    Methyl pentene - another name for polymethyl
    pentene.

    (2)   Families of compounds or further generic
         groupings.
                         20

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The product, category "cellulose derivatives" was created  by
combining   methyl  cellulose,  ethyl  cellulose,  cellulose
propionate,  cellulose  acetate  propionate,  and  cellulose
acetate  butyrate from the original list plus two additional
materials,  hydroxymethyl  cellulose  and   carboxy   methyl
cellulose   (CMC).  This category was established because the
total production of these cellulose derivatives  was  judged
to  be important for the development of effluent limitations
guidelines, although none of the individual products is made
by more than two companies.  These  products  are  regrouped
below  into  general processes and the specific products are
shown.
                         21

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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
Nitrile barrier resins
Polyamides  (other than Nylon 6 and 66)
Polyester resins (thermoplastic)
Polyester resins (unsaturated)
Polypropylene fibers
Polytetrafluoroethylene
Polyvinyl butyral
Polyvinyl ethers
Polyvinylidene chloride and copolymers
Silicones
Spandex fibers
                        22

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Derivative

Alkali Processes

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

    Acid Processes

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

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

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

    DuPont's NR-16 (R)

    Monsanto*s Lopac (R)

    Sohio1 s Barex (R)

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

    (3) Insufficient number of production sites.

The remaining 20 products were eliminated from consideration
because no more than two manufacturing plants could be found
or  because  they  are manufactured in less than one million
pounds per year quantities at a  plant.   The  products  are
listed in Table III-3.
                        23

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                        TABLE III-3

           PRODUCTS ELIMINATED FROM CONSIDERATION
    FOR ESTABLISHMENT OF EFFLUENT GUIDELINE LIMITATIONS
     Product

Chlorinated Polyethers
Chlorinated Polyethylene
Diallyl Phthalate Compounds
lonomers
Parylene
Phenoxy Resins
Phosphonitrilic Resins
Polyallomer
Poly-alpha-Methyl styrene
Polyaryl Ethers
Polybenzimidazoles
Polybenzothi azoles
Polybutylene (called polybutene
  in Table I)
Polycarbonates
Polyethylene Imine
Polymethyl Pentene
Polyphenylene Oxides
Polysulfone
Polyvinyl Carbazole
Polyvinyl Pyrrolidone
Urethane Prepolymers
                       24

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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  whereas  polybutylene  is  a  specific
isomer of polybutylene used in film and pipe formation) , (2)
poly (vinyl  and  vinylidene)   chloride  was reinterpreted to
mean  polyvinylidene  chloride  since  effluent  limitations
guidelines  for  polyvinyl  chloride  were  developed in the
Phase I study, and (3) polymethyl  methacrylate  was  placed
into the more generic category "acrylic resins."

Those  companies  which  were determined to be manufacturers
(not  suppliers  or  distributors  only)  of  the   products
selected  for  consideration  in the development of effluent
limitations guidelines are shown in Table III-4.

Product and Process Technology

Brief descriptions of the chemical nature  of  the  products
and  the  manufacturing  process technology are presented in
this section  with  special  emphasis  on  indicating  those
process  operations  which  generate  waste  waters.   These
descriptions are presented in  alphabetical  order  for  the
products regardless of whether guidelines are established or
not.   In  some instances the only available information was
from  patents  and  the   literature   since   manufacturing
processes   remain   proprietary;   in   some  instances  no
information was available.
                       25

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                                      TABLE III-4
MANUTACTURERS OF PRODUCTS TO BE CONSIDERED FOR DEVELOPMENT OF EFFLUENT LIMITATION GUIDELINES


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Acrylic Resins

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

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

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

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

The  polymerization  of  methyl methacrylate shown in Figure
III-l, Equation 2, may be conducted in a  variety  of  ways.
In commercial casting of sheets of poly(methyl methacrylate)
each  sheet  is  cast in a mold assembled from two sheets of
plate glass spaced apart at  the  edges  by  a  gasket  (see
Figure III-2).  The mold is filled by pouring in a charge of
monomer with exact amounts of catalyst, colorant if desired,
or  other  additives  for  special effects.  The closed mold
then goes through a controlled temperature cycle,  generally
                        27

-------
(1)
       (CH3)2C(OH)(CN) +  H2SO4	 CH2 = C(CH2 )CONH2 • H2S04
       CH2 =C(CH2)CONH2 • H2SO4 +  CH2OH —CH2 = C(CH2 )COOCH3 + NH4HSO4
(2)     n

PPiOTH
1
_ CH3 _



COOCH3
pu p
— onT — *-* — ^— — ^~
OH ^


n
                                        (where n is 500 to 3000)
    FIGURE 111-1  TYPICAL REACTIONS TO FORM POLY (METHYL METHACRYLATE)
                  INCLUDING MONOMER MANUFACTURE
                                     28

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                                      REUSED MOLDS

MONOMER _
MIYIMf! _^_to*

f ATAI Y'lT
ADDITIVES
PARTING
AGENT

J
1 '


,.A. n POLYMERIZATION
MOLD » BATH OR
FILLING QVFW

i
AIR


OR
WATER
(CONTROLLED




I
CAST
SHEET
PRODUCT
i

MOLD
CLEANING

\

WASTE
WATER

TEMPERATURE)
FIGURE 111-2 ACRYLIC RESIN PRODUCTION - BULK POLYMERIZATION PROCESS

-------
between  40  and  75°C  (113  and  158°F).   Annealing often
follows the casting process.

Homo- and copolymers can also be conveniently prepared by an
emulsion technique.  In a representative procedure shown  in
Figure  III-3,  methyl  methacrylate  is  emulsified with an
anionic emulsifier and deionized water containing  a  little
ferrous sulfate and ammonium peroxysulfate.  The emulsion is
flushed  with  nitrogen and then treated at 20°C (68°F)  with
small  quantities  of  sodium  metabisulfite   and   t-butyl
hydroperoxide.   The temperature rises spontaneously to 70°C
(158°F)  and  the  polymerization  is  completed   at   this
temperature  in about 15 minutes.  After the batch is cooled
to room  temperature,  the  product  typically  contains  35
percent total solids with a viscosity of about 6 cp and a pH
of 2.5.

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

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

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

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

    3.   Inorganic  salts  are  often  added to increase the
         density of the aqueous medium, to reduce the  water
         solubility  of  the  monomers,  and to increase the
         interfacial tension of the system.
                       30

-------
                  VENT
MONOMER
           HOLD

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

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


      •* NON-CONTACT WATER


           FIGURE 111-4 ACRYLIC RESIN PRODUCTION - SUSPENSION
                       POLYMERIZATION PROCESS
                                  32

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

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

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

Other Pollutants

Oil and grease are due to the presence  of  lubricants  used
for  the extrusion process.  Depending on the specific waste
water chemical conditions and the analytical  methods  used,
cyanides may be detected due to the presence of cyanoacrylic
esters and acetone cyanohydrin.
                       33

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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
similar to unsaturated polyesters (see Unsaturated Polyester
Resin  section  of  this report).  The primary difference is
that in alkyds the acid component is supplied by long  chain
unsaturated  acids  rather  than  the  phthalic  and  maleic
anhydrides which are used in  unsaturated  polyesters.   The
primary  use  of alkyd resins is for paint formulations, but
they are also used in molding compounds.   The  alkyds  used
for  paints  are often made in the same plant as unsaturated
polyesters.  When used for paints, the  alkyds  are  diluted
with  the  appropriate paint solvent and sold as a liquid in
drums.  In this form  they  contain  no  monomeric  reactive
diluent.

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

Waste Water Generation - Waste water production in the poly-
merization process is  similar  to  that  described  in  the
section  on Polyester Resins.  The compounding steps are all
mechanical and do not generate liquid waste
                         34

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Cellulose Derivatives

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

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

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

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

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

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

Waste  Water  Generation - Wastes generated in production of
cellulose  derivatives  constitute  alkali,  salt,    solvent
residues,  pulp,  and  treatment  chemicals.   These  wastes
indicate relatively high  BOD,  COD,  and  dissolved  solids
levels   (41).   Organic nitrogen may be present in the waste
waters of facilities  where  nitrogen  containing  cellulose
derivatives  (other than cellulose nitrate) are produced.
                         35

-------
(1)   (C6Hi0Os)n +  CH3CI + NaOH	 methyl cellulose + NaCI + H20
(2)   (C6H1005)n +  C2H5CI + NaOH	 ethyl cellulose + NaCI +H2O
(3)   (C6H10O5)n +  CIC2H3O2Na+NaOH	 carboxymethyl cellulose + NaCI + H2O
(4)   (C6H100,L +  H2C-CH2 	-hydroxyethyl cellulose
                      \ /
                       0
  FIGURE  111-5  TYPICAL REACTIONS TO FORM CELLULOSE DERIVATIVES
                                     36

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 FRESH
SOLVENT
        I
SOLVENT
RECOVERY
  WASTE
                          CELLUOSE'     ALKALI
                               REACTION
PURIFICATION
   DRYING
   PACKING
                       REACTANT
                     { ETHYL CHLORIDE,
                   -METHYL CHLORIDE,
                    CHLORACETIC ACID,
                     ETHYLENE OXIDE)
-w-WASTE
  .WASTE
          FIGURE 111-6 CELLULOSE ETHERS PRODUCTIOIM
                             37

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Cellulose Nitrate

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

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

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

    1.   Washing with water to remove all acid.

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

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

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

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

Waste Water Generation - Aqueous  wastes  generated  in  the
manufacture  of  nitrocellulose  constitute  primarily acids
(both  nitric  and  suit uric)  and  alcohol  lost   in   the
dehydration  process.   Spent  acids are recovered as far as
possible,  but  some  are  inevitably  lost.    Alcohol   is
recovered  and  recycled.   Suspended  solids  in the wastes
include a small amount of cellulosic material.  The strongly
acidic wastes are handled by neutralization with lime.   The
calcium  sulfate  which is formed may be removed by settling
                          38

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(C6H1005)n  +  3HN03  +  H2S04^n±(C6H-,02 (IMO3)3)n  +  H20  +  H2SO4
     FIGURE 111-7  TYPICAL REACTION TO FORM CELLULOSE NITRATE
                                 39

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NITRICACID 	 - AC|D M|J(
TANKS *
OLEUM >
f
SPENT ^
ACID









f
1
SPENT
ALCOHOL
RECOVERY
SI ILLS "* 	 ' 	 	
1
1
WASTE
WATER
DRYFR

\
NITRATING
POTS
1
CFNTRlFUGF




BOILING TUBS
(STABILIZATION)

1
DIGESTER
(VISCOSITY
CONTROL)
1
BLENDING

\

DEHYDRATING
PRESS

\
PACKAGING
(ALCOHOL
WET)











	 ^.WASTE
WATER












FIGURE 111-8 CELLULOSE NITRATE PRODUCTION
                 40

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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 (122-1U9°F) are
used, and a suitable  catalyst  is  necessary  to  establish
economic reaction rates at atmospheric pressure.  Artificial
light  of  wavelength below U785 A and certain azo compounds
are effective for accelerating the reaction.  No catalyst is
needed, however, at reaction temperatures when pressures are
greater than 7  atmospheres   (100  psig)  or  greater.   The
reaction equation is given in Figure III-9.

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

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

Waste Generation - The primary waste generated  is  the  by-
product  hydrogen  chloride.   Recovery or other disposal of
hydrogen chloride (or hydrochloric acid vapor  or  solution)
would  be the primary environmental concern.  About 590 mass
units of HCl (dry basis) would be generated  per  1000  mass
units of product  (5t 10, 11, 40, 44, 45).
                          41

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        -f- CH2 — CH2 -b  +  CI2—*--(- CHCI— CH2 -b  +  HCI
FIGURE 111-9  TYPICAL REACTION TO FORM CHLORINATED POLYETHYLENE
                              42

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

       450
      1140
SOURCE; u.s. PATENT 2,954,509 BY D.M.HURT (TODUPONT)
       (DECEMBER 13, 1960).
         FIGURE 111-10 CHLORINATED POLYETHYLENE PRODUCTION
                                 43

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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  ortho-
phthalic   anhydride   to   produce  diallyl  orthophthalate
(trademark Dapon 35, FMC Corp.)  or  with  the  isophthalate
acid.   The isophthalate ester is identified as Dapon M, FMC
C orporati on.

The product can be used as either a low viscosity monomer or
as a higher molecular weight thermoplastic prepolymer.   The
allyl  monomers  and,  in  some  cases, the prepolymers find
utility as crosslinking agents for other  unsaturated  poly-
ester  resins, either in conjunction with or as a substitute
for styrene  monomer  which  is  the  conventional  reactive
diluent.   The  low  vapor  pressure at molding temperatures
(2.4 mm of mercury at 149°C or  300°F)   favors  the  use  of
diallyl  phthalate  over  styrene,  particularly  for larger
parts.  This low volatility permits allylic polyesters to be
molded at higher temperatures than styrene  polyester,  and,
as  a  result,  faster  molding cycles can be achieved  (30).
Another advantage of using the allylic monomers or  prepoly-
mers  as  the  reactive diluent in unsaturated polyesters is
that they result in formulations with lower volume shrinkage
on curing.

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

Diallyl phthalate prepolymer is also  used  as  a  surfacing
medium  for  decorative  laminates  and  in combination with
polyester resin systems  to  meet  the  growing  demand  for
economical, low pressure laminates.
                         44

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



            - COO CH2 CH = CH2
FIGURE 111-11  TYPICAL REACTIONS TO FORM DIALLYL PHTHALATE
                          45

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Manufacture  -  Conventional  polycondensation batch reactor
type technology is  used  to  form  the  diallyl  phthalate.
Conventional  free radical methods are used in extending the
molecular weight of the monomeric diallyl phthalate  (30).
                          46

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Ethylene-Vinyl Acetate Oopolymers

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

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

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

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

An EVA copolymer with distinctly  different  characteristics
from  those described above is produced by an emulsion poly-
merization process.  The emulsion copolymer has a very  high
vinyl  acetate content.  It is made at only one plant, which
is unrelated to those plants using the  LDPE  process.   The
emulsion  polymerization  process and associated waste water
loads are essentially the same as those reported  for  poly-
                         47

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                                       PEROXIDE
                                       INITIATOR
  VINYL
ACETATE'
ETHYLENE-
                COMPRESSOR
                     T
                                         l
                                   VINYL ACETATE
                                     RECYCLE
                           ETHYLENE
                            RECYCLE
AUTOCLAVE
SEPARATOR
               OIL LEAKAGE AND
                  SPILLS TO
               PROCESS SEWER
               EVA POLYMER
               a 450-500°C
              PLUS ENTRAINED
                  GASES
MONOMER
RECOVERY
                                                      OILS & WAXES
                                                      -  TO BOILER
                                                         AS FUEL
                                 ETHYLENE
                                 RECYCLE
                WET PELLETS
                                                       DRIED
                                                    EVA PELLETS
                                                   (7-40% VA byWt.)
                                                                                         MAKE-UP WATER



REFRIGERATION
COOLING


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

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vinyl   acetate  homopolymer  emulsion  in  EPA  Development
Document No. EPA 440/1-73/010 (61).

Waste Water Generation - In plants using LDPE equipment  for
EVA  production,  the  pelletizer cooling water is generally
recirculated through the refrigeration  cooling  system.   A
continuous  purge is maintained to control vinyl acetate and
polymer  fines  contamination  in  the  recirculated  water.
Vinyl  acetate  which enters the waste waters from the purge
stream is biodegradable both as the intact compound  and  in
the  form  of  its  hydrolysis  products,  acetaldehyde, and
acetic acid.

Other waste sources are oil leakage and spills from compres-
sors and pumps  which  enter  area  surface  water  drainage
ditches.   Washdown  water from processing and loading areas
also flows to the drainage ditches and is another source  of
vinyl  acetate  contamination.   The  waste  stream from the
ditches is skimmed to recover oil and  EVA  particles.   The
oil is incinerated and the EVA is either land-filled or sold
to scrap reprocessors (16, 25) .
                         49

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Fluorocarbon Polymers

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

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

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

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

A.  Polytetrafluoroethylene (PTFE)

1.  TFE Monomer Process
                         50

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

Manufacture  - TFE monomer is produced by continuous process
based on pyrolysis of chlorodifluromethane (Refrigerant  22)
as  indicated  by the flowsheet shown in Figure 111-13.  The
main reaction involved is shown at the top of Figure III-1U.
Various other fluorinated side products may also  be  formed
in minor amounts.

The  process  stream  from  the reaction furnace is scrubbed
first with water,  then  with  dilute  caustic  solution  to
remove  by-product  HC1 and other soluble components.  After
the caustic scrub, the  gas  stream  is  dried  either  with
concentrated sulfuric acid or with ethylene glycol.  The dry
gas  stream  is compressed and distilled to recover purified
TFE  monomer.   Extremely  pure  monomer  is  required   for
subsequent polymerization.

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

2.  PTFE Polymerization

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

PTFE is produced for sale in several forms:  a  granular  or
pellet form, a fine powder, and aqueous dispersion.  The dry
                         51

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               FURNACE
               REACTOR
Oi
K)
ALTERNATIVE
  DRYING
 METHODS
                              DILUTE
                               HC*
                                                    GLYCOL LOSS
                                                   AQUEOUS WASTE
DISTILLATION
                                            PURE
                                            TFE
                 FIGURE 111-13 POLYTETRAFLUOROETHYLENE (PTFE) PRODUCTION - TFE MONOMER PROCESS

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       Feedstock
                  Monomer
                                            Polymers
2CHF2CI 	 »-2HCI +
heat
(chlorodifluoromethane)
\



CF2CI-CH3 	 »- HCI
heat
(chlorodifluoroethane)

pr PI pr PI b»
" Metal Cat.
(trichlorotrifluoroethane)

CF2 =CF2
(TFE)

CH2 — (_,H2
(ethylene)
CF3
CF2 = CF
(HFP)

, pc pu
(VDF)

CI2 + CF: = CFCI
(CTFE)
+ CH2 =CH2
(ethylene)
. 	 ^-fCF2-CF2-)-n
(PTFE)
»» / ri i pi i rr
(ETFE)
	 *--fCF2-CF2-CF2
(FEP)
	 0— <-CF2~CH2-CF2
(VDF-HFP)
> ( CF CH )
(PVDF)
	 *— (-CF2-CH2-CF2
(CTFE-VDF)
	 »•- <-CF,-CFCI1-n
(PCTFE)

-CF2-)-n
CF3
-CF^n

CF3
-CF+n

-CFCI-hn

	 »--(-CH2-CH2-CF2-CFCI4-n
(ECTFE)
HC=CH
(acetylene)
  HF
(hydrogen
fluoride)
-*-  CH2 = CHF
      VF
-t-CH2-CHF-hn
   (PVF)
Source: Chemical Economics Handbook, Stanford Research Institute.
    FIGURE 111-14   TYPICAL REACTIONS TO FORM FLUOROCARBON POLYMERS
                                       53

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TFE
INITIATORS
WATER STABILIZERS
1 1
BATCH
POLYMERIZATION




if i

DISPERSION
GRADE

POLYMER
RECOVERY/ WASH
1
WASH
WATER


AQUEOUS WASTE
(SUPERNATE LIQUOR)




GRANULE

EXTRUSION/
PELLETIZING
CHILL WATER
FINE
POWDER
           FIGURE 111-15 POLYTETRAFLUOROETHYLENE (PTFE) PRODUCTION -
                      PTFE POLYMER PROCESS

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product  forms,  granular  and  fine powder, account for the
major portion of  PTFE  production.   Guidelines  have  been
proposed for these dry product forms only.  Dispersion grade
is  made by only two of the three plants presently producing
PTFE.

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

For granular or pellet grades, process water use in addition
to  polymerization  medium  includes polymer wash water and,
for   pellets,   chill   water   for   extrusion/pelletizing
operations.    The   process  water  discharged  from  these
operations is very clean.  In one  plant,  all  the  process
water  is  collected  and  recycled  through  a purification
system.  In the production of fine powder grade  PTFE,  wash
water  is  required  to  purify  the polymer particles.  The
conditions required to produce fine powder  grade  are  such
that  the  water  discharged  from  the  polymerization  and
washing steps may contain a higher level  of  suspended  and
dissolved solids than in the case of granular product.

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

B.  Other Fluor ocarbon Polymers

The  nature  of  other  fluorocarbon  polymers  produced  is
indicated  by the list presented in Table III-5.  Since most
of these polymers are proprietary and process technology  is
considered  highly  confidential, it is not possible to give
detailed process descriptions.   Reactions  taken  from  the
literature, indicating the routes to most of these polymers,
are given in Figure
The  polymerization step is comparable to that used for PTFE
in  that  the  polymerization  is  carried  out  in  aqueous
(purified  water) medium in batch kettles.  Subsequent steps
may vary significantly with the type of polymer and form  of
product  made.   These  steps  may include concentration and
stabilization  of  a  dispersion  form   of   the   product;
filtration  or  coagulation  to  recover  polymer particles;
polymer washing with water or solvent; conversion  to  final
                         55

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product,  form  by  drying  granules  or powder, extrusion of
pellet  or  film  forms,  or  solvent   casting.    Recovery
operations  to recover organic solvents or other proprietary
additives may also be associated with some  of  the  polymer
processes (6, 29, 30).
                         56

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                        TABLE III-5

              COMMERCIAL FLUOROCARBON POLYMERS


             Polymer                             Abbreviation


Polytetrafluoroethylene                               PTFE
Fluorinated Ethylene - Propylene                      FEP
Poly (ethylene - tetrafluoroethylene)                  ETFE
Chlorotrifluoroethylene                               CTFE
Poly(ethylene - chlorotrifluoroethylene)              ECTFE
Poly (chlorotrifluorothylene - vinylidene fluoride)    CTFE-VDF
Polyvinyl Fluoride                                    PVF
Polyvinylidene Fluoride                               PVDF
Poly(vinylidene fluoride - hexafluoropropylene)       VDF-HFP
                         57

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Nitrile Barrier Resins

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

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

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

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

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

A  typical polymerization procedure would involve a two-step
process in which the acrylonitrile butadiene graft copolymer
is made by batchwise emulsion  polymerization  of  a  recipe
such as that listed below (U8) .
                        58

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     Typical Latex Recipe               Parts   A^
                  ~~  ~                        ^/J!
     Acrylonitrile I3"   ^                40

     1,3-butadiene                       60

     Emulsifier                           2.4

     Azodiisobutyronitrile                0.3

     t-dodecyl mercaptan                  0.5

     Water                              200

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

The final resin is then prepared by mixing the following:

     Latex  (from reaction above)         31.9

     Acrylonitrile (or methacrylonitrile) 70

     Ethyl acrylate                      30

     Potassium persulfate                 0.06

     Emulsifier                           3.0

     n-dodecyl mercaptan                  1.0

     Ethylene diamine tetracetic acid     0.5

     Water                              200

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

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

Manufacture - The generalized batch process description  for
emulsion polymerization shown below is taken from EPA.
Development  Document  No.  440/1-73/010   (16)  along with a
generalized flowsheet shown as Figure III-16.
                        59

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A batch process, as shown  in  Figure  111-16,  is  commonly
used.   Typical  reactor  size  is 19 cu m (5000 gal.).  The
batch cycle consists of the  continuous  introduction  of  a
water-monomer    emulsion    to    the    stirred   reactor.
Polymerization occurs at about the rate of monomer addition;
the heat of reaction  is  removed  to  cooling  tower  water
circulated  through  the  jacket.   The  reactor  is  vented
through  a  condenser  for   monomer   recovery;   and   the
condensate, including any water, is returned directly to the
vessel.   On completion of the batch, a short "soaking" time
is allowed for completion of the reaction, and water is then
added to dilute to the desired end composition.   The  batch
is  drawn off through a screen to product storage.  Oversize
screenings  (a  very  small  amount)   are  disposed  of   to
landfill.

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

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

     o  Reactor cooling water

     o  Cooling tower and boiler blowdown

     o  Monomer washing

     o  Liquid or solid waste from monomer stripping
        or recovery operations

     o  Discarded Latex batches

     o  Coagulant wastes

     o  Startup, spills, etc.

     o  Demineralizer wastes

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

Other Pollutants

Organic nitrogen occurs as a result of losses from
dissolution and emulsification of reactants.
Cyanides will be detectable by analytical
methods due to the presence of acrylonitrile.
                        60

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     EMULSIFIER
PROCESS
 WATER
CATALYST
        i
   MONOMERS'
                       COOLING
                       WATER
   WASH WATER	
                         BATCH
                        REACTOR
                         CYCLE
              0*0
                        RECYCLED
                        MONOMER
                                    WASTE
                                    WATER
                                           SOLID
                                           WASTE
                                         COAGULATION
                                            TANK
                                                         c>o
                                                                     WASTE
                                                                     WATER
                                                                                   DRY
                                                                                 PRODUCT
         FIGURE 111-16 NITRILE BARRIER RESIN PRODUCTION - EMULSION POLYMERIZATION PROCESS

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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
dichlorodip-xylylene,  through  a  process  called pyrolytic
vapor  deposition  polymerization.   Di-p-xylylene  and  the
chloro  derivative  dichlorodi-p-xylylene  are  white,  high
melting crystalline solids.   Di-p-xylylene  has  a  melting
point  of  28<4°C  (543°F)  and  a  density  of  1.22  g/cm3.
Dichlorodi-p-xylylene has a melting point of 1UO-160°C (284-
320°F) and a density of 1.3.  Both are insoluble  in  water.
The reactions are illustrated in Figure 111-17, Equation 1.

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

The  polymerization  process is exceptional in that it takes
place in two completely distinct and  separate  steps.   The
first  involves  the cleavage of the two-methylene-methylene
bonds in di-p-xylylene by pyrolysis to form two molecules of
the reactive intermediate, p-xylylene.  This latter molecule
is stable in the  vapor  phase  but,  in  the  second  step,
spontaneously  polymerizes  upon  condensation  to form high
molecular-weight poly(p-xylylene) .
                        62

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(1)
               X =  H
                 or
               X =  Cl
                          2CH,
                                                                 X
                :CH2
                                                       -CH-
                                                    CH
(    )\—CH2	CH2
                                                  CH2'   +    CH2
(2)
           • CH-,
         CH2 —f-CH2
                                 V
CH2J— CH2.
    ' n
                  FIGURE 111-17 TYPICAL REACTIOWS TO FORM PARYLENE POLYMERS
                                         63

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

The first step is probably reversible.  However,  subsequent
reaction  with  p-xylylene  by addition to either end of the
reactive diradical of the intermediate results in the  form-
ation of stable species (Figure 111-17, Equation 2)  in which
n  is  1, 2, or 3.  Growth then progresses by addition of p-
xylylene to each end of the radical.  Growth  is  terminated
by reaction of the radical end groups with reactive sites in
other  growing  polymer  chains,  by  reaction  of the free-
radical sites with chain transfer agents  (e.g.,  oxygen  or
mercaptans), or by the reactive sites becoming buried in the
polymer matrix.

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

Manufacture - Manufacture is accomplished in a batch process
requiring relatively simple equipment (see  Figure  ITT-18).
For example, the reactions may be carried out in a 61 cm (24
in.) section of 28 cm (11 in.)  I.D. Vycor tubing.  The first
15 cm (6 in.) of the tube serves as a distillation zone, and
the  following 46 cm (18 in.) section as the pyrolysis zone.
The pyrolysis  tube  is  connected  to  a  glass  deposition
chamber.    System  operating  pressure  is in the range of 1
Torr.  The distillation zone is maintained  at  temperatures
ranging  from  140-220°C   (284-428°F),  depending  upon  the
derivative.  The pyrolysis zone is heated to 600°C  (1112°F)
and   the   deposition  chamber  is  usually  held  at  room
temperature.  With some derivatives, it is heated as high as
160°C (320°F) to permit deposition of polymer over a  fairly
broad area.
                       64

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DI-P-XYLYLENE
VAPORIZER
                                PYROLYSIS
                                DEPOSITION
                                 CHAMBER
                                COLD TRAP
       FIGURE 111-18 PARYLENE PRODUCTION
                   65

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

Waste Water Generation - The waste water generation from the
manufacture of parylene is  minimal  since  it  requires  no
catalysts  or  solvents.   Any waste water generated will be
that from the washing and cleaning of processing  equipment,
which  with  housekeeping  and operational procedures can be
contained in the process area.  Provided the  cold  trap  is
efficient, air pollution would be minimal (27, 34) .
                       66

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Poly-Alpha-Methyl Styrene

The  poly(alpha-methyl styrene)  homopolymer is apparently of
little commercial importance.  The  homopolymer  has  a  low
ceiling    temperature   (61°C   or   im.8°F),   and   thus
depolymerization can occur easily  during  fabrication.   In
addition,  the homopolymer is difficult to fabricate because
of its high melt viscosity.

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

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

Manufacture  -  Adequate  information  is  not  available on
commercial methods used, if any.   Presumably,  small  batch
processing may be employed  (25).
                         67

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                  CH3

                  I

           ""5     0  ~  OH2
  Cll
 ens



c —
FIGURE 111-19   TYPICAL REACTION TO FORM ALPHA-METHYL STYRENE

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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 Develop-
ment Document No. EPA 4UO/1-73/010 (16).  Thus, the category
would  include  Nylon  6/12,  Nylon 11, and other polyamides
having special structures.  Among  resins  produced  in  the
U.S.A. are Nylon 6/12 (DuPont) and Nylon 11 (Rilsan, Inc.).

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

Nylon  11  is  produced  by   polymerization   of   11-amino
undecanoic acid in a process that is comparable to that used
for Nylon 6.  In the production of Nylon 11, the reaction is
such   that   very   little   free   monomer   remains  when
polymerization is complete.  Wastes developed in the process
are negligible
                         69

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Polyaryl Ether  (Arylon)

The polyaryl ethers, also known as the polyphenyl ethers  or
polyphenylene oxides are a new class of polymers.  They have
the  structure  shown in Figure 111-20, Equation 1, where Ar
is an aromatic radical and R may be aromatic  or  aliphatic.
The  best  known  examples  of  this type of polymer are the
thermosetting epoxy resins.  Recently, several new polymeric
ethers have become commercially important as thermoplastics.
These polymers have outstanding hydrolytic  resistance,  and
most of them are unaffected by corrosive environments.

The polyaryl ether resins are made by the oxidative coupling
of hindered phenols.  The reaction of 2,6-dimethyl phenol to
produce polyphenylene oxide is illustrated in Figure 111-20,
Equation  2.   The  di-substituted  phenol, copper salt, and
amine are  dissolved,  and  oxygen  is  passed  through  the
solution  producing  the  polyphenylene  ethers  and a minor
amount of diphenyl quinone (Figure 111-20, Equation 3).  The
polymer obtained  is  an  extremely  high  molecular  weight
material,  has  a  useful temperature of -170°C to -H90°C (-
274°F to +374°F), and is chemically inert.

An alternative method of producing the polyphenylene  ethers
is  the  oxidation  of  p-bromophenol.   A  solution of 2,6-
dimethyl-U-bromophenol in  aqueous  potassium  hydroxide  is
reacted  with  potassium-ferricyanide,  producing  poly-2,6-
dimethyl-1,4-phenylene ether.

One  manufacturer  produces  poly-2,6-dimethy1-1,t-phenylene
ether  by  another method, the copper-catalyzed oxidation of
2,6-xylenol.  The polymer  product  is  marketed  under  the
trademark  PPO.   The  commercial  polyphenylene  ether is a
linear polymer  having  a  molecular  weight  of  25,000  to
30,000.   The electrical properties of PPO (R)  are such that
the material has been used  extensively  for  high-frequency
insulation  of electrical equipment.  Because PPO  (R) can be
autoclaved in medical sterilizers, it  is  used  to  replace
glass  and  stainless  steel  in  a  variety  of medical and
surgical instruments  in  hospital  utensils.   It  is  also
employed   in   household  appliances,  in  food  processing
equipment and in plumbing fittings.

A modified form  of  polyphenylene  oxide  resins  has  been
introduced  under  the  trademark  NORYL,  also  by  General
Electric.   This  material   is   based   on   polyphenylene
technology  and  is  intended for applications not requiring
performance of polyphenylene oxide.  The properties  of  PPO
(R) and NORYL  (R) are given in Table III-6.
                          70

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(1)
-f ArO-R-04-n
(2)
                             O2, R., N
                               Cu+
(3)
                                                                  = O
             FIGURE III-20  TYPICAL REACTIONS TO FORM POLYARYL ETHER
                                          71

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                      TABLE III-6

             PROPERTIES OF POLYARYL ETHERS


 Property                      2F.OJR1.         NORYL  (R)


Density                             1.06          1.06

Tensile strength, psi         111,000         9,600
 kg/sq cm                         740           675

Elongation, %                      80            20

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

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

Heat deflection temp., °F at
 26H psi fiber stress             375           265

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

Dielectric constant, 60 cycles      2.58          2.64
                         72

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A  typical  synthesis  from  the  literature  is as follows.
Oxygen was passed for 10 minutes  into  a  reaction  mixture
containing 5 g of 2,6-dimethy1 phenol, 1 g of Cu2Cl2 and 100
ml  of  pyridine.   During  the  course of the reaction, the
temperature rose to a maximum of 70°C (158°F) and  no  water
was  removed.   The  product was precipitated by pouring the
reaction mixture into about 500 ml  of  dilute  hydrochloric
acid  and  was  separated by filtration.  The product, poly-
2,6-dimethyl-l,4-phenylene   ether,    was    produced    in
substantially quantitative yields.

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

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

Waste  Water Generation - Waste water effluents will contain
small fractions of all components of the  reaction  mixture,
including  monomers, catalysts  (copper-salts), and amine and
possibly the by-product diphenyl quinone, or other reactants
and catalysts depending upon the process  of  interest.   In
general, there is one mole of water of reaction produced per
mole   of   oxide  linkage  or,  for  poly-2,6-dimethy1-1,4-
phenylene ether, 159 mass units of water per  1000 mass units
of polymer product  (23).
                           73

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Polybenzimidazoles

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

Essentially,  the benzimidazole is formed by the reaction of
a 1,2-aromatic diamine with a carboxyl group.  The  reaction
may be written as shown in Equation 2 of Figure 111-21.

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

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

Polybenzimidazoles  have  been synthesized to high molecular
weight by solution, melt,  or  solid  state  polymerization.
Solution  condensation  can  take place in either an organic
solvent having a boiling point  sufficiently  high  for  the
reaction  to  proceed, or in polyphosphoric acid.  A typical
high-boiling organic solvent is either phenol  or  m-cresol.
Phenol  has  the ability to provide an easier, more complete
polymerization than  most  solvents.   It  is  necessary  to
conduct  all condensations under inert atmosphere to prevent
oxidation  of  the  tetraamine.   Condensations  have   been
reported   in  which  solvents  such  as  dimethylacetamide.
                            74

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                                                                        (Equation 1)
                                                N
                                                H
                                       benzimidazole
                        NH2
                        NH,
                               HC02H
                              HNOCH
                                       H20     (Equation 2)
            o-Phenylenediamine  Formic acid
                              NH2
                  Amide intermediate    Water
                       HNOCH
                             A
                       NH2
            Amide intermediate
                 NH
                                                      +  H,O
         Benzimidazole      Water
H, N
                      Generalized Synthesis of Polybenzimidazole
NH2
   H2N                     NH2
        3,3'-Diaminobenzidine
C0,(
            Diphenyl isophthalate
                                            Polybenzimidazole
(Equation 3)
                                                                                0OH
                                                 Phenol
              FIGURE 111-21    TYPICAL REACTIONS TO FORM POLYBENZIMIDAZOLES
                                         75

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                                                   0
                                                   II
                                                 HOC
COM
           Isophthalic Acid
           Terephthalic Acid
TABLE 111-7    ACIDS WHOSE DERIVATIVES ARE USED IN POLYBENZIMIDAZOLE SYNTHESIS
                                  76

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dimethylformamide,  dimethylsulfoxide,  N-methylpyrrolidone,
phenol,  and cresol were used.  Polyphosphoric acid has been
investigated because the oxidation sensitivity of the tetra-
amines   could   be   circumvented    by    use    of    the
tetrahydrochloride   salt.    Upon   heating   in  an  inert
atmosphere, hydrogen chloride is evolved at about  mO-150°C
(284-302°F),   giving   a   solution   of   tetraamine   and
polyphosphoric acid.

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

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

In  general,  if  equimolar  quantities  of  reactants   are
employed,  the  polymerization will continue with heating to
produce high  molecular  weight  polymers  soluble  only  in
formic  or  sulfuric  acids.   These  cannot conveniently be
processed  further.   Accordingly,  the  reaction   may   be
interrupted  at  some intermediate stage to produce soluble,
low-melting compounds which can be  applied  in  the  liquid
phase.   Alternatively,  through  the  use  of  an excess of
amine, an amine-terminated prepolymer may be produced, which
is then combined with an  acid-terminated  prepolymer,  with
the  remainder  of  the  polymerization  being  subsequently
conducted either from solution or as a hot melt.  During the
final  polymerization,  there  will  be  the  evolution   of
considerable  volumes  of  volatiles,  which must be removed
from the polymerizing structure.  Thus, at  high  pressures,
low  molecular  weight polymers may be developed as a result
of entrapped volatiles.  For some  purposes,  high  volatile
content is desirable.  For example, porous laminates provide
better   strength   properties   than   do  the  more  dense
structures.  For other purposes, systems with  low  volatile
contents  have  been developed.  The envisioned applications
for polybenzimidazoles are as high temperature adhesives and
laminating resins for the aerospace industry.  They  may  be
                            77

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employed  as  secondary  structural  members  in  supersonic
aircraft, and as adhesives for honeycomb bonding and similar
applications.   Among  the  civilian  potential   of   these
materials    are    their   use   as   ultrafiltration   and
hyperfiltration membranes.

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

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

The quality of water effluent will depend upon pretreatment,
but  some  dissolved  phenol  and/or  HCl  and  some monomer
reactant will likely be present (29).
                            78

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Polybenzothiazoles

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

Typical  reaction conditions for the polymerization to poly-
benzothiazoles are temperatures of 160-250°C  (320-U82°F)  and
times of one to 25 hours.

Waste Water Generation - As with the polybenzimidazoles, the
polymerization leads to the release of 2 moles of water  per
mole  of  benzothiazole  group  and 2 moles of phenol if the
diphenyl  ester  is  used.   For  the  condensation  of  the
isophthalic  ester, this corresponds to 110 mass units water
and 550 mass units phenol per 1000  mass  units  of  polymer
product  (29).
                             79

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(1)
                          SH
                                                                     Polybenzothiazole
(2)
       HCI •  H2N
NH, • HCI + CIOC  .,
                    HS                SH
             3,3'-Dimercaptobenzidine dihydrochloride
                                                                             -HCI
                   --HN
   NH 	 OC
                                                                                             	I n
                   FIGURE III-22   TYPICAL REACTIONS TO FORM POLYBENZOTHIAZOLES
                                          80

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                                               HO2C        C02H
                                        NH2  +
                    HS             SH

                    3,3'-Dimercaptobenzidine
           Isophthalic acid
H,N
                         Poly-2,2'-(m-phenylene)-6,6'-bibenzothiazole
             H2N
NH2
o-
CO2H
                  HS                SH
                  3,3'-Dimercaptobenzidine
                p-Oxydibenzoic acid
                             Poly-2,2'-[p,p'-oxybis(phenylene)] -6,6'-bibenzothiazole
                   Poly-2,2'-[p,p'-oxybis(phenylene)-6,6'-bibenzothiazolyl] -2,2'-(3,5-pyridinediyl)-
                                         6,6'-bibenzothiazole
   FIGURE 111-23  TYPICAL STRUCTURES PRODUCED IN THE SYNTHESIS OF POLYBENZOTHIAZOLES
                                        81

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Polybutene

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

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

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

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

Solid polymer is recovered from the centrifuge,  dried,  and
sent  to  bins  where additives are added prior to extrusion
and pelletizing.  A flow chart is shown in Figure 111-25.
                             82

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         CH2 - CH =
CH—CH2~-

CH2
I
CH3
FIGURE 111-24   TYPICAL REACTION TO FORM POLYBUTENE
                    83

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DISTILLATION
 COLUMNS
03
-P-
                                                                                           EXTRACTION    EXTRACTOR
                                                                                SOLVENT       AGENT
                                                                                                   WATER
             FRESH BUTENE
               (C4 CUT)
                                                                             POLYMERIZATION REACTORS
                                          ATACTIC
                                        POLYBUTYLENE
                                   FIGURE 111-25  POLYBUTENE PRODUCTION - HUELS PROCESS

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

Waste Water Generation - The major aqueous wastes are likely
to be minimal  in  both  processes,  and  especially  so  in
Mobil's process.  In the Huels process, liquid residues from
columns  and some aqueous wastes from C-4 washing are likely
(25).
                            85

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Polycarbonates

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

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

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

In contrast to base-free condensation, which  proceeds  only
at  high  temperatures  in the presence of special catalysts
and yields polymers  with  insufficient  molecular  weights,
condensation in the presence of basic substances proceeds at
high rates at room temperature to give high molecular weight
polycarbonates.   As  shown in the above equation, two moles
of  hydrochloric  acid  are  formed  per  mole  of  phosgene
consumed.  To maintain basic conditions in the reactant mix,
the  hydrochloric  must  be  either neutralized or consumed.
Pyridine is added, usually in excess,  to  act  as  an  acid
acceptor  and  so  that  the resulting polycarbonate forms a
more  or  less  viscous  solution.   Alternatively,  a  good
portion  of  the  pyridine  may  be  replaced  by an organic
solvent in which the polycarbonate is soluble.  The reactant
is strongly  catalyzed  by  Lewis  acids  such  as  aluminum
chloride,   aluminum   isopropoxide,  stannic  chloride  and
titanium tetrachloride.  Suitable  reaction  media  solvents
are   the   chlorinated   aromatic   hydrocarbons,  such  as
                           86

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       C5 H5 N + (CHsh + C(C6H4OH)2 +  COCI2
                                             Solvent
          Pyridine         Bisphenol A   Phosgene

(1)
       CSH5N  +-4-OC6H4C(CH3)2 C6H4Of4- +  2 HCI

       Pyridine          Polycarbonate  Unit
(2)     [C5H5N]  +HCI	-CSH6NCI
      FIGURE 111-26 TYPICAL REACTION TO FORM POLYCARBONATE
                                 87

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chlorobenzene, methylene chloride, or o-dichlorobenzene.   A
typical  catalyst  is benzyl triethyl ammonium chloride.  It
is important to use equimolar  quantities  of  phosgene  and
bisphenol  A, since the molecular weight of the product will
depend on the ratio of the starting materials.  It  is  also
important  to  avoid  the  presence  of  substances  such as
monofunctional  alcohols  or  phenols  which  act  as  chain
terminators.    The  molecular  weight  is  also  indirectly
dependent on possible concurrent side  reactions,  which  in
turn  depend  on  the  usual parameters such as temperature,
time, and reactants.  In choosing the solvent, chlorobenzene
is preferable since the  pyridine  hydrochloride  formed  is
insoluble  in  this  medium  and may be readily separated by
filtration.   Traces  of  the  hydrochloride  that  are   in
solution may be removed by distillation.

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

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

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

Here  the  polymer is precipitated by addition of an organic
11 an ti sol vent" such as an aliphatic hydrocarbon.  This  forms
a  solution  with the carrier solvent and causes the polymer
to precipitate.  The  resulting  slurry  goes  to  a  rotary
filter,   and  the  separated polymer goes to a hot air dryer
where the remaining solvent is removed.  The polymer  leaves
the  dryer  as  a powder and is sent to blending, extrusion.
                           88

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                                  POLYCONDENSATION
           PYRIDINE
           RECOVERY

            SODIUM
           CHLORIDE
           SOLUTION
                                                       WATER
                                                   HYDROCHLORIC
                                                       ACID
                                      SEPARATION
                                           ORGANIC PHASE
                                    PRECIPITATION
                                                    PRECIPITANT
                                      FILTRATION
                                          1
DRYING
                                         I
                                     PELLETIZING
FIGURE 111-27 POLYCARBONATE PRODUCTION - SEMI-CONTINUOUS PROCESS
                             89

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and pelletizing.  Aqueous pyridine hydrochloride solution is
combined with caustic solution in a mix tank for removal  of
chloride ions as sodium chloride.  The stream then goes from
the  mix  tank  to a fractionating column where steam strips
out any solvent present.

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

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

Waste  Water  Generation  - The waste water originating from
the process is principally  due  to  polymer  washing.   The
major  substance  present  in the waste water stream will be
sodium chloride.  The amount  and  concentration  of  sodium
chloride  will  depend  upon the excess of pyridine required
and the dilution necessary to effect adequate  washing.   It
is  expected  that  the  waste  waters will be alkaline from
excess sodium hydroxide used in the  recovery  of  pyridine.
Also,  the  waste  water stream would be expected to contain
traces of pyridine, solvents,  breaking  agents,  bisphenol,
polycarbonate,  and  side reaction products (25, 28, 36, 40,
46) .
                           90

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Polyester Resins (Thermoplastic)

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

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

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

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

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

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

Manufacture - Many plants still use the batch polymerization
process.   A typical continuous polymerization process based
on DMT consists of a DMT melter, ester exchange vessel,  and
                           91

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a   polymerization   reactor(s).    This  process  is  shown
schematically in  Figure  111-28.   The  alternative  system
based  on  TPA  involves a direct esterification rather than
ester interchange.

In the case of plants producing both resin  and  fiber,  the
molten  polymer  stream  from  the final reactor is divided.
Polymer destined to become resin is chilled by  once-through
cooling  water during a band casting operation and broken up
into chip form for shipping.   The  figure  shows  polyester
resin production from ethylene glycol or butanediol.

Waste  Water  Generation  -  Liquid  wastes  result from the
condensation of steam ejector vapors (suction and  discharge
sides).   Process  materials  present  in  these streams are
methanol and ethylene glycol when  ethylene  glycol  is  the
diol  feed,  and methanol and tetrahydrofuran in the case of
butanediol  feed.   In  the  latter  case,  when   unreacted
(excess)  butanediol  is  removed  from  the  process  under
vacuum,   it    spontaneously    dehydrates    to    produce
tetrahydrofuran (25).
                           92

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

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

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Polyester Resins (Unsaturated)

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

The chemical structure of the various materials involved  in
polyester  resin  fabrication  are  shown  in Figure 111-29,
along with a representation of the basic reactions involved.

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

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

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

Manufacture - There are two  somewhat  different  procedures
for carrying out the polyester polymerization reaction.  The
differences  are related to the manner in which the water of
reaction is removed.  The fusion process removes  the  water
by  passing  an  inert  gas,  usually  nitrogen, through the
                           94

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HYDROCARBON STARTING MATERIALS
     H
 HC     CH
  I      II
 HC.    CH
     H
ACIDS
             Benzene
           COOH


           COOH
                              COOH
                        COOH


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

Meta-xylene
HC-COOH           HC-COOH

 II                    II
HC - COOH     HOOC -CH




 MaleicAcid     Fumaric Acid (FA)
           CO


           CO


Phthalic Anhydride (PA)

 GLYCOLS


    HOCH (CH3)CH2 OH


     Propylene Glycol (PG)


 REACTIVE SOLVENT

           CH =CH2
                                                      HCCO

                                                        II >
                                                      HCCO



                                                 Maleic Anhydride (MA)




                                                 HOCH2 C (CH3)2 CH2 OH


                                                   Neopentyl Glycol (NPG)
   Styrene (S)


 POLYESTERS

     HOOC - R-COOH + HO - Ft' - OH	*> (- OOC - R - COOR' -)p + H2O

 Note: Some of the R groups contain the reactive ethylenic linkage.



 RESIN


     PA + MA + PG  = Base Resin (Solid)


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

                       UNSATURATED POLYESTER RESIN
                                           95

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reaction  mixture.   In  the  second  technique,  which   is
referred  to as the solvent or azeotropic process, a solvent
(usually xylene or toluene) is added to the reaction mixture
and forms a constant boiling azeotrope  with  the  water  of
reaction.   This  azeotrope  is  distilled  off  during  the
esterification reaction and the solvent is recovered.

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

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

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

    Water of Reaction

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

    Scrubber Waste

    Scrubbers are used on the overheads leaving the  reactor
    in  crder  to  reduce  the  concentration  of  entrained
                           96

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

    Caustic Cleanout of Reactors

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

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

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

The  nature  of the effluents in alkyd resin and unsaturated
polyester resin manufacture is also quite similar, with  the
notable exception of an increased amount of an oily material
                           97

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which  originates  from  the  long  chain, unsaturated fatty
acids used in the alkyd recipe.  The presence  of  this  ma-
terial  often appears as a high "oil and grease" analysis in
the discharge.  It is also worthy to note  that  although  a
typical polyester reaction gives off about 12 percent of the
original  weight  of the reactants as water of reaction, the
alkyds,  because  of  the  high  molecular  weight  of   the
reactant,  typically give off 5 percent of the weight of the
original reactants as water of reaction.

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

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

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

    o The use of once-through vs. recirculating scrubbers.
    o The extent to which cooling water is recycled.
    o The frequency of reactor washout.
    o The product mix (polyesters vs. alkyds).
    o Whether or not polymerization catalysts are used.
    o Whether or not wastes are incinerated  (U1).
                           98

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Polyimides

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

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

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

Polyimides  with  aromatic  units  in the main chain (of the
general formula shown in  Equation  4,  Figure  111-30)   are
generally   synthesized  by  a  two-stage  poly-condensation
method.  This method has recently found very widespread use,
since soluble products are obtainable in the first stage  of
the  reaction.   This  first  stage,  carried out in a polar
solvent, consists  of  the  acylation  of  a  diamine  by  a
dianhydride  of  a  tetracarboxylic  acid,  leading  to  the
                           99

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(1)
               fco    co       ~i
           -N<  >R<  \N-R'-    .
             ^C0/  ^CO/     J  n
(2)
        CO    CO
          >R<   >N-(CH2)m-
        COX  ^CO'
(3)
         HOOC  /^.   COOH
                           + H2N-(CH2)m-NH2-
                                              A
       CH3OOC  ^^  COOCH3
             HOOC ^\ ,COONH3-(CH2)m-NH2
                                            A
          CH3OOC      COOCH3

                            ,CQ
                    CO'
                                 N-(CH2)m-
(4)
    CO.    CO.      ~|
-N/   \R<  \N-R-   ,
   \COX  NCOX     J n
where R' = Ar
(5)
   CO    CO
  '  ">R<  \0 +H2N-R'-NH2
  "C0_   CO
         HOOC.   „ CO-NH-R'-
(6)
                        CO-NH-R'-
                                     -2nH20
                              cov

                       CO     CO
          FIGURE 111-30  TYPICAL REACTIONS TO FORM POLYIMIDES
                                100

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formation of a polyamic acid  according  -to  Equation  5  of
Figure  111-30.   The  second  stage  of the reaction — the
dehydrocyclization of the  polyamic  acid  (imidization)   —
proceeds  according  to  Equation  6,  and  is  carried  out
thermally or chemically.

The first stage  of  the  synthesis  of  polyimides  —  the
preparation  of polyamic acid — is effected as follows.  To
a solution of an aromatic  diamine  in  a  suitable  solvent
there  is  added  in  small  portions,  with  agitation,  an
equimolar  quantity  or  a  slight   excess   of   the   dry
tetracarboxylic dianhydride.  The reaction is carried out at
temperatures   of  -20-70°C  (-U-158°F),  with  the  optimum
reaction temperature in most cases being 15-20°C   (59-68°F).
The  reaction  is carried out in polar solvents, the best of
which   are   N,Ndimethylacetamide,   N,N-dimethylformamide,
dimethylsulfoxide, and N-methyl-2-pyrrolidone.  The polyamic
acids  as  a  rule  apparently  have  a low molecular weight
(below 100,000) and a low degree of polymerization  (110  or
lower) .

The conversion of polyamic acids to polyimides, imidization,
consists  of  the intramolecular evolution of water from the
polyamic acid to form a cyclic polyimide.   The  imidization
reaction  can  be  carried  out  in  two  ways, thermally or
chemically.  The thermal imidization generally  consists  of
heating  the  dried polyamic acid with a continuous or step-
wise increase of temperature.   Thermal  treatment  at  high
temperatures  (above 200°C or 392°F) is carried out in vacuum
or an inert medium.

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

Most polyimides, particularly the thermally stable  aromatic
polyimides  which  are  of great practical significance, are
inert toward organic  solvents  and  oils.   They  are  also
little  affected  by  dilute  acids,  but dissolve in strong
acids such as fuming nitric or concentrated  sulfuric  acid.
Polyimides  have  a  relatively low stability toward alkalis
and superheated steam, and under the action of both they are
hydrolyzed.
Polyimides have been used as  electrical  insulating  films,
for  wire  enamel, for testing compounds, and for adhesives.
They are being  produced  for  the  most  part  on  a  semi-
industrial scale.
                          101

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

The main area for application of polyimide film at this time
is as a heat resistant insulating,  gasketing,  and  winding
material  for  electric  machines,  and  also  for  electric
cables.  The use of polyimide  films  for  flexible  printed
circuits  is  of great interest.  Thin polyimide film can be
used for condenser insulation for operating temperatures  up
to 250°C (U82°F) .

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

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

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

Waste Water Generation -  The  generation  of  water  wastes
during polyimide manufacture is not documented.  The general
synthesis of interest, that represented by Equations 5 and 6
in  Figure  III-30,  leads to the generation of two moles of
                         102

-------
water per mole of imide linkages.  If  R  and  R«  refer  to
phenyl  groups,  then  this corresponds to generation of 125
mass units of water per 1000 mass units of polymer products.

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

The melt polycondensation method is now  obsolete  for  most
purposes.    However,   it   is   worth   noting  that  this
polymerization and related polymerization  methods  lead  to
the  release  of  two  moles  of  methanol per mole of imide
linkage  (25).
                         103

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Polymethyl Pentene

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

In a typical polymerization, the diluent serves as a solvent
for monomer, activator, and the  atactic  product  which  is
carried  out in the temperature range of 20-80°C  (68-176°F).
The titanium trichloride and the  isotactic  polymer  remain
insoluble.   Thus,  the  monomer polymerizes at the titanium
trichloride-liquid  interface,  and  the  isotactic  polymer
precipitates  out  on the TiCl# crystals forming a slurry of
catalyst-polymer particles in the diluent.  To  isolate  the
isotactic  polymer, the slurry of catalyst-isotactic polymer
particles in the diluent is treated with agents  which  kill
the  catalyst  activity and solubilize the catalyst residues
so that they can be  washed  out.   An  alcohol  is  usually
employed  for  this  purpose.  The polymer is separated from
the wash liquors by filtration or centrifugation.   Residual
liquor  held in the polymer particles can then be removed by
steam distillation and/or drying.  An important  feature  of
the  H-methy1-1-pentene polymer is its optical clarity which
can only be attained  by  the  almost  complete  removal  of
catalyst  residues.   In order to obtain this high degree of
catalyst residue  removal,  aqueous  washings  (as  used  in
polypropylene  manufacture) are inadequate, and more complex
systems involving washing with hydrocarbons or with alcohols
are required.

Waste Water Generation - The waste water  generation  occurs
during  washing,  and  solid/liquid  separations  since  the
polymerization reaction does not produce water.  The polymer
                         104

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


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


              CH3
-J_CH-CH2- —

   CH2
   I
   CH
   A
 CH3  CH3
  FIGURE 111-31  TYPICAL REACTIONS TO FORM POLYMETHYL PENTENE
                             105

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washing step may use water or, in some cases, hydrocarbon or
alcohol.   Consequently,  the  wash  liquids   may   contain
dissolved  metals.   The  volume of waste waters per unit of
production is expected to vary  widely  depending  upon  the
specific  operations,  and the waste waters may also contain
hydrocarbons or alcohols from other washing operations (25).
                        106

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Polyphenylene Sulfide

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

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

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

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

The reaction is carried out at a temperature in the range of
130-175°C   (266-3U7°F).  The mole ratio of p-dichlorobenzene
to sodium sulfide should be in the range of 0.9:1 to  1.3:1.
If  ratios  above  this  range  are  employed, the amount of
unreacted  dichlorobenzene  will  be  increased,   requiring
separation  and  recycle.   Larger  excess of either reagent
leads to lower molecular weight polymers, and still  shorter
polymers  are  produced  by  an  increase  in  the  reaction
temperature.

In  general,  the  synthesis  reaction  is  carried  out  by
reacting  a  polyhalo-substituted  compound  with  an alkali
metal sulfide which has been  partially  dehydrated  by  the
polar  organic  compound that also serves as the solvent for
the reactants.  The solvent should be stable at the elevated
temperatures for the reaction.  The polymer  formed  may  be
                        107

-------
        + Na2S
                C,H9NO
-+2NaCI
FIGURE 111-32  TYPICAL REACTION TO FORM POLYPHENYLENE SULFIDE
                         108

-------
heat  treated  in  the  absence  of oyxgen to yield a higher
molecular weight polymer.  Molecular weight control  may  be
achieved by introducing a monohalo-substituted aromatic com-
pound  to  the  reaction medium, which causes termination of
the chain growth.  Yields of finished polymer are higher  if
a  catalyst  such as copper or a copper compound is added to
the reaction medium.

It is possible to  obtain  a  cross-linked  polymer  through
addition  of  a polyhalo-substituted aromatic compound which
contains substituents  through  which  crosslinking  can  be
effected by further reaction.

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

The  hydrated  sodium  sulfide  in  n-methyl-pyrrolidone  is
charged  to a stainless steel autoclave.  The temperature is
brought up to 190°C (37U°P) while flushing with nitrogen  to
remove  the  water of hydration.  Upon removal of water, the
p-dichlorobenzene  is  charged  to  the  autoclave  and  the
temperature  raised  to  approximately 250°C (482°F)  for the
desired reaction time after which the polymer  and  reaction
medium  is  dropped to a stainless steel tank.  The contents
are washed with water and then with acetone,  which  carries
along  unreacted  reaction  media.   The finished polymer is
dried and packaged.

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

    1.   Water of hydration.

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

The water of hydration is associated with the water bound to
the sodium sulfide which is removed in a  pre-reaction  step
by heating.  It is likely that the water removal would carry
along  traces  of  sodium  sulfide  and n-methyl pyrrolidone
which may or may not be recovered.  Process  wash  water  is
used to wash sodium chloride from the reaction mass.   Due to
the  high  solubility  of  n-methyl-pyrrolidone  and  sodium
sulfide in water, the waste generated from  this  source  is
most  apt  to  contain  a large waste loading.  It is likely
that solvent  extraction  and  subsequent  further  recovery
operations will be applied to this stream to recover the raw
materials for recycle.
                        109

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 N-METHYL
PYRROLIDONE
LLE
 P-DICHLORO-
 BENZENE
                RECOVERY
                                      SEPARATION
                                                      WATER
                                AQUEOUS
                                WASTES
         FIGURE 111-33 POLYPHENYLENE SULFIDE PRODUCTION
                            110

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

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Polypropylene Fibers

Manufacture   -  The  polymerization  of  polypropylene  was
described previously in EPA  Development  Document  No.  EPA
140/1-73/010  ±161.   Polypropylene  fibers are made by melt
spinning.  The general  process,  shown  in  Figure  111-34,
consists of coloring polypropylene flake by some type of dry
blending  of  the  flake with pigments followed by a melting
and  extrusion  process   that   regenerates   the   colored
polypropylene  as  pellets.   The  pellets are then extruded
through a spinnerette into a column of air which  solidifies
the   molten  filaments.   The  filaments  are  subsequently
stretched or spun and crimped, depending on the applications
of the final fiber.

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

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

    Monofilaments

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

    Fibers

    Polypropylene fibers are produced from 1-1/2  denier  up
    to  about  15 denier by a technique basically resembling
                       112

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     DRY PIGMENT OR
   "COLOR MASTERBATCH
                                            PINERETT
                                            CLEANING
                                             WASTE
PP FIBER PRODUCTS
   IN BALES OR
    ON TUBES
          FIGURE 111-34 POLYPROPYLENE FIBER PRODUCTION

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

-------
    that  used  for  nylon  and  polyester  fibers.    After
    extruding  the  filaments  downward and quenching by air
    under carefully controlled conditions, the  now  undrawn
    filaments  are  collected on bobbins in bundles and then
    passed to  the  stretching  operation.   There  are  two
    different methods of stretching depending on the desired
    end  product:  one for continuous multifilament yarn and
    another for staple fiber.  For continuous  multifilament
    yarn,  the  bundles  are  removed  from  the  individual
    bobbins and are drawn under heat to four to eight  times
    their  original  length   (stretch ratios of 1:4 to 1:8).
    Typical drawing equipment consists of heated metal  shoe
    over  which  the  bundles are run; occasionally steam or
    hot air heating is used.

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

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

    Fibrillated or Slit Film

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

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

The  applications of polypropylene fiber include carpet face
yarns,  carpet  backing,   and   various   industrial   yarn
applications.
                        115

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

Sources of waste include rinse water from the blending step,
extensive  quantities of cooling and air conditioning water,
and  the  spin  and  crimping  finish  waste.    These   are
lubricants  that  will  contribute  to  an  oil  and  grease
analysis.  The crimping finish wastes are sometimes directly
drummed and sent to landfill rather than being put into  the
waste  water  stream  because  of  their  high  BOD's.  Some
dissolved solids are generated by the rinsing of  gear  pump
parts that are periodically removed from service and cleaned
in   a  molten  salt  bath.   In  common  with  other  fiber
production plants, polypropylene plants have a large  number
of employees due to the number of hand operations associated
with  the  handling  of  the product, and therefore sanitary
wastes account  for  a  significant  portion  of  the  total
effluent  load  from  the  plants   (41).   Phosphate  can be
present  in  the  wastes   due   to   phosphate   containing
surfactants.
                        116

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

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

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

All  but  traces  of water must be removed from the reaction
mixture before polymerization.  Hydrolysis of  the  dihydric
phenol  salt occurs otherwise, resulting in the formation of
sodium  hydroxide,   which  reacts  very  rapidly  with   the
dichlorodiphenyl  sulfone, forming the monosodium salt of 4-
chloro-4•-hydroxydiphenyl sulfone (Figure  111-36,  Equation
3).
                        117

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(1)
         HO
  CH
   I
   C

  CH3
 OH+ 2 NaOH
            NaO
     CH3
     I
     C
     I
     CH3
    ONa + 2H,0
(2)
     NaO
CH3

C
I
CH3


CH3
ONa + Cl
          O--Q
           	    CH3  x	'
          O
           SO,
 0
+2NaCI
(3)    Cl Ca H4 S02 C6 H4 Cl + 2 NaOH—Cl C6 H4 S02 C6 H4O Na + NaCI + H2O
(4)
        CH3
        CH3
             SO2 	 + OH~
                 CH3

                 - C

                 CH3
O-'
                             + HO
                   o
                 SO,
             FIGURE 111-36  TYPICAL REACTIONS TO FORM POLYSULFOIME RESINS
                            118

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

Another, somewhat less important, side reaction may occur if
caustic  soda is present during polymerization.  Cleavage of
polymer chains para to the sulfone  groups  results  in  the
formation  of  two  phenoxides,  as  shown in Figure III-36,
Equation 4, for polysulfone.

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

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

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

A  50  percent  solution  of  4,4»-dicholordiphenyl  sulfone
(DCDPS)  in  DMSO  maintained  at  110°C  (230°F)   is   fed
stoichiometrically to the polymerizer.  The temperature must
not  drop below about 150°C  (302°F) until the polymerization
is  well  along,  since   sodium-ended   low   polymer   may
precipitate  on  the  walls  of  the  reactor.   Too  high a
temperature during addition of the  sulfone  and  subsequent
polymerization  is  to be avoided, as the reaction is mildly
exothermic,  extremely  rapid  over   160°C    (320°F),   and
                        119

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BISPHENOL A
  SODIUM
 HYDROXIDE
 DIMETHYL
 SULFOXIDE
COAGULANTS
                TO
             RECOVERY
1
                                     REACTION

DICHLORO
DIPHENYL
SULFONE


1
» POLY*^
         DISODIUM
         SALT
                                   FILTRATION
COAGULATION
                                       I
                                   SEPARATION
                                       I
      SOLIDS
                                      DRYING
                                   PELLETIZING
                                                        WATER
                                                          I
            FIGURE 111-37 POLYSULFONE RESINS PRODUCTION
                             120

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excessive solvent decomposition and/or discoloration or even
gelation of the reaction mass may occur.

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

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

Waste  Water  Generation - The reaction products include 810
mass units of water per 1000  mass  units  of  the  disodium
salt,  and  an  estimated  1800 mass units of water is added
with the sodium hydroxide for a total of  2610.   The  waste
water from the azeotropic distillation are likely to contain
DMSO  and  traces  of  bisphenol.   In addition, appreciable
concentrations of sodium chloride  are  expected  to  occur.
The  waste waters are expected to be alkaline because of the
excess sodium hydroxide required for pH control.  The volume
of waste water generated is highly dependent upon  operating
conditions,  especially  those  associated  with the washing
operations  (25, 27).
                        121

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Polyvinyl Butyral

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

Manufacture - Two processes, shown  in  Figures  111-39  and
111-40, are used for production of polyvinyl butyral.

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

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

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

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

Wastes generated by the Monsanto process,  shown  in  Figure
III-40,  are  considerably more complex than those generated
by  the  DuPont  process.   The  Monsanto  process  requires
ethanol,  which  is  not  needed  in the DuPont process; the
ethanol combines with acetic acid which is liberated in  the
hydrolysis  step  to  give ethyl acetate, which is recovered
(31,
                        122

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                           x-
[CH2CHOHCH2CHOHln + C3H7C ^  	- [CH2CH CH2CH] n  +  H20
                            H

                                        o     o
                                         \  /
                                           c

                                         /  \
                                        C3H7   H
  FIGURE 111-38  TYPICAL REACTION TO FORM POLYVINYL BUTYRAL
                              123

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

-------
VINYL
ACETATE
1
\
SUSPENDING AGENT
1 	 WATER
r CATALYST
LIME 	 ^
POLYMERIZATION
SLURRY
i— »-TO WASTE WATER TREATMENT
NEUTRALIZING
FACILITY
A
OTHER
M 	 PLANT
WASTE

STORAGE
 ETHYL
 ALCOHOL
MINERAL
CATALYST
          CENTRIFUGE
          DISSOLVING
                           0.9% FLOW
                                WATER-
  PV
ACETATE
          HYDROLYSIS
                                    30.6% FLOW
                                       MISC.
                                                   DRYING
                            68.5% FLOW
                                                 CENTRIFUGE
                                                      STEAM
                         SOLVENT

                        RECOVERY

                          SYSTEM
                  PV
                ALCOHOL
          CENTRIFUGE
  ETHYL
  ALCOHOL-
                LT
    BUTYRALDEHYDE

       WATER
                                                          •r
                                                              WATER
                                                                  WASHING
                                                         WATER
                                                              ~1
                                                PRECIPITATION
BUTYRALDEHYDE
            ACETAL
           REACTION
                                                 FILTRATION
                                      PV BUTYRAL
      FIGURE 111-40 POLYVINYL BUTYRAL PRODUCTION - MONSANTO INC. PROCESS
                                     125

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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,  resembling  mica.   The  polymer  is
soluble    in    chloroform,   trichloroethylene,   aromatic
hydrocarbons,  etc.   Despite   its   excellent   dielectric
properties,  the  polymer  has  not  been  used to any great
extent for electrical insulation, mainly because of the high
cost of the monomer.

Poly(N-vinyl carbazole)  can be prepared via  the  use  of  a
Lewis  acid  catalyst.  The polymerization is illustrated in
Figure III-U1.

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

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

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

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

Waste Water - While the reaction  itself  does  not  produce
wastes, washing of the product polymer would produce aqueous
wastes  containing  the catalyst  (such as boron trifluoride)
and small amounts of the solvent.  Adequate  information  is
unavailable  to make projections of quantities involved  (25,
29).
                        126

-------
FIGURE 111-41   TYPICAL REACTION TO FORM POLYVINYL CARBAZOLE
                                 127

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Polyvinyl Ethers

The various vinyl alkyl ether monomers (the  reactants)   are
normally  colorless  liquids  or  low  melting  solids.   All
readily add halogens across their double bonds.   The  lower
alkyl  vinyl  ethers  are sparingly soluble in water.  These
monomer ethers hydrolyze slowly in water at room temperature
(and  more  rapidly  in  the  presence  of  mineral  acids),
producing acetalydehyde, as shown in Figure 111-42, Equation
1,

Hydrolysis  of  the  monomers  is avoided by adding alkaline
stabilizers (for example 0,1 percent of triethanolamine)   to
the stored vinyl ethers.  Stabilizers and impurities such as
alcohol,  acetaldehyde,  and acetals are then removed before
polymerization by washing with water or very  dilute  KOH.
Vinyl ethers produce high molecular weight homopolymers when
reacted  in  the  presence  of  Lewis  acid  catalysts.   The
catalysts  used  are  related  to  Zeigler  catalysts,   for
example, diethyl aluminum chloride or Grignard reagents.

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

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

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

Manufacture  -  Commercial  processes  are  typical  for the
various  polymerization  techniques.    Solution   or   bulk
techniques  are  presently  used  in  the U.S.  Typical flow
diagrams for these processes are shown in Figures III-U3 and
III-4U.  In the  solution  polymerization  process,  when  a
solvent-free  product  is  desired,  it  is dried by heating
                        128

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                          H+               H+
 (1)    CH2 =CHOR  + H20	 [CH2 = CHOH]	 CH3CHO
 (2)

H
1
1
VW-CH-,-CH +
1

1
O
1
R
H
1
1
+ CH2 =CH-OR 	 -M/CH2-C-Ch
I
I
O
II
R
H
1
i
1
I
O
1
R
FIGURE III-42 TYPICAL REACTIONS TO FORM POLYVINYL ETHERS
             INCLUDING MONOMER MANUFACTURE
                             129

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                                                               COOLING WATER
                                                              OR REFRIGERATED
                                                              BRINE (INDIRECT)
                                                                    STEAM
               COOLING WATER
                (INDIRECT)
MONOMERS'

CATALYST

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

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                                                                                 STEAM
                                                                      VACUUM
                                                                    FOR AQUEOUS
                                                                     OPERATION
MONOMER    CATALYST
  ORGANIC
OR AQUEOUS
  SOLVENT
  ORGANIC
OR AQUEOUS
  SOLVENT
                                                                                      STEAM
                                                                                     EJECTOR
1
1
1
POLYMERIZER



FINAL
REACTOR





DILUTION
ADJUSTMENT
                                       BAROMETRIC
                                        CONDENSER
                                                                                           COOLING
                                                                                            WATER
                                                                                 WASTE
                                                                                 WATER
                                                                                  PRODUCT TO
                                                                                   PACKAGING
            FIGURE 111-44 POLYVINYL ETHER PRODUCTION - BULK POLYMERIZATION PROCESS

-------
under vacuum.  In  the  bulk  process,  aqueous  or  organic
solvent  is  sometimes  added  to  the  product depending on
desired properties.

Waste Water Generation - Sources of waste water will  depend
upon  the  polymerization  process  employed.   In  solution
polymerization, when no drying step is employed,  there  are
no  direct  contact  waste waters.  When drying is employed,
some contamination of  the  water  from  the  steam  ejector
barometric condenser results.

There is no water of reaction in the polymerization of poly-
alkyl vinyl ethers (25).
                        132

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Polyvinylidene Chlorides

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

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

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

Waste  Water  Generation  -  Wastes developed in the process
consist of tank washings.  These wastes include a low  level
of  all  of  the  ingredients  used,  and  suspended  solids
corresponding to the polymer produced  (41) .
                        133

-------
CClI]
                                      (CH2-CCI2)
                                               n
FIGURE 111-45  TYPICAL REACTION TO FORM POLYVIIMYLIDENE CHLORIDE
                            134

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Polyvinyl Pyrrolidone

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

The  monomer  reactant  is  N-vinyl-2-pyrrolidone,  shown in
Figure 111-16, Equation 1.  This is a colorless liquid  with
a freezing point of 13.6°C  (56.5°F), a boiling point of 96°C
(204.8°F)  at  50  mm, and 123°C (253. H°F) at 114 mm.  It is
completely miscible with water and  most  organic  solvents.
The  monomer is manufactured by the vinylation of 2-pyrroli-
done with acetylene in the presence of alkali metal salts of
pyrrolidone.

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

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

Copolymerization  of N-vinyl-2-pyrrolidone has been success-
fully accomplished with  a  number  of  co-monomers.   Among
these   are   ethylene  glycol  monovinyl  ether,  ethylene,
laurylacrylamide,  C12   to   C1J3    methacrylate,   divinyl
carbonate,  cinnamic  acid,  and  crotonaldehyde.  A typical
process utilizes solvents such  as  alcohol  or  benzene,  a
                        135

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 (1)
Monomer


N-Vinyl-2-Pyrrolidone
CH2


CH2

 \
— CH2

    I
    c = o

N
 I
CH = CH2
 (2)
Polymer
                             CH2 - CH2

                              1      I
                              CH2    C = O
                                CH-CH2
                              NH4OH
                          H202       2HO-
                  HO- +  CH2= CH—-HO-CH2-C'
HO-CHj-C-  +  nCH2=CH
         I            I
 (3)
                 V
                                 H
                        HO-CH2- C—  (CH2 - CH)nl -CH2- CH-
                                 I             I            I
   FIGURE 111-46  TYPICAL REACTIONS TO FORM POLYVINYL PYRROLIDONE
                                  136

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reaction temperature of 50-75°C (122-167°F), and catalyst at
concentrations  0.1  to  1  percent.   Typical catalysts are
benzoyl      peroxide,      lauroyl      peroxide,       and
azobisisobutyronitrile.

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

The  homopolymer polyvinyl pyrrolidones are produced in four
viscosity grades corresponding to average  number  molecular
weights:   10,000, 40,000, 160,000, and 360,000.  Pharmaceu-
tical grades, beverage  grades,  and  textile  leveling  and
stripping grades are produced domestically.   Copolymers with
vinyl  acetate  of  varying  proportions  are  also marketed
domestically.

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

Waste Water Generation - The typical solution polymerization
in  water  would yield only a small waste water stream since
the solvent is  recycled  whenever  possible.    The  polymer
product  is probably washed, depending upon its end use, and
the wash water would contain small fractions of  all  agents
in  the  reaction  mix including some catalyst.  There is no
water of reaction (25).
                       137

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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-47  and  III-18  are
simplified  flowsheets  which  suggest  the  complexity   of
silicones  plants.   Figure  111-47 shows processes used for
production of several different chlorosilanes and hydrolysis
of  dimethyl  dichlorosilane  to  dimethyl  silicone  fluid.
Figure  III-U8 shows transformation of the dimethyl silicone
fluid to finished fluids, greases,  emulsions,  rubber,  and
resins.   These  figures  do  not  include several processes
conducted at the plants.

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

    1.   Production  of  methyl   chloride,   generally   by
         reaction  of methanol and hydrogen chloride. Figure
         III-U9, Equation 1.

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

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

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

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

    The  above  equation represents the "direct" process for
    making chlorosilanes; it is widely used for  the  methyl
    compounds,  the  phenyl  compounds,  and perhaps others.
                       138

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                                                                                                 >. Transistor-grade silicon
vo
                   Benzene,
                   olefins,
                   acetylene, and
                   other reagents
                                                     T
                                                    Fluids,
                                                    rubber
                                 FIGURE 111-47 PRODUCTION OF SILANE MONOMERS, OLIGOMERS AND
                                                       DIMETHYL SILICONE FLUID

-------
Catalyze
and use
 Blends of
chlorosilanes
s


— *i
Water
"* t

'/



Catalysts
,
/ /
/
" 7
                     Hydrolysis
                       kettle "
                               Bodying
                               ' kettle
            I
        Hydrochloric
           acid
                                                       ^Silicone
                                                        resins
                                                                      Room temperature
                                                                        curing rubber
 Silicone
emulsions
            FIGURE 111-48 PRODUCTION OF SILICONE FLUIDS, GREASES, COMPOUNDS,
                                 EMULSIONS, RESINS AND RUBBER

-------
(1)     CH3OH  +  HCI	-CH3CI +  H20
                           Cu
(2)     CH3CI  +  Si +  HCI	     SiCI4 + CH3SiHCI2  +  CH3SiCI3 + (CH3)2SiCI2
                          300°C
(3)     CH3CI + Mg
                                            Cl
                                             i
(4)     2CH3MgCI +  SiCI4	^2MgCI2  +  CH3-Si-CH3
                                             i
                                            Cl
(5)     (CH3)2SiCI2  +  H20	-(CH3)j Si{OH)2 +  2 HCI
(6)     
-------
Chlorosilanes may also be made by  a  Grignard  process,
represented  by Equations 3 and 4 in Figure III-49.  The
Grignard process finds  limited  use,  in  part  because
large  amounts  of  solvent  are required, and the metal
salts go into a waste stream.  We  believe  that  it  is
used only for special chlorosilanes.

Trichlorosilane   (HSiCl3)    is   produced  by  reacting
directly silicon and hydrogen chloride.  For  production
of  still  other chlorosilanes, olefins or acetylene may
be reacted with appropriate silane monomers,

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

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

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

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

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

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

Two types of polymer-filler mixtures are produced, those
which  cure  to  rubber by application of heat and those
which are cured at room temperature.  Catalysts used for
products  cured  at  room  temperature  may  be  tin  or
organotin salts.
                   142

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

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

    Coupling agents are monomeric  silanes  which  serve  as
    glass  surface primers to increase the adhering strength
    of a resin  subsequently  applied.   The  typical  final
    composition  is  glass-silane-resin.   The  resin may be
    epoxy, polyester,  melamine,  or  other.   One  coupling
    agent  which  has  been  used  is  aminopropyl triethoxy
    silane.  Production of such chemicals generally involves
    reaction of a chlorosilane with an  appropriate  organic
    compound, followed by exchange of the halogen atoms with
    alcohol   groups.    Coupling  agents  are  produced  in
    significant quantities at  one  manufacturing  location.
    These resins require a vacuum to be applied to the batch
    reactor  kettle  during  the  hydrolysis reaction (5) in
    Figure  U9.    Existing   plants   employ   once-through
    barometric condensers to achieve the vacuum; use of such
    condensers  increases  the  process  water flow from the
    vicinity of 17,000 to 27,000 gallons per 1000 pounds  of
    product.   These  extra  waters cannot be recycled until
    concentrated, as is  practiced  in  the  manufacture  of
    polyesters and alkyds, for instance, since the materials
    of  construction  of  the  process  equipment  will  not
    withstand the more concentrated hydrochloric acid.   New
    plants, however, could incorporate such a change without
    undue  penalty.   On  existing  plants,  this additional
    condenser water  may  be  used  as  scrubber  water  for
    incineration,  thereby not adding to the total hydraulic
    load  by  the   addition   of   incineration.    Surface
    condensers of current design are very expensive for this
    application  due  to  the need for hastalloy type alloys
    for the metal parts in contact with the process  waters,
    and  are  also  subject  to  frequent  plugging from the
    products of reaction.

Waste  water  Generation  -   Resin   production   generates
significant  amounts of acid wastes due to the liberation of
hydrogen chloride in the hydrolysis step.  The acid  may  be
                       143

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recycled,  for example in the production of methyl chloride,
but in many cases it is impractical to recover it.   Organic
solvent  wastes,  such  as  naphtha  or  toluene,  are  also
produced.  Most of the solvents  are  recovered,  but  trace
quantities  may  appear  in  the  waste water.  Quantitative
information  on  the  waste  water  generated  in   silicone
polymerization processes is not documented in the literature
(25, HI).

Source  of  heavy  metals  -  copper  catalyst  used for the
chlorosilane  production  process  enters  the  waste  water
during  the  hydrolysis  step  and  in  subsequent  water of
reaction produced during polymerization.  Fluorides  may  be
present  in  the waste water where fluorosilicones are being
manufactured.
                       144

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Spandex Fibers

Spandex  fibers  are  made  from  conventional  polyurethane
ingredients.  Textile Organon C*3)  defines spandex fibers as
being  composed  of  "at  least  85  percent  by weight of a
segmented  polyurethane.11   In  common  with   other   fiber
processing  reactions,  extremely  careful  control  must be
maintained in  raw  materials  specifications  and  reaction
techniques to insure adequate quality of fiber.

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

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

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

Another  U.S.  producer  produces  spandex fibers by the wet
spinning process.  This process is similar to that  employed
by  DuPont  in that a spinning solution is used, but instead
of spinning into  a  column  of  circulating  hot  air,  the
spinning  solution is spun into a water bath which serves to
                       145

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(1)
                 HIOROCO CH2 CH2 CH2 CH2 CO)nOROH
(2)
                         H [0(CH2)3CH]nOH
(3)
                         H [0(CH2)5CO]nOROH
(4)
                          H,C
           NCO
                              NCO
(5)
                 OCN—
— CH2-
— NCO
                         0
(6)   OCN-0-CH2 -0-N-C-OCH2CH2O
                      H
                                        O       0
                                        • C-(CH2 )4 C-OCH2 CH2O
                                 -N -0-CH2 -0NCO
                                   H
(7)    OCN- R -
      Prepolymer
                     H2NCH2CH2IMH2
            O            0
            C-N-R-N-C-N-CH2-CH2-N4
                                             H
                      H
             H
H
            FIGURE  111-50  TYPICAL REACTIONS TO FORM SPANDEX FIBERS
                                   146

-------
MAKE UP
                          Dl ISOCYANATE
                                 DIAMINE
                           POLYMER-
                            IZATION
                            VESSEL
                     BLOW-DOWN
                                                 RECYCLE
            SOLVENT
          PURIFICATION
                                            (N-DIMETHYLFORMAMIDE)
                                                 SOLVENTS
                                                WASTE  SOLUTION
                                                TO  INCINERATION
                                                                                WASTE TO INCINERATION
                               SOLVENT +
                                HOT AIR
                                                                                 SPINNING
                                       SPINNING WASTE
                                       TO INCINERATION
                                                                                                    J
  SOURCE: BASED ON DISCUSSION
         WITH DU PONT.
T
                                      HOUSEKEEPING WASTE WATER
                                      TO  BIOLOGICAL TREATMENT
                  FIGURE 111-51 SPANDEX FIBER PRODUCTION - DRY SPINNING PROCESS

-------
00
                            TOLUENE
                          Dl ISOCYANATE
          POLYTETRAMETHYLENE
               GLYCOL
                                                                                           LUBRICANT
            COOLING
          WATER FROM
             CITY
                           POLYMER-
                             ZATION
                            VESSEL
                                                  WELL WATER
                                                    COOLANT
                       TO
                     SEWER
             SOURCE: ADL, BASED ON DISCUSSIONS
                    WITH AMELIOTEX, INC.
                                                                    TO
                                                                   STORM
                                                                   SEWER
                                                                                         REGENERATION
                                                                                            WASTES
PRODUCT
                                                                                                          CITY
                                                                                                         WATER
                             FIGURE 111-52 SPANDEX FIBER PRODUCTION - WET SPINNING PROCESS

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extract the solvent and coalesce a  multifilament  yarn.   A
schematic   of  the  process  based  on  a  discussion  with
Ameliotex is shown in Figure 111-52.

Another U.S. producer produces spandex fibers by a variation
of wet spinning which  is  known  as  reaction  or  chemical
spinning.   The isocyanate-terminated prepolymer is extruded
into a bath  containing  toluene  and  a  diamine  (ethylene
diamine).    The  diamine  reacts  with  the  prepolymer  by
crosslinking or chain extending to convert  it  to  a  solid
elastomeric   fiber.    Although  individual  filaments  are
produced in this way,  usually  the  individual  fibers  are
brought  together  to  form a coalesced, multifilament yarn.
After leaving the ethylene diamine/toluene  spin  bath,  the
coalesced  yarn  is washed with water, dried, and lubricated
prior to winding.  A schematic of the process based on  dis-
cussions  and  communications  with Globe is shown in Figure
111-53.

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

    1,   Waste polymer — incinerated.

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

    3.   Spinning waste — incinerated.

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

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

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

The primary  source  of  waste  from  the  other  producers1
reaction  or  chemical  spinning process originates from the
washing step which follows the spinning bath.   This  stream
containing  wash  water,  toluene,  and  ethylene diamine is
                      149

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

-------
passed to a continuous decanter which allows  separation  of
toluene  and  water  by  gravity.   Toluene  is  removed and
purified by distillation prior to being recycled to the spin
bath.  Solid dregs remaining after distillation are  drummed
and  hauled to a landfill.  In the method used by Globe, the
continuous decanter has a retention  time  of  160  minutes.
This is said to be sufficient to give a water effluent  (con-
taining  a  faint  odor  of  toluene)  which is subsequently
discharged to a municipal sewage system  (41, ^3) .

Other Pollutants

Depending on the particular waste water chemical  conditions
and  the  analytical  methods used, cyanides may be detected
due to the presence of isocyanates.  Oil and grease presence
is due  to  lubricants  used  in  the  spandex  fiber  after
extrusion.   Organic  nitrogen  derives from the presence of
ethylene diamine.
                      151

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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 111-54,
Equation 1.

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

In  some  cases,  prepolymers are utilized to make the poly-
urethane resin.  A prepolymer in the common commercial  form
is  a  liquid reaction product of a polyol with an excess of
isocyanate  to  produce  a  low  molecular  weight   polymer
containing  reactive isocyanate end groups as exemplified by
Equation 3 in Figure  111-54.   This  low  molecular  weight
polymer  normally becomes one part of a two-component system
in which the second  component  is  additional  polyol  with
which  the prepolymer can react to form a cross-linked cured
urethane.

There are a number of reasons for using the prepolymer tech-
nique rather than the one-shot approach in  which  the  iso-
cyanate,  polyol,  and other components of a formulation are
simply mixed together and allowed to react.  The  prepolymer
approach  often  provides better control of rate of reaction
and improved compatibility and mixing characteristics in the
components.   Improved  product  properties  can  often   be
obtained  both  through  better  control of the reaction and
through  the  use  of  different  polyols  in   making   the
prepolymer  and  for  the  final  curing.  Another important
reason for using the prepolymer technique  in  polyurethanes
                      152

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                                  o
                                  (I
  (1)     R-OH + R'-NCO	^R-0-C-N-R'
                                     I
                                     H
  (2)     R'-NCO + H20—~R'-NH2 + CO2
  (3)     3R (NCO)2  + HO R'-OH	-




                 OCN - R (NHCOO - R' - OCO IMHR)2 NCO
FIGURE 111-54 TYPICAL REACTIONS TO FORM URETHANE PREPOLYMERS
                             153

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which    utilize    relatively    low    molecular    weight
polyisocyanates such as toleuene diisocyanate (TDI)  is  that
prereaction  of  the  polyol with the isocyanate reduces the
isocyanate vapor pressure and therefore lowers the  toxicity
of the formulation.

Most large volume polyurethane products such as flexible and
rigid foams are produced primarily by the one-shot technique
in  which  all  components  are  blended  together  with  no
prereaction.  The one-shot approach is used for large volume
products because it is the most economical  method  to  make
polyurethanes.  Prepolymers are generally used where smaller
volumes  and  more specialized applications of polyurethanes
are involved.  For instance, foam systems that are  sold  as
two-component  liquid  formulations  for  field  spraying or
cast-in-place applications frequently  utilize  prepolymers.
Similarly,  for  other  high  value  products  where maximum
control  of  the  reaction  is  necessary,  prepolymers  are
frequently used.  Such applications include cast elastomers,
sealants,   adhesives,   and   two-component  and  air  cure
polyurethane coatings.

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

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

Waste  Water  Generation  -  Basically  there  is  no  water
involved  in  the  prepolymer  production  except  for minor
amounts which may purposely be added to the mix  to  produce
some  biuret  linkages.   In  fact,  every effort is made to
assure that all unwanted water is  excluded  both  from  the
                       154

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feed  materials  and the product because the isocyanate will
rapidly react with any water  to  form  an  unwanted  amine.
Even  a  minor amount of such unplanned reaction drastically
changes the properties of the prepolymer and may even  cause
it to gel in the reactor or drum.  The only water used is in
the  cooling  jacket  of the reactor, and this is completely
separated from the reaction mixture.  It  is  unlikely  that
any  water  would  be  used  for  cleaning a reactor between
batches because the water would produce a rapid cure of  the
prepolymer  and  make the cleaning operation more difficult.
In addition, the reactor would have to be  thoroughly  dried
before  processing  of  a new batch could begin.  There is a
remote possibility that in some instances a  water  miscible
solvent  might be used to clean the reactor and the solvent-
prepolymer solution then mixed with water in order to  react
with  the prepolymer, and that such contaminated water might
be discharged.  We are not aware of any such operations, and
the possibility  of  such  contamination  occurring  on  any
significant  scale is remote because of the significant loss
of raw materials that would be involved (25) .
                       155

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                         SECTION IV

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

    Major Subcategory I - Low raw waste load (less  than  10
    units/1000   units  of  product) ;  attainable  low  BOD5_
    concentration (less than 20 mg/liter).

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

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

    Major  Subcategory  IV  -  High  or  low raw waste load;
    attainable high BOD5_ concentration (over 75 mg/liter).

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

In  Major  Subcategory I where reported BOD5_ raw waste loads
are less than 10  units/1000  units  of  product  and  where
hydraulic  flows  ranged  from  O.U  to  153 cu m/kkg (55 to
18,300 gal/1000 Ib), the influent concentrations ranged from
8 to 720 mg/liter.  While the influent concentrations varied
over a 90-fold range,  the  effluent  concentrations  varied
over a 3-fold range, i.e., 8 to 25 mg/liter.  This indicates
that  practicable  waste  water  treatment  plants should be
capable of retaining effluent concentrations in the vicinity
of 15   mg/liter  when  using  properly  designed  and  well
operated biological  systems.

*  Production  basis  for  establishing  the  unit  effluent
guidelines has been  on the basis of actual  production,   not
rated capacity of a  plant.
                          157

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The plants in Major Subcategory II are characterized by high
raw  waste loads, but the waste waters can be treated to low
attainable BOD5 concentrations.  Hydraulic flows varied from
1H.2 to  116  cu  m/kkg  (1700  to  14,000  gal./lOOO  Ibs).
Influent  concentrations  of from approximately 600 to 4,300
mg/liter were reported.  Although only one  treatment  plant
was  found  in  Category  II and this was producing effluent
concentrations of approximately 25  mg/liter,  it  is  known
that  the  waste waters from the other processes are readily
treated by biological methods.

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

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

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

Additional  subcategorization  within  the  above major sub-
categories was necessary to  account  for  the  waste  water
generation  which is specific to the individual products and
their various processing methods.  The  separation  of  each
individual  product  into  separate subcategories simplifies
the application of the effluent limitations  guidelines  and
standards  of  performance  by  providing  a clearly defined
context  for  application  of  the  numerical  values.   The
advantages  of  this  subcategorization  appear  to outweigh
technical advantages that might be  connected  with  product
group   characterization   alone.    The   resulting   major
subcategories  and  component  product   subcategories   are
summarized in Table IV-1.
                        158

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                             TABLE IV-1
                      INDUSTRY SUBCATEGORIZATION
       Major
   Subcategory I
                        Major            Major            Major
                    Subcategory II  Subcategory III   Subcategory IV
Ethylene-vinyl    Acrylic resins  Alkyds  and un-     Nitrile barrier
                                    saturated poly-   resins
                                    ester resins     Spandex fibers
                                   Cellulose nitrate
                                   Polyamids
                                    (Nylon 6/12)
                                   Polyesters (therm-
                                    plastic)
                                   Polyvinyl-
                                    butyral
                                   Silicones
 acetate          Cellulose
 copolymers        derivatives
Polytetrafluoroethylene
Polypropylene
 fibers
Polyvinylidene
 chloride
                               159

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Several  other methods for subcategorizing the industry were
considered.  These  included  plant  size,  plant  age,  raw
materials  and  products,  and air pollution and solid waste
generation.   The  utilization  of  municipal  systems   was
considered  as  a  method  of characterization for the alkyd
molding and unsaturated polyesters category, however,  since
the  waste  waters  are  generally  accepted  into municipal
systems  and   since   pretreatment   standards   would   be
applicable,   it  was  decided  to  establish  a  guidelines
limitation as though the plants were treating  waste  waters
in  private waste water treating facilities.  The age of the
plants  in  this  industry   are   determined   largely   by
obsolescence due to size or process changes and not physical
age.    Similar   raw  materials  are  often  used  to  make
dissimilar products.  The impact of  air  pollution  control
systems  using  water  scrubbing  and  the disposal of solid
wastes are not sufficient to warrant segmentation. For these
reasons none of the aforementioned  factors  was  judged  to
have sufficient relationships with raw waste load generation
or  effluent compositions to warrant their use as a basis of
categorization.
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                         SECTION V

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

Raw Waste Loads

Raw  waste  water  flow  ranges  are shown in Table V-l, and
waste loads of BODJ5, COD, and suspended solids are shown  in
Table  V-2.  These data are based on information provided by
the companies contacted during the  course  of  this  study.
Much  of  the  data  was  provided  as  units  per  unit  of
production by the manufacturers and was  not  obtained  from
daily   production   rates   and   waste   water  flows  and
concentrations.  Furthermore, it is known that much  of  the
data  on  waste  water  flows  and  raw waste loads has been
derived from limited numbers  of  samples  over  short  time
periods.   Because  the synthetic polymers industry is based
to a large extent on batch production methods and  often  on
the  commercial  need  to  produce a large number of product
types of a basic polymeric material, the waste  water  flows
and  raw waste loads per unit of production were reported to
vary from  essentially  no  water  use  (water  leaves  with
product or no water is used in manufacture) to nearly 300 cu
meters/kkg   (36,000  gal./lOOO  Ibs).   The  major pollutant
parameters for which data were obtained are BOD5,  COD,  and
suspended  solids.   Inspection  of  the  ranges recorded in
Table V-2 shows that these pollutants vary by factors of  up
to 30 from low to high values for an individual polymer.

Other  pollutants  which  may  occur in the waste water from
various polymer manufacturing processes are listed in  Table
V-3.   These  elements,  compounds, and characteristics were
developed  from   information   obtained   from   industrial
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                              TABLE V-l

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

Alkyd molding compounds and
unsaturated polyester resins

Cellulose derivatives

Cellulose nitrate

Ethylene-vinyl acetate copolymers

Fluorocarbon polymers

Nitrile barrier resins

Polyamides

Polyester resins (thermoplastic)

Polypropylene fibers

Polyvinyl butyral

Polyvinyl ethers

Polyvinylidene chlorides

Silicones

Spandex fibers
 (gal/1000*)

 1700 - 5600

   38 - 1440


 1700 - 14000

13300 - 20400

  275  -  300

 2200 - 18300

  900 - 4700

     N.A.

  260 - 770

  160 - 3700

 7800 - 14200

    0 - 6250

  500(E)

 1000 - 33500

 1000 - 1700
  (cu m/kkg)

 14.2 - 46.7

  0.3 - 12.0


 14.2 -116.8

110.9 -170.2

  2.3  - 2.5

 18.4 -152.7

  7.5 - 39.2

     N.A.

  2.2 -  6.4

  1.3 - 30.9

 65.1 -118.5

  0   - 52.2

  4.2(E)

  8.3 -279.5

  8.3 - 14.2
NA = Not available

E  = Estimated
                               162

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                                          TABLE V-2
                        SYNTHETIC POLYMERS PRODUCTION RAW WASTE LOADS
                  (All units expressed as kg/kkg (lb/1000 Ibs of production)
                                                  Observed, Reported,  or Estimated  (E) Ranges of
                                                  	Average Waste Loads	
                                                       BOD	COD	SS	
Acrylic resins                                         2-30          3-55         5-10
Alkyd molding compounds  and  unsaturated
polyester resins                                       9-25         15-80         1-2
Cellulose derivatives                                 140 - 220       340 - 950        1-42
Cellulose nitrate                                     55 -  110 (E)   75  - 275 (E)      35 (E)
Ethylene vinyl acetate copolymers                    0.44  -  4.4(E)   0.2 -  54 (E)   0 - 4.1
Fluorocarbon polymers                                    0  -  6.6(E)  4.4  - 44(E)  2.2 - 6.6(E)
Nitrile barrier resins                                  5 - 10(E)       10 - 30(E)       3 - 10(E)
Polyamides                                              NA              NA             NA
Polyester resins (thermoplastic)                        0-10          1 - 30          NA
Polypropylene fibers                                 0.4 -  1.1 (E)   1.8  - 2.6(E) 0.2 - 2.2(E)
Polyvinyl butyral                                     30 - 200        40 - 400         NA
Polyvinyl ethers                                        NA         10(E) - 40(E)        NA
Polyvinylidene chlorides                                0(E)            8(E)           0.2(E)
Silicones                                              5 - 110        15 - 200        50(E)
Spandex fibers                                         20(E)           40(E)            NA
         E = Estimated
        NA «• Not available

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representatives,  literature  sources.  Corps  of  Engineers
Permit Applications for a number of plants in  the  plastics
and  synthetics industry, reviews with personnel in Regional
EPA offices, and internal industrial consultants.
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                      TABLE V-3
      OTHER ELEMENTS, COMPOUNDS AND PARAMETERS

PH
Color
Turbidity
Alkalinity
Temperature
Nitrogenous Compounds(organic, ammonia  and nitrates)
Oils and Greases
Dissolved Solids - principally inorganic chemicals
Phosphates
Phenolic Compounds
Sulfides
Cyanides
Fluorides
Mercury
Chromium
Copper
Lead
Zinc
Iron
Cobalt
Cadmium
Manganese
Aluminum
Magnesium
Molybdenum
Nickel
Vanadium
Antimony
Numerous Organic  Chemicals
                   165

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                         SECTION VI

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

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

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

Selected Parameters

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

BOD5

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

Dissolved oxygen  (DO) is a water quality  constituent  that,
in appropriate concentrations, is essential not only to keep
organisms  living  but also to sustain species reproduction,
vigor,  and  the  development  of  populations.    Organisms
undergo  stress  at reduced DO concentrations that make them
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less competitive and able to sustain  their  species  within
the   aquatic   environment.    For   example,   reduced  DO
concentrations  have  been  shown  to  interfere  with  fish
population  through  delayed  hatching of eggs, reduced size
and vigor of embryos, production of  deformities  in  young,
interference  with  food  digestion,  acceleration  of blood
clotting, decreased tolerance to certain toxicants,  reduced
food   efficiency  and  growth  rate,  and  reduced  maximum
sustained swimming speed.  Fish food organisms are  likewise
affected  adversely in conditions with suppressed DO.  Since
all aerobic aquatic  organisms  need  a  certain  amount  of
oxygen,  the  consequences of total lack of dissolved oxygen
due to a high BOD can kill all inhabitants of  the  affected
area.

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

COD

Chemical oxygen demand   (COD)  provides  a  measure  of  the
equivalent  oxygen required to oxidize the materials present
in a waste water sample under acid conditions with  the  aid
of a strong chemical oxidant, such as potassium dischromate,
and a catalyst (silver sulfate).  One major advantage of the
COD  test is that the results are available normally in less
than three hours.  Thus, the COD test is a  faster  test  by
which to estimate the maximum oxygen exertion demand a waste
can  make  on  a stream.  However, one major disadvantage is
that  the  COD   test   does   not   differentiate   between
biodegradable  and  nonbiodegradable  organic  material.  In
addition,  the  presence  of  inorganic  reducing  chemicals
(sulfides,  reducible metallic ions, etc.)  and chlorides may
interfere with the COD test.  As a rough generalization,  it
may  be  said that pollutants which would be measured by the
BOD5 test will also show up under the  COD  test,  but  that
additional pollutants which are more resistant to biological
oxidation (refractory) will also be measured as COD.
Total Suspended Solids

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

In  raw  water  sources for domestic use, state and regional
agencies generally specify that suspended solids in  streams
shall  not  be  present  in  sufficient  concentration to be
objectionable  or  to  interfere   with   normal   treatment
processes.   Suspended  solids  in  water may interfere with
many industrial processes and cause foaming in  boilers,  or
encrustations  on  equipment exposed to water, especially as
the temperature rises.  Suspended solids are undesirable  in
water  for  textile  industries;  paper and pulp; beverages;
dairy  products;  laundries;  dyeing;  photography;  cooling
systems;  and  power plants.  Suspended particles also serve
as a transport mechanism for pesticides and other substances
which are readily sorbed into or onto clay particles.

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

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

Turbidity  is  principally  a measure of the light absorbing
properties of suspended solids.  It is frequently used as  a
substitute  method of quickly estimating the total suspended
solids when the concentration is relatively low.
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pH, Acidity and Alkalinity

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

The term pH is a logarithmic expression of the concentration
of  hydrogen  ions.  At a pH of 7, the hydrogen and hydroxyl
ion concentrations are essentially equal and  the  water  is
neutral.   Lower  pH  values  indicate  acidity while higher
values indicate alkalinity.  The relationship between pH and
acidity or alkalinity is not necessarily linear or direct.

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

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

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

Other Pollutant Parameters

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

Phgnolic Compounds

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

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

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

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

Nitrogenous Compounds

Nitrogenous  compounds  can  occur as a result of biological
activity in the waste water treatment and can also come from
manufacturing  processes  such  as  urea,  melamine,  nylon,
ABS/SAN,  cellulose  nitrate, cellulose derivatives, nitrile
barrier resins, and acrylics.  Ammonia is a  common  product
of  the  decomposition of organic matter.  Dead and decaying
animals and plants along with human and animal  body  wastes
account  for  much  of  the  ammonia  entering  the  aquatic
ecosystem.  Ammonia exists in its non-ionized form  only  at
higher  pH  levels and is the most toxic in this state.  The
lower the pH, the more ionized ammonia  is  formed  and  its
toxicity  decreases.   Ammonia, in the presence of dissolved
oxygen,  is  converted  to  nitrate  (NO.3)   by   nitrifying
bacteria.   Nitrite   (NO2.) , which is an intermediate product
between ammonia and nitrate, sometimes  occurs  in  quantity
when  depressed oxygen conditions permit.  Ammonia can exist
in several other chemical  combinations  including  ammonium
chloride and other salts.
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Nitrates   are   considered   to   be  among  the  poisonous
ingredients of mineralized waters,  with  potassium  nitrate
being  more  poisonous than sodium nitrate.  Excess nitrates
cause   irritation   of   the   mucous   linings   of    the
gastrointestinal  tract  and  the  bladder; the symptoms are
diarrhea and diuresis,  and  drinking  one  liter  of  water
containing 500 mg/1 of nitrate can cause such symptoms.

Infant methemoglobinemia, a disease characterized by certain
specific  blood  changes and cyanosis, may be caused by high
nitrate concentrations  in  the  water  used  for  preparing
feeding  formulae.   While  it  is still impossible to state
precise concentration limits, it has been widely recommended
that water containing more than 10 mg/1 of nitrate  nitrogen
(NO_3-N)  should  not be used for infants.  Nitrates are also
harmful in fermentation processes and can cause disagreeable
tastes in beer.  In most natural water the pH range is  such
that  ammonium ions (NH4+) predominate.  In alkaline waters,
however,  high  concentrations  of  un-ionized  ammonia   in
undissociated  ammonium  hydroxide  increase the toxicity of
ammonia solutions.  In streams polluted with sewage,  up  to
one-half of the nitrogen in the sewage may be in the form of
free  ammonia,  and  sewage may carry up to 35 mg/1 of total
nitrogen.  It has been shown that at a level of 1.0 mg/1 un-
ionized ammonia, the ability of hemoglobin to  combine  with
oxygen   is  impaired  and  fish  may  suffocate.   Evidence
indicates that ammonia exerts a considerable toxic effect on
all aquatic life within a range of less than 1.0 mg/1 to  25
mg/1,  depending  on  the  pH  and  dissolved  oxygen  level
present.

Ammonia  can  add  to  the  problem  of  eutrophication   by
supplying  nitrogen  through  its  breakdown products.  Some
lakes in warmer climates, and others that are aging  quickly
are  sometimes  limited  by  the  nitrogen  available.   Any
increase will speed up the plant growth and decay process.

Fluorides

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

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

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

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

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

Phosphates

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

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

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

Oils and Greases

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

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

Dissolved Solids

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

    Acrylic resins
    Cellulose derivatives
    Cellulose nitrate
    Polytetrafluoroethylene
    Silicones

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

Many communities in the United States and in other countries
use water supplies containing 2000 to 4000 mg/1 of dissolved
salts, when no better water is available.  Such  waters  are
not  palatable,  may  not  quench  thirst,  and  may  have a
laxative action on new users.  Waters containing  more  than

-------
other aquatic life, primarily because  of  the  antagonistic
effect of hardness on metals.

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

Dissolved solids in industrial waters can cause  foaming  in
boilers  and  cause interference with cleanliness, color, or
taste of many finished products.  High contents of dissolved
solids also tend to accelerate corrosion.

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

Toxic and Hazardous Chemicals

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

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

These  pollutants  may  be  present  in  waste  waters  from
selected  processes  in  varying  amounts;  however, no data
could be obtained which would  permit  establishing  raw  or
treated  waste  loads.   Therefore,  they are listed so that
appropriate cognizance can be taken to determine whether  or
not   they   are   present  in  amounts  requiring  effluent
limitation because of  receiving  water  quality  standards.
Where  appropriate  the particular parameters are summarized
in Table VI-1.
                           176

-------
                         TABLE VI-1

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

Polytetrafluoroethylene

Spandex Fibers



Acrylic Resins

Polypropylene Fibers


Nitrile Barrier Resins


Polyamides

Cellulose Derivatives

Cellulose Nitrate

Silicones
Polyvinylidene Chloride
Polyester Resins  (Thermoplastic)
Lead
Cobalt

Fluorides

Cyanides
Oils and Grease
Organic Nitrogen

Oils and Grease

Oils and Grease
Phosphates

Organic Nitrogen
Cyanides

Organic Nitrogen

Inorganic Nitrogen

Inorganic Nitrogen

Polychlorinated
  Organics
Copper
Fluorides

Polychlorinated
  Organics

Cobalt
Manganese
Cadmium
                           177

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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  specific  to  the  industry  but can utilize any of the
broad  spectrum  of  technologies  found  in   waste   water
treatment.   These technologies can be divided into the same
three broad categories found in the rest of  the  synthetics
and plastics industry.  These are:

    1.   Presently used waste water treatment technology.

    2.   Potentially   usable    waste    water    treatment
         technology.

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

The application of presently  or  potentially  usable  waste
water  treatment  technologies  may  be  applied on selected
bases to segregated streams or may be  incorporated  into  a
centralized   waste   water   treatment   plant.    Although
categories 1 and 2, often denoted as end-of-pipe  treatment,
may  be applied regardless of the manufacturing process, in-
process control to prevent pollutants  from  entering  water
streams  has  a  great  potential  for  reducing the load of
pollutants  as  well  as  the  waste   water   flows.    The
application  of  in-plant  control technology falls into two
broad categories:  (1) process requirements  and  (2)  plant
practices.  Process requirements for water usage depend upon
the  types  of  reactions  being carried out, the amounts of
unreacted raw materials or undesired by-products  that  must
be    removed   by   water   washing   to   attain   product
specifications, the removal of catalyst activators or  other
additives  necessary  to  control the reaction or create the
appropriate chemical characteristics, and the use  of  water
for  quenching,  creating  vacuum,  or other operations that
contact process streams.  The emission  of  pollutants  into
waste  streams  outside of the direct process operations may
come from poor housekeeping practices or from the  excessive
usage of water for cleaning up spills, leaks, and accidental
occurrences  due  to  equipment  failure or personnel error.
Water used to control accidental  occurrences  or  hazardous
conditions,   such   as   fires,   etc.,  is  employed  very
occasionally, and usually is not considered as  contributing
to  the  pollution  loads  in  the waste waters.  Recycle of
                         179

-------
treated waste waters for such uses as housekeeping,  cooling
tower  makeup and fire ponds is currently being practiced in
the industry.  One plant reports reuse of up to  75  percent
of its treated effluent. (50)

As  indicated  earlier,  the  survey  found  no  waste water
treatment  technologies  unique  to  this  segment  of   the
plastics and synthetics industry.  The waste water treatment
technology is similar to that found during the survey of the
first  segment  of  the industry and is generally similar to
that  of  other  industries.   Obviously,   application   of
basically   similar   technology,   e.g.,  activated  sludge
biological treatment, often requires unique  conditions  for
specific  waste  water and results in considerable variation
in  performance  characteristics  such  as   efficiency   of
pollutant removal.

Presently Used Waste Water Treatment Technology

This  segment  of  the  plastics and synthetics industry was
found to have relatively few waste  water  treatment  plants
devoted  solely  to the treatment of the waste waters from a
particular product.   A  major  portion  of  the  individual
manufacturing  plants,  except  in  the  alkyd and polyester
resins categories, was visited  or  otherwise  contacted  to
determine  if  water treatment facilities were installed. It
was found that a large portion of the waste waters from  the
various   products   enter   either   centralized  treatment
facilities for multi-plant chemical complexes  or  municipal
sewage  systems.  The major portion of the waste waters from
the manufacture of silicones is treated or will  be  treated
in   their   own  waste  water  treatment  plants.   Typical
operating data or design information on silicone waste water
treatment plants are included in  Tables  VII-1  and  VI1-2;
however,  one-half  of  the companies requested confidential
handling of the data provided and, therefore, those data are
not included.  In addition, confidentiality was requested by
a  polytetrafluoroethylene  and  a  nitrile  barrier   resin
manufacturer.   Although a significant portion of the design
and operating data shown in Tables VII-1 and VII-2 are  from
waste  water  treatment plants receiving waste waters from a
number of different chemical  manufacturing  processes,  the
inclusion  of  data from multi-process waste water treatment
plants was made to indicate  the  operating  conditions  and
efficiencies  found  even though the load of pollutants from
the particular process was a small portion of the total load
on the waste water treatment plant.  It must  be  recognized
that  the  efficiency of pollutant removal from waste waters
would not necessarily be the same as  that  demonstrated  by
the  multi-process  treatment  plant unless the waste waters
                          180

-------
                                                                                              TABLE VII-1

                                                                          OPERATIONAL PARAMETERS  OF VASTEHATER TREATMENT PLANTS
                                                                                             (Metric Units)
00
Type of Plant Methyl* Polyvlnyl Thermoplastic*
Methacrylate Butyral P/E
Acrylic* Vinyl Acetate EVA Polypropylene
*1* 12*
1 Type of Treatment Neut, screen, Equal, aer Equal S neut (30-70Z of wastes Skin, oil sep skim, filter. Skim, oil aep Skim before
equalize, lagoon coag aer lagoons due to acrylic equal, bio-aer burn recovered clar, aoaerob discharge
cool, nutrient, add, clarlf mfg) equal, 2 clarif w/chem oil, recycle bio
bio Ox, clarify, trickling filters add, bio-anaer-recovered
Polyvinylidene*
Chloride
Aerated lagoon
settling basin
sludge aeration parallel or serial oblc polymer
& centrlfuglng clarlf 4 polish (primary only) (primary only)
lagoons (57 acres)
2 Hydraulic Load (cu m/day) 11,000(6800 actual) 1,135 43,906 3,936 409 4.807 30.280 1,890 4.656
3 Residence Time (hours) Cl) "' 	 	 ~"
4 BODj (kg removed/ day /cu m)
5 COD (.kg removed/day/cu m)
6 Power (HP/cu m)
7 Suspended solids (mg/llter)
8 Clarlfler overflew (m/day)
9 Blomass (mg/llter)
10 BOD$ (kg removed/day/kg HLSS)
11 Typical Values KBy-H out (mg/lltar)
12 Typical Values TKH out (mg/litar)
13 BODj In (mg/llter)
14 BODj out (mg/ liter)
15 COD BODj In
16 COD in (mg/llter)
17 COD out (mg/llter)
18 COD/BODj out
19 Iff. BODj Removal
20 Eff . COD Removal
Contents I

194- 34 120(2904)
0.85+ 0.36 0.009
0.46
0.106+ 0.06 0.018
50* 135
24.5 7.7
30004- 2991
0.17
14.6
14.8
800+ 543 1.476
120+ 39.7 422
1.5
839
179
4.5
854- 92.7+ 71+
79+ -
+ Design Values
Submerged aerators
41.5(424) 36 0.3 ' 8760
°-l°9 1.0? (API type skimmer) -
0.58 _
* 0.007 - 40.7
42 28 23 - 33
24.4 & 57.0 o.20 - 51
1200-1800 -
- - - -
1-89 - .1 to 1.5
8.33 - _
!.'*6 1,562 - (154) +
11 17 13 -
0.6(TOC/BOD) . (4.2) +
904(TOC) - 20.000(100)
" 37(TOC) 47 SOO(TOC) 27
I'*5 2.2(TOC/BOD) 3.6
99.4 99+
96+(TOC) - 96(TOC)


-
-
"
~
35
-
-
***
"
—
59
22
13
776
251
11.4
63+
68+


        Notes:
horsepower
calculated froa
size of blowers.
* Indicates wastewater plant serves a chemical manufacturing

(1J  First value is residence time In aerobic biological system.
     Values In ( ) is residence time in total system.

-------
                                                                      TABLE VII-1
                                                                      (Continued)

                                                OPERATIONAL PARAMETERS OF HASIEUATER TREATMENT PLANTS
                                                                    (Metril Unite)















1-1
CO
NJ














I



2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Co



Type of Plant

Type of Treatment (Neut.)
municipal
treatment


Hydraulic Load (cu m/day) 5-'
Residence Time (hours)*1'
BOD- (f removed/day/ cu •) ~
COD (fremoved/day/cu a) ~
Power (HP/cu m)
Suspended solids (mg/liter) -
Clarlfier overflow (a/day)
Blomass (mg/liter) -
"BODj (kg removed/day/kg MLSS)
Typical Values NHyN out (mg/llter)
Typical Values TKN out (ag/lic«r) ~
BOD, in(mg/liter) -
BODj out (mg/llter)
COD BODj In
COD in (mg/llter)
COD out (ag/llter)
COD/BODj out
Eff. BODj Removal
Eff. COD Removal
•menu! +Deslgn Values
Submerged aerators
horsepower
calculated from
Alkyd/Polyester Resins

Settling, bio* Municipal
aerobic (4 treatment
»tage)clarify (neut) *
hold lagoon


170 2
252
0.28
0.36
0.034
64
12.7
4,000
0.7
(Nutrients added) -
-
2,960
28
1.36
3,890
146
5.2
99+
96.2+
Includes lagoon
separator -
skinner, sump
* pH controller.
Silicones

Neut screen Neut. clsrify Bio-aerobic,
sedimentation sludge dewster clarify
screen) , skia. basin
filtration
(proposed
(primary onlf) (priaary only) secondary)
1,022 25,740 25,740
1.3 3+
(clarlfier)
- -
-
_
20 100
43.2 24.4
6500+
0.04
-
1.12
276+
24 - 38+
2.5
688
13.9 - 205+
0.58 - 5.4+
86.2+
70.2+




Cellulose* Polyvinyl Ether Spandex
Nitrate
*1* »2*
Neut. aedlaent Equal, naut. Settle 6 neut Biological Municipal
spray oxidation process wastes coagulation, treatment
wastes act. atlon
sludge clarify

2.0 *.«0 34,440
8.4 - 7.5 plant
2 city
i 0.93
0.66
0.02 - -
40.6 60 208 120
52.3
_ -
- - -
156
- 16 - -
219 - 776 2.200 3,900
30 1,100 104 225
3.05 2.1
2,370 4,440
123 .4 • S40 * ~
4.1+ 1.6 6.2 6.4
86 - 8*. 6 73
73 65-70+




size of blowers,
* Indicates wastewater plant serves a
  chemical manufacturing complex.
(1) First value Is residence tine In
    aerobic biological systea.
    Valuea in ( ) is residence tlaa in
    total system.

-------
                                                 TABLE VI1-2
                            OPERATIONAL PARAMETERS OF MASTEWATER TREATMENT PLANTS
                                               (English Units)


1
2
3
4
5.
6
7
8
9
00 10
11
12
13
14
15
16
17
18
19
20
Type of Plant

Type of Treatment
Hydraulic Load (MGD)
Residence Time (hours)
BODj (*removed/day/1000 ft3)
COD (fremoved/day/1000 ft3)
Power (HP/1000 ft3)
Suspended solids (mg/llter)
Clarifier overflow (CPD/ft2)
Biomaas (mg/llter)
BODS (1 renoved/day/IMLSS)
Typical Values NH.-ti out(mg/liter)
Typical Values TKN out (me/liter)
BODS in (mg/liter)
BODj out (mg/liter)
COD/BODj in
COD in (mg/liter)
COD out (mg/liter)
COD/BOD5 out
Eff. EODj Removal
Eff. COD Removal
Methyl*
Methacrylate

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

-
-
-
85+
_
Polyvinyl
Butyral

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

Equal & neut, (30-702 of wastes
aer lagoons due to acrylic
mfg) equal, 2
tricking filters
clarif 4 polishing
lagoonn (57 acres)
11.6 1.04
120(2904) 41.5(424)
0.54 6.8
-
0.5
42
600 t 1400
-
-
1.89
8.33
1,476 1,946
422 11
-
-
16
1.45
7Hf 99.4
-
Vinyl Acetate

EVA
tl 12
Skim, oil sep Skim, filter, Skim, oil sep
equal, bio-aer burn recoverd clar, aoaerob
clarif w/chem oil, recycle bio
add, blo-anaer-recovered
obic polymer
(primary only)
0.108
36
1.27 8
0-3 8.760
Polypropylene Polyvinylidene*
Chloride

Skim before Aerated lagoon
discharge settling basin
(primary only)
Q.5 1.23 MGD
-
64 (API type skimmer) -
36 (TOC)
0.2
28
5
1200-1800
—
—
"

17
0.6(TOC/BOD)
904 (TOC)
37 (TOC)
2.2(TOC/BOD)
99+
96+(TOC)
-
-
23
1,257
-
•- —
.1 to 1.5
~ ~
(154)+
13
(4.2)+
20,000(TOC)
47 800 (TOC)
3.6
* -
96 (TOC)
-
-
33 35
-
-
- -
- -
— —
59
22
13
776
27 251
11.4
63+
68+
+ Design value

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

-------
00
TABLE VII-2
(Continued)
OPERATIONAL PARAMETERS OF WASTEWATER TREATMENT PLANTS
(English Units)
Type of Plant
1
2
3
4
5
6
7
8
»
10
11
12
13
14
15
J6
17
18
19
20
Type of Treatment
Hydraulic Load (MOD)
Residence Time (hours) (1)
BODj (*removed/day/1000 cu ft)
COD (fremoved/day/1000 cu ft)
Pover (HPAOOO =u ft)
Suspended solids (mg/liter)
Clarlfier overflow (m/day)
Biomass (mg/llter)
BODj ( I removed/day/ ' MLSS)
Typical Values NHyH out (mg/liter)
Typical Values TKN out (mg/lttar)
BOD. In (mg/llter)
BODj out (m«/llt«r)
COO BOD5 in
COD in (mg/liter)
COD out (mg/liter)
COD/BODj out
Eff. BODj Removal
Eff. COD Removal
Alkyd/Polyester Resins
Sllicones Cellulose* Polyvinyl Spandex
Nitrate Ether
ii
(Neut.) Settling, Municipal Neut screen Neut. clarify Bio-aerobic, Neut. sediment Equal. Settle & neut Biological
Municipal aerobic (4 treatment sedimentation sludge dewater clarify spray oxidation neut process wastes coagulation
treatment stage) (neut.) I hid screen, skim, basin chlorinate city centrifuga-
clarify lagoon filtration wastes act. tion
(proposed sludge clarify
(primary only) (primary only) secondary)
0.0015 0.045 0.00053
252
17.4
22.2
0.95
64 -
312.5
4,000
0.7
(Nutrients added)
-
2,960
28 -
1.36
3,890
146
5.2
99+ -
96.2+
0.27 6.8 6.8 2.0 1.3 9.1
1.3 3+ 8.4 - 7.5 plant
(clarifier) 2 city
- ... 58
- - - 41
- 0.6 -
20 100 - 40.6 60 208 120
1,060 6CO+ - - 1,283
r - 6,500+ - - -
0.04 - - -
156
1.12 - 16
276+ 219 - 776 2,200
24 - 38+ 30 1,100 104 225
2.5 3.05 2.1
- 688 - ,S70 4,400
13.9 - 205+ 123.4 1,800 640 1.440
0.58 - 5.4+ 4.1+ 1.6 6.2 6.4
86.2+ 86 - 86.6 90+
70.2+ - '* 65-70+
12
Municipal
treatment
_
-
-
-'
-
-
-
-
-
-
3,900
-
-
-
-
-
-
-
      Kott*:
+Design Values

Submerged aerators
horsepower
calculated from
•lea of blowers.
^Indicates vastewater plant serves  a  cheaical
 manufacturing complex.
(1) First v.lue la residence tliM la  aerobic
    biological system.
    Values in ( ) is residence; tiste in total
    eystea.
                                                                               Includes lagoon
                                                                               separator -
                                                                               akissMr. sunp
                                                                               ft pH controller*

-------
                                                 TABLE  VII-3

                              PERFORMANCE OF OBSERVED WASTEWATER TREATMENT PLANTS
                                              BOD.
                                                                      COD
                                                                                     Suspended  Solids
                                         Inlet      Outlet
                                       mg/liter   rag/liter
                         Inlet     Outlet       Inlet       Outlet
                       mg/liter  mg/liter     mg/liter    mg/liter
Major Subcategory I

  Ethylene-Vinyl Acetate*


  Ethylene-Vinyl Acetate*


  Fluorocarbons


  Polypropylene Fibers


  Polyvinylidene Chloride*


Major Subcategory II

  Acrylic Resins*


  Acrylic Resins**


  Cellulose Derivatives


  Polyvinyl Butyral


Major Subcategory III

  Alkyds & Unsat. Polyesters


  Cellulose Nitrate


  Polyamids (Nylon 6/12 only)


  Polyesters (Thermoplastic)*


  Polyvinyl Ethers***


  Sillcones**


Major Subcategory IV

  Nitrile Barrier Resins


  Spandejc*
  59
 630
 666
1476


 776


 276
                      20,000(TOC) SOO(TOC)


             10          -           48
              8


             22
             17


             66
 543         40




2960         28


 251         34
422


104


 38
                                     27
                         776         251
                                     24
                        839
            3890
2370
                         688
                                    179
                         146
                                    124
             640


             205
                                                            21
                                                           360
                                                            42
                                                           135
                                                64


                                                41
                                   208
2200        225
                        4400        1440
                                                           120
*     Part of a multi-plant  wastewater  treatment facility :  Polyester  operations  contribute  app.  14Z  of  the
      lo adin g
**    Design values - facility  not  operable at time of visit

***   Combined  industrial municipal  treatment facility
                                                          185

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                                                                                                  TABLE VII-4






                                              OBSERVED TREATMENT  AND AVERAGE  EFFLUENT LOADINGS FROM WASTE WATER TREATMENT PLANT INSPECTIONS
Produce Acrylic Resinfl Acrylic Resins Alkyds and Cellulose Ethylene-
Unsaturated Nitrate* Vinyl Acetate'
Polyester
Ccscrol and Treat- Equalization, Neutralization, Settling. Four- Neutralization, Skianning
Currently in Use Polishing Lagoons Bio-oxidation oxidation Spray Oxidation
(design)
Polypropylene Polyvinyl
* Fibers Butyral Silicones
Skimming Equalization, (Multi-Product) (Fluid Product)
Sludge Bio-oxidation Sedimentation
(design) S timing, Fi It rati<
of Product]









BOD5




too






Suspended Solids
                            o.fo
                                               3.1






                                              30.8
0.09






0.47






0.21
                                                                            Observed or Reported Effluent Loading
 3.34                     0.07






13.7                      0.25






 4.4                      0.15
0.24






0.78






0.98
 2.6






13.6






 6.5
 8.6






46.0






25.0.
•Multi-plant vastevater treatment facility

-------
 represented  the  major  portion of  the hydraulic  and pollutant
 load.   Because of  the   many  variables   that  can  influence
 performance   of   a    waste   water  treatment plant,   the
 performance  of a multi-process waste water  treatment  plant
 can  only be taken as  a qualitative indicator of the removal
 efficiency that  might  be achieved when  operating exclusively
 on the  waste waters from a single process.  The paucity   of
 data  on  waste  water treatment facilities, as recorded in
 Tables  VII-1, VII-2, VII-3, and VII-4,  for this segment   of
 the  industry  is   not surprising because of the relatively
 small production capacities of the products and the  use   of
 municipal  sewerage systems  or  multi-process waste water
 treatment plants.

 Biological treatment of the waste waters from   this  segment
 of  the industry   appears  to  be  the method chosen   for
 effecting  removal of soluble   substances.    Pretreatment
 before  biological systems  is   often   required whether  the
 biological system  is operated by  the manufacturer  or  is a
 municipal    sewage  treatment  plant.   This   treatment   is
 predominantly neutralization for  the control of pH prior   to
 biological treatment.   Primary treatment such as required in
 municipal  treatment   plants  is  not routinely  necessary  for
 these waste  waters; however,  when  significant amounts   of
 oils  or  solvents do occur,  the  use of oil separators,
 skimmers, and settling basins or  lagoons is used.

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

 The  applicability and limitation  of  biological treatment
 processes as well   as   physico-chemical processes  to  this
 segment of the plastics and synthetics  industry are the same
 as  outlined for   the first  segment   and will be found in
 Section VII  of EPA Document 440/1-73/010 (16).
                         187

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Copper

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

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

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

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

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

Lead

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

Under alkaline conditions (usually created by  the  addition
of  lime)  lead  will  precipitate  out of solution and form
solid particles of lead carbonate and  lead  hydroxide.   As
with  the  removal  of copper, it is often necessary to also
                         188

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add coagulants to produce precipitates of  sufficient  size.
Precipitation followed by sedimentation has been reported to
produce  effluent  lead  concentrations  on the order of 0.5
mg/liter.   If  the  sedimentation  step  is   followed   by
filtration,  an effluent lead concentration of 0.03 mg/liter
may be achieved.

Ion  exchange,  while  reported  to   produce   lower   lead
concentrations,  usually  entails  a much higher capital and
operating cost than lime precipitation.

Mercury

The  most  promising  and   technically   proven   processes
currently available for the removal of low concentrations of
soluble  mercury  from  large  waste  water  streams are ion
exchange or sulfide precipitation.

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

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

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

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

Fluoride

Precipitation with lime is the standard  technique  for  the
reduction  of  high concentrations of soluble fluoride.  The
fluoride is precipitated as  calcium  fluoride.   While  the
                         189

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

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

In such processes the fluoride containing  water  is  passed
through   contact   beds  of  hydroxylapatite  or  activated
alumina.  Adsorptive on activated alumina has been  reported
to  be capable of producing effluent fluoride concentrations
as low as 1.0 mg/liter.  The use  of  adsorptive  techniques
has  largely  been  confined  to  the treatment of municipal
drinking water containing undesirably high concentrations of
fluoride.

Cyanide

The process most frequently employed for  the  treatment  of
waste   water   containing   cyanide   is   destruction   by
chlorination under alkaline conditions.  In this process the
cyanide may be partially  oxidized  to  cyanate  or  totally
oxidized  to  carbon  dioxide and nitrogen, depending on the
chlorine dosage.

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

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

Both the alkaline chlorination and ozonation  processes  can
become  prohibitively  expensive  if  the cyanide containing
waste water also contains  large  quantities  of  oxidizable
organic  material  which  will unavoidably be oxidized along
with the cyanide.
                         190

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Oil and Grease

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

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

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

Depending  on  conditions, varying amounts of emulsified oil
may be removed along with other  biodegradable  material  in
standard biological treatment processes.
                          191

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                        SECTION VIII

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

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

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

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

In  order  to  reflect  the different treatment economics of
existing versus new plants, large versus small plants, free-
standing versus joint  treatment  facilities,  or  municipal
versus  industrial  facilities,  costs  have  been developed
typically for more than one plant situation in each  product
subcategory.   These  productspecific analyses are presented
in Tables VIII-H/I to VIII-^/30.
                          193

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Cost Models of Treatment: Technologies

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

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

Cost-Effectiveness Perspectives

Rough  estimates  were  made  of the existing degree of BOD5
removal by either industrial or  municipal  systems  in  the
fifteen  product  groups.   A  7U  percent  weighted average
removal of BOD5_ was calculated for these synthetic  polymers
in  1972.   This is substantially higher than the H2 percent
removal for resin products because  of  the  higher  use  of
municipal systems for polymer wastes and the availability of
larger  central  industrial  treatment systems to handle the
lower volumes of these wastes.  By 1977, the average removal
implicit in BPCTCA requirements is estimated at 90  percent.
This  is  lower  than the 95 percent to be required of resin
production because,  again,  of  the  larger  proportion  of
municipal  treatment  -  for  which  85  percent  removal is
expected.

Annual cost Perspectives

Annual costs for existing plants were roughly  estimated  at
$1.8  million.   The  expected  annual  costs  for  existing
synthetic polymers  plants  in  1977  consistent  with  best
practicable  technology was estimated at $5.0 million.  This
estimate (Table VIII-2) was  the  result  of  the  following
considerations:   the production volumes and waste loads for
each of the fifteen product groups;  the  average  costs  of
treatment  for  different  plant  sizes;  or the costs to be
expected from handling these wastes  as  part  of  a  larger
                         194

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municipal  or  industrial  system.   Similarly, by 1983, the
estimated costs (Table VIII-2)  for  existing  plants  using
best  available  technology were $12.0 million.  It is noted
that these costs were associated with  endof-pipe  treatment
only.   Costs  for  in-plant additions or modifications were
not included.

The above annual cost  estimates  for  existing  plants  for
1972,  1977,  and  1983  indicate  average  increases  of 23
percent per year between 1972 and 1977, and 20  percent  per
year  between 1977 and 1983.  Much of the estimated increase
in costs between 1972 and 1977 was tied to the assumed  full
payment  of  charges  for  the  use of municipal facilities.
User  charges  for  treatment  services   beyond   secondary
biological   treatment   in   municipal   systems  were  not
considered appropriate  before  1983.    To  the  costs  for
existing  plants must be added the costs associated with new
plants, governed  by  BADT-NSPS.   Assuming  the  production
volume  of  new plants to be equal to the expected growth in
production, the potential annual cost  associated  with  new
plants in 1977 was estimated at $3.4 million (Table VTII-2).
Altogether,  that means that the industry's annual costs are
expected to increase 36 percent per year (from $1,8  million
in 1972 to $8.3 million (5.0 + 3.3) in 1977), this supported
by  a  sales  growth  of  14  percent  per  year.  A similar
estimate for 1983 has  been  precluded  by  the  lack  of  a
meaningful forecast of product growth.

Cost Per Unit Perspectives

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

Waste Water Treatment Cost Estimates

The  average  range  of water pollution control costs (Table
VIII-4) under  BPCTCA,  BATEA,  and  BADT-NSPS  technologies
respectively  were  $0.16  ($0.63), $0.40 ($1.52), and $0.17
($0.66) per cubic meter (per thousand gallons).  Table VIII-
4 and its 30 associated tables portray the  costs  of  major
                          195

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treatment   steps   required   to  achieve  the  recommended
technologies.   Where  municipal  user   charges   are   not
considered  directly,  the appropriate charge would be $0.39
or  $0.63  per  thousand  gallons  depending  on  the   size
economies of the representative municipal system.

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

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

Industrial Waste Treatment Model Data

In Tables VIII-5/1 to VIII-5/3 the total discharges for each
product  subcategory  are  estimated for 1972 and 1977.  The
quality  of  effluents  remaining  untreated  in   1977   is
indicated  as that consistent with the application of BPCTCA
technology.  Finally, the current  status  of  treatment  in
each  product  group is estimated in terms of the proportion
utilizing primary treatment and that  utilizing  a  form  of
biological treatment, whether industrial or municipal.

Energy Cost Perspectives

Each  of  the representative plant analyses in the 30 tables
summarized by Table VIII-H includes an  estimate  of  energy
costs   (of  control).   The  basis  for  these  energy  cost
estimates was explained in the earlier development  document
for   resins  production.   The  most  important  assumption
therein was one of 1972 energy prices.  That assumption  has
been  retained, for purposes of comparison, in this analysis
of polymers production.

Generally, the  biological  treatment  systems  employed  by
industries  and  municipalities  are  not large consumers of
energy.  By the cost models employed  in  this  report,  the
energy  costs  of  BPCTCA and BADT-NSPS technologies in this
industry were estimated at about  2  percent  of  the  total
annual  waste  water  treatment  costs in Table VIII-2.  The
                         196

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add-on technologies  for  BATEA  compliance,  however,  were
estimated to raise that proportion to 7 percent by 1983.

Non Water Quality Effects

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

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

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

Alternative Treatment Technologies

The  range  of  components  used  or  needed  to effect best
practicable control technology currently available (BPCTCA),
best available technology economically  achievable  (BATEA) ,
and  best  available  demonstrated technology for new source
performance standards (BADT-NSPS)  in  this  portion  of  the
                         197

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plastics  and  synthetics  industry  have been combined into
eight alternative end-of-pipe treatment steps.  These are as
follows:

    A.   Initial Treatment;  For removal of suspended solids
         and   heavy   metals.     Includes    equalization,
         neutralization,     chemical     coagulation     or
         precipitation,   API   separators,   and    primary
         clarification.

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

    c-   Multi-stage Biological;  For further removal of BOD
         loadings.   Either  another  biological   treatment
         system in series or a long-residence-time polishing
         lagoon.

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

    E.   Physical-Chemical Treatment;  For  further  removal
         of  COD,  primarily that attributable to refractory
         organics, e.g., with activated carbon adsorption.

    F-   Liquid Waste Incineration;  For complete  treatment
         of small volume wastes.

    G.   Municipal   Treatment;    Conventional    municipal
         treatment   of   industrial  discharge  into  sewer
         collection systems.  Primary settling and secondary
         biological stages assumed.
                         198

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                                             TABLE VIII-1
                         PERSPECTIVES ON THE PRODUCTION OF SYNTHETIC POLYMERS
                                              WATER USAGE
     Guidelines Subcategory
             Product
                                    Number of
                                     Company
                                  Operations(1)
                Percent of
            Total 15 Product
              Production(2)
             Percent of
             Water Used
           by 15 Products
Percent of Growth
In Water Usage of
   15 Products:
    1972-1977
II
 EVA Copolymers
 Fluorocarbons
 Polypropylene Fibers
 Polyvinylidene Chloride
I
 Acrylic Resins
 Cellulose Derivatives
       Subtotal - A&B
III
  Alkyd and Unsaturated
  Polyester Resins
  Cellulose Nitrate
  Polyamids
  Polyesters (thermoplastic)
  Polyvinyl Butyral
  Polyvinyl Ethers
  Sillcones
IV
  Nitrile Barrier Resins
  Spandex Fibers
       Subtotal - C&D
       Total - 15 Products
  5
  5
  3
  4

 >4
 _3
>24
                                        2
                                        3
                                        3
                                        2
                                        2
                                        4

                                        3
                                       _3
                                      >36
                                      >60
 5.9
 1.0
 5.5
 1.0

11.8
 3.9
29.1
                    58.8
                     2.0
                     1.0
                     0.2
                     1.6
                     0.4
                     5.1

                     1.0
                     0.8
                    70.9
                   100.0
                                                                            0.8
                                                                            4.6
                                                                            1.7
                                                                            0.4
                                                                           14.6
                                                                           17.6
                                                                           39.7
                 7.5
                10.9
                 0.8
                 0.4
                 5.9
                 0.4
                33.2
                 0.8
                 0.4
                 60.3
               100.0
      0.7
      2.6
      1.3
      0
      34.4
       8.6
      47.6
      11.9
      0
      0.6
      0.6
      2.6
      0.6
      32.9

      3.2
      0	
      52.4
    100.0
(1)    Number of companies producing each of the products; the number of plants is greater because
       of multiple sites for any one company.
(2)    Estimated annual 15-product production in 1972-73 period: 1.15B kkg (2.55 B Ibs).
(3)    Result of projected product growth  at current representative hydraulic loads.
                                               199

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                                  TABLE VIII-2
                   PERSPECTIVES ON SYNTHETIC  POLYMERS PRODUCTION
                             ANNUAL TREATMENT COSTS
Guidelines Subcategory
                                                 Total  Annual Costs, $MM

I




n


in







IV


Product

EVA Copolyners
Fluorocarbona
Polypropylene Fibers
Polyvlnylidene Chloride

Acrylic Resins
Cellulose Derivatives

Alkyds and UnsaturaCed
Polyester Resins
Cellulose Nitrate
Polyamldes
Polyesters (thermoplastic)
Polyvlnyl Butyral
Polyvlnyl Ethers
Slllcones

Kltrlle Barrier Resins
Spandex Fibers
Exist in? Plants
1977

0.12
0.36
0.17
0.01

0.58
0.97

0.45
0.30
0.08
0.03
0.30
0.03
1.56

0.04
0.04

1983

0.37
0.36
0.17
0.04

0.64
2.84

0.59
0.51
0.22
0.07
0.92
0.07
5.21

0.08
0.08
New Plants
1983

0.10
0.13
0.08
0.00

0.86
0.34

0.45
Q.OO
0.04
0.03
0.09
0.03
1.13

0.12
0.00
  Total
                                    5.04
                                                         12.17
                                                                              3.40
                                      200

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                                   TABLE VItl-3
                  PERSPECTIVES ON SYNTHETIC POLYMERS  PRODUCTION
                                    COST IMPACT
                                                Control Cost  Range as Z of  Sales  Price
Guideline Subcategory
Product
jt




11


III








IX



EVA Copolyners
Fluorocarbons
Polypropylene Fibers
Polyvlnylidene Chloride

Acrylic Resins
Cellulose Derivatives

Alkyd and Bnsaturated
Polyester Resins
Cellulose Nitrate
Folyamids
Polyesters (thermoplastic)
Polyvinyl Butyral
Polyvlnyl Ethers
Silicones

Nitrile Barrier Resins
Spandex Fibers
Price Level
c/lb

15
325
35
55

70
50


20
50
130
70
70
100
100

60
100
BPCTCA
X

1.0
0.1
0.7
0.1

0.1
1.1


0.4
0.8
0.1
0.1
0.4
0.2
0.6

0.1
0.1

- 2
- 0
- 1
- 0

- 0
- 2


- 1
- 1
- 0
- 2
- 2
- 0
- 1

- 0
- 0

.0
.6
.4
.2

.4
.0


.9
.7
.9
.9
.1
.7
.2

.6
.3

2.
0.
0.
0.

0.
3.


0.
1.
0.
0.
0.
0.
1.

0.
0.
BATEA
Z

3 -
1 -
7 -
1 -

1 -
3 -


4 -
0 -
2 -
3 -
4 -
2 -
7 -

1 -
1 -

6
0
1
0

0
5


3
3
2
6

.2
.6
.4
.7

.4
.7


.8
.6
.5
.4
10.7
1
3

1
0
.8
.5

.3
.5
BAM
X

1.
0.
0.
0.

0.
1.


0.
0.
0.
0.
0.
0.
0.

0.
0.

0
1
7
1

1
2


8
9
2
2
8
3
7

3
2
Unweighted Average
                                            0.4 - 1.3
0.7 - 3.3
                                                                                   0.5
                                       201

-------
                                       TABLE VIII-4

                          SUMMARY OF WATER EFFLUENT TREATMENT COSTS3
                                COST PER UNIT VOLUME BASIS
  Guidelines Subcategory
BPCTCA COSTS
                      BATEA  COSTS
BADT COSTS'
r ruuuci.
EVA Copolymers
Fluorocarbons
Polypropylene Fibers
Polyvinylidene Chloride
rc
Acrylic Resins
Cellulose Derivatives
III
Alkyd and Unsaturated
Polyester Resins
Cellulose Nitrate
Polyamids
Polyesters (thermoplastic)
Polyvinyl Butyral
Polyvinyl Ethers
Silicones
lY.
Nitrile Barrier Resins
Spandex Fibers
Average
$/cu m $/1000 gal
0.16
0.26
0.33
0.9 - 0.13

0.13
0.18

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

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

0.50
0.70

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

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

0.15
0.54

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

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

0.55
2.05

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

0.50 - 1.50
0.50 - 2.50
1.52
0.16
0.26
0.33
0.12

0.13
0.21

0.20
0.11
0.32
0.26
0.18
0.24
0.18

0.18
0.33
0.17
0.60
1.00
1.25
0.45

0.50
0.80

0.75
0.40
1.20
1.00
0.70
0.90
0.70

0.70
1.25
0.66
 Assume  330 day /year operation.  Estimated proportions treated
 municipal  systems  factored in  at  $0.50/1000  gal.
^Assume   new plants  are  larger  facilities with  minimum flows.   New
 plant production assumed equivalent to growth  between 1972  and
 1977.
                                       202

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                           TABLE VIII-4/1

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:  Ethylene Vinyl Acetate

Plant Description:  Small  Plant - Large Industrial Complex
Representative Plant Capacity
    million kilograms (pounds) per year:     11.3
Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)
                   11.9
Treatment Plant Size
    thousand cubic meters per day  (MGD):      6.4
                  (25)


                  (1.3)



                  (1.7)'
Costs -  $1000
              Alternative Treatment Steps
Initial Investment
             28
         65
15
106
Annual  Costs:

     Capital Costs  (8%)
     Depreciation  (10%)
     Operation and  Maintenance
     Energy and Power

            Total  Annual  Costs         5.4     15        3

Effluent  Quality  (expressed  in  terms of yearly averages)
2.2
2.8
0.3
0.1
5.2
6.5
3
0.3
1.2
1.5
0.3
—
8.5
10.6
15.9
4
                                       39
 B.O.D.
 C.O.D.
 Suspended  Solids
                     Raw Waste Load
 1
 2
N/A
    Resulting Effluent Levels
 (units per 1000 units of product)
 A        1        .2.        I
         0.1       -       0.08
         1         -       0.7
0.3       -       0.05
*The EVA contribution is 0.4 thousand cubic meters per day (0.1 mgd).   This
 is approximately 6% of the total flow to be treated.
                                 203

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                           TABLE VIII-4/2

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY



Industry Subcategory:  Ethylene Vinyl Acetate

Plant Description:  Large  Plant -  Industrial Complex

Representative Plant Capacity
    million kilograms  (pounds) per year:    22.7         (50)

Hydraulic Load
    cubic meters/metric ton of product:     11.9         (1*3)
    (gal/lb)

Treatment Plant Size
    thousand cubic meters per day (MGD):     6.8         (1.8)*


Costs - $1000                          Alternative Treatment Steps
Initial Investment                   53       124       29       204


Annual Costs:
    Capital Costs (8%)                4.1        9.8       2.3      16
    Depreciation  (10%)                5.3       12.4   ,    2.9      20
    Operation and Maintenance         0.5        5.3       0.4      32
    Energy and Power                  0.1        0.5       -        8

            Total Annual Costs       10         28         5.6      77

Effluent Quality  (expressed in  terms  of yearly  averages)
                     Raw Waste Load       Resulting Effluent Levels
                                        (units per 1000 units of product)
                                      A       JB        I)        E
 B.O.D.                     1                   0.1               0.08
 C.O.D.                     2          -       1         -       0.7
 Suspended Solids         N/A         0.3        -       0.05


 * The EVA contribution is  0.8 thousand  cubic meters per day  (0.2 mgd).
   This is approximately 11% of the total  flow to be treated.
                                  204

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                           TABLE VIII-4/3

                    WATER EFFLUENT TREATMENT COSTS
                   PLASTICS AND SYNTHETICS INDUSTRY


Industry Subcategory:  Fluorocarbons

Plant Description:  Small Plant  -  Free  Standing

Representative Plant Capacity
    million kilograms (pounds) per year:   1.4         (3)

Hydraulic Load
    cubic meters/metric ton of product:  125           (15.0)
    (gal/lb)

Treatment Plant Size
    thousand cubic meters per day (MGD):   0.5         (0.14)


Costs - $1000                          Alternative Treatment Steps

                                       A
Initial Investment                    44


Annual Costs:
    Capital Costs (8%)                 3.5
    Depreciation (10%)                 4.4
    Operation and Maintenance          2.0
    Energy and Power                   0-1

            Total Annual Costs        1°

Effluent Quality (expressed in terms of yearly averages)
                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)
                                       A
B.O.D.                    3            2
C.O.D.                   20           20
Suspended Solids          5            5
                               205

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                           TABLE VIII-4/4

                    WATER EFFLUENT TKEATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY



Industry Subcategory:  Fluorocarbons

Plant Description:     Small Plant - Municipal Discharge

Representative Plant Capacity
    million kilograms (pounds)  per year:  1.4         (3)

Hydraulic Load
    cubic meters/metric ton of product:  125           (15.0)
    (gal/lb)

Treatment Plant Size
    thousand cubic meters per day (MGD):  0.5         (0.14)


Costs - $1000                          Alternative Treatment Steps

                                       P*        M         M
Initial Investment                    102


Annual Costs:

    Capital Costs (8%)                  8
    Depreciation (10%)                 10
    Operation and Maintenance           4        -
    Energy and Power                    1        -

            Total Annual Costs         23       18          29

Effluent Quality (expressed in terms of yearly averages)


                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)

B.O.D.                     3
C.O.D.                   20                   (municipal treatment)
Suspended Solids           5

 * Neutralization of  acids

 MI  is the municipal  treatment  charge  associated with  a  38  to  76  thousand cubic
    meters per  day  (10-20 mgd)  treatment plant.  A charge of 39
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                           TABLE VIII-4/5
                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:  Fluorocarbons

Plant Description: Large Plant - Free Standing

Representative Plant Capacity
    million kilograms (pounds) per year:    6.8

Hydraulic Load
    cubic meters/metric ton of product:   125
    (gal/lb)

Treatment Plant Size
    thousand cubic meters per day (MGD):    2.6
                             (15)


                             (15.0)



                             (0.7)
Costs - $1000
              Alternative Treatment Steps
                                       A
Initial Investment
             145
Annual Costs:

    Capital Costs (8%)
    Depreciation (10%)
    Operation and Maintenance
    Energy and Power
              11.6
              14.5
               8.6
               0.3
            Total Annual Costs          35

Effluent Quality (expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
                     Raw Waste Load
 3
20
 5
    Resulting Effluent Levels
 (units per 1000 units of product)
 A
 2
20
 5
                                207

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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

                                       I*       %        M2



Initial Investment                     285


Annual Costs:

    Capital Costs (8%)                 23       -         -
    Depreciation (10%)                 29       -         -
    Operation and Maintenance            6       -
    Energy and Power                     1       -

            Total Annual Costs         59      88        142

Effluent Quality (expressed in terms of yearly averages)
                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)

B.O.D.                    3
C.O.D.                   20                 (Municipal treatment)
Suspended Solids          5


* Neutralization of Acids
                                208

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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)
                                       All
B.O.D.                    0.5          0.3   -      0.1
C.O.D.                    1.5          1.3   -      0.2
Suspended Solids          1.0          0.5   0.1
                                209

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                            TABLE VIII-4/8

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:     Polypropylene Fibers

Plant Description:        Municipal Discharge

Representative Plant Capacity
    million kilograms (pounds) per year:     20.4         (45)

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                  8.3         (1.0)

Treatment Plant Size
    thousand cubic meters per day (MGD):      0.5         (0.14)


Costs - $1000                          Alternative Treatment Steps
                                       P*    MI     M2

Initial Investment                     89    -


Annual Costs:

    Capital Costs (8%)                 7
    Depreciation (10%)                 9
    Operation and Maintenance         18     -      -
    Energy and Power                   i     -      -

            Total Annual Costs        35     18     29

Effluent Quality (expressed in terms of yearly averages)
                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)

B.O.D.                    0.5
C.O.D.                    1.5          (Municipal Treatment)
Suspended Solids          1.0

*Air flotation for oil and grease removal.
                               210

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                                TABLE VIII-4/9

                        WATER  EFFLUENT  TREATMENT  COSTS

                       PLASTICS AND  SYNTHETICS  INDUSTRY



     Industry  Subcategory:       Polyvinylidene Chloride

     Plant Description:          Small Plant - Industrial  Complex

     Representative Plant Capacity
        million kilograms  (pounds) per  year:    2.3            (5)

     Hydraulic Load
        cubic meters/metric  ton of product:
        (gal/lb)                                4.2            (0.5)

     Treatment Plant  Size
        thousand  cubic meters  per day (MGD):    1.7            (0.45)*


     Costs - $1000                         Alternative Treatment Steps
     Initial  Investment                       4        2        11


     Annual Costs:

         Capital  Costs  (8%)                   0.3      0.2       0.9
         Depreciation  (10%)                   0.4      0.2       1.1
         Operation and Maintenance            0.06      0.1       1.8
         Energy and Power                     0.04      -        0.2

                 Total Annual  Costs           0.8      0.5       4.0

     Effluent Quality  (expressed  in  terms of  yearly  averages)


                         Raw  Waste  Load       Resulting Effluent  Levels
                                           (units per 1000 units  of product)

     B.O.D.                     0
     C.O.D.                     8              (No specific  guidelines)
     Suspended Solids           0.2

*The PVC1 contribution  is 0.03 thousand cubic meters per day  (0.007 MGD);
 this is  approximately  1.5%  of the total flow to be  treated.
                                  211

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                            TABLE VIII-4/10

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY



Industry Subcategory:     Polyvinylidene Chloride

Plant Description:        Large  Plant - Industrial Complex

Representative Plant Capacity
    million kilograms (pounds) per year:   11.3            (25)

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                4.2            (0.5)

Treatment Plant Size
    thousand cubic meters per day (MGD):    1.7            (0.45)*


Costs - $1000                          Alternative Treatment Steps
Initial Investment                      21       11       55


Annual Costs:

    Capital Costs (8%)                  1.7      9        4.4
    Depreciation (10%)                  2.1      11       5.5
    Operation and Maintenance           0.2       0.1     9.4
    Energy and Power                    0.1      -        1.5

            Total Annual Costs          4        20.1    21

Effluent Quality (expressed in terms of yearly averages)
                     Raw Waste Load       Resulting Effluent Levels
                                        (units per 1000 units of product)

B.O.D.                     0              (No specific guidelines)
C.O.D.                     8
Suspended Solids           0.2

*The  PVC1 contribution  is  0.13 thousand cubic meters per day (0.035 MGD);
  this is approximately  20% of the  total flow to be treated.
                            212

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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     1.9
    Depreciation (10%)                  5     11     2.4
    Operation and Maintenance           0.4    6.5   0.2
    Energy and Power                    0.1    0.5

            Total Annual Costs          9.5   27     4.5

Effluent Quality (expressed in terms of yearly averages)


                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)

B.O.D.                    15
C.O.D.                    30           (No specific guidelines)
Suspended Solids           7.5

*The  acrylic resin contribution is 0.9 thousand cubic meters per day (0.23 MGD),
 this is approximately 5% of the total flow to be treated.
                           213

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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         (120)

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                 32           (3.8)

Treatment Plant Size
    thousand cubic meters per day (MGD):      13.1         (3.46)*


Costs - $1000                          Alternative Treatment Steps

                                       A     B      D
Initial Investment                    296   724    156


Annual Costs:

    Capital Costs (8%)                 24    58     12
    Depreciation (10%)                 30    72     16
    Operation and Maintenance           3    36      1
    Energy and Power                    13-

            Total Annual Costs         58   169     29

Effluent Quality (expressed in terms of yearly averages)
                     Raw Waste Load       Resulting Effluent Levels
                                        (units per 1000 units of product)

B.O.D.                    15
C.O.D.                    30            (No specific guidelines)
Suspended Solids           7.5

*The acrylic resin contribution is 5.2 thousand cubic meters per day
 (1.38 MGD), this is approximately 40% of the total flow to be treated.
                            214

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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

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                117

Treatment Plant Size
    thousand cubic meters per day (MGD):      8
                                (10)



                                (14)


                                (2.1)*
Costs - $1000
            Alternative Treatment Steps

            A       B       D          E
Initial Investment
           104
   256
56
334
Annual Costs:

    Capital Costs  (8%)
    Depreciation  (10%)
    Operation and Maintenance
    Energy and Power

            Total Annual Costs
8
10
3
0.5
20
26
18
8
4.5
5.6
0.6
-
27
33
33
8
            21.5
    72
10.7
Effluent Quality  (expressed in  terms of yearly averages)
101
B.O.D.
C.O.D.
Suspended Solids
                     Raw Waste Load
180
650
 20
               Resulting Effluent Levels
             (units per 1000 units of product)
(No specific guidelines)
*The cellulose derivative contribution is 1.6 thousand cubic meters per day
 (0.42 MGD); this is approximately 20% of the total flow to be treated.
                            215

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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.
                             216

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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         (0.4)

 Treatment Plant Size
     thousand cubic meters per day (MGD):      0.15        (0.04)


 Costs - $1000                          Alternative Treatment Steps

                                        A     B*     C**
 Initial Investment                     30    84     84


 Annual Costs:

     Capital Costs (8%)                  2.4   6.7    6.7
     Depreciation (10%)                  3.0   8.4    8.4
     Operation and Maintenance           2.4  15.3   10.4
     Energy and Power                    0.2   0.6    0.5

             Total Annual Costs          8    31     26

 Effluent Quality (expressed in terms of yearly averages)
                    ,  Raw Waste Load       Resulting Effluent Levels
                  ','..,;  :.,.-.-               (units per 1000 units of product)
                                        A     B_      £
 B.O.D.                    10           -      0.2    0.0?
 C.O.D.                    25           -      1      0.3
 Suspended Solids           1            0.1  -       0.02

 *Two-stage biological treatment
**Two additional stages of biological treatment
                             217

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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*    MI     M2


Initial Investment                     5.0


Annual Costs:

    Capital Costs (8%)                 Q.4
    Depreciation (10%)                 Q.5
    Operation and Maintenance          I.Q
    Energy and Power                   _     _      _

            Total Annual Costs         1,9   o.l    0.2

Effluent Quality (expressed in terms of yearly averages)
                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)

B.O.D.                    10
C.O.D.                    25           (Municipal Treatment)
Suspended Solids           1

*Pretreatment is Clarification or Filtration.
                             218

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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     B**    C***


  Initial Investment                     30    84     84


  Annual Costs:

      Capital Costs (8%)                   2.4   6.7    6.7
      Depreciation (10%)                   3.0   8.4    8.4
      Operation and Maintenance           2.4  15.3   10.4
      Energy and Power                    0.2   0.6    0.5

              Total Annual Costs          8    31     26

  Effluent Quality (expressed in terms of yearly averages)


                       Raw Waste Load       Resulting Effluent Levels
                                         (units per 1000 units of product)
                                         A     _B      £
  B.O.D.                    10           -     0.2    0.07
  C.O.D.                    25           -     1      0.3
  Suspended Solids           1           0.1   -      0.02

  *Dilution of 7:1 for effective operation of the biological treatment has
   been allowed.
 **Two-stage biological treatment,
***Two additional stages  of biological treatment.


                               219

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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%)                  0.8    -
    Depreciation  (10%)                  1.0
    Operation and Maintenance           1.0    -
    Energy and Power                    -            -

            Total Annual Costs          2.8    0.7     1.1

Effluent Quality  (expressed in  terms of  yearly averages)
                     Raw Waste Load       Resulting Effluent  Levels
                                        (units per  1000 units  of  product)

B.O.D.                     10
C.O.D.                     25           (Municipal  Treatment)
Suspended Solids            1

 *Pretreatment is  clarification or filtration.
                             220

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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         ,-,      ,„„       „,

Effluent Quality (expressed in terms of yearly averages)
27
33
6.4
0.6
62
78
43
9
14
18
2
-
77
97
79
22
                                      275
B.O.D.
C.O.D.
Suspended Solids
                     Raw Waste Load
35
75
85
   Resulting Effluent Levels
 (units per 1000 units of product)
A        JL        P_       JL
         7-2
        23        -      14
4        -        1
*The cellulose nitrate contribution is 9.2 thousand cubic meters per day
 (2.43 MGD); this is approximately 20% of the total flow to be treated.
                                221

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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
                               222

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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

             ABODE
Initial Investment
                                        18
                   42
             42
10
60
Annual Costs:

    Capital Costs  (8%)
    Depreciation  (10%)
    Operation and Maintenance
    Energy and Power
            Total Annual Costs           3.7   13      13      2

Effluent Quality (expressed in terms of yearly averages)
1.4
1.8
0.4
0.1
3.4
4.2
3.7
1.7
3.4
4.2
3.7
1.7
0.8
1.0
0.2
-
4.8
6.0
7.1
1.1
                                       19
B.O.D.
C.O.D.
Suspended Solids
                     Raw Waste Load
N/A
N/A
N/A
   Resulting Effluent Levels
(units per 1000 units of product)
A     JL      £     D.      1
-            0.3   -      0.1
             3     -      1.2
0.2   -      -     0.07
 *The polyamide contribution  is 0.23 thousand cubic meters per day
  (0.06 MGD),  this is approximately 5% of  the total flow to be treated.
                               223

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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_      £     ID      .E
-     -      0.4   -      0.2
      -      5     -      1
0.2   -      -     0.08
 *The  thermoplastic  resin  contribution  is 0.06 thousand cubic meters per day
  (0.015 MGD);  this  is  approximately 3% of the total flow to be treated.
                               224

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                            TABLE  VIII-4/23
                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:     Polyvinyl Butyral

Plant Description:        Free Standing Treatment Plant

Representative Plant Capacity              9.1           (20)
    million kilograms (pounds) per year:

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                              96             (11.5)

Treatment Plant Size
    thousand cubic meters per day (MGD):   2.6           (0.7)
Costs - $1000
             Alternative Treatment Steps

             A     1      D     E
Initial Investment
            285   725
      135  1614
Annual Costs:

    Capital Costs (8%)
    Depreciation (10%)
    Operation and Maintenance
    Energy and Power
             23    58     11   129
             29    73     14   161
              3    50      2   525
              0.5   4      -   155
            Total Annual Costs         55.5 185     27   970

Effluent Quality (expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
                     Raw Waste Load
30
40
N/A
                Resulting Effluent Levels
              (units per 1000 units of product)
             A     B      D     E
0.9
9
       0.5   -
                               225

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                            TABLE VIII-4/24

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY



Industry Subcategory:     Polyvinyl Ether

Plant Description:        Plant in Industrial Complex

Representative Plant Capacity
    million kilograms (pounds) per year:     i.g          (4)

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                12.5          (1.5)

Treatment Plant Size
    thousand cubic meters per day (MGD):     2.3          (0.6)*


Costs - $1000                          Alternative Treatment Steps

                                       A     B      D     E
Initial Investment                     8     21     4     25


Annual Costs:

    Capital Costs (8%)                 0.6   1.7    0.3   2.0
    Depreciation (10%)                 0.8   2.1    0.4   2.5
    Operation and Maintenance          0.1   1.1    0.1   4.0
    Energy and Power                   -     0.1    -     0.5

            Total Annual Costs         1,5   5      0.8   9

Effluent Quality (expressed in terms of yearly averages)
                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)
B.O.D.
C-O.D.                    25           (No specific guidelines)
Suspended Solids
*The polyvinyl ether contribution is 0.07 thousand cubic meters per day
 (0.018 MGD); this is approximately 3% of the total flow to be treated.
                               226

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                            TABLE VIII-4/25


                    WATER EFFLUENT TREATMENT COSTS
                   PLASTICS AND SYNTHETICS INDUSTRY


Industry Subcategory:     Silicones

Plant Description:        Fluids  Only  -  Free Standing

Representative Plant Capacity
    million kilograms (pounds) per year:     22.7          (50)

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                 54            (6.5)

Treatment Plant Size
    thousand cubic meters per day (MGD):      3.8          (1.0)


Costs - $1000                          Alternative Treatment Steps

                                       A    *L      P.     1.



Initial Investment                     305   745    232   1338


Annual Costs:
    Capital Costs (8%)                 24    60     19    107
    Depreciation  (10%)                 31    75     23    134
    Operation and Maintenance            6    40      2    228
    Energy and Power                   0.6     9      -      53

            Total Annual Costs       61.6   184     44    522

Effluent Quality  (expressed in terms of yearly averages)
                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)
                                       A     B_      D     IS
B.O.D.                    N/A          -     1.5    -     0.6
C.O.D.                    15           -     7.5    -     4.0
Suspended Solids          N/A          1.0   -      0.2
                               227

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                            TABLE VIII-4/26

                    WATER EFFLUENT  TREATMENT  COSTS

                   PLASTICS AND  SYNTHETICS  INDUSTRY
Industry Subcategory:      Silicones
                           Fluids Only - Industrial Complex
Plant Description:

Representative Plant Capacity
    million kilograms  (pounds) per  year:      22.7         (50)

Hydraulic Load
    cubic meters/metric  ton of product:
    (gal/lb)                                  54           (6.5)

Treatment Plant  Size
    thousand  cubic meters  per day  (MGD) :      43.5         (11.5)*
 Costs -  $1000                          Alternative  Treatment  Steps

                                       A     :B      p_     E



 Initial  Investment                     143   334     77   436


 Annual Costs:
     Capital  Costs  (8%)                  11    27      6    35
     Depreciation  (10%)                  14    33      8    44
     Operation  and Maintenance            3    18      1    36
     Energy and Power                     0.3   4      -    10

             Total Annual  Costs          28.3  82     15   125

 Effluent Quality  (expressed  in  terms  of  yearly averages)
                      Raw Waste Load       Resulting Effluent Levels
                                        (units per 1000 units of product)
                                        A     Bi      D     E_
 B.O.D.                     N/A          -     1.5    -     0.6
 C.O.D.                     15           _     7.5    _     4.0
 Suspended Solids           N/A          1.0   -      0.2
*The silicone contribution is 3.8 thousand cubic meters per day (1.0 MGD); this is
 approximately 9% of the total flow to be treated.
                               228

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                            TABLE VIII-4/27

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:      Silicones
                           Multi-product  -  Free  Standing
Plant Description:

Representative Plant Capacity
    million kilograms (pounds) per year:      22.7          (50)

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                 142            (17.0)

Treatment Plant Size
    thousand cubic meters per day (MGD):      17.2          (4.55)
Costs - $1000                          Alternative Treatment Steps

                                       A    1     R.    Ji



Initial Investment                     720   1760   441   3044


Annual Costs:

    Capital Costs (8%)                   53     141     35     244
    Depreciation (10%)                   72     176     44     304
    Operation and Maintenance            15     74     4     646
    Energy and Power                     2     14     -      200

            Total Annual Costs         147     405     83   1394

Effluent Quality (expressed in terms of yearly averages)
                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)
                                       A     _B      £    E
B.O.D.                    85                 7            3
C.O.D.                   115           -     35      -    18
Suspended Solids          50           5     -      1
                              229

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                            TABLE VIII-4/28

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:

Plant Description:
 Silicones
 Multi-product - Industrial Complex
Representative Plant Capacity
    million kilograms (pounds) per year:

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)

Treatment Plant Size
    thousand cubic meters per day (MGD):
                    22.7
                   142
                                             42.8
                   (50)



                   (17.0)


                   (11.3)*
Costs - $1000
              Alternative Treatment Steps
Initial Investment
             509   1187   289   2191
Annual Costs:

    Capital Costs (8%)
    Depreciation (10%)
    Operation and Maintenance
    Energy and Power

            Total Annual Costs
41
51
9
1
95
119
66
13
23
29
2

175
219
622
194
             102
      293
i>4   1210
Effluent Quality (expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
                     Raw Waste Load
 85
115
 50
   Resulting Effluent Levels
(units per 1000 units of product)
A     B_      D     E_
      7-3
     35      -     15
5            1     -
*The silicone contribution is      thousand cubic meters per day
             this is approximately 20% of the total flow to be treated.
                               230

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                            TABLE VIII-4/29

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY



Industry Subcategory:     Nitrile Barrier  Resins

Plant Description:        Plant  in  Industrial  Complex

Representative Plant Capacity
    million kilograms (pounds) per year:     4.5           (10)

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                 25            (3.0)

Treatment Plant Size
    thousand cubic meters per day (MGD):     8.3           (2.2)*


Costs - $1000                          Alternative Treatment Steps
Initial Investment                     23    59     12    67


Annual Costs:

    Capital Costs (8%)                  25      15
    Depreciation (10%)                  2617
    Operation and Maintenance           0.3   5      0.1   6
    Energy and Power                    0.1   1      -     1

            Total Annual Costs          4.4  17      2.1  19

Effluent Quality (expressed in terms of yearly averages)


                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)

B.O.D.                    10
C.O.D.                    30           (No specific guidelines)
Suspended Solids           5

*The nitrile barrier resin contribution is 0.34 thousand cubic meters per day
  (0.09 MGD); this is approximately 40% of the total flow to be treated.
                               23i

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                            TABLE VIII-4/30

                    WATER EFFLUENT TREATMENT COSTS

                   PLASTICS AND SYNTHETICS INDUSTRY



Industry Subcategory:      Spandex Fibers

Plant Description:         Plant  in Industrial Complex

Representative Plant Capacity
    million kilograms (pounds) per year:     2.3           (5)

Hydraulic Load
    cubic meters/metric ton of product:
    (gal/lb)                                 8.3           (1.0)

Treatment Plant Size
    thousand cubic meters per day (MGD):     3.4           (0.9)*


Costs - $1000                          Alternative Treatment Steps

                                       A     B      D      E
Initial Investment                     8    16      3    21


Annual Costs:
    Capital Costs (8%)                 0.6   1.3    0.2   1.7
    Depreciation (10%)                 0.8   1.6    0.3   2.1
    Operation and Maintenance          0.2   1.4    0.1   3.7
    Energy and Power                   -     0.2    -     0.5

            Total Annual Costs         1.6   4.5    0.6   8

Effluent Quality (expressed in terms of yearly averages)


                     Raw Waste Load       Resulting Effluent Levels
                                       (units per 1000 units of product)

B.O.D.                    20
C.O.D.                    40           (No specific guidelines)
Suspended Solids          N/A

*The Spandex contribution is 0.06 thousand cubic meters per day (0.015 MGD);
 this is approximately 2% of the total flow to be treated.
                               232

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                                          TABLE VIII-5/1

                INDUSTRIAL WASTE TREATMENT MODEL DATA SYNTHETIC POLYMERS PRODUCTIOH
                                 EVA      Fluorocarbons  Polypropylene Polyvinylidcne  Acrylic
                              Copolymers	Fibers	Chloride	Resins


Total Industry Discharge
 1000 cubic meters/day
4


80
65
20
                                                  233

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                         TABLE VIII-5/2
INDUSTRIAL WASTE TREATMENT MODEL DATA  -  SYNTHETIC  POLYMERS PRODUCTION
Cellulose
Derivatives
Total Industry Discharge
1000 cubic meters/day
(or million gallons/day)
1972 15.9(4.2)
1977 20.9(5.5)
Quality of Effluents in 1977
(Expressed in terms of yearly averages)
Parameters :
(in units/1000 units of product)
BODS NA
COD NA
Suspended Solids NA
Hydraulic Load: 1972-1977
(cu m/kkg (or gal/lb) NA
Numbers of Companies 3
Percent of Treatment in 1972
(in percent now treated)
A. Industrial Pretreatment 100
B. Industrial Biological 100
C. Municipal 0
Alkyds and
Unsaturated
Polyesters

6.8(1.8)
13.7(3.6)



0.4
2.0
0.1
3.2(0.4)

10
10
90
Cellulose Polyamides Polyesters
Nitrate Thermoplastic

9.8(2.6) 0.8(0.2) 0.4(0.1)
9.8(2.6) 1.2(0.3) 0.8(0.2)



5.0 0.3 0.35
25 3.0 5.3
4.2 0.2 0.24
142(17) 6.7(0.8) 2.2(0.95)
2 33
100 100 100
40 60 50
60 00
                             234

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                         TABLE VIII-5/3
INDUSTRIAL WASTE TREATMENT  MODEL DATA - SYNTHETIC POLYMERS PRODUCTION
Total Industry Discharge
1000 cubic meters/day
(or million gallons/day)
1972
1977
Quality of Effluents in 1977
Polyvinyl
Butyral
5.3(1.4)
6.7(1.8)
(Expressed in terms of yearly averages)
Parameters :
(in units/1000 units of product)
BOD5 NA
COD NA
Suspended Solids NA
Hydraulic Load: 1972-1977
cu m/kkg (or gal/lb)
Numbers of Companies
Percent of Treatment in 1972
(in percent now treated)
A. Industrial
B. Industrial Biological
C. Municipal
NA
2
100
25
75
Polyvinyl Silicones Nitrile Spandex
Ethers Barrier Resins Fibers
0.4(0.1) 29.9(7.9) 0.8(0.2) 0.4(0.1)
0.6(0.2) 48.5(12.8) 2.7(0.7) 0.4(0.1)
NA 10.5 NA NA
NA 53 NA NA
NA 7.0 NA NA
NA 233(28) NA NA
24 33
70 100 100 100
0 20 70 60
30 0 30 10
                                235

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                         SECTION IX

  BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
                 GUIDELINES AND LIMITATIONS
Definition of Best Practicable Control Technology
Currently Available  (BPCTCA)

Based on  the  analysis  of  the  information  presented  in
Sections IV to VIII, the basis for BPCTCA is defined herein.
Best  practicable  control  technology  currently  available
(BPCTCA)  for  existing  point  sources  is  based  on   the
application  of  end-of-pipe  technology  such as biological
treatment  for  BODjj  reduction  as  typified  by  activated
sludge,   aerated   lagoons,   trickling  filters,  aerobic-
anaerobic  lagoons,  etc.,  with   appropriate   preliminary
treatment   typified   by   equalization,  to  dampen  shock
loadings, settling, clarification, and  chemical  treatment,
for  removal  of suspended solids, oils, other elements, and
pH   control,   and   subsequent   treatment   typified   by
clarification  and  polishing  processes for additional BOD5
and suspended solids removal and dephenolizing units for the
removal of  phenolic  compounds.   Application  of  in-plant
technology  and  changes  which  may  be  helpful in meeting
BPCTCA include segregation of  contact  process  waste  from
noncontact   waste   waters,   elimination  of  once-through
barometric  condensers,   control   of   leaks,   and   good
housekeeping practices.

The  best practicable control technology currently available
has been found to be capable of generally effecting  removal
efficiencies  of  upwards  to  85  percent  in  single-stage
biological systems.  The design and operating parameters  of
the  biological  treatment  system may vary from essentially
those  of  a  municipal  sewage  treatment  plant  to  those
uniquely   tailored   to   a   specific  plant  waste.   The
acceptability of many of the  waste  waters  into  municipal
sewage  systems  has been established and often proves to be
one of the best  methods  of  waste  water  treatment  where
suitable   pretreatment   can  be  effected  and  where  the
synergistic effects of  treating  with  sewage  ocsur.   The
applicability   of   biological   systems  has  been  proven
regardless of the age or size of the manufacturing plant.

Because of the relatively small  number  of  single  product
waste  water  treatment  plants  (much  of the industry uses
either  multi-plant  waste  water  treatment  or   municipal
treatment)  the amount of data on which effluent limitations
can be based is limited, and it has been necessary  to  rely
                         237

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on  analogy  and  technology transfer for guidelines in some
instances.  Because of the  variabilities  inherent  in  the
performance   characteristics   of  industrial  waste  water
treatment plants, especially those affecting the  growth  of
microorganisms    such    as    temperature   and   variable
concentrations, the guidelines have taken into consideration
demonstrated unique properties such as  high  concentrations
of  COD  that  can  exist  in the treated waste waters.  The
parameters of primary concern are BOD5, COD,  and  suspended
solids.   Other  parameters  such as pH, metals, nitrogenous
compounds and specific chemicals such as phenolics are  also
of concern to the industry.

In  Table  Vll-4  of Section VII the effluent loadings which
are currently being attained by  the  product  subcategories
for  BOD£, COD, and suspended solids are presented.  In some
instances it was necessary to  calculate  effluent  loadings
based  on  the hydraulic flows emanating from the production
plant and the concentrations of the particular parameters in
the effluents from a waste  water  treating  plant  handling
waste  water streams from a number of other processes.  This
procedure was adopted when it was known that  a  significant
fraction  of  the waste water treatment plant load came from
the process under consideration or where the treatability of
the waste waters could be expected to be analogous to  those
of the major product, e.g., the similarity of ethylene-vinyl
acetate  wastes  to  low density polyethylene wastes.  Using
this approach, it was apparent from the results of this work
that  practicable  waste  water  treatment  plants  are   in
operation   and   that   their  operational  parameters  are
comparable to those of the resins segment of  this  industry
as  well  as  with  biological  treatment  systems  in other
industries.   It  is  apparent,  therefore,  that  the  most
significant  factors  in  establishing  effluent limitations
guidelines on a basis of units of  pollutants  per  unit  of
production are  (1) the waste water generation rates per unit
of production established for an exemplary plant and  (2) the
concentration  levels  in  the  waste  waters  from the best
practicable waste water treatment techniques.

The Guidelines

The effluent limitations guidelines as kg of  pollutant  per
kkg  of  production   (lb/1000  Ibs)  are based on attainable
effluent concentrations and demonstrated waste  water  flows
for  each product and process subcategory where a sufficient
number of similar products or processes could be identified.
                         238

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Attainable Effluent Concentrations

Based on the definition of BPCTCA, the  following  long-term
average  BOD5.  and suspended solids concentrations were used
as a basis for the guidelines.
                                 BOD5       TSS...
                               mg/liter   mg/liter

Major Subcategory Z               15         30
Major Subcategory II              20         30
Major Subcategory III             45         30
Major Subcategory IV              75         30

The BOD5 and total suspended solids concentrations are based
on observed  or  reported  performance  of  water  treatment
plants.   In  many  subcategories  of  this  segment  of the
plastics and synthetics industry, the in-place  waste  water
technology  and  treatment levels are inadequate.  By proper
design and application  of  the  defined  technologies,  the
levels  proposed  are  attainable  as  demonstrated by other
subcategories within this industry and other industries such
as organics and petroleum  refining.   The  COD  limitations
were  included  in  the proposed regulation because COD is a
measure  of   the   chemical   by-product   waste   of   the
manufacturing  process  and  falls  under  the definition of
pollutant contained  in  the  Act  [5502(6) ].   All  of  the
proposed  1977  COD  limitations  were non-controlling as to
technology.  That is, the COD  limitations  were  such  that
adequate  removal  of  BOD5  will usually result in adequate
removal of COD.  The proposed numbers were derived from data
showing the removal of COD which  accompanies  reduction  of
BOD5  to the levels proposed in the effluent limitations for
each subcategory.  A  plant  which  is  achieving  the  BOD5
removal  required  by  the  regulations  need  not  use  any
additional technology to meet the proposed  COD  levels  for
BPCTCA.   The  presence  of  a  COD  limitation  nonetheless
fulfills  an  important  function  by   requiring   adequate
handling   and  treatment  of  discarded   (bad)  batches  of
reactants and products, so as to avoid  shock  or  peak  COD
loadings  which  would be inadequately treated but would not
be discovered by a BOD^ analysis.  Also, the COD test  is  a
much  quicker  and  more convenient test for the presence of
oxygen demanding pollutants than is the BOD5 test.  However,
since the proposed BPCTCA (1977) COD limits are liberal  and
would  be easily attainable if the BOD5_ limits are met, they
are being dropped  as  a  limitation  parameter  for  BPCTCA
(1977).

The  COD  characteristics  of  the  polymer  segment  of the
synthetics and plastics  industry  vary  significantly  from
                           239

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                            TABLE 1X-1
                          COD/BOD  RATIOS
                                         Raw
Acrylic Resins

Alkyd and Unsaturated
Polyester Resins

Cellulose Derivatives

Cellulose Nitrate

Ethylene-Vinyl Acetate/
Polyethylene

Polytetrafluoroethylene

Nitrile Barrier Resins

Polyesters  (thermoplastic)

Polypropylene Fibers

Polyvinyl Butyral

Polyvinyl Ether

Polyvinylidene Chloride

Silicones
1.3 - 2.7


2   - 3.7

2.4 - 4.2

2.5 - 4.1


4.2

1.8

2.3 - 2.9



3.2 - 3.8

1   - 4.8
                  Treated
1.4 - 3.3
5.2
5.0
4.6 - 23
2.5
5.1
                          240

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product to product and within an individual plant over time.
The ratio of COD and BODJ5 in the raw waste water and treated
waste waters are shown in Table IX-1 and range from a low of
1.0  to a high of 23.  There is a real need for more data in
all sections of the polymer  segment  of  the  plastics  and
synthetics industry to provide a better understanding of the
waste water loads, the treatability of the waste waters and,
in  particular,  a better understanding of the nature of the
COD component and methods for its reduction.   In  order  to
promote  the  collection  of  data  on  the oxygen demanding
parameters of BOD5, COD and TOC (total organic carbon),  the
Agency  is planning to require that a majority of the plants
in each  subcategory  monitor  their  raw  waste  loads  and
treated  effluents for BOD5, COD and TOC.  This data will be
collected for a reasonable period at which time  the  Agency
will consider revising the limitations and standards.

In  applying  the BOD5_ limitation guidelines, if a plant can
show a direct  relationship  over  a  long  period  of  time
between  BOD5_,  COD  and  TOC (total organic carbon), or TOD
(total oxygen demand), the parameter measurement of the COD,
TOC, or TOD could be substituted for BOD5 if the  COD,  TOC,
or  TOD limitations are set such that the BOD5 limitation is
not exceeded.

Although guidelines are not established for phenolics in the
polymers  segment  of  the   industry,   wherever   phenolic
compounds  are  identified  their  removal should remain the
same as for the resins portion of  the  industry,  i.e.,  an
attainable concentration level of 0.5 mg/liter monthly limit
as demonstrated by dephenolizing units (12) activated carbon
(13, 14, 35, 39) or biological degradation.

The  removal  of  oil  and  grease  is  based on 30 mg/liter
monthly limit attainable concentrations as  demonstrated  by
various  physical and chemical processes in other industries
(35).

The  removal  of  fluorides  is  based  on   an   attainable
concentration  of  20 mg/liter by lime precipitation as used
in effluent guidelines for the iron and steel industry.   It
should  be  noted  that  the  fluoride  level  shown for the
polytetrafluoroethylene (PTFE)  subcategory  applies  to  the
fluoride  content of the effluent from the water scrubber in
the TFE monomer process only, not to the total  waste  water
discharge  from  the  overall  PTFE  process.   The scrubber
effluent, a dilute HCl solution,  is  the  only  significant
source  of fluoride discharge from the PTFE process.  At all
present  PTFE  manufacturing   operations,   this   scrubber
effluent  is segregated from other waste waters and disposed
                           241

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of by various means, including deep well, ocean dumping,  or
off-site  contract  methods.   The waste water flow from the
scrubber amounts to 1/5 or less of  the  total  waste  water
generated  by  the  process.  The guideline for fluoride was
derived on the basis of 20 mg/1 attainable concentration and
a scrubber effluent flow of 3500 gal/1000 Ibs product.

Cyanides,  mercury,  and  cadmium  limitations   should   be
consistent  with  the  limitations  of  toxic  and hazardous
chemicals prepared in the Federal Register of  December  27,
1973(38).

The  removal  of  copper  and lead is based on an attainable
concentration of 0.5 mg/liter as  demonstrated  by  alkaline
chemical precipitation (35) .

The   copper   limitations   for   the  silicone  production
facilities were established in the following manner.

    1.   Precipitation of soluble copper by  means  of  lime
         treatment  was  selected  as  the  most  applicable
         treatment technology.  It  has  been  shown  to  be
         capable of achieving effluent copper concentrations
         of less than 0.5 mg/liter.

    2.   It  was  assumed  that  no  internal  waste  stream
         segregation  would  be  employed and that the total
         volume of waste water emanating from the production
         facilities would be subjected  to  the  above  lime
         treatment.

    3.   The average waste flows in terms  of  gal/1000  Ibs
         were used for the silicones plants by averaging the
         values of the reported range of waste flows.

    H.   The maximum average for a 30-day period for  BPCTCA
         was  then  developed  using the average waste flows
         established  in   (3)  in   conjunction   with   the
         demonstrated  0.5  mg/liter  copper  effluent using
         lime  treatment.    The   maximum   average   daily
         limitations  were taken as twice the average 30-day
         limitations.

Since  the  lime  treatment  process  theoretically  removes
copper  to  a  fixed solubility limit rather than removing a
certain percentage of the influent copper, the  quantity  of
copper  in  the  raw  waste  water is of no consequence with
respect to the  attainable  effluent  copper  concentration.
Thus, the fact that different silicone production facilities
may  produce  waste waters with vastly varying quantities of
                           242

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copper  is  irrelevant  with  respect  to  the   established
limitations.   The  net  result  is  that the limitations on
copper, in pounds/1000 pounds of product, are  dependent  on
hydraulic  load  attainable.   In  one  respect,  the copper
limitations  are  actually  conservative  in  favor  of  the
industry,  because  it  was not presumed that copper-bearing
waste streams would be segregated from other  waste  streams
for  treatment,  a  practice  which  would  reduce the total
quantity of copper in the effluent,

Demonstrated Waste Water Flows

The waste water flow basis for BPCTCA  is  based  on  demon-
strated   waste  water  flows  found  within  the  industry.
Because of the small number of manufacturing plants in  most
categories,  and/or  the limited data base, the demonstrated
waste  water  flows  shown  in  Table  IX-2  were  based  on
engineering  judgments  taking  into  consideration reported
flows and other assessments such as the type  of  operation,
nature  of  housekeeping, and apparent operational attention
to good  water  conservation  practices.   The  demonstrated
waste  water  flows  are  based  (where  possible)  on direct
contact process water only and do not include  boiler  water
blowdown, water treatment regeneration wastes, cooling water
blowdown,  and  any other waters deriving from utilities and
supporting services.  The resultant  wastewater  flows  used
for  calculating  the  limitation guidelines were reasonable
and representative of what most plants in  each  subcategory
are  or  should  be achieving.  It is essential to take into
consideration the fact that waste water  flow  is  often  an
integral  part  of the basic process design and operation of
the process and plant and, therefore, would  be  subject  to
significant   reduction   only   at   considerable  expense.
Although generally the unit hydraulic loads are  larger  for
older  plants,  the  availability  of  water  influences the
design as does the designer's philosophy and  the  company's
operating  procedures.  No simple formula has been found for
relating hydraulic load to plant age, size or location.

Statistical Variability of a Properly Designed and Operated
Waste Treatment Plant

The effluent from a properly designed and operated treatment
plant changes continually  due  to  a  variety  of  factors.
Changes   in   production  mix,  production  rate,  climatic
conditions, and reaction chemistry influence the composition
of raw waste load and, therefore, its treatability.  Changes
in  biological  factors  influence  the  efficiency  of  the
treatment  process.   A  common  indicator  of the pollution
characteristics of the discharge from a plant is  the  long-
                           243

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                            TABLE  IX-2

                   DEMONSTRATED WASTEWATER FLOWS
                                    WASTEWATER FLOW RATES
Alkyd Molding Compounds and
Unsaturated Polyester Resins
                                cum/kkg
   Greases, Emulsions,
   Rubbers, and Resins

   Coupling Agents
  3.3

 142

  8.34

150

  6.7
Cellulose Nitrate

Ethylene-Vinyl Acetate

Polytetrafluoroethylene

Polyamides (Nylon 6/12 only)

Polyester Resins (Thermoplastic)    7.9

Polypropylene Fibers               16.7

Silicones

   Fluids
  10.4


 133

  83.4
gal/1000 Ibs


        400

     17,000

      1,000

     18,000

        800

        950

      2,000



      1,250


     16,000

     10,000
                              244

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term  average  of  the  effluent load.  The long-term  (e.g.,
design or yearly) average is not  a  suitable  parameter  on
which  to base an enforcement standard.  However, using data
which show the variability in the effluent load, statistical
analyses can be used to compute short-term  limits   (monthly
or  daily)   which  should not be exceeded, provided that the
plant is designed and run in the proper way to  achieve  the
desired  long-term  average  load.   It  is these short-term
limits on which the effluent guidelines are based.

In  order  to  reflect  the  variabilities  associated  with
properly  designed and operated treatment plants for each of
the major subcategories as discussed  above,  a  statistical
analysis  was  made  of  plants  where  sufficient  data was
available to determine these variances  for  day-to-day  and
month-to-month operations.  The standard deviations for day-
to-day  and  month-to-month operations were calculated.  For
the  purpose   of   determining   effluent   limitation,   a
variability factor was defined as follows:

         Standard deviation          = Q monthly, Q daily
         Long-term average (yearly or design)  = x
         Variability factor = y monthly, y daily
         y monthly = x * 2Q monthly
                       x
         y daily = x + 3Q daily
The variability factor is multiplied by the long-term yearly
average  to determine the effluent limitations guideline for
each product subcategory.  The monthly effluent  limitations
guideline is calculated by use of a variability factor based
on  two  standard  deviations  and  is  only exceeded 2 to 3
percent of the time for a plant that is attaining the  long-
term  average.   The daily effluent limitations guideline is
calculated by the use of a variability factor based on three
standard deviations and is exceeded only 0.0-0.5 percent  of
the  time  for  a  plant  that  is  attaining  the long term
average.  Any plant designed  to  meet  the  monthly  limits
should never exceed the daily limits.  The data used for the
variability   analysis  came  from  plants  under  voluntary
operation.  By the application  of  mandatory  requirements,
the  effluent  limitations  guidelines  as discussed in this
paragraph should never be exceeded by  a  properly  designed
and operated waste treatment facility.

The  variability factors in Table IX-3 are based on the data
obtained in the synthetic resin segment  (16) of the plastics
and synthetics industry.
                          245

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The variability factors for suspended solids removal are the
same as used in the resins segment of the industry, i.e.,  a
monthly variability of 2.2 and a daily variability of 4.0.

The  variability  factors  recommended  for  total chromium,
phenolics, copper, lead, and oils and grease  are  based  on
the  monthly  limits and a variability factor of 2.0 for the
daily maximum.

Based on the factors discussed in this section, the effluent
limitations guidelines for BPCTCA are  presented  in  Tables
IX-* and IX-5.
                            246

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                            TABLE   IX-3

                   VARIABILITY FACTORS FOR BODC
                                   BOD5       Variability Factors
                                 Monthly      	Daily	
Major subcategory I                1.6                3.1

  "        "      II               1.8                3.7

  "        "      III              2.2                4.0

  "        "      IV               2.2                4.0
                              247

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                                      TABLE   IX-4

BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE  EFFLUENT LIMITATIONS GUIDELINES
                           fkg/kkg  (Ib/jOCO 1h)  of  production]
Foot-
note
No.
1
. 2
3
4

5
6
7
K5 8
*-
00 9
10
11

12
13




14

15
BODr
Subcategory Kaxinum Average of Maxixurc for Any
Daily Values for Any Ope !\*y
Period of Thirty
Consecutive Days
Etbylene-Vinyl Acetate Copolymera 0.20 0.39
Poly tatraf luoroethylens 3.6 7.0
Poljpropylene Fiber 0.40 0.73
Polyvl.-.yiiclene Chlorldts No numerical guidelines -see discussion
ir. footnote
Acrylic Resins " "
Cellulose Derivatives " "
Alkyds and Ur.aaturated folyester Reains 0.33 0.60
Cellulose Nitrate 14 26

?olya;3ide5 (Nylon 6/i2 only) O.&S 1.20
Polyester Resins (thermoplastic) 0.73 1.4
Polyvlnyl Butyral No numerical guidelines-see discussion
ia footnote
Polyyinyl Ethers " "
Sillcones
fl"1~" 1.0 1.9
Creases, Eiuilsions,
Rubber;), Kesins ,, » 2i
— j . *.
Coupling Agents 8.2 I5
.Kltrile Barrier E«cica Ko nuaerlcal ^uidtliac s-see dis-
cussion in footnote
Spandex Fibers " "
SUSPE.VJKD SO-iDS
Maximum ^VPr^gc of Kaxic.uzi for A-iy
Ji-ily Values for Any One Day
Period of Thirty
Coiisecutlve D.-.vs
0.53 1.0
9.9 18.0
1.1 2.0
Ko numerical guidelines-see discussion
in footnote
M . II
„
0.22 0.40
9.4 17

0.44 O.SO
0.52 0-95
No numerical guidelines-see discussion
in foctnote
"

0.69 1.25

8.8 I*
5.4 -0
No nuMricai guidelines-*** din-
cufisicn in footnote
ii «

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                                                               FOOTNOTES   FOR  TABLES    IX-4 and  IX-5
- 1.  Zl.}iy_lexe^'inyl_At'.etate_ (EVA) Copolymer. Two of the five
      knirwn producers verc contacted.  All plants are located
      at polyethylene production facilities.  Water use and
      vastewater characteristics for EVA are essentially iden-
      tical to those for low density polyethylene.  However,
      en emulsion polymerization process is known and produces
      e distinctly different waste load which is essentially
      that of polyvinyl acetate csulsion polymerization
      reported in EPA 440/1-73/010.  Both multi-plant and
      n.unicipal si-wage t r oat cent is used.

   2 . Po]y_t_e_i r^J^l 11 o r^ic t: ViyJ JVTK^. Three of  the s~t Ion vary widely depend i:ia upon the tvpc of cooling
      tyt c oa  ust J.   "iiie was ce loads :ire for pi ant a where selec-
      ted concentrated wastes are negragatcd and disposed  of
  l^i  by landfilllng, etc. I*riisary treatment at  one plant  alto
  VO  *as observed while the other plant discharges to a
      municipal sewage system.

  *•  P^Jyv- ".•'! *_d£ n_"^j-^A9^1J^' ^e two Kjjor tt'-inulacturers
      veie contacted. Beth plant sites Bend wastcwaters to
      xultt-plant treaincnt plants of which the  polyvinylidena
      chloride is a £.r:all port ion,  Consequently, there was
      insufficient data to develop reconar.ended guidelines.

  '-  A£ry!Jc  Kc,sj"^.' ^-iree -°* tne four manufacturers were
      contacted.  Large numbers of product grades are produced
      by b-.il.k,  solution, suspension and emulsion polyneriza-
      ticn.  The  widely varying hydraulic loads  for the large
      number  of products in addition to treatment of the waste-
      watnrs  by cultt-pl.-tnt wastcvater trcatr.ent facilities
      prohibited  obtaining sufficient meaningful data to
      zecozr^end effluent limitation guidelines.

  ^"  £5JJL^°s- P?r-iy^_civcs^- Cellulose derlvatea investigated
      Included ethyl cellulose, hydroxyethyl cellulose, tacthyl
      cellulose and carboxyccthyl cellulose. Wide variations
      in unit flow rates for two plants producing the same
      produce,  differences in nanufacturiag techniques and the
      availability of data prevented recoixicncling guidelines.
      The wastew^ters from the three manufacturers are being
      treated in  multi-plant waatewater treatment facllltiea
      or will enter municipal ecwage aysterna.
 7.  Alkyds and t/ris.'tturated Po^'escer Kesins. Six carefully
     selected plants were visited to provide a crosa-section
     of the Industry for size of operation, type of manufac-
     turing process and wastew.iter treatment methods.  Hydrau-
     lic loads vary widely depending upon the process  designs.
     Similarly, raw waste loadu vary widely because some
     plants segragnte wastca foi disposal in other manners.
     Generally, the industry dit?charges wastcwaters into
     municipal sewage systems ard should continue.  Also,  the
     type of air pollution control, e.g. combustion or scrub-
     bing, has a significant effect on the wastewater  loads.
     The recommended guidelines are for plantd having  their
     own wastewater treatment system - a very infrequent
     occurrence.

 ^*  Cellulose Nicrajc. The two aajor manufacturers of the
     four manufacturers were contacted.  These wastes  require
     pH control and contain lar^e amounts of nitrates.  One
     plant discharges to a municipal sewage system while  the
     other goes into a multi-plant treatment complex,

 9.  Polywnl^es. Various polyamides are produced but only
     Nylon 6/12 produces significant amounts of wastewater,
     e.g. Nylon 11 UBOS no proceja water. Consequently, the
     guidelines are restricted to Nylon 6/12 and were  develop-
     ed en the basis of similarity with waste loads from
     Nylon 66 production.

10.  Vol^vxtGT T\ i e r ri op1 a B t ic: R es i_n s. There ore three manu-
     facturers, two of which produce poly(ethylene, terephtha—
     late) in quantities leas than 22 of their total thermo-
     plastic production. The guidelines are recommended for
     poly(ethy 1 one teroptithalate) since the other product
     poly(butylene tercplitlulate) is produced at only  one
     plant and the wastewater gees into a municipal sewage
     system, so no data en performance could be obtained.

11,  P_oI_vyijiy 1 Butv£aJ_. Of three production sites,two  have
     processes beginning with vinyl-acetate monomer which
     generates much larger wastewater volumes than the pro-
     cess beginning with polyvinyl alcohol. Since the  manu-
     facturing sites where production starts with a monomer
     discharge into municipal sewage systems, there was no
     data available.  Consequently, there  are no recommended
     guideline* since they would b'e ' tantamount~ to establishing
     a permit for the direct discharger production site.
Polyvinyl ethers. The three present planta use  differ-
ent processes each of which produces several  grades  of
product.   The different chemical compositions  used  In
both bulk and solution polyaerlzacion processes and  the .
lack, of data on both raw and treated wastewatere  pre-
vented establishing guidelines.  The wautewaters  are
presently sent to either cmXti-plant treatment  faclllti*
or municipal a e wage ayateics.
                                                                ,  Slllconeg. Four companies manufacture silicones at f,
                                                                  locations.  Three plants vere visited and data were
                                                                  obtained from all planes. The major processing steps
                                                                  the five plants are chovn belov.
                                                                         Major Processes nt Five Silicone Plants

                                                                     Plant No.            32345

                                                                  CH.C1                   x     xx
                                                                  Chlorosilane prod.      x  x  x  x  x
                                                                  Hydrolysis              x  X  x  x  x
                                                                  Fluids, greases,
                                                                   emulsions prod.
                                                                  Resin production        x  x  x
                                                                  Elastomer production    x  x  x     x
                                                                  Specialties prod.*      x  x  x
                                                                  Fumed silica prod.            x
                                                                  HC1 production                      x
                                                                  * e.g. surfactants, tluorinated silicones*  coupling
                                                                    agents, and other materials.

                                                                  Based on the msnufacturir.a process, the waste
                                                                  watc-r flov-s  a.id  tVe rrv vaat.&  loaiie, the plants
                                                                  1, 2, 3 dn
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                                                   TABLE  IX-5

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

                         Mercury

Polytetrafluoroethylene  Fluorides
         Spandex fiber

         Nitrile barrier resins

         Polypropylene fibers

         Silicones

            Fluids
                          Cyanides

                          Cyanides

                          Oils & grease



                          Copper
Toxic and hazardous  chemicals guidelines to apply

            0.6                   1.2

Toxic and hazardous  chemicals guidelines to apply
            0.5
           0.005
1.0
 0.010
            Greases, Emulsions,
            Rubbers and Resins    Copper

            Coupling Agents       Copper

         Polyester resins         ...mi urn
         (Thermopl ast.i c)
                                                         0.067                   0.13

                                                         0.042                   0.084

                                                    and hazardous  chemic?.7   auidel

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                         SECTION X

     BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
Definition of Best Available Technology Economically
Achievable (BATEA1

Based  on  the  analysis  of  the  information  presented in
Sections IV to VIII, the basis for BATEA is defined below.

Best available technology  economically  achievable  (BATEA)
for  existing  point  sources  is based on the best in-plant
practices of the industry which minimize the volume of waste
generating water  as  typified  by  segregation  of  contact
process  waters  from  noncontact waste water, maximum waste
water  recycle  and  reuse,  elimination   of   once-through
barometric  condensers,  control of leaks, good housekeeping
practices, etc., and end-of-pipe technology, for the further
removal of suspended solids and other elements  typified  by
granular  media  filtration,  chemical  treatment, etc., and
further COD  removal  as  typified  by  the  application  of
adsorption processes such as activated carbon and adsorptive
floes,   and   incineration  for  the  treatment  of  highly
concentrated small volume wastes and  additional  biological
treatment for further BOD5 removal when needed.

Best  available  technology  economically  achievable can be
expected to rely upon the usage of those technologies  which
provide  the  greatest  degree of pollutant control per unit
expenditure.   Historically, this has been  the  approach  to
the  solution of any pollution problem — as typified by the
mechanical and biological  treatment  used  for  removal  of
solids   and   biochemically  active  dissolved  substances,
respectively.  At the present stage of  development,  it  is
technologically  possible  to  achieve  complete  removal of
pollutants from waste water streams.  The economic impact of
doing this must be assessed by computing  cost  benefits  to
specific plants, entire industries, and the overall economy.
The  application  of  best  available technology will demand
that the economic achievability be determined, increasingly,
on the basis of considering  water  for  its  true  economic
impact.    Unlike  best  practicable  technology,  which  is
readily applicable across the  industry,  the  selection  of
best  available  technology  economically achievable becomes
uniquely  specific  to  each  process  and  in  each  plant.
Furthermore, the human factors associated with conscientious
operation   and   meticulous   attention  to  detail  become
increasingly important if best available  technology  is  to
                            251

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achieve   its   potential   for  reducing  the  emission  of
pollutants from industrial plants.

The Guidelines

Achievable Effluent Concentrations

Suspended Solids

The removal of suspended solids from waste water effluent is
based  on  well-understood  technology  developed   in   the
chemical  process  industries and water treatment practices.
Application of filtration to the effluents from waste  water
treatment  plants  has  not been applied often, although its
feasibility has been demonstrated in projects  sponsored  by
the  Environmental  Protection  Agency.   The  operation  of
filtration systems, such  as  the  in-depth  granular  media
filter  for  waste waters, is not usually as straightforward
as it is in water treatment.  This is  due,  especially,  to
the  biological  activity  still present in waste waters and
sometimes to the nature of the colloidal particles from  the
process.

Long  residence  time  lagoons  with  their low flow-through
rates are often effective means for the removal of suspended
solids, although the vagaries of climatic conditions,  which
can cause resuspension of settled solids, and the occurrence
of   algal   growth  can  cause  wide  fluctuations  in  the
concentration of suspended solids in the effluent.  Although
technology is available for  reducing  suspended  solids  in
effluents  to  very low levels (approaching a few mg/liter),
the capital and operating  cost  for  this  technology  adds
significantly   to   waste   water   treatment  costs.   The
concentration basis for BATEA is 10 mg/liter for all product
and process subcategories (1, 15, 35).   This  concentration
is  achievable  by  use  of  filtration techniques including
mixed  media  filtration.   Mixed  media  filtration  is   a
pollution control technique which is well established and is
currently  used  with  considerable  success  in a number of
treatment works -  including  municipal  systems  and  waste
treatment  systems  used  in  the  petroleum  industry.  The
wastes from biochemical treatment systems consists mostly of
microbial cells regardless of the original source of the raw
wastes.   Microbial  cells  have  similar   solids   removal
characteristics.   While it has not been demonstrated in the
plastics and synthetics industry, the success shown in other
uses convinces the Agency that  mixed  media  filtration  is
fully  adaptable  to  this  industry  and  will  achieve the
effluent concentration required, if necessary.
                            252

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Oxygen-Demanding Substances

Removal  of   biochemical-oxygen-demanding   substances   to
concentration  levels  less  than  the  range  proposed  for
municipal  sewage  treatment   plants   will   require   the
utilization of physical-chemical processes.  It is expected,
however,  that the chemical-oxygen-demanding substances will
present a far greater removal problem than BOD5 because  the
biochemically  treated  waste water will have proportionally
much higher ratios of COD to BOD5  than  entered  the  waste
water  treatment  plant.   In  the  case  of  a  few polymer
products, the waste waters may contain substances  giving  a
significant  COD  concentration  while  being  resistant  to
biological degradation under the  most  optimum  conditions.
To  reduce  the  COD  in  a  treated  effluent,  it  will be
necessary either to alter processes so that nonbiodegradable
fractions  are  minimized  or  attempt   to   remove   these
substances by some method of waste water treatment.  Both of
these  approaches may be difficult.  Alteration of processes
so that they produce  less  refractory  wastes  may  not  be
possible  within  the  constraints  of the required chemical
reactions.  However, reduction in the quantities  of  wastes
generated  by spills, leaks, and poor housekeeping practices
can contribute  significantly  to  reducing  the  total  COD
discharges,   especially  where  a  large  fraction  of  the
pollutants  are  refractory   to   biological   degradation.
Consequently,  one of the first steps in a program to reduce
emissions should be a thorough  evaluation  of  the  process
operation   alternatives   and   techniques  for  preventing
pollutants from entering the waste water streams.

In other methods for removal of oxygen demanding  substance,
adsorption by surface-active materials, especially activated
carbon,  has gained preeminence.  Although the effectiveness
of activated carbon adsorption has  been  well  demonstrated
for removing BOD5 and COD from the effluents of conventional
municipal sewage treatment plants, its effectiveness for the
removal  of  the complex chemical species found in the waste
water  of  this  industry  can  be  expected  to  be  highly
specific.   Evidence  of  the  low  adsorption efficiency of
activated carbon for a number of different chemical  species
is   beginning   to  appear  in  the  technical  literature.
However, the only  way  to  determine  if  activated  carbon
adsorption  is  an  effective  method for removing COD is to
make direct determinations in the laboratory  and  in  pilot
plants.   In some instances, activated carbon adsorption may
be used  to  remove  substances  selectively   (for  example,
phenols)  prior  to  treatment  by  other methods.  Although
activated carbon adsorption is proving to be a powerful tool
for the  removal  of  many  chemical  oxygen  demanding  and
                           253

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carbonaceous  substances from waste water streams, it is not
a panacea.  Its use must be evaluated in terms of  the  high
capital   and   operating  costs,  especially  for  charcoal
replacement and energy, and the benefits accrued.

Removal of carbonaceous and oxygen demanding substances  can
sometimes  be achieved through oxidation by chlorine, ozone,
permanganates, hypochlorites, etc.  However, not  only  must
the cost benefits of these be assessed but certain ancillary
effects,  such  as  (1)  the  production  of chlorinated by-
products which may be more toxic than  the  substance  being
treated,  (2)  the  addition of inorganic salts, and (3) the
toxic effects of the oxidants themselves, must be taken into
account.  Consequently, when chemical oxidation is  employed
for  removal  of  COD,  it  may  be  necessary to follow the
treatment with another step to remove the residuals of these
chemicals prior to discharge to receiving waters.

Degradation of oxygen demanding substances  may  take  place
slowly in lagoons if sufficiently long residence time can be
provided.   If  space  is available, this may be an economic
choice.  Also, the use of land irrigation,  or  the  "living
filter"   approach   to  water  purification,  is  receiving
selected attention.  Ultra-filtration and  reverse  osmosis,
both of which are membrane techniques, have been shown to be
technically  capable of removing high molecular species, but
they  have  not  been  shown   to   be   operationally   and
economically   achievable.    With   these  techniques,  the
molecular distribution of the  chemical  species  determines
the  efficiency  of  the  separation.   They  probably  have
limited potential in the plastics and  synthetics  industry,
due   to   the  particular  spectrum  of  molecular  weights
occurring in the waste waters.

The concentration basis for BATEA  for  COD  is  either  130
mg/liter as demonstrated in an activated carbon plant  (4) in
the  plastics and synthetics industry, or that concentration
documented  by  plants  in  Table  VTI-3  as  attainable  in
biological treatment systems or retention lagoons.  The BOD5
concentrations  which are attainable by biological treatment
plants as expressed in  the  better  waste  water  treatment
plants  as  presented  in  data  from  the  synthetic resins
segment  (16) of this industry, are  15  mg/liter  for  Major
Subcategory  I  and  II  products  and 25 mg/liter for Major
Subcategory III and IV products.  The removal  of  fluorides
is  on  the  same basis as for BPCTCA as outlined in Section
IX.  Similarly, the limitations  on  mercury,  cadmium,  and
cyanides  should be those prescribed for toxic and hazardous
chemicals.
                           254

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The removal of oils and greases to  a  concentration  of  10
mg/liter,  copper  to  a concentration of 0.25 mg/liter, and
lead  to  0.03  mg/liter  is  based  on  the  concentrations
attainable  (35) when filtration is used for solids removal.

Waste load Reduction Basis

The  waste load recommendation for BATEA is based on overall
loading reduction through the use  of  the  best  achievable
concentrations  and  the reduction of waste water flows from
BPCTCA to a level between the BPCTCA waste water  flows  and
the  verified BADT waste water flows as described in Section
XI.  The wastewater flows  are  given  in  Table  X-1.   The
wastewater  flows  used for calculating BATEA are reasonable
estimates of reductions which industry  should  be  able  to
achieve  by  1983,  using  the various methods of wastewater
flow reduction and recycle as outlined in sections  VII  and
IX.
                           255

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  BATEA Waste Water
TABLE X-1

           Flow Rates

      cum/kkq     gal/1000 Ibs
Alkyd Molding Compounds and
 unsaturated Polyester Resins    1.83

Cellulose Nitrate              125

Ethylene-Vinyl Acetate           7.92

Polytetrafluoroethylene         91.7

Polyamides  (Nylon 6/12 only)     6.67

Polyester Resins
 (Thermoplastic)                 7.92

Polypropylene Fibers             9.17

Silicones
 fluid products                 10.*
 multi products                133
                     220

                  15,000

                     950

                  11,000

                     800


                     950

                   1,100
                   1,250
                  16,000
                            256

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Increased  efficiency  in  the utilization of water combined
with closer operational control to prevent  pollutants  from
entering  waste  water streams have the greatest promise for
reducing the amounts of  pollutants  discharged  from  waste
water  treatment plants.  While the reduction of water usage
may  directly  reduce  the   total   emission   of   certain
pollutants,  it may mean that advanced waste water treatment
systems become more economically feasible.

Variability

The variability factor for BATEA guidelines is based on  the
variability  determined  by  data  from  BPCTCA.   Both  the
monthly and daily variabilities are based  on  two  standard
deviations.   As technology and plant operations improve, it
is  expected  that  these  variabilities  will  become  more
stringent.    The  BOD5,  COD,  and  TSS  variabilities  are
presented in Table X-2.  The TSS factors are based  on  data
obtained  from  multi-media  filters  used  in the petroleum
refining industry.  The other parameters are  based  on  the
achievable   concentration   for   monthly   maximum  and  a
variability factor of 2 to determine the daily maximum.

                         TABLE X-2
                 Variability Factors BATEA

                          BOD5 and COD
                      Monthly"     Daily
                TSS
         Monthly    Daily
Major Subcategory I     1.6
Major Subcategory II    1.8
Major Subcategory III   2.2
Major Subcategory IV    2.2
2.4
2.8
3.0
3.0
1.7
1.7
1.7
1.7
2.0
2.0
2.0
2.0
Based on the factors discussed in this section, the Effluent
Limitations  Guidelines  for   Best   Available   Technology
Economically  Achievable, BATEA, are presented in Tables X-3
and X-4.
                            257

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                                       TABLE  X-3

5LST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE EFFLUENT LIMITATIONS GUIDELINES
                         [kg/kkg  (lb/1000 Ib)  of production]
Subcategory
ZtV.ylt r.e-Vinvl Acetate Copoly/cers
Polytctrafluorocthylene
P_-;y;rc;,;er.e Fiber
rclyvU.ylidcne Chlcride

A ryl ic RCK ins
AiVvds and Unpaturated Polyester Resins
Cellulose Nitrate
££ polyjaiJes (Nylon 6/12 only)
00
Pollster fc <; * i n G (thi-naoplastic)
Polyv :;v I EuLyraL

?ciyv;;:vl Ethers
Sili.cor.es
Flu I A
Greases, Eculstons,
Rubbers, Keslna, end
Coupling Amenta
Ni-.rili: Barrier Xusins
BOD.

Kaximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive DOTS
0.19
2.2
0.22
No numerical guidelines-see
in footnote

0.10
6.9
0. 37
0.44
No numerical guidelines-see
In footnote
"

0.57

6.4

No numerical guidelines-see
0.29
3.3
0.33
discussion


0.14
9.4
0.50
0.59
discussion

"

0.28

8.8

discussion

COD
Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecut tve Davs
1.63'
4.0
0.40
No numerical


0.52
34
1.9
2. 3
No numerical

"

3

33.4

Kn niimp^'trAl
2.43
5.9
0.59
guide] inos-see discussion
in footnote

0. 74
47
2.6'
3.1
guldel ines-ste discussion
in footnote
"

4

45.5

fuiirfpl 1 nt>K— seo dl fidustii on
s.,_ 	 -, c.. ....
?trii-d c: T'r.irty
0-1* 0.16
1.6 i . -'
0.16 C"f'
No nu-.:rical ^ui _< ! .::- - -^-v . •.---,
in : > v-l.'.' t v

0.03 C . C t
2.1 if
0.11 C.I.)
°'14 C..C
No r..UT.v*r ieal •t'J\.'.^- i ;•.>:--•-<-•
i.-i f,- t>.> u-
ii

0.21 0.1B

2.0 2.3


                                    in footnote                         jn footnote
Spandtx Tibars                        "              "

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                                                              FOOTNOTES  FOR   TABLES     X-3 and  X-4
*-  Ethyl ere-Vinyl_^ jte_etate  (EW\>  Copolymcr.  Two of the fiva
    kp.t-Vii producers were contacted.   All plants tre located
    at polyethylene production  facilities.   Water use and
    vsKtewater characteristics  for  EVA are  essentially Iden-
    tical to these for  low  density  polyethylene.  However,
    en es'jlsion polycerization  process is known and producer
    a distinctly different  waste  load which is essentially
    that of puly vinyl acetate emu Is ion polyrccr izat Ion
    reported in EPA 440/1-73/010.  Both multi-plant and
    cur.iclpal suuoLg c treat, cent  is used.

 2. Po3 vtej_Tiiif'J_ti'jroe"!i_\'7enjp_. Three of the seven  manufacturing
    plrnts wc-ra visited. A wide ran^e of products are produced,
    Tie rr.ost  itnjior tr.nt is poly tetrof luoroatiiylene  (PTFK) and
    these guidelines are re contended for PTFE  granular and
    fire powder graces only. The wastewater discharges differ
    considerably depending upon the process recovery schemes
    for hydrochloric acid and the  disposal of  selected fitreams
    by deep well, ocean dumping or off-site contract cr^thods.
    The use of ethvlt;r.c glycol in  ,-. process can  significantly
    effect the w.is :o loadr;.  Fluoride ccr.cer.trations in
    untreated wast.tracers are generally below  lev Is attain-
    able by a3kft.Vlnu precipitation.

3*  Poj. v}>ro;->• I_gj,o^Fib £T_s . Two of  the  three  producers were
    c:--r.r..acted.  Iht vtixiae'. r Ic flow  ranges per  unit of pro-
    duction vary widely dtperidinx upon the  tyoe of coolin?
    system use-!.   Tue waste loads are for plants where eelec-
!    ted concentrated wastes are Bcgragated  and disposed  of
    by lar. it 11 ling, etc. Primary  treatment  at  one plant sittt
    w;?s observed while the  other  plant discharges to a
    Bun*cipsl sevage system.
                                  two
                                            manufacturers
*•  Z.9- * y_X_' yy J- *Ae n_e . , - -Q1 !-. ° -r-AJ- ^
    were contacted.  Both plant  sites  send wastewaters  to
    cul ti-plr.nt treatment plants  of which the polyvinylidene
    chloride is a s~all portion.   Consequently,  there  was
    insufficient data to develop  rec&ncr.ended guidelines.

5-  Acj-y 11 c_ Ra s i_ns_ . Three of  the  four manufacturers were
    contacted. Large numbers  of product gr-ides are produced
    by bulk, solution, suspension and emulsion polymeriza-
    tion.  The widely varying hydraulic loads for the  large
    number cf products In addition to treatment  of the waste*
    waters by multi-plant wastcwater  treatment facilities
    prohibited obtaining sufficient oeaningful data to
    reccrcicnd effluent limitation guidelines.

^»  Ce^ulosc Dcriya' ivcs. Cellulose  derivates Invest 'r.^.ted
    included ethyl cellulose, hydroxyethyl cellulose,     nyl
    cellulose anJ carboxynethyl cellulose. Wide  variations
    in unit flow rates for two  plants producing the same
    product, differences In manufacturing techniques and the
    availability of data prevented recormcnding guide-1 '.
    Hit vasteujters from the  three manufacturers are beinft
    treated in aultl-plant wastewater treatment  '  liitlt-j
    or viil enter municipal acwdge »y elects.
                                                                10.
                                                                11.
        ftd^y^jatjir^ji^                   Six carefully
selected plants were visited  to  provide  a cxosa-cection
of the Industry for size of operation,  type of manufac-
turing process and uastcw.itcr  treatment  method.-a.  Hydrau-
lic loads vnry widely  depending  upon  the process  designs.
Similarly, raw waste lo;tdH vary  widely because some
plants segragate wastes for' disposal  In  other manners.
Generally, the Industry dlechargcs wastewaters into
municipal sewage systems ar.d  should continue.  Also, the
type of air pollution  conttol, e.g. combustion or scrub-
bing» lias a significant effect on the wastewater  loads.
The recomracnded ftuldelines are for plants having  their
own wastewater treatment system  - a very infrequent
occurrence.
CcHulos_e^Nj.t1ra_te_. The two ni.ijor manufacturers of the
four manufacturcra wcri; contacted.  The;;e wastes  require
pH control and contuin lar^e  amountc  of  nitrates. One
plant discharges to a municipal  sewage system while the
other goes into a multi-plant  treatment  complex.

Polyami OPS. Various polyaraldeo are produced but only
Nylon 6/12 produces signifleant  amounts  of wastewater,
e.g. Nylon 11 tides no  process water.  Consequently,  the
guidelines are restricted to Nylon 6/12  and wore  develop—.
ed on the basis of aliuilnrity with waste loads from
Nylon 66 production.

Polyester Thermoplastic Pcslna*  There are three manu-
facturers, two ot which produce  poly(et.hylene, terephtha—
late) in quantities less than  2'? of their total thermo-
plastic production. The guidelines are  recommended for
poly(ethylen<: terephtlialate) cince the other product
poiy(butyler.o tcrephth;ilate)  Is  produced ot only  one
plant and thy waste-water fn>es  into a  njniclpal sewage
system, so no data on  performance could  be obtained.

Polvvir.yl Butyra_I. Of  three production cites,two  have
processes beginning with vinyl-acetate monomer which
generates much larger wastewater volumes than the pro-
cess beginning with polyvinyl  alcohol* Since the  manu-
facturing sites where  production starts  with a monomer
discharge into municipal sewage  systcirs,  there was no
data available.  Consequently*  there are no recotnended
guidelines  aince they would be  tantamount  to establishing
a permit for  the direct discharger production «ite.
                                                                12.
                                                                               ethers.  The throe
                                                                     ent  processes each of which
                                                                     product.    The different t.
                                                                     both bulk and solution i .". -;\
                                                                     lack of data on both raw -
                                                                     vented establishing guide
                                                                     presently sent to eithe   ..
                                                                     OL* municipal sewage ays  ;
                                 nt  plants  uae dlffer-
                                 .ces several grades of
                                 *  compositions used in
                               nation processes and the .
                                v'tcd wactewaters pre-
                                 The wastewaters are
                               :\ ant treatment facllitla
                                                                                                                                   13. Slliconcs. Four ccncpanieti canufBctv.re  sillcones  at  fivo
                                                                                                                                       locations.  Three plants were visited  and  data vera
                                                                                                                                       obtained front all plants. The major  processing steps  a:
                                                                                                                                       the five plants are stiovn below.
                                                                                                                                              K.ijor Processes gt___Piy_c___Sj He one  Plants

                                                                                                                                          Plant No.            1  2  3   4   5

                                                                                                                                       CH.C1                   x     xx
                                                                                                                                       Chlorosilane prod.      x  x  x   x   x
                                                                                                                                       Hydrolysis              x  x  x   x   x
                                                                                                                                       Fluids, greases,
                                                                                                                                        emulsions prod.
                                                                                                                                       Resin production        x  x  x
                                                                                                                                       Elastomer production    x  x  x      x
                                                                                                                                       Specialties prod,*      x  x  x
                                                                                                                                       Fuiatd silica prod.            x
                                                                                                                                       HC1 production                       x
                                                                                                                                       * e.g. surfactants, fluorinatcd  etlicones, coupling
                                                                                                                                         agents, and other materials.

                                                                                                                                       Based on the mnnufacturing process, the waste
                                                                                                                                       water fU-w:;  ji.tl th-i itw v;:stc  loode, the plants
                                                                                                                                       1, 2, 3 and  5 w«rt iiesl;-.'"-itfid  as multi-product
                                                                                                                                       plants while i was dt:BignRt^d  EB « fluid
                                                                                                                                       product [)lant.
                                                                                                                                   Z4. Nlt_rUe Barrier
                                                                                                                                                                Com:erciAl  scale
sale of  these  resins  has not yet begun. The ce^p_nies
expected  to Iiave  production facilities were crr.tactc-,
and two  provided  estirMtts  of raw waste lo-ds.  Btcsase
of the lack of demcnstratcd flows and raw waste loaJs
It was impossible to  establish effluer.t guiJclin*;
limitations.

Spntviex FJbo^s. Three c5r^;f acturcrs eje*h'p-foJuce* •
Spandex fibers by significantly different processes.
These are dry, wet and reaction spinning cethois.  '
Because of United data on  raw w^ste loid.v nra
because each plant operates a differoce process,
it waa iBp->G6ibZe to  establish ceaningful guicelinaa.

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to
c*
o
                                                  TABLE   X-4

                 BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE EFFLUENT LIMITATIONS GUIDELINES
                                         (Other  Elements  and Compounds)
                 Product
           Greases, Fmulslons,
           Rubbers, Resins and
           Coupling Agents

        Polyester resins
        (thermoplastic)
                               Parameter
Alkyds and unsaturated
polyester resins

                          Mercury

Polytetrafluoroethylene   Fluorides

Spandex fibers

Nitrile barrier resins

Polypropylene fibers

Silicones

   Fluids
                                  Cyanides

                                  Cyanides

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

            0.6                    1.2

Toxic and hazardous chemicals guidelines to apply
            0.092
              .0026
0.18
  .0052
              .029                    .058

   ..  and hazardous chemicals gui -1?lines to ap^l

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                         SECTION XI

              NEW SOURCE PERFORMANCE STANDARDS
           BEST AVAILABLE DEMONSTRATED TECHNOLOGY
Definition of New Source Performance Standards Best
Available Demonstrated Technology JNSPS-BADT)

Based on  the  analysis  of  the  information  presented  in
Sections  IV  to  VIII,  the  basis for NSPS-BADT is defined
below.

Best available demonstrated technology (BADT) for new source
performance standards  (NSPS) is based on BPCTCA, the maximum
possible reduction of process waste water  generation  along
with  the  application  of solids removal operations such as
granular  media  filtration  and  chemical   treatment   for
additional  suspended  solids  and  other element removal as
well as additional biological  treatment  for  further  BOD£
removal as needed.

The Standards

Achievable Effluent Concentration

The  concentration  basis  for NSPS-BADT is the same as that
for  BATEA  for  BOD5,  TSS,  oil  and  grease,  copper  and
fluoride.   The  COD  concentration  basis  for NSPS-BADT is
based  on  the  concentrations  which  were  attainable   in
observed biological treatment plants or retention lagoons as
expressed  in  Table  VII-3, or were rationally transferable
from similar  type  products.   In  cases  where  attainable
concentrations   were   not   available   as  long  term  or
transferable data, COD is not required as a standard.

Waste Load Reduction Basis

The waste water flow basis for NSPS-BADT  is  based  on  the
lowest  verified flows associated with each product.  Use of
the  lowest  verified  existing  waste   water   flows   for
calculation of new source standards is fully justified since
a  new plant can be planned and designed for the lower flows
which are currently being demonstrated by plants within each
subcategory.  The product specific  waste  water  flows  are
summarized in Table XI-1.

It is apparent that effluent limitations standards requiring
significant   reductions   over   that  attainable  by  best
practicable control technology currently available   (BPCTCA)
                             261

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                            TABLE XI-1

               LOWEST DEMONSTRATED WASTEWATER FLOWS
Product Subcategory                 cu meter/kkg      gal/1000 Ibs


Alkyd molding compounds
and unsaturated polyester
resins                                     0.33              40

Cellulose nitrate                        108             13,000

Ethylene-vinyl acetate                     7.51             900

Polytetrafluoroethylene                   33              4,000

Polyamides (Nylon 6/12 only)               6.7              800

Polyester resins -  (thermoplastic)         7.9              950

Polypropylene fibers                       1.67             200

Polyvinyl butyral                         47              5,600

Silicones

   Fluids                                 10.4            1,250

   Greases, Emulsions,
   Rubbers, Resins and
   Coupling Agents                       100             12,000
                               262

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requires   considerable   attention   to  both  the  process
generation of waterborne pollutants as well as the water use
practices of the plant.

Variability

The variability factors for BADT standards are based on  the
variability  factors determined for BPCTCA for BOD5 and COD.
The TSS variability factors are 1.7 monthly and 2.5 daily as
demonstrated by multi-media filtration  data  obtained  from
the  petroleum  industry.  The other parameters are based on
the achievable  concentration  for  monthly  maximum  and  a
variability factor of 2 to determine the daily maximum.

Alkyds gnd Unsaturated Polyesters

The   new   source  standards  for  alkyds  and  unsaturated
polyesters are based on a  process  wastewater  flow  of  40
gal/1000 Ibs of production as demonstrated by several plants
within  the  subcategory.   Since  the  flow  basis for this
subcategory  is  substantially  lower  than  for  any  other
subcategory in the plastics and synthetics industry, a brief
description  of  how  it  is  currently  being  attained  is
discussed below.

In the manufacture of  alkyds  and  unsaturated  polyesters,
there are three main sources of process-related waste water:
    1.   Water of reaction
    2.   Scrubber water
    3.   Reactor cleanout water
(Surface condensers  are  assumed  to  be  used  instead  of
barometric type.)

Minimum  discharge  may be achieved by (1)  reducing in-plant
water usage through good housekeeping and water conservation
practices,  (2)  recirculating  scrubbing  water  until  the
concentration   of   organic   material  in  that  water  is
sufficiently high to allow for  periodic  incineration.   If
the  organics  are  sufficiently concentrated the combustion
may be self-supporting,  (3)  reusing reactor  cleanout  water
to the maximum permissible,  then combining it with the water
of  reaction,  concentrating  the  blend  by evaporation and
sending the resulting waste to contract disposal.

Based on the factors discussed  in  this  section,  the  New
Source Performance Standards for Best Available Demonstrated
Technology  (NSPS-BADT) are presented in Tables XI-2 and XI-
3.
                             263

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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
7
$10
6*
11
12
13

Subcategory
Ethylene-Vi.iyl Acetate Copolymcrs
Polytetraflucroethylene
Polypropylene Fiber
Polyvlnylider.e Chloride
Acrylic Resins
Al'^yds and Unsaturated Polyester Resioa
Pel yam Idee (Hyloa 6/12 only)
Polyester Resins (thermoplastic)
Pclyvinyl E^tyral
Polyvinyl Ethers
Sl'iccnen
Fluid
Rubbers, !>sins, and
BOD,

Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Days
0.1S
0.80
0.04
No numerical guidelines-see
in footnote
0.02
6.0
0.37
0.44

No numerical guidelines-see
In footnote
.57
5.5
0.35
1.60
0.08
discussion
0.0 3
11
0.67
0.80

discussion
1.0
10
COD
Maximum Average of Maximum for Any
Daily Values for Any One Day
Period of Thirty
Consecutive Days
1.8 3.5
1.4 2.9
0.07 0.14
No numerical guidelines-see discussion
in footnote
00.11 0.20
30 54
1.9 3-«
6.5 12

No numerical guidelines-see discussion
iu footnote
4.7 8.5
45 82
Suspended Solids
Maximum Average of
Daily Values for Any
Period of Thirty
Consecutive Days
0.13
0.57
0.03
No numerical guidelines-see
in footnote
0.0 06
0.11
0.14

No numerical guidelines-see
in footnote
0.18
1.7
Kaximiua fcr Any
One Dsy
0.19
0.83
0.04
discussion
0.008
0.17
0.20

discussion
0.26
2.5
14     Xitriie Sarrier Resins

15     Spandex Fibers
                        No ouaerical guide linen -see discussion
                                  in footnote
Ho numerical  guidelines-see discussion
           In footnote
So numerical guidelines-see discussion
          in footnote

-------
FOOTNOTES  FOR  TABLES    XI-2 and  XI-3
1*  Ethyl en*-^Jnyl Acetate (EVA) Cepolymer. Two of the five
    known producers were contacted.  All plants are located
    at polyethylene production  facilities.  Water use and
    vasttvattr characteristics  for EVA are essentially iden-
    tical to these for low density polyethylene.  However,
    an exulsion polymerization  process is known and produces
    a distinctly dHfeicnt waste load which Is essentially
    that of polyvinyl acetate emulsion polymerization
    reported in EPA 440/1-73/010.  Both multi-plant and
    Kunlcipal sewage treatment  is Used.

 2. Poly.ticj.mfluoroethyjene^. Three of  the seven manufacturing
    plants were  vioitied. A ult!c range  of prctV-ets are produced.
    The n?or. t  iR!;nrti~rit is polytetraf luorouthyltine (1'TFfc) ond
    these ^uitJelLnas Are recormended for ?TFE granular and
    fire povder  prccles only. The wastcwater discharges differ
    considerably depending upon the process recovery schemes
    for hydrochloric acid and the disposal of selected streams
    by deep well,  ocey_Ltlr ~^'^^Til ^u° °^  t'%e tn^ee producers were
    Ci.rr.acled.  "ilie v:ilu--i--'. r Ic flow ranges per  unit of pro-
    duction vary  widely  depending upon  the  type  of coolin*
    syitea U3ti.  'Ilie waste  Joada  are  for plants where selec-
    ted  concentrated wastes  are segregated and disposed  of
    by land!illing, etc. Primary  treatment at  one plant  site
    was  observed vtiiT.c the other  plant discharges  to a
    ttunlclpal sewage eystcra.


    v^rc contacted. Sotti plant  sites send wastewaters to
    zuiti-plant treatment  plants  of  which  the  polyvinyliden*
    chloride is a snail  portion.   Consequently,  there was
    insufficient  data to develop  recoKr«nded  guidelines.

5.  AHIi.LLS_^~s!—* T'V'ree  °*  c^c  four aanufacturers were
    contacted,  Lar^e r.osbers  of product  grades are produced
    by bulk, solution, suspension  and emulsion polyiaeriza-
    ticn.  Die  vldfely vaiyJng hydraulic  loads  for the large
    r:ur.btfr cf products  in  aJJlticn to treatment  of  the wasts*
    waters by n.ulti-pl.ir.t  wastewater treatment facilities
    prchibitcj  obtaining sufficient  raeaningful data to
    reccsszcnd effluent  limitation guidslincs.

6,  Cellulose Derivatives.  Cellulose dcrlvates investigated
    included ethyl cellulose, hytiroxyethyl  cellulose* methyl
    cellulose and carboxyaothyl cellulose. Wide  variations
    in unit  flow  rates  for two  plants producing  the same
    product, ciftercnces in  manufacturing  techniques  and the
    availability  of, data prevented recortscadinjj  guidulinea.
    The  vj£tevaters from the three manufacturers are  being
    treated  in  multi-plant wastewater treatment  facilities
    or vlll enter aunicipal  sewage systems.
N>
Oi
                                                                 11.
       AlkydB and Unoaturatcd Polyester Rosins, Six carefully
       selected plants were visited to provide a cross-section
       of the industry for size of operation, type of manufac-
       turing process and wastcw.itcr treatment methods. Hydrau-
       lic loads vtry widely depending upon the process designs.
       Similarly, rav waste loads vary widely because some
       plants ecgragate wastes for disposal in other manners.
       Generally, the Industry discharges wastewaters Into
       municipal sewAge syntens ard should continue.  Also, the
       type of air pollution contzol, e.g. combustion or scrub-
       bing, has a significant effect on the wastewater loads.
       The recommended guidelines are for plants having their
       own wastevater treatment system - a very infrequent
       occurrence.

       Cc 11 u lose N11 ra te_. The two major manufacturers of the
       four rs.-mufacturers were contacted.  These wastes require
       pH control and contain larga amounts of nitrates. One
       plant discharges to a municipal sewage system while the
       other goes into a mulci-plant treatment complex.

       Po^l^^f'i^pg. Various polyamideo are produced but only
       ilylon 6/12 produces significant amounts of wascewater,
       e.g. Nylon 11 USOB no process water. Consequently, the
       guidelines are restricted to Nylon 6/12 and wore develop-
       ej on the basis of similarity with waste loads from
       Nylon 66 production.

       Fgly^tgr The moping t i c Res ins. There are three manu-
       facturers, two ot which produce poly(ethylanet tercphtha—
       Ince) in quantities less than 2? oC their total thermo-
       plastic production. The guidelines are recommended for
       poly(ethylcii(; tetephthalatc) since the other product
       poly(iiutylene tercplithalate) is produced at only one
       plant aid the wasrtwater goes into a municipal sewage
       system, sc no un'a en pertora.ince could be obtained.

       Pqlyyinyl JJutvral. Of Llnoe or'oduction sites, two have
       processes btgin.-i.ing with vinyl-acetate Dvonoiiie-r which
       generates much larger Wiist^wsttr volumes than cite pro-
       cess beginning with polyviuyl alcohol. SLnc'p £'ie manu-
       facturing aitfis where producrion r>tatts with a wunomor
       discharge into municipal sewage systems, there was no
       data available.  Consequently, there are no recon«tendcd
       tuldelinev since they would be tantamount  to eetablishlns
       • permit for the direct discharger production site.
       T;felyyinyl cthera* The three present  plants  use differ-
       ent processes each of which produces jcv^ral  gradus  of
       product.   The different »:hetnical  compositions used  in
       both bulk and solution polymerization processes and  the
       lack, of data on both raw and  treated wastewaters pre-
       vented establishing guidelines.  The wastewaters are
       presently sent to either cmltl-plant treatment facilitte
       or municipal sewcge systems.
Sllicones. Four companies xumufacture siliconct at five
locations.  Three plants were visited and data wera
obtained from all plants. The major processing steps at
Che five plants are shown belov.
       Ka.lor Processes at..Five Siliccne Plants
   Plant No.            1  2  3  4  5
Chlorosilane prod.      z  x  x  x  x
Hydrolysis              x  x  x  x  x.
Fluids t greases,
 cnulsions prod,
Resin production        ac  x  x
Elastomer production    x  x  x     x
Specialties prod.*      x  x  x
Fumed silica prod.            x
HC1 production                      x

* e.g. surfactants, fluorinatcd  silicones,  coupling
  agents, and other materials.

Based on the manufacturing process, the waste
water flcvs at-d  the r&u waote loads,  the plants
1, 2, 3 and 5 ware desife^atcd as mlti-product
plants while A was dfislgnatad as a fluid
product plant.
Nitrile  »arrier_Ref;ln&.  Cocnscrcial scale rrojucticn anj
sale  of  these resins has not yet begun.  The ccxpcr.ics
expected to  have  production facilities were contacted,
and two  provided  estimates of raw waste  loads,  because
of the lack  of demonstrated flows ind raw waste loads,
it was impossible to establish efiltent  guideline
lioitatlons.

-Spar.dax  Fibers. Three manufacturers each produce-.
Spandex  fibers by sl^nlficantly different processes.
These are dry,  wet and reaction spinning methods.
Because  of lintted data on rav waste loads- and
because  each plant operates a different  process,
it was impossible to establish meaningful guidelines.

-------
                                             TABLE  XI-3

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

                          1-leicury

PolvtetrafIuoroethylene   Fluorides

Spandex fibers

Nitrile barrier resins

Polypropylene fibers
Silicones
   Fluids

   Greases, Emulsions,
   Rubbers, Resins  and
   Coupling Agent0

Polyester resins
(thermop la.« tic)
Cyanides

Cyanides

Oils and grease
 opper
  ;,.mium
 Toxic and hazardous chemicals guidelines to c?.pply

             0.6                    1.2

 Toxic and hazardous chemicals guidelines to apply
             0.017
                                 0.0026
0.034
                                    0.0052
             0.025                  ^.050

T(  .. .   id hazardous chemicals s,u: Alines to ap

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                        SECTION XII

                      ACKNOWLEDGMENTS
The preparation of the initial draft report was accomplished
through a contract with Arthur  D,  Little,  Inc.,  and  the
efforts  of  their staff under the direction of Henry Haley,
with James I. Stevens and Terry Rothermel as  the  Principal
Investigators.   Industry  subcategory  leaders  were Robert
Eller, Charles Gozek, Edward Icteress, and Richard Tschirch.
J. E. Oberholtzer coordinated the  sampling  and  analytical
work and Anne Witkos was Administrative Assistant.

David   L.  Becker,  Project  Officer,  Effluent  Guidelines
Division, through his assistance,  leadership,  advice,  and
reviews  has  made an invaluable contribution to the overall
supervision of  this  study  and  the  preparation  of  this
report.

Allen  Cywin,  Director, Effluent Guidelines Division, Ernst
Hall, Assistant Director, Effluent Guidelines Division,  and
Walter  J.  Hunt,  Chief,  Effluent  Guidelines  Development
Branch, offered many helpful suggestions during the program.

The members of  the  working  group/steering  committee  who
coordinated the internal EPA review are:

    Walter J. Hunt - Effluent Guidelines Division  (Chairman)
    Allen Cywin - Effluent Guidelines Division
    David Becker - Effluent Guidelines Division
                     (Project Officer)
    William Frick - Office of Enforcement and
                     General counsel
    Bruce Diamond - Office of Enforcement and
                     General Counsel
    Judy Nelson - Office of Planning and Evaluation
    Robert Wooten - Region IV
    Walter Lee - Region III
    Frank Mayhue - Office of Research and Monitoring  (Ada)
    Wayne Smith - National Field Investigation Center
                    (Denver)
    David Garrett - Office of Categorical Programs
    Paul Des Rosiers - Office of Research and Monitoring
    Herbert Skovronek - Office of Research and Monitoring
    Murray Strier - Office of Enforcement and
                     General Counsel

Acknowledgment   and  appreciation  is  also  given  to  the
secretarial staffs of both the Effluent Guidelines  Division
                             267

-------
and   Arthur   D.   Little,  Inc.,  for  the  administrative
coordination, typing of  drafts,  necessary  revisions,  and
final  preparation of the effluent guidelines document.  The
following   individuals   are   acknowledged    for    their
contributions.   Brenda Holmone, Kay Starr, and Nancy Zrubek
- Effluent  Guidelines  Division.   Mary  Jane  Demarco  and
Martha Hananian, Arthur D. Little, Inc.

Appreciation is extended to staff members from EPA's Regions
III and IV offices for their assistance and cooperation.

Appreciation  is  also  extended  to  both the Manufacturing
Chemists Association  and  the  Synthetic  Organic  Chemical
Manufacturers  Association  for  the valuable assistance and
cooperation given to this  program.   Appreciation  is  also
extended  to  those  companies  which  participated  in this
study:

    Air Products and Chemicals, Inc.
    Allied Chemical corporation
    Ameliotex
    American Cyanamid
    Aquitaine Societe Nationale des Petroles
    Ashland Chemical Company
    BASF Wyandotte
    Celanese Chemical company
    Chemplex Company
    Cook Paint and Varnish company
    Diamond - Shamrock
    Dow Chemical company
    Dow-Corning Company
    E.I. duPont de Nemours and Co., Inc.
    Durez
    FMC Corporation
    Freeman Chemical Corporation
    GAF Corporation
    General Electric Corporation
    Globe Manufacturing Corporation
    Goodyear Tire and Rubber Conpany
    Hercules, Inc.
    ICI American, Inc.
    Koppers Company
    Monsanto Company
    Pennwalt Corporation
    Phillips Fibers Company
    Plastics Engineering company
    Reichhold chemicals. Inc.
    Rilsan Industrial, Inc.
    Rohm and Haas Company
    SCM-Glidden-Durkee
                             268

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SWS Silicones
Sherwin-Williams Company
Standard Oil Company
Swedlow, Inc.
Tennessee Eastman
3 M company
Union Carbide Corporation
U.S. Industrial Chemicals
U.S. Polymeric Company
W. R. Grace, Inc.
                         269

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                        SECTION XIII

                         REFERENCES
1.  "Advanced Wastewater Treatment as Practiced at South
    Tahoe," EPA Water Pollution Control Research
    Series Report No. 17010 ELP, Washington, B.C.
    (August 1971).

2.  "An Act to Amend the Federal Water Pollution Control
    Act," Public Law 92-500, Ninety-Second Congress,
    S.2770 (October 18, 1972).

3.  Arthur D. Little, inc., "Technical Proposal:  Effluent
    Limitations Guidelines for the Plastics and
    Synthetics Industry to the Environmental Protec-
    tion Agency," Cambridge, Massachusetts
    (November 16, 1972).

4.  Black and Veatch, "Process Design Manual for Phosphorus
    Removal," Environmental Protection Agency,
    Contract 14-12-936, October 1971.

5.  Boardman, Harold, "Penton (Chloroethers) ," from
    Manufacture of Plastics, Vol._It edited by
    W. Mayo Smith, Reinhold Publishing Corporation,
    New York, 535-7, 550 (1964) .

6.  Chemical Economics Handbook. Stanford Research Institute,
    Menlo Park, California  (1971).

7.  Chemical Engineering Flowsheets, Prepared by the editors
    of Chemical and Metallurgical Engineering, McGraw-
    Hill, New York (1940) .

8.  Chemical Horizons File. Predicasts, Cleveland,
    Ohio.

9.  Chemical Marketing Reporterj "Chemical Profile" Section,
    from June 26, 1972 through July 23, 1973.

10. Chopey, N. P., ed., "Chlorinated Polyether," Chemical
    Engineering 68 (2), 112-115  (January 23, 1961).

11. Connelly, F. J., "Case History of a Polymer Process
    Development," Chemical Engineering^Proqress
    Symposium Series 60 (19), 49-57 (1964).
                           271

-------
12. Contract for Development of Data and Recommendations
    for Industrial Effluent Limitations Guidelines
    and Standards of Performance for the Plastics
    and Synthetics Industry, No. 68-01-1500, Issued
    to Arthur D. Little, Inc., Cambridge, Massachusetts
    (December 1972).

13. Conway, R. A., et al., "Conclusions from Analyzing
    Report 'Treatability of Wastewater from Organic
    Chemical and Plastics Manufacturing - Experience
    and Concepts'," Unpublished document (January
    1973).

14. Conway, R. A., J. C. Hovious, D. C. Macauley, R. E.
    Riemer, A. H. Cheely, K. S. Price, C. T. Lawson,
    "Treatability of Wastewater from Organic
    Chemical and Plastics Manufacturing - Experience
    and Concepts," Prepared by Union Carbide
    Corporation, South Charleston, W. Virginia
    (February 1973).

15. Gulp, Gordon L. and Robert W. Gulp, Advanced Waste-
    Water Treatment, Van Nostrand Reinhold Company,
    New York, New York  (1971).

16. Development Document for Proposed Effluent Limitations
    Guidelines and New Source Performance Standards
    for the Synthetic Resins Segment of the Plastics
    and Synthetic Materials Manufacturing Point
    Source Category. Report No. EPA 440/1-73/010,
    Effluent Guidelines Division, Office of Air and
    Water Programs, U.S. EPA, Washington, D.C.
    (September 1973).

17. Directory of Chemical Producers, Chemical Information
    Services, Stanford Research Institute, Menlo
    Park, California (1973).

18. "Directory of the Plastics Industry, 1972-1973,"
    special edition of Plastics World 30 (11)
    (August 1972) .

19. Federal Water Pollution control Act Amendments of  1972,
    House of Representatives, Report No. 92-1465,
    U.S. Government Printing Office, Washington, D.C.
    (September 28, 1972).

20. Forbath, T. P., ed., "For Host of Silicones:  One
    Versatile Process," Chemical Engineering 64
    (12) , 228-231 (1957) .
                        272

-------
21. Galanti, A. V. and Mantell, C. L., Propropvlene Fibers
    and Films. Plenum Press, New York, New York  (1965).

22. "Integration of Chemical Plant Facilities," Chemical  and
    Metallurgical Engineering 52  (9), 129-141
    (September 19*5).

23. Johnson, R. N., A. G. Farnham, R. A. Clendinning,  W.  F.
    Hale, c. N. Merriam, "Poly(aryl  Ethers) by
    Nucleophilic Aromatic Substitution.  I. Synthesis
    Part A-l  (5), 2375-2398  (1967).

24. Jones, R. Vernon, "Newest Thermoplastic - PPS,"
    Hydrocarbon Processing 51  (11),  89-91  (November
    1972).

25. Kirk-othmer, eds.. Encyclopedia  of Chemical Technology,
    2nd Ed.t Interscience Division of John Wiley and
    Sons, New York, New York (1963-1971).

26. Labine, R. A., ed., "Flexible Process Makes Silicone
    Rubber,"  Chemical Engineering 67 (14), 102-105
    (1960).

27. Lee, H.r D. Stoffey, K. Neville, New Linear Polymers.
    NcGraw-Hill, New York  (1967).

28. "Making Polycarbonates:  A First Look," Chemical
    Engineering 67  (23), 174-177  (1960).

29. Mark, H., ed., EncYclopedia of Polymer Science and
    Technology, Interscience Division of John Wiley
    and Sons, New York, New York  (1964-1972).

30. Modern Plastics Encyclopedia. McGraw-Hill, New York,
    New York  (1973-1974).

31. Monsanto Flow Sheet, Chemical Engineering. 346-349
    (February 1954).

32. Mudrack, Klaus, "Nitro-Cellulose Industrial Waste,"
    Proc, of the 21st Industrial Waste Conference
    May 3f 4, and 5, 1966, Engineering Extension
    Series No. 121, Purdue University, Lafayette,
    Indiana.

33. "National Pollutant Discharge Elimination System,  Proposed
    Forms and Guidelines for Acquisition of Information
    From Owners and Operators of Point Sources,"
    Federal Register 37 (234), 25898-25906  (December
    5, 1972) .
                           273

-------
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, for the
    State of Illinois Institute for Environmental
    Quality.

36. "Polycarbonates - General Electric Company," Hydro-
    carbon Processing, p. 262 (November 1965) .

37. "Procedures, Actions and Rationale for Establishing
    Effluent Levels and Compiling Effluent Limitation
    Guidance for the Plastic Materials and Synthetics
    Industries," Unpublished report of the Environmental
    Protection Agency and the Manufacturing Chemists
    Association, Washington, D.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., Organic Chemical Process Encyclopedia,
    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 Document for Proposed Effluent Limitations
    Guidelines and New Source Performance Standards
    For the Synthetic Resins Segment of the Plastics
    and Synthetic Materials Manufacturing Point
    Source Category, Report No. EPA 440/1-73/010,
    Effluent Guidelines Division, Office of Air and
    Water Programs, U.S. EPA, Washington, D.C.
    (September 1973).

**3. Textile Organ, Textile Economics Bureau, Inc., New
    York, 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).
                        274

-------
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 OlConnors, Ralph J., "Manu-
    facture of Basic Silicone Products,'1 Modern
    Chemical Processes, 6, 7-11 (1961).

50. "Wastewater Treatment Facilities for a Polyvinyl
    Chloride Production Plant," EPA Water Pollution
    Control Research Series Report No. 12020 DJI,
    Washington, D.C.   (June 1971),

51. "Water Quality Criteria 1972," National  Academy of
    Sciences and National Academy of Engineering for
    the Environmental Protection Agency, Washington, D.C.
    1972  (U.S. Govt. Printing Office  Stock  No. 5501-00520)
                         275

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                        SECTION XIV

                          GLOSSARY
Refers to that portion of a  molecular  structure  which  is
derived from acetic acid.

Addition Polvmerization

Polymerization   without   formation  of  a  by-product   (in
contrast to condensation polymerization.)

Aerobic

A living or active biological  system  in  the  presence  of
free, dissolved oxygen.

Alkyl

A general term for monovalent aliphatic hydrocarbons,

Allophanate

A derivative of an acid, NH2CONHCOOH, which is only known in
derivative forms such as esters.

Alumina

The oxide of aluminum.

Amorphous

Without apparent crystalline form.

Anaerobic

Living or active in the absence of free oxygen.

Annealing

A  process  to  reduce  strains  in a plastic by heating and
subsequent cooling.

Arvl

A general term denoting the  presence  of  unsaturated  ring
structures in the molecular structure of hydrocarbons.
                          277

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Atactic Polymer

A  polymer  in  which  the  side  chain  groups are randomly
distributed on one side or the other of the  polymer  chain.
(An atactic polymer can be molded at much lower temperatures
and  is more soluble in most solvents than the corresponding
isotactic polymer, g.q.).

Autoclave

An enclosed vessel where various conditions  of  temperature
and pressure can be controlled.

Azeotrope

A liquid mixture that is characterized by a constant minimum
or  maximum boiling point which is lower or higher than that
of any of the components and that distills without change in
composition.

Bacteriostat

An agent which inhibits the growth of bacteria.

Slowdown

Removal of a portion of  a  circulating  stream  to  prevent
buildup  of dissolved solids, e.g., boiler and cooling tower
blowdown.

BODS

Biochemical  Oxygen  Demand  (5  days   as   determined   by
procedures   in   standard   Methods)  19th  Edition,  Water
Pollution Control Federation, or EPA's  Manual  16020-07/71,
Methods for Chemical Analysis of Water and Wastes.

Catalyst

A   substance  which  initiates  primary  polymerization  or
increases the rate of cure or  crosslinking  when  added  in
quantities  which  are  minor as compared with the amount of
primary reactants.

Caustic Soda

A name for sodium hydroxide.
                          278

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Chain Terminator

An  agent  which,  when  added  to  the  components   of   a
polymerization  reaction,  will stop the growth of a polymer
chain, thereby preventing the addition of MER units.

COD

Chemical Oxygen Demand  (determined by methods  explained  in
the references given under BODS.)

copolvmer

The  polymer obtained when two or more monomers are involved
in the polymerization reaction.

Cross-link

A comparatively short connecting unit (such  as  a  chemical
bond   or   a  chemically  bonded  atom  or  group)  between
neighboring polymer chains.

Crystalline

Having regular arrangement of the atoms in a  space  lattice
— opposed to amorphous.

Delusterant

A  compound  (usually  an inorganic mineral)  added to reduce
gloss or surface reflectivity of plastic resins or fibers.

Dialysis

The separation of substances in solution by means  of  their
unequal diffusion through semipermeable membranes.

Diatomaceous Earth

A  naturally  occurring  material  containing  the  skeletal
structures of diatoms - often used as an aid to filtration.

Effluent

The flow of  waste  waters  from  a  plant  or  waste  water
treatment plant.

Emulsifier

An  agent  which  promotes formation and stabilization of an
emulsion, usually a surface-active agent.
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Emulsion

A suspension of fine droplets of one liquid in another.

Facultative Lagoon or Pond

A  combination  of  aerobic  surface  and  anaerobic  bottom
existing  in  a  basin  holding  biologically  active  waste
waters.

Fatty Acids

An organic acid obtained by the hydrolysis  (saponification)
of  natural fats and oils, e.g., stearic and palmitic acids.
These acids are monobasic and may or may  not  contain  some
double  bonds.   They usually contain sixteen or more carbon
atoms.

Filtration

The removal of particulates from liquids by membranes on in-
depth media.

Formalin

A solution of formaldehyde in water.

Free Radical

An atom or a  group  of  atoms,  such  as  triphenyl  methyl
(C6H5>)3C»,  characterized  by  the  presence of at least one
upaired electron.  Free radicals are effective in initiating
many polymerizations.

Godet Roll

Glass or plastic rollers around  which  synthetic  filaments
are passed under tension for stretching.
Gallons per day.

GPM

Gallons per minute.
                            280

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Halogen

The  chemical  group containing chlorine, fluorine, bromine,
iodine.

Isotactic Polymer

A polymer in which the side chain groups are all located  ^n
one side of the polymer chain.  See also "Atactic Polymer."

Lewis Acid

A  substance  capable  of  accepting from a base an unshared
pair of electrons which then form a covalent bond.  Examples
are boron fluoride, aluminum chloride.

Homopolymer

A polymer containing only units of one single monomer.

Humectant

An agent which absorbs water.  It is often  added  to  resin
formulations  in  order  to  increase  water  absorption and
thereby  minimize  problems  associated  with  electrostatic
charge.

Influent

The flow of waste waters into a treatment plant.

M

Thousands (e.g., thousands metric tons).

MM

Millions (e.g., million pounds).

Monomer

A  relatively  simple  compound  which  can  react to form a
polymer,

EH

A measure of the relative acidity or alkalinity of water  on
a  scale  of 0-14.  A pH of 7 indicates a neutral condition,
less than 7 an acid condition, greater than  7  an  alkaline
condition.
                            281

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Phenol

Class  of cyclic organic derivatives with the basic chemical
formula C6H5OH.

Plasticizer

A  chemical  added  to  polymers  to   impart   flexibility,
workability or distensibility.

Polymer

A   high  molecular  weight  organic  compound,  natural  or
synthetic, whose structure can be represented by a  repeated
small unit (MER).

Polymeri zation

A  chemical reaction in which the molecules of a monomer are
linked together to  form  large  molecules  whose  molecular
weight  is  a  multiple  of  that of the original substance.
When two or more  monomers  are  involved,  the  process  is
called copolymerization.

Pretreatment

Treatment  of waste waters prior to discharge to a publicly-
owned waste water treatment plant.

Primary Treatment

First stage  in  sequential  treatment  of  waste  waters  -
essentially limited to removal of readily settlable solids.

Quenching

Sudden cooling of a warm plastic, usually by air or water.

Reflux

Condensation of a vapor and return of the liquid to the zone
from which it was removed.

Resin

Any  of  a  class  of solid or semisolid organic products of
natural or synthetic origin,  generally  of  high  molecular
weight  with  no  definite  melting  point.  Most resins are
polymers.
                             282

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 Scrubber

Equipment for removing condensable vapors  and  particulates
from gas streams by contacting with water or other liquid.

Secondary Treatment

Removal  of  biologically  active  soluble substances by the
growth of microorganisms.

Slurry

Solid particles dispersed in a liquid medium.

gpinnerette

A type of extrusion die consisting of  a  metal  plate  with
many  small  holes  through  which a molten plastic resin is
forced to make fibers and filaments.

Staple

Textile fibers of short length, usually  one-half  to  three
inches.

Stoichiometric

Characterized  by  being  a proportion of substances exactly
right for a specific chemical reaction with no excess of any
reactant or product.

TDS

Total dissolved solids - soluble substances as determined by
procedures given in reference under BOD5.

Thermoplastic

Having property of softening or fusing when  heated  and  of
hardening to a rigid form again when cooled.

Thermosetting

Having  the  property of becoming permanently hard and rigid
when heated or cured.

TOG

Total Organic Carbon - a method for determining the  organic
carbon content of waste waters.
                             283

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TOW

A  large number of continuous filaments of long length.  Tow
is the usual form of fibers after  spinning  and  stretching
and prior to being chopped into short lengths of staple.

Transesterification

A reaction in which one ester is converted into another.

Vacuum

A condition where the pressure is less than atmospheric.

Ziegler-Natta Catalyst

A  catalyst  (such  as  a  transition  metal  halide  or  an
organometallic compound) that  promotes  an  ionic  type  of
polymerization  of  ethylene or other olefins at atmospheric
pressure with the resultant formation of a relatively  high-
melting polyethylene or similar product.
                             284

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                                     TABLE  XIV-1

                                   METRIC  TABLE

                                 CONVERSION  TABLE

MULTIPLY  (ENGLISH UNITS)                   by                 TO OBTAIN (METRIC UNITS)

    ENGLISH UNIT      ABBREVIATION     CONVERSION    ABBREVIATION   METRIC UNIT
acre                    ac
acre - feet             ac  ft
British Thermal
  Unit                  BTU
British Thermal
  Unit/pound            BTU/lb
cubic feet/minute       cfm
cubic feet/second       cfs
cubic feet              cu  ft
cubic feet              cu  ft
cubic inches            cu  in
degree Fahrenheit       °F
feet                    ft
gallon                  gal
gallon/minute           gpm
horsepower              hp
inches                  in
inches of mercury       in  Hg
pounds                  Ib
million gallons/day     mgd
mile                    mi
pound/square
  inch (gauge)          psig
square feet             sq  ft
square inches           sq  in
ton (short)             ton
yard                    yd
* Actual conversion, not a multiplier
 U.S. GOVERNMENT PRINTING OFFICE: 1975-582-420:233
0.405
1233.5
0.252
0.555
0.028
1.7
0.028
28.32
16.39
0.555(°F-32)*
0.3048
3.785
0.0631
0.7457
2.54
0.03342
0.454
3,785
1.609
(0.06805 psig +1)*
0.0929
6.452
0.907
0.9144
ha
cu m
kg cal
kg cal/kg
cu m/min
cu m/min
cu m
1
cu cm
°C
m
1
I/sec
kw
cm
atm
kg
cu m/day
km
atm
sq m
sq cm
kkg
m
hectares
cubic meters

kilogram - calories

kilogram calories/kilogram
cubic meters/minute
cubic meters/minute
cubic meters
liters
cubic centimeters
degree Centigrade
meters
liters
liters/second
killowatts
centimeters
atmospheres
kilograms
cubic meters/day
kilometer

atmospheres (absolute)
square meters
square centimeters
metric ton (1000 kilograms)
meter
                                        285

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U.S. ENVIRONMENTAL PROTECTION AGENCY (A-107)
WASHINGTON, D.C. 20460
           POSTAGE AND FEES PAID
ENVIRONMENTAL PROTECTION AGENCY
                        EPA-335

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