12CO ?'xth
                     Seattle, i/VA

  POLYMER INDUSTRY RANKING BY
   VOC EMISSIONS REDUCTION
    THAT WOULD OCCUR FROM
NEW SOURCE PERFORMANCE STANDARDS

 Pullman  Kellogg
     ... \
 Division of Pullman Incorporated

-------
                                                    August 30, 1979
                     POLYMER INDUSTRY RANKING BY

                       VOC EMISSIONS REDUCTION
                        THAT WOULD OCCUR FROM

                  NEW SOURCE PERFORMANCE STANDARDS
                                 by
                             C.N. Click
                            O.K.  Webber
                           PULLMAN KELLOGG
                 16200 Park Row, Industrial Park Ten
                        Houston, Texas 77084


                Contract No.  68-02-2619, Task No.  7
Project Officer

Dennis Grumpier
U.S. EPA, OAQPS, ESED, CPB, CAS
Room 730 Mutual Building (MD-13)
Research Triangle Park,
North Carolina, 27711
Project Manager

J.A. McSorley
Operations Program Officer
Industrial Environmental
 Research Laboratory
Research Triangle Park,
North Carolina  27711
            INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
                 OFFICE OF RESEARCH AND DEVELOPMENT
                U.S. ENVIRONMENTAL PROTECTION AGE*"""
                  RESEARCH TRIANGLE PARK, NC  277]

-------
                       .  ,     CONTENTS


Section
1.0  INTRODUCTION                                                 1
2.0  SUMMARY                                                      3
3.0  PRIORITY RANKING                                             5
4.0  DISCUSSION AND DATA                                         15

     4.1  General                                                15
     4.2  Processes and Flowsheets                               16
     4.3  Company Visits and Categories of Plastics              16
     4.4  VOC Emissions Data                                     17
     4.5  Applicable Controls and Efficiencies                   17
     4.6  Data Reduction                                         19
     4.7  References and Credits                                 19

5.0  ACRYLIC RESINS                                              20

     5.1  Industry Description                                   20
     5.2  Acrylic Resin Manufacture by Hydrocarbon Based         27
           Processes

          5.2.1  Hydrocarbon Based Process,. Descriptions          27
          5.2.2  VOC Emissions for the Hydrocarbon Based         30
                  Processes
          5.2.3  Applicable Controls for the Hydrocarbon         33
                  Based Processes

     5.3  Acrylic Resin Manufacture by Water Based Processes     34

          5.3.1  Water Based Process Description                 34
          5.3.2  VOC Emissions for the Water Based Processes     37
          5.3.3  Applicable Control Systems (Water Based         40
                  Processes)

6.0  ALKYD RESINS                                                42

     6.1  Industry Description                                   42
     6.2  Alkyd Resin Manufacture By Solvent Process             50

          6.2.1  Process Description                             50
          6.2.2  VOC Emissions                                   52
          6.2.3  Applicable Control Systems                      55

7.0  MELAMINE - FORMALDEHYDE RESINS                              58

     7.1  Industry Description                                   58
     7.2  Manufacture Of Melamine-Formaldehyde Resin And A       60
            Butylated MF Resin

          7.2.1  Process Description                             60
          7.2.2  VOC Emissions                                   77
          7.2.3  Applicable Control Systems                      80

                            ii

-------
                              CONTENTS


Section                                                        Page

8.0  NYLON 6 FIBER                .                               81

     8.1  Industry Description                                   81

          8.1.1  General                                         81
          8.1.2  Nylon 6                                         82
          8.1.3  Production Levels for Nylon and Aramid          83

     8.2  Nylon 6 Manufacture by  the Continuous Chip Process     85

          8.2.1  Process Description                             85
          8.2.2  VOC Emissions                                   89
          8.2.3  Applicable Control Systems                      92

9.0  NYLON 66 FIBER                                              94

     9.1  Industry Description                                   94
     9.2  Batch or Continuous Polycondensation of Nylon 66       94

          9.2.1  Process Description                             94
          9.2.2  VOC Emissions                                  101
          9.2.3  Applicable Control Systems                     105

10.0 PHENOL-FORMALDEHYDE (PHENOLIC) RESINS                      107

     10.1 Industry Description                                  107
     10.2 Manufacture of Phenol-Formaldehyde (Phenolic) Resins  108

          10.2.1 Process Description                            108
          10.2.2 VOC Emissions                                  112
          10.2.3 Applicable Control Systems                     116

ll.O POLYESTER FIBERS                                           118

     11.1 Industry Description                                  118
     11.2 P.P. Manufacture by Dimethyl Terephthalate Process    123

          11.2.1 Process Description                            123
          11.2.2 VOC Emissions (DMT Process)                    126
          11.2.3 Applicable Control Systems (DMT Process)       130

     11.3 P.P. Manufacture by Terephthalic Acid (TPA) Process   130

          11.3.1 Process Description (TPA)                      130
          11.3.2 VOC Emissions (TPA Process)                    130
          11.3.3 Applicable Control Systems (DMT & TPA          130
                 Processes)

                               iii

-------
                              CONTENTS
Section                                                        Page

12.0 HIGH DENSITY POLYETHYLENE                                  137
     12.1  Industry Description                                 137
     12.2  HOPE Manufacture by Liquid Phase Processes           138

           12.2.1  Process Description (Liquid Phase)           138
           12.2.2  VOC Emissions (Liquid Phase)                 143
           12.2.3  Applicable Control Systems  (Liquid Phase)    146

     12.3  HOPE Manufacture by Gas Phase Processes              147

           12.3.1  Process Description (Gas Phase)              147
           12.3.2  VOC Emissions (Gas Phase).  ...                 150
           12.3.3  Applicable Control Systems  (Gas Phase)       152

13.0 LOW DENSITY POLYETHYLENE                                   154
     13.1  Industry Description                                 154
     13.2  LDPE Manufacture by Liquid Phase (High Pressure)     159

           13.2.1  Process Description (Liquid Phase)           159
           13.2.2  VOC Emissions (Liquid Phase)                 161
           13.2.3  Applicable Control Systems  (Liquid Phase)    164

     13.3  LDPE Manufacture by Gas Phase Processes              166

           13.3.1  Process Description (Gas Phase)              166
           13.3.2  VOC Emissions (Gas Phase)                    169
           13.3.3  Applicable Control Systems  (Gas Phase)       171

14.0 POLYPROPYLENE                                              173
     14.1  Industry Description and Status                      173
     14.2  Polypropylene Manufacture                            179
                              iv

-------
 Section
                   CONTENTS

                                                    Page

14.2.1  Process Description                          179
14.2.2  VOC Emissions                                122
14.2.3  Applicable Control Systems
15.0 POLYSTYRENE RESINS                                         187
     15.1  Industry Description
     15.2  Manufacture of Polystyrene Resin by Bulk (Mass),
            Suspension, or Bulk-Suspension Processes

           15.2.1  Process Description                          188
           15.2.2  VOC Emissions                                195
           15.2.3  Applicable Control Systems                   198

16.0 POLYVINYL ACETATE                                          200
     16.1  Industry Description                                 200
     16.2  Polyvinyl Acetate by Emulsion Polymerization         203

           16.2.1  Process Description                          203
           16.2.2  VOC Emissions                                211
           16.2.3  Applicable Control Systems                   213

17.0 POLYVINYL ALCOHOL                                          215
     17.1  Industry Description                                 215
     17.2  Manufacture of Polyvinyl Alcohol                     217

           17.2.1  Process Description                          217
           17.2.2  VOC Emissions                                221
           17.2.3  Applicable Control Systems                   224
                               v

-------
                              CONTENTS
Section
18.0 STYRENE  BUTADIENE  LATEX                                     227
     18.1   Industry  Description                                  227
     18.2   Styrene-Butadiene  by  Emulsion Polymerization         229

            18.2.1  Process  Description                          229
            18.2.2  VOC  Emissions                                233
            18.2.3  Applicable Control  Systems                   236

19.0 UNSATURATED POLYESTER  RESINS                               238
     19.1   Industry  Description                                  238
     19.2   Unsaturated  Polyester Resin Manufacture              245

            19.2.1  Process  Description (Fusion and Solvent      245
                     Processes)
            19.2.2  VOC  Emissions                                249
            19.2.3  Applicable Control  Systems                   252

20.0 UREA- FORMALDEHYDE  RESINS                                   254
     20.1   Industry  Description                                  254
     20.2   Urea Formaldehyde  Syrup and Filled Powder Manufacture256

            20.2.1  Process  Description                          256
            20.2.2  VOC  Emissions                                253
            20.2.3  Applicable Control  Systems                   261

REFERENCES                                                       263
                                VI

-------
                               FIGURES
Figure                                                         Page

 3-1   Capacity regulated by existing standards and by NSPS       9
        versus year since NSPS promulgation.
 5-1   Acrylics resins manufacture by bulk/solution processes.   28
 5-2   Acrylics resins manufacture by emulsion/suspension        35
        processes.
 6-1   Alkyd resins by a batch solvent process.                  51
 7-1   Melamine-formaldehyde resin - Batch process.              73
 8-1   Nylon 6 - Continuous chip process.                        87
 9-1   Nylon 66 by batch or continuous polycondensation.         97
10-1   Phenol-formaldehyde resin using one. step or two          109
        step processes.
11-1   Polyester fibers using DMT/TPA processes.                124
12-1   HDPE by liquid-phase (diluent) processes.                142
12-2   HDPE by gas-phase processes.                             149
13-1   LDPE by liquid-phase (high-pressure)  processes.          160
13-2   LDPE by gas-phase (low-pressure)  processes.              167
14-1   Polypropylene - Continuous slurry process.               180
15-1   Polystyrene by suspension, bulk,  or bulk-suspension      191
        processes.
16-1   Polyvinyl acetate - Emulsion polymerization.             209
17-1   Polyvinyl alcohol - Solution polymerization.             218
18-1   Styrene-butadiene latex using emulsion polymerization.   232
19-1   Unsaturated polyester resin using fusion or solvent      247
        processes.
20-1   Urea formaldehyde resin - Batch process.                 257
                               VII

-------
                               TABLES
Tables                                                         Page

3-1    VOC Data Summary and Results For Plastics Ranking         12
3-II   Ranking Comparison                                        13
5-1    Producers of Acrylic Resins and Related Products       22-26
5-II   VOC Emissions from Acrylic Resins - Bulk/Solution         31
        Processes
5-III  VOC Emissions From Acrylic Resins - Emulsion/             38
        Suspension Processes
6-1    Estimated Consumption of Alkyd Surface Coatings By        44
        Major Market, 1976 - 1981
6-II   Estimated Consumption of Industrial Alkyd Surface         45
        Coatings
6-III  VOC Emissions from Alkyd Resins By Solvent Process        53
7-1    Producers of Amino and Phenolic Resins                 61-72
7-II   VOC Emissions From Butylated Melamine-Formaldehyde        78
        Resin
8-1    Nylon 6 Yarn, Staple, and Tow Annual Capacity as of       86
        September 1976
8-II   VOC Emissions From Nylon 6 - Continuous Chip Process      90
9-1    Nylon 66 Yarn, Staple, and Tow Annual Capacity as of      91
        September 1976
9-II   VOC Emissions from Nylon 66 Batch or Continuous Process  102
10-1   VOC Emissions from Phenol Formaldehyde Resins            113
11-1   Polyester Yarn Staple and Tow Producing Companies    120-122
        as of September 1977
11-11  VOC Emissions from Polyester Fiber - DMT Process         127
ll-III VOC Emissions from Polyester Fiber - TPA Process         132
12-1   U.S. Manufacturers of HOPE Resins and Their Locations 139-140
        and Capacities
12-11  VOC Emissions from HOPE - Solvent Processes              144
12-111 VOC Emissions from HOPE - Gas Phase Processes            151

                              viii

-------
                               TABLES
                              Continued

Tables                  .                                       Page

13-I(a)  Summary of U.S. Manufacturers of LDPE Resins and Their  155
         Capacities
13-I(b)  U.S. Manufacturers of LDPE Resins and Their Locations   157
         and Capacities
13-11   VOC Emissions from LDPE - Liquid Phase (High Pressure)  162
         Processes
13-111  VOC Emissions from LDPE - Gas Phase (Low Pressure)      168
         Processes
14-1    U.S. Producers of Polypropylene Resins              177-178
14-11   VOC Emissions from Polypropylene -. Continuous Slurry    183
         Process
15-1    U.S. Producers of Polystyrene Resins                189-190
15-11   VOC Emissions from Polystyrene Resin Manufacture        196
16-1    Producers of Merchant PVAc Emulsions and Resins     204-205
16-11   Producers of PVAc Emulsions and Resins for Compounding  206
16-111  VOC Emissions from Polyvinyl Acetate Latex - Emulsion   216
         Polymerization
17-1    U.S. Producers of Polyvinyl Alcohol            .         216
17-11   VOC Emissions From Polyvinyl Alcohol Manufacture        222
18-1    U.S. Producers of Styrene-Butadiene Latexes         230-231
18-11   VOC Emissions from Styrene-Butadiene Latex - Emulsion   234
         Polymerization
19-1    U.S. Producers of Unsaturated Polyester Resins      240-243
19-11   Common Raw Materials For Unsaturated Polyester          244
         Manufacture
19-111  VOC Emissions From Unsaturated Polyester Resin - Fusion
         or Solvent Processes                                   250
20-1    VOC Emissions From Urea Formaldehyde                    259
                                IX

-------
                           SECTION 1
                         INTRODUCTION
Pullman  Kellogg performed  this  study  for  the  Environmental
Protection Agency (EPA) under  Contract Number 68-02-2619 ,  Work
Assignment No.  7.   The  study ranks the plastics surveyed  for the
.impact on volatile organic compound (VOC)  emissions  that new
source performance  standards (NSPS) would have.   In  alphabetical
order, the plastics studied were:
Acrylics
Alkyds
Melamine Formaldehyde
Nylon 6
Nylon 66
Phenol Formaldehyde
Polyester Fibers
High Density Polyethylene
Low Density  Polyethylene
Polypropylene
Polystyrene
Polyvinyl  Acetate
Polyvinyl  Alcohol
Styrene  Butadiene Latex
Unsaturated  Polyester Resins
Urea Formaldehyde
The objectives of  this  study were to estimate the  amount of VOC
that  could  be prevented from  going  to atmosphere  during  the
period 1979  through  1989 if new production facilities constructed
during  this period met NSPS and  to  rank the sixteen  plastic
industries according  to  their potential for reducing  VOC.   The
production  facilities  included  for  each of the  16 industries
studied  were monomer storage; polymerization;  and  plastics
processing,  handling, and storage.
                              -1-

-------
The study was completed  by obtaining background information  about
the sources of VOC  emissions from manufacturers  that polymerize
and process the chosen polymers.   The information obtained was
used to determine the magnitude of the current emissions,  to show
their sources (vents, etc.), and  to estimate  their growth  rate
and the level of control achievable.

The scope of the study included an evaluation and report based  on
literature surveys,  calculation, 114 letters, telephone contacts,
and visits to company headquarters.  Data collection was limited
to the 16 plastics  listed.

Since a description of  the  content of this  report will aid  in
reading it,  a brief outline  of the  approach follows.   An
Introduction and Summary establish the parameters and findings  of
the report.   They  are  followed  by Section  3 on Ranking  which
discusses the EPA's Model IV (_!) system which is  used to rank the
products.

Section  4,  Data and Controls,  describes the approach used  to
select data, the data obtained, data reduction methods, flowsheet
development, and the VOC tables and controls selected.  Sections
5 through 20 describe each of the sixteen plastics products and
are meant to stand  alone.  Generally these sections begin with  an
"Industry Description" sub-section.  This sub-section contains a
brief summary of the plastic product and emphasizes name,  loca-
tion, and capacity of all known  manufacturers;  information  on
production and growth rates; and the most common processes, raw
materials, and catalysts used.   The second  sub-section, "Manu-
facturing by (Specified) Process", contains  a  brief process de-
scription and flowsheet, a table of VOC emissions, and a descrip-
tion of the applicable controls and efficiency.  The "References"
list following Section 20 cites all the literature used for the
study.
                              _ O 

-------
                           SECTION 2
                            SUMMARY
This  study ranks plastics  industries on  the basis  of  the
calculated impact on VOC  emissions that  new  source performance
standards (NSPS)  would  cause.  The' names of the plastics and  the
resultant ranking are  tabulated below for  convenience  in
summarizing the  study findings.
   RANKING FOR NSPS  IMPACT  FOR 10 YEAR VOC EMISSIONS REDUCTION
Plastic
 Impact
Ranking
      Model  Impact
(Millions  of Pounds - MMP)
HOPE
Polypropylene
LDPE
SB Latex
PE Fiber
Polystyrene
Polyvinyl Acetate
Acrylics
Unsaturated Polyester
Nylon 66
Phenol Formaldehyde
Melamine Formaldehyde
Polyvinyl Alcohol
Nylon 6
Alkyds
Urea Formaldehyde
  #1
  #2
  #3
  #4
  #5
  #6
  #7
  #8
  #9
 #10
 #11
 #12
 #13
 #14
 #15
 #16
          61.2
          18 .2
          16.3
          15.4
          14.3
          10.4
           6.6
           5.7
           2.2
           1.04
           0.96
           0.50
           0.50
           0.20
          -0.04
          -0.45
                                3 

-------
The model  used  for the ranking, EPA  Model  IV, calculates  the
difference  (impact)  between emissions  under baseline year
regulations  and  under new source performance standards.   The
components  of the model are K, the utilization  factor; Eg and
EN, which are respectively, emissions  factors for the
baseline year regulations and for NSPS;  and  B and C, the  new
capacities  used for replacement and  for growth.  Values of K were
obtained from the literature.  Emissions  factors, expressed  in
units of pounds per 1000 pounds (#/1000#), were determined  for
each plastic from  data obtained from industry.   Capacity  and
growth  were  obtained  from industry and the literature  and
obsolescence  was arbitrarily chosen  at  0 and 5%.

Data were obtained  for  the plastics  and flowsheets were  prepared
indicating  the major  VOC emission  sources.  Tables of VOC
emissions were made showing "Uncontrolled"-, "Current Practice",
and "Well  Controlled" emissions  factors.   Finally,  a brief
discussion  of applicable control  technology was  provided.

The following observations were made:

1.  EPA's Model IV  should be used  to rank  the  plastics  surveyed
    for the impact  of NSPS on VOC  emissions.  Current emissions,
    TA, is  also a good  indicator of  the impact,  but it should
    not be  relied upon  for decision  making.

2.  Because  of  inherent uncertainty  in  the  data used for  the
    model,  plastics whose rankings differ  by  only a  few percent
    like LDPE, SB Latex, and  PE Fiber, should  be considered  as
    equal-ranked.

3.  The decrease in emissions per  plastic  in the descending order
    of the  ranking  table is greater  than two orders-of-magnitude.
    Relatively large changes in production  or emissions would  not
    likely  change these rankings more  than  one  or two places.
                               -4-

-------
                           SECTION 3
                       PRIORITY RANKING
This study  and ranking  were  undertaken because new source
performance  standards  may be established for those new stationary
sources which contribute significantly to air pollution.   The  EPA
Model  IV  (jj  priority ranking system, which  was developed  to
determine  priorities  in the NSPS setting  process, was used  in
this work.  Section  114 letter  responses and information  obtained
from visits  to various manufacturers was used to obtain emissions
data, and  these were combined with other industry data as well  as
information  from the literature.

Model IV determines  the difference or "impact" between emissions
under baseline year  regulations and under new source performance
standards  (NSPS).  The model incorporates  a factor for  capacity
use and factors for  both obsolescence and growth rates..  Various
refinements  are available  for  the model  (including the use  of
different  standards  for new and existing plants and for  designa-
ted pollutants),  but none of these were used in this study.

There  are several  limitations of Model   IV which affect  its
applicability to the plastics studied.  Among  these limitations
are:

1) Little  impact is  shown for plastics whose production  capacity
   is on the decline (e.g., alkyds and urea-formaldehyde).
2) Little  impact is  shown for plastics with either little,  or,  no
   known BDCT or with  high  fugitive emissions (e.g., acrylics).
                             -5-

-------
3) The model is sensitive  to  all  the  component factors.   But two
   of these,  K and  B,  are  especially variable  and hard  to
   determine.   Generally historic  K's are desired for consistency
   but when using them the model  depends  on greater-and-greater
   time intervals.   Estimates for  B can be  based on  depreciation
   schedules (tax-based) or on experience,  and they  probably vary
   significantly from industry to  industry.
4) The condfidence  with  which any  of  the  impacts shown  should  be
   valued decreases  with  time from  the  base year  (1979),  and,
   therefore,  10 year projections might  err appreciably due  to
   changes in  the growth,  obsolescence, or  utilization rates.

The model is responsive  to data updating, and it improves as the
time  interval of the impact is reduced.   Also it provides a
quantitative estimate of the  impact of NSPS.  The impact  of  NSPS
is taken as the difference between emissions  under baseline  year
regulations (Ts) and emissions under  NSPS (TN).  The
model relationship  is:

(Ts - TN) = K  (Es -  EN)  (B +  C)
                                                            (1)
from  Ts = KES (A -  B) + KEg  (B+C) and
      TN = KES (A -  B) + KEN  (B+C)

Where:

Ts = total emissions in  the ith year  under  baseline  year
     regulations (MMP)
TN = total emissions in  the ith year  under  new or revised
     NSPS which have been  promulgated in  the  the jth year
     (MMP)
K  = normal utilization  rate  of existing  capacity, (ratio of
     production to  capacity)  assumed  constant during time
     interval
Eg = allowable emissions under existing regulations  (mass/
     unit capacity)             _,-_

-------
EN = allowable emissions under  NSPS  (mass/unit capacity)

A  = baseline year capacity (production  units/yr)
B  = capacity from construction and  modification to replace
     obsolete facilities (production units/yr)
C  = capacity from construction and  modification to increase
     output above baseline  year capacity (production units/yr)

The values of K used in the model have  either an historic or a
recent (1978 - 1979) data base.  Historic values were  used most
and were obtained from the  literature.   Often  the appropriate SRI
documents were the source (See  References) for historic K values.
For HDPE, LDPE, Polypropylene,  Polyester Fiber, and Polystyrene,
recent data were available and were  used (2) .   Of the  top six
ranked plastics, all impacts were  calculated from current  K data
except that for SB latex.  Current K's were calculated  from known
1978 production and the construction growth rate (P^) and es-
timated 1979 industry  capacity.  Generally,  utilization  rates
cluster around 0.8  to 0.9 representing production of 80 to 90% of
name plate capacity.

The emissions factors,  Eg and EN,  were obtained from
industry data (see  Sections 5 through .20)  and were.based on
actual emissions and actual production  (not  capacity)  data.  It
was recognized that these factors might change  with changes in
production, but because such changes were  not  predictable,  Eg
and EN were used as obtained.  The values  obtained were low
compared to those  for  the major acrylonitrile using polymer
industries, for example (3J .

The construction rate necessary to  replace  obsolete equipment,
Pg, was arbitrarily chosen  at two  values,  0 and 0.05, for
comparison purposes.  Because of this, Table 3-1 has two  columns
of estimated VOC emissions  reductions, Tg-TN,  one for
each PB value assumed.

                               -7-

-------
Figure 3-1  illustrates  the  effects  of both  B and  C  on  the
applicability of  NSPS  with  time.  Thus, given initial capacity  A
in  the  baseline year (1979),  the effect  of B,  capacity
replacement  due to obsolesence, is to reduce  the capacity  (A-B)
regulated by the  existing standards and increase that regulated
by NSPS.   Likewise the effect  of C, capacity addition for  growth,
is to increase the capacity (B+C) regulated by NSPS.   Thus,  both
B and C  are  working  with time  to increase the capacity regulated
by the new standards.

All the  capacity  variables  in  the model (A,B  and C)  are  assumed
to be related and B and C  may be  expressed  as  functions  of A.
Simple growth was assumed for  B to reduce the errors^
introduced over large  time  spans and  compound growth was  assumed
for C.

Thus, with B limited to simple growth and C  to  compound  growth,

         B = [PB  10]A   and
         C = [(Pc +  l)10_i]A
       all baseline  year  capacity, A, has been replaced by
 capacity, B,  (constructed  to  replace obsolete equipment)  100% of
 the industry  capacity is regulated by NSPS and no further growth
 of the regulated  percent (100%)  is possible.   Either method of
 growth (simple or compound) applied to B for a long enough  time
 will result in calculated values of B  that  exceed 100% of A.
 Use of simple growth  instead of compound  simply prolongs  the
 time until this occurs.  A better method would be to limit  B to
 the value of  A as a maximum.
                              -8-

-------
     Q
     W
     s
       CO
     0
       co
       o
     U
       "
                        TOTAL END-OF-PERIOD  CAPACITY
                          A (BASELINE YEAR CAPACITY)
           END OF f(P^)  PERIOD CAPACITY
           ___ _^^_  B   _____ _____ ______ ______  _____

            REGULATED BY EXISTING STANDARDS
                                                                REG. BY
                                                                 EXIST.
                                                                  STDS.
                                YEARS                         i



                  (A-B)=CAPACITY REGULATED BY  EXISTING STANDARDS.

                  (B+C)=CAPACITY REGULATED BY  NSPS.
Figure 3-1.-  Capacity regulated  by existing standards  and by NSPS versus

              year since NSPS promulgation.
                                  -9-

-------
Where:

Pg = construction  and  modification rate to replace obsolete
     capacity (decimal fraction of baseline capacity/yr)
PC = construction  and  modification rate to increase industry
     capacity (decimal fraction of baseline capacity/yr)
10 = elapsed time,  years

For the purposes of this  study, ith year is defined as 1989 and
the jth year is 1979.

The form of the model  used  for this study was:

(TS-TN) = K(ES-EN)  [(PB 10) + (PC+

Table  3-1  is a summary  of the  data used for  calculating  the
ranking, and it includes  the  impacts (emissions reductions)  for
both PB = 0 and PB = 5%.  Both historic and
current-estimate  K's  are  listed,  with the  latter  footnoted.
Emissions factors,  Eg  and E^, are based on production as
noted above.  Construction  growth rate, Pc, estimates are
historic.  The estimated  1979 Industry Capacity values, A,  were
derived from published data.

The table  in Section 2,  Summary, orders  the industries  in
descending value of Tg-TN,  thus providing a priority
ranking according  to EPA's  Model IV.

The priority rankings  given in the ranking table are based  on the
EPA Model IV in accordance  with equation (2)  with PB = 5% (5%
obsolescence) for  all plastics  with  positive growth  rates
(PQ>O).  The two plastics that were studied having negative
growth  rates, alkyds  and  urea  formaldehyde,  were ranked  last
arbitrarily.  Table 3-1 shows the  data used  to apply the  model
and is  in alphabetical order.
                              -10-

-------
The data needed  to  calculate current VOC emissions,  TA =
KEg A are included  in Table 3-1.  Values for TA are
listed  in  Table 3-II so  they  can be  compared  to  the  impact
rankings Ts -  TN*  (at 5% obsolescence), and the estimated
1979  capacities,  A.  Table 3-II lists TS-TN for two,
fixed-obsolescence  rates,  0 and 5%, and lists TA and  A for
comparison.  Refer  to Table 3-II.  The model  rankings are based
on 5% obsolescence  but agree between 0 and  5%  obsolescence for
the first 12 rankings with the exception of SB latex, #4,  and PE
Fiber #5.  SB  Latex and PE Fiber are close  in either case and
switch between ranks #4 and #5.  Thus, though  obsolescence rate
variations between  0 and 5% may interchange  close  rankings for
the plastics that were studied, they do not change rankings that
vary significantly.

Next, with two exceptions,  [polypropylene,  (#2), and PE Fiber,
(#5); and polyvinylacetate, (#7),  and acrylics,  (#8)],  ranking
according to current emissions, TA, shows the same order as
the model through the first 12  rankings.  Polypropylene  and PE
Fiber both are similar-sized (5000 MM PPY) ,  plastics industries
with relatively  low existing emissions (Eg) and good  control
(low EN).  Both  are experiencing good growth (PC).  The
reason for  the difference  in  ranking between  th.e  model,
Tg-T^j, and current  emissions (TA) can be seen in
Table 3-1.   TA the  product of K, Eg and A is similar  for
polypropylene  and PE Fibers with TA slightly higher  (<10%)
for polypropylene.  However, the  model takes  into  account that
polypropylene  has better control technology  available resulting
in lower estimated  EN and  greater impact for polypropylene.
Polyvinylacetate and acrylics have their difference  in size made
up for  by  their difference in  controllable  emissions,  and,
therefore,  are about equally ranked.
                             -11-

-------
                                    TABLE 3-1.-  VOC DATA SUMMARY AND RESULTS  FOR  PL'ASTICS  RANKING
 SECT.    PLASTIC

    5    ACRYLICS
    6    ALKYD
    7    MELAMINE FORMALDEHYDE
    8    NYLON 6
    9    NYLON 66
   10    PHENOL FORMALDEHYDE
   11    POLYESTER FIBERS
   12    HIGH DENSITY
          POLYETHYLENE
   13    LOW DENSITY
          POLYETHYLENE
   14    POLYPROPYLENE
!_,  15    POLYSTYRENE
   16    POLYVINYL ACETATE
   17    POLYVINYL ALCOHOL
   18-    STYRENE BUTADIENE
          LATEX (SB LATEX)
   19    UNSATURATED POLYESTER
          RESIN
   20    UREA FORMALDEHYDE
to
I
                                 0.83
                                 0.85

                                 0.71
                                 0.80
                                            VOC EMISSION
INDUSTRY
FACTOR
K
0.85
0.68
0.80
0.72
0.72
0.80
0.80
FACTORS ESTIMATES NEW/MODIFIED PLANT CAPACITY
EXIST Eo NEW EN FOR GROWTH P FOR REPLACE P
8/1000S #/1000# % %
3.97
0.88
2.81
0.24
0.90
0.60
2.87
1.64
0.19
0.18
NIL
0.21
0.02
0.30
6.7
-1.0
3.5
5
4
4
6.5
0/5
0/5
0/5
0/5
0/5
0/5
0/5
                                           10.28
20.92

 1.51
 2.93
           2.17
0.91
0.69
0.75
0.85
0.80
3.69
3.85
2.54
7.44
2.37
1.89
0.54
0.25
1.40
0.11
2.19

0.44
0.02
                        8

                        5.5
                        8
                        5
                        6
                        8
  8
-1.5
0/5

0/5
0/5
0/5
0/5
0/5

0/5

0/5
0/5
MMPPY
  A

 2100
 1062
  261
 1049
 2153
 2102
 5050

 5480

 8245
 4795
 5373
  999
  167

  856

 1735
 1382
                                                                                                              1979-1989 ESTIMATED
                                                                                                                  VOC EMISSIONS
                                                                                                                    REDUCTIONS
                                                                                                                     (IMPACT)
                                                                                                                      T  - T
                                                                                                                        MMP

3
-0
0
0
0
0
9
42
9
12
5
4
0
8
1
-0
RATE,
0
.64
.04
.23
.11
.51
.47
.11
.74
.56
.69
.80
.06
.34
.57
.53
.45
V5%
5.73
0.20
0.50
0.20
1.04
0.96
14.30
61.19
16.32
18.17
10.42
6.62
0.50
15.39
2.19
1.16
   3.
       THE  VALUES  OF  Eg AND EN SHOWN WERE USED IN THE  CALCULATIONS AND ARE DERIVED FROM THE VOC TABLES.   THESE VALUES
       ARE  BASED ON PRODUCTION RATHER THAN CAPACITY.
       SOME ACRYLIC PRODUCTS CONTAIN WATER OR SOLVENT.   CAPACITY (2100)  USED FOR ACRYLICS CALCULATIONS WAS  ADJUSTED FROM
       ESTIMATED 1468  RESIN CAPACITY TO INCLUDE THESE  WEIGHTS.
       K ADJUSTED  FROM HISTORIC TO CONFORM TO KNOWN  PRODUCTION/CAPACITY RATIOS.

-------
                                                           TABLE 3-II.- RANKING1 COMPARISON
U)
 I
                          RANK
#11
#12
113
#14

#15
#16

1.
                                  PLASTIC
#1
#2
#3
#4
#5
#6
#7
#8
#9
#10
HOPE
POLYPROPYLENE
LDPE
SB LATEX
PE FIBER
POLYSTYRENE
POLYVIHYL ACETATE
ACRYLICS
UNSATURATED POLYESTER
NYLON 66
                                  PHENOL FORMALDEHYDE
                                  MELAMINE  FORMALDEHYDE2
                                  POLYVINYL ALCOHOL2
                                  NYLON 6

                                  ALKYDS
                                  UREA FORMALDEHYDE

10 YR
T -T
VUC IMPACT
MMP MODEL
e o%
42.7
12.7
9 .6
8.6
9 .1
5.8
4.1
3.6
1.5
0.51
0.47
0.23
0.34
0.11
-0.04
-0.45
@ 5%
61.2
18 .2
16.3
15.4
14.3
10.4
6.6
5.7
2.2
1.04
0.96
0.50
0.50
0.20
0.20
1.15
1979 ANNUAL
ESTIMATED
EMISSIONS
T , MMPPY
 A 	
46.3
12.7
27.7
15.2
11.6
10.2
6.3
8.3
1.86
1.40
1.01
0.59
0.32
0.18
0.64
3.2
1979 ANNUAL
ESTIMATED
CAPACITY
A, MMPPY
5480
4795
3245
856
5050
5373
999
2100
1735
2153
2110
261
167
1049
1062
1382
                              RANKING BY IMPACT.   IMPACT  BASED ON  5%  OBSOLESCENCE RATE (PB) FOR ALL PLASTICS
                              WITH POSITIVE  GROWTH.   ALKYDS  AND UREA-FORMALDEHYDE WERE BASED ON PB = 0.
                          2.  EQUAL IMPACT.

-------
Referring  again to Table 3-II,  the  model ranks PE Fiber  (#5)
close to SB Latex (#4), and not  far  below LDPE (#3).  Thus  the
model shows all  four plastics ranked after HOPE (polypropylene,
LDPE, SB Latex,  and PE Fiber) to  be closely ranked with  little
impact  difference from plastic-to-plastic.   However, current
emissions,  TA,  for  the four reflect the  large differences in
capacity, A,  between LDPE and  the  others; and in the  existing
emissions factor,  Eg, between SB Latex and the  others.
Although TA ranks  polypropylene significantly (>10%) below
LDPE and SB Latex,  the model shows that  the long-term  impact of
NSPS on  VOC  emissions actually  will be  slightly greater  for
polypropylene than  for either LDPE  or SB  Latex.  Thus  Model IV
should  be  used  to rank  these plastics  rather than current
emissions,  TA.   Surprisingly, rankings #8  through #14 agree
between the model  (TS-TN for PB =  5%)  and  .current
emissions,  TA.

Finally though  capacity, A, has a  direct influence on emissions,
ranking by either  the model or current emissions does not  relate
to capacity in  a direct fashion.
                              -14-

-------
                           SECTION 4
                      DISCUSSION AND DATA
4.1  GENERAL
     Some VOC emissions data were received for  all  the plastics
     surveyed.   All data were screened and,  in cases where there
     were questionable data, the manufacturers were  contacted to
     resolve the questions.  This was an important function and,
     in some  cases, resulted  in significant  changes.   The
     resultant data were weighted for the production represented;
     and then  used with  the  appropriate  bias.   Batch  data
     (generally high emissions) were assumed  in all cases where
     continuous data were  not  available and/or  the production
     split between batch and continuous was  not known.

     Many vents and emissions sources were combined  to  reduce  the
     total number of vents  considered in these survey studies.
     Every  effort was  made to gather  only  similar or  related
     sources.  This merging helped to indicate the nature of  the
     major emissions sources such as feed section, reactor area,
     polymer recovery, etc.  The combinations also helped  to make
     comparisons between processes possible,  helped  to  facilitate
     applicable control studies, and helped  to arrive at overall
     emissions factors Eg and EN.
                              -15-

-------
4.2  PROCESSES AND FLOWSHEETS

     One or two composite flowsheets  were prepared for each
     plastic surveyed that  represent  most-used  processes.
     Specific equipment configurations and  the number  and  types
     of  process trains will  vary quite widely depending on  the
     product grades, the specific  process or processes,  and
     whether operation is  batch or continuous.  Block diagrams
     provided by industry  were  combined with classic  flowsheets
     from the literature to  produce  flowsheets  showing  the
     primary emissions points.   Some of the flowsheets  contain
     equipment enclosed  in dashed  boxes  to indicate optional
     steps  or processes for making special products.   The aim of
     each flowsheet was to represent the process simply and to
     facilitate consolidating  the emissions.

4.3  CATEGORIES OF PLASTICS AND COMPANY VISITS

     The plastics surveyed in  this study have been grouped into
     three  categories based  on decreasing process  complexity.
     Category I plastics contain high volume, continuous, complex
     technology processes   that generally have  only  a  few
     manufacturers  -  ones who cannot readily switch  products.
     The products include  HOPE, LDPE, polypropylene,  polyester
     fiber, polyvinyl  alcohol, and the  nylons.   Category 2
     plastics contain the  products resulting from simple  batch
     processes with  variations.   Generally, they have many
     manufacturers  (and they can sometimes switch  products by
     changing recipes and  operations).  This category  includes SB
     latex  and  polyvinyl  acetate  emulsions  and  also  the
     formaldehydes, unsaturated polyesters, and  alkyds.  Category
     3 plastics include products that don1t fit  into  the  other
     categories. These include  polystyrene and  acrylics.
                            -16-

-------
     When  industry visits were  planned, only those  companies that
     manufacture 5 to 10 of the plastics surveyed  were chosen.
     The six headquarters  visits decided on  were chosen  to
     include  all  of  the Category 1 and 3 plastics,  plus those
     that  produce the  largest volume of  Category 2 plastic's,
     including  pheno 1-formaIdehyde ,  urea-forma 1dehyde,
     unsaturated polyster, polyvinyl acetate, alkyds,  and  SB
     latexes.

4.4  VOC EMISSIONS DATA

     Detailed VOC emissions data are  reported  in  tables in the
     appropriate plastics sections.  National emissions  factors,
     ES"and EN are summarized  in  Section 3,  Table 3-1.
     All data reported are in  units of  #/1000#  product, unless
     other units are specified  with the numbers.    Generally, the
     data  reported in  the  VOC tables for  each section  are  in
     three columns called, "Uncontrolled",  "Current  Practice",
     and "Well-Controlled".  Where it is known, "Uncontrolled"
     data  are either inlet control  device values or  they are
     presently, or recently, uncontrolled emissions  estimates.
     "Current Practice"  data (basis for Eg)  are properly
     weighted VOC emissions  from control device ou.tlets  or
     estimates  as submitted by industry.   Finally, "Well
     Controlled" data (basis for  EN estimates)  are  estimates
     based either  on  BDCT as  submitted by  industry or on good
     engineering judgement with regard to the nature  of the
     emission source and applicable controls (see 4.5  below).

4.5  APPLICABLE CONTROLS AND EFFICIENCIES

     Methods  considered to bring process emissions to  a "well-
     controlled" or BDCT status included process modifications as
     well  as add-on  control  technology.   The  process
                              -17-

-------
modifications  considered included product stripping to
remove residual monomers/solvents  prior  to finishing (both
stripping and  soaking);  increased conversion  reactions,
e.g.,  Urea-Formaldehyde; underwater  pelletization; recycle
drying; switching  from steam jets to  mechanical  vacuum
systems; use of vapor return lines and ^-blanket
controls.

Fugitive  emissions were  not  considered controllable, but
reductions are generally achieved  by new plants or by major
process changes, and values are  shown when available.

The add-on controls considered included  flares and thermal
incinerators;  catalytic incinerators; water and caustic
scrubbers;  water  or  refrigerated.condensers; carbon
adsorption; once-through-water  spray  condensers  for steam
jets;  mist  eliminators;  and  electrostatic precipitators.
Control  efficiencies  used were  based either on  data
submitted or on the following guidelines:

Control                             Assumed Efficiency (%)
                                   (based on 100% capture)

Flares                                       90
Thermal Incinerators                         95-99
Catalytic Incinerators                       60  - 98
Scrubbers and Condensers                     80-90
Carbon Adsorption                            80-90
Water  Spray Condensers                       80-90
Mist Eliminators                               70
Electrostatic Precipitators                  90-98
Vapor  Return Lines                              60
                        -18-

-------
4.6  DATA REDUCTION

     Some form of data  reduction was used  on  most of the VOC
     emissions data  in  the  report.  Most  individual plastics
     sections  VOC tables are direct  estimates of  the  national
     emissions factors, Eg and EN, the table  in  the
     Summary and  in Table 3-II.   A few,  e.g. Acrylics,  HOPE  and
     LDPE had  to be  weighted between two  types of  processes
     before  inclusion in these tables.

     The data  reduction used to  obtain the  individual VOC  tables
     included, for  example, weighting  for process variations;
     assuming  fugitive emissions for solution was the same as  for
     bulk processes; and arbritrary lumping  together data for  two
     processes whose product distribution  was unknown (Table
     5-III).

4.7  REFERENCES AND CREDITS

     Literature references for the whole  report  are  listed at  the
     end of  the  report.   The  references are  divided  into
     "general" and specific  (cited).   General references  are
     listed separately  and  were used for  information on  the
     model,  chemical processes,  chemicals,  control technologies,
     etc.  Specific references were cited for each  industry  and
     make up the  bibliography.  However,  special notice should be
     given  the following references because  the  authors used them
     extensively.  "Impact of New Source  Performance Standards on
     1985 National Emissions from Stationary Sources", Volume  I,
     The Research Corporation  of New England.  The  Chemical
     Economics Handbook and the  Process  Economics Program Reports
     of Stanford  Research Institute.
                               -19-

-------
                           SECTION 5
                        ACRYLIC RESINS
5.1  INDUSTRY  DESCRIPTION

     Acrylics  are a family of vinyl  polymers made from  acrylic
     acid  and  methacrylic acid and  their esters.  The products
     range from  thermo-plastics to thermosets and from glass-like
     sheets,  through  enamels,  to resin powders, to  latexes.
     Methyl  methacrylate, ethyl acrylate  and butyl acrylate  are
     the  largest volume acrylic monomers used.  Most potential
     VOC  emissions  are these monomers plus whatever solvents,
     modifiers,  and volatile organic additives  are used.   Almost
     all  acrylics are produced in  batch processes, and only batch
     processes will be treated in  this  report.   The four  common
     polymerization methods are all  used  (bulk  or mass, solution,
     suspension and emulsion)  and these  may be grouped  as
     "hydrocarbon-based" or  "water-based" processes  for
     discussion.

     The  estimated 1978 U.S.  production  of  all acrylics monomers
     was  1314  MM PPY for all uses, and  indicates 6 to 7%  overall
     annual  growth  rate over 1977  (some 31 MM PPY (4_)  used in
     fiber co-polymers  was not  included).   While  nameplate
     capacity  for acrylic resins was unknown, production was 1100
     MM PPY  in 1977 (j[) .  Using an estimated  utilization  rate of
     85%   and  an average growth rate  of  6.5%,  capacity  is
     estimated to be 1468MM PPY in 1979.
                            -20-

-------
The estimated  1980  MMA and acrylate ester  consumption
markets have been grouped as follows:

Process             % Monomers Consumed

Bulk                        25  Hydrocarbon-based
Solution                    10
Suspension                  10  Water-based
Emulsion                    55
                           100

As the table indicates, about 35% of production will be
hydrocarbon-based,  and 65% will be water-based.  Within
these two groups, the  processes have similarities in VOC
emissions, emission points, and applicable  controls and
therefore, they  will be treated by group.

Although  more than a hundred  U.S. manufacturers of
acrylics resins  are listed (]_, pp 21 - 23),  only a few
are  large chemical companies  that also  produce  the
monomers.   Most  of  the large monomer producers  also make
finished  products  such as cast sheets  and/or latex
paints.  Table 5-1  lists  all the U.S.  acryl-ic resins
manufacturers (ca 1970)  and  indicates  the  product
distribution they make.  Some of the  larger  U.S.
producers are Rohm and  Haas,  DuPont,  and  American
Cyanamid.

The  largest  single  raw material used  is methyl
methacrylate (MMA), the second is ethyl acrylate (EA),
and the third  n-butyl  acrylate (n-BA) so  these make up
the potential  monomer  VOC.  Total  use proportions are
estimated (by  Pullman  Kellogg) to be about  75%  MMA, 15%
EA, and 10% n-BA.   Product recipes vary widely  from  100%
poly MMA (sheets) to 100% poly EA dissolved  in toluene
                     -21-

-------
                        TABLE 5-1.-
PRODUCERS OF ACRYLIC RESINS AN  RELATED PRODUCTS (Concluded)
Company

Tenneco Chem. (NJ)
Thielex Plastics (NJ)
Triangle Conduit & Cable (NJ)
Tylac Chem. Div., Int'l Latex
  & Chemical (DL)

U.S. Plastics & Chem., sub.
  Kopper Co. (NY)
United Resins Co. (NJ)
Union Carbide (NY)
Union Oil of California (CA)
Upaco Adhesives Inc. (MA)

Vacuum Plastics Corp. (OH)
Vernon-Benshoff Co. (NY)

Westlake Plastics (PA)
World Plastics Extruders (NJ)
                                   Resins
       Molding
         and
      Extrusion
        Powder
Solution
   or
Emulsion
Or Both
                           X
                           X
                                                                                 Films and Sheets
Cast   Extruded
                 Biaxially
                 Oriented
   Rods, Tubes
Standard Profiles
                             Cast
                                                                    X
                                                                    X
         Extruded
Yates Company (PA)

-------
                        TABLE 5-1.-
    PRODUCERS OF ACRYLIC RESINS AN  RELATED PRODUCTS (Continued)
Company
Resins
                                              Molding
                                                and
                                             Extrusion
                                               Powder
Polymer Industries (CT)
Polytech Co. (HO)
Polyvinyl Chem. (MA)
PPG Industries (PA)
Purethane Div., Easton RS Corp. (NY)
Purex Corp. (CA)

RA Chemical (NY)
Raffi & Swanson (MA)
Rayll Plastics (NY)
Reichhold Chem. (NY)
Research Sales Inc. (NY)
Rohm & Haas (PA)
Rubba, Inc. (NY)

Sandee Mfg. Co. (IL)
Sartoraer Resins,  Inc.
Seven-K Color Corp. (CA)
Sherwin-Williams  Co.  (IL)
Silraar Div., Vistron (CA)
Southern Plastics (SC)
Stanley, A.E. Mfg. Co.  (IL)
Standard T Chem.  (NY)
Sterling Varnish  (PA)
Sun Chemical (PA)
Swedlow, Inc. (CA)
Solution
   or
Emulsion
Or Both
                               X
                               X
                               X
                               X

                               X
                               X

                               X
                               X
                               X
                               X
                               X
                               X
                               X

                               X
                               X
                               X
                               X
                                              Films and Sheets
Cast   Extruded
                                                          Biaxially
                                                          Oriented
                                Rods, Tubes
                             Standard Profiles
Cast

  X
  X
                                      Extruded

-------
                            TABLE 5-1.-
                                       PRODUCERS OF ACRYLIC RESINS AN  RELATED PRODUCTS (Continued)
 I
NJ
Company                            Resins

Jersey State Chem. (NJ)
Jet Plastics (CA)
Jodee Plastics (NJ)                  X
Johnson, S.C. & Sons (WI)
Jones-Blair Paint (TX)

Key Polymer Corp. (MA)                X
Koro Corp. (MA)

Laminations Inc. (PA)
Landover Mfg. Div.,
National Lead  (MD)
Leathertone, Inc. (MA)

M.R. Plastics and Coatings (MO)
3M Co. (MN)                          X
McClosky Varnish (PA)
Midland Ind. Finishes (IL)
Milligan, J.G. & Co. (WI)
Mobil Chemical (OH)
Monsanto (MO)
Morton Chemical (IL)
Munray Prod't. Div., Fanner MEg .  (OH)

National Lead (NY)
National Starch & Chem (NY)

O.C. Adhesives Corp. (NY)
O'Brien Corp. (IN)
                                                  Molding
                                                    and
                                                 Extrusion
                                                   Powder
Solution
   or
Emulsion
Or Both
                                                                                 Films and  Sheets
                 Biaxially
Cast   Extruded  Oriented
                                Rods, Tubes
                             Standard Profiles
                                                                                                         Cast
                                                                                                                  Extruded

-------
TABLE 5-1.-
                                           PRODUCERS  OF ACRYLIC  RESINS  AND RELATED  PRODUCTS  (Continued)
    Company

    Daylite Industries  (NY)
    Dennis  Chemicals  (MO)
    De  Soto Chem.  Coatings  (IL)
    Dimensional  Plastics  (FL)
    Dow Chemical  (MI)
    Du  Pont (DE)
    Dura Plastics  (NY)

    Electro-seal  Glasflex  (NJ)
    Extron  Corp.  (TN)
    Franklin Fibre-Lamitex  (DL)
    Freeman Chemical  (WI)
    Fuller,  H.B.  Co.  (OH)
    Fusecolor Corp.  (NJ)

^   General Latex  & Chem.  (MA)
(j\   George,  P.O.  Co.  (MO)
 I   Glidden Co.  (MD)
    Goodyear Aerospace  (OH)
    Goodyear Tire  and Rubber  (OH)
    Guardian Chem.  Coatings  (MI)

    Hand R  Plastics  Inc.  (PA)
    Heath Tecna  Corp. (WA)
    Hunt Foods &  Industries  (CA)
    Hyde, A.L. Co.  (NJ)

    Interchemical  Corp.  (NJ)
    International  Coatings  (CA)
    Isochem Resins Co.  (RI)
           Resins
                                                  Molding
                                                    and
                                                 Extrusion
                                                   Powder
                                       Solution
                                          or
                                       Emulsion
                                       Or Both
Films and Sheets
                                                    Cast
            Biaxially   	
  Extruded  Oriented    Cast
   Rods, Tubes
Standard Profiles
         Extruded
                                                                                              X
                                                                                              X

-------
                                   TABLE 5-1.-  PRODUCERS OF ACRYLIC RESINS  AND RELATED  PRODUCTS  (7)
 I
to
en
 I
Company                            Resins

Acco Polymers (MI)                   X
Ace Plastics (NY)
Aero Chemical Prod't (NJ)
Adam Spence Corp. (NJ)
Allied Chemical  (NJ)
American Acrylic Corp.  (NY)
American Cyanamid (U.S.)
American Mineral Spirit (IL)
American Polymers Inc.  (NJ)
Anesite Div., Clow Corp.   (IL)
Armstrong Paint & Varnish ( IL)
Ashland Chemical                     X
Avecor Inc. (CA)
Axel Plastics Res. Lab. (NY)         X

Baltimore Paint & Chem. (MD)
BASF Corporation (NY)
Bay Plastics (CA)
Borden Chemical  (NY)
Cadillac Plastics & Chem. (MI)
Caig Lab. Inc.  (NY)                  X
Cast Optics Corp. (NJ)
Celanese
Chemical Coatings & Engineering (PA)
Clearfloat Inc.  (MA)
Colab Resin Corp. (MA)
Colonial Kolonite Co. (IL)
Columbia Technical Corp.  (NY)
Columbian Carbon Co. (NY)
Contours Unlimited (MA)
Cook Paint & Varnish
Crystal-X Corp.  (PA)
Custom Chemical  (NJ)
                                                  Molding
                                                    and
                                                 Extrusion
                                                   Powder
Solution
   or
Emulsion
Or Both

   X

   X

   X

   X
   X
                                                                      X
                                                                      X
                                                                      X
   X
   X

   X

   X

   X
   X

   X

   X


   X

   X
                                                                                 Films and  Sheets
                                                                            Cast
                                                                                             Biaxially
                                                                                   Extruded   Oriented
   Rods, Tubes
Standard Profiles
Cast     Extruded

-------
       (laquers) and  include many miscellaneous acrylates  and
       organic additives.   All present U.S. MMA production  uses
       the acetone cyanohydrin process and is dependent  on  both
       the acetone and methanol supply situation.

       The  most common poly-acrylate  solvents  and process
       liquids, and thus potential non-monomer VOC,  are  toluene,
       methanol,  acetone and methylene  chloride.   Toluene  is
       likely the plant solvent-of-choice for  clean  up as well as
       the  most  likely process and/or  product  solvent.   The
       primary use of methanol is to regenerate  the  ion-exchange
       resin beds  used to  remove  hydroquinone (or other
       inhibitor)  from monomers before polymerization.   Acetone
       and methylene chloride are alternate solvents.

5.2    ACRYLIC RESIN MANUFACTURE BY HYDROCARBON  BASED PROCESSES

5.2.1   Hydrocarbon Based Process Descriptions

       Figure 5-1, Acrylic  resins manufacture by bulk/solution
       processes,  is the flow  schematic for  both  bulk  and
       solution  processes.  Both are completely  hydrocarbon
       based,  that is process solvents  are  monomers.or other
       hydrocarbons.  These processes  are simpler than water
       based processes because they do not require emulsification
       or suspension and have simpler polymer recovery  sections
       (if required at all).   Most of Figure 5-1 is for a  bulk
       process making cast  sheet  (above  the heavy  dotted  line)
       but  below  the line alternate equipment  and  lines  are
       indicated for a solution  process  that makes lacquer  and
       enamel coatings.  For  clarity two process descriptions are
       given (first bulk,  then solution)  but only  one flowsheet,
       VOC  discussion, table  of emissions, and  "applicable
       controls" section.
                             -27-

-------
 I
NJ
CO
                         [1]
                                 -r-H
FILTERJ
                     	       f

                         nil                 I
                                                                                         LIQUID PRODUCT
                                                                                         STORAGE TANKS
                                                                MONOMER
                                                               SOLVENT/
                                                             MIX TANK
                        FEED
                                                        REACT
                                                                           RECOVERY/FINISH
             Figure  5-1.-Acrylics resins manufacture  by bulk/solution-processes.  '
                     r

-------
5.2.1.1  Bulk process.-
        A batch process for polymethyl-methacrylate  sheets is
        described  but it  applies to  all batch  monomer  and
        polymer-monomer syrup  casting processes.

        Referring  to Figure 5-1, above  the  heavy horizontal
        dashed  line,  the  bulk process for cast sheets  starts
        with  inhibitor removal from  stored MMA  via an  ion-
        exchange resin bed  system.  Purified MMA  flows from the
        resin bed to a monomer  surge/mix tank before  filtration
        and subsequent reaction.  A catalyst, usually benzoyl
        peroxide, is dissolved  in monomer or solvent  in a small
        tank (not shown) and joins the purified monomer  in the
        reactor.  For the  bulk  process, reaction is  started in
        the presence of  the catalyst and  (if  desired)
        accelerator by heating  to 70-95C for 5-10  minutes  with
        constant  agitation  in  the reactor.   As  soon  as
        polymerization is  adequate  (about 10%  solids)  the
        mixture  is  cooled  rapidly  to 4C  to  halt   the
        polymerization temporarily.  Any  additional  chemicals
        used  are  added now (plasticizers,  U.V.   inhibitors,
        etc.), and the partially polymerized  syrup is dearated
        with vacuum to remove  bubbles before casting.

        Dearated syrup can be  stored temporarily  at  4C.   For
        immediate casting  the  syrup is reheated, filtered, and
        cast.  Polymerization  is completed in the casting cells
        and the sheets are discharged to  curing ovens.   Cured
        sheets  are paper  coated for  protection  and sent to
        storage or sales.   Spent ion-exchanger  resin beds are
        regenerated with methanol and reused.
                           -29-

-------
5.2.1.2   Solution process.-

         A  batch process for copolymer methyl methacrylate/ethyl-
         acrylate lacquer is shown.  The  liquid product is 40%
         polymer 60% solvent but  various recipes could be used'.

         Figure 5-1, Acrylic resins manufacture by bulk/solution
         processes, is the flowsheet.  Referring to Figure 5-1,
         both above and below the heavy horizontal dashed line,
         the solution process for coatings starts with inhibitor
         removal from stored monomers. Both  MMA and EA monomers
         are  fed  to ion-exchange resin  beds and the purified
         monomers flow to a surge/mix tank.   Toluene solvent  is
         fed from  storage to the monomer/solvent mix tank and
         blended  with purified monomers  from  the monomer
         surge/mix tank.  A separate flow of toluene goes to  a
         catalyst  and solvent mix tank  (not shown).  From the
         monomer  and  solvent mix tank the  mix flows through  a
         filter to the reactor.   Catalyst  and solvent mix is fed
         to the reactor and polymerization is begun by heating.
         Reactor cycles are long  and may  be  complex as solution
         polymerization  is  slower  than bulk, suspension  or
         emulsion polymerization. Polymerization is essentially
         completed in the  reactor.   Product flows from the
         reactor  to the  liquid  product   storage tank  without
         filtering.  Liquid product goes directly to a finishing
         line (pails)  or to bulk  shipment.

5.2.2     VOC Emissions For The  Hydrocarbon Based Processes

         All  significant  emissions  from  acry1ic-resin
         manufacturing by hydrocarbon based  processes are shown
         in Figure 5-1 and listed in Table  5-II with bracketed
         numbers  (8_) .  The  tabular  values in Table  5-II  were
         calculated from industry product  distribution data.  The

                             -30-

-------
        TABLE  5-II.-    VOC  EMISSIONS FROM ACRYLIC RESINS MANUFACTURED BY BULK/SOLUTION PROCESSES
             Stream
                              Uncontrolled
                              (Bulk Only)   Current Practice  Well Controlled
                            #/1000f Product  #/1000# Product   #/1000# Resin  Composition
U>
H
I
[1]   Monomer and Solvent
     Storage and Handling          

[2]   Monomer Mix Tanks,
     Reactor/De-aerator,
     Polymer Surge Tank            

[3]   Casting, Cells and Shapes     20

[4]   Curing, Product Storage       30

[5]   Fugitive,  includes Solvent
     Cleaning of Equipment         

     TOTALS                        50
                                                           0.09
0.09
                                                                                       Pure VOC
2.55
2.46
0.54
3.75
9 .4
0.26
0.25
0.05
3.75
4.4
VOC in N2
VOC in air
VOC in air
VOC in air


-------
distribution was  assumed to be (25/35)  =  70%  bulk, and
(10/35)  = 30% solution products.

Note that VOC emissions  are based on  pounds  of actual
product  which may include up to 60% solvent  for  solution
products (lacquers and enamels) but none for bulk since
the products are  cast sheets and  molded shapes.

The major emission points of these processes are:

[1] Monomer and  solvent storage and  handling  - The
    emissions are working  and breathing losses  from
    tankage  as well  as  valve and  line  losses and pump
    seal leaks (storage and handling  only).
[2] Monomer  mix  tanks,  reactor/.deaerator  and  polymer
    surge tank -  Emissions arise  from working  losses on
    all  tanks and reactors and consist of  monomers and,
    for  solution  processes, solvent vapors in  N2
    Emissions also arise  from deaerating bulk  process
    syrup, from evacuating the reactor to  remove oxygen
    before the batch and from the polymer  surge  tank.
[3] Casting, sheets  and  molded shapes  -  For  bulk pro-
    cesses  only,  deaerated and  partially  polymerized
    syrup is cast or molded then  completely  polymerized.
    Emissions are monomer  vapors only and arise from
    filling  the  molds  with  syrup and  from
    polymerization.   Solution  processes have  no
    comparable step.
[4] Curing and product  storage -  For  sheets, products
    are  oven cured.  Lacquers and other liquid solution
    products are  stored for bulk shipment or  packaged.
    Emissions are residual monomers  from sheets and
    solvent  vapors  from  liquid  products  during
    packaging.
                     -32-

-------
         [5] Fugitive - The majority of these emissions  are plant
            cleaning solvent,  usually toluene.  Emissions arise
            from washings required  to remove polymerized
            material  from pipes, agitators,  coils etc.  when
            changing recipes  and  cleaning equipment. Some waste
            materials (syrups)  are also polymerized  and land
            filled for disposal and therefore emit some monomers
            and solvent.

5.2.3  Applicable  Controls Systems For The  Hydrocarbon Based
       Processes

       [1]  Monomer  and solvent storage  and  handling - Present
           emissions are relatively small.  Existing  controls are
           primarily conservation vents on  fixed-roof  tanks.
           Some tanks have cooling water  condensers  on  the vent
           for volatile solvents.  Refrigerated vent condensers
           can be used for methyl methacrylate monomer.   No
           additional controls  are presently warranted.
       [2]  Monomer mix tanks,  reactor/deaerator, polymer/syrup
           surge  tanks - These  vent streams constitute one  of the
           largest emission points.  Emissions are working  losses
           on tankage, inert gas purges,  and  vacuum  deaeration.
           All losses are  VOC  in small flows of N2  Existing
           controls are generally  limited to  a reflux condenser
           on the reactor.  Applicable controls are refrigerated
           condensers or  incinerators.  It  was  assumed  90%
           control could be achieved.
       [3]  Casting, sheets and molded  shapes  (Bulk processes
           only)  -  One of  the largest  emission  sources  for
           acrylics  processes, VOC are  monomer vapors arising
           during mold filling  and polymerization.  Ventilation
           is provided for worker  health and flows are generally
           too large for  direct control.   Applicable  controls
           require tighter hooding to reduce flows; incineration,

                             -33-

-------
          especially in an  existing boiler,  should  be  examined.
          It was assumed 90% control could be  achieved.
       [4] Curing  and  product  storage (For sheets  and  shapes,
          products are oven-cured) - VOC are unreacted monomers
          in large flows of air.  Relatively small  emissions may
          not warrant additional controls.  For  solutions  warm
          products are pumped  into cooling/surge  tanks before
          packaging  or bulk  storage.   VOC are  solvents  in
          air/N2 from working  losses of these  tanks.
          Applicable controls  are refrigerated  condensers and
          incinerators and  90% efficiency was  assumed.
       [5] Fugitive - Emissions are  solvent VOC  in air  from
          cleaning  and residual monomers  in scrap  and waste.
          These  are  a major  VOC emissions point for hydro-
          carbon-based acrylics resins..   Applicable controls
          include alternate disposal for partially  polymerized
          scrap and  waste syrup  (incineration  instead  of
          landfill)  and  better  housekeeping.  No  control
          efficiency was assumed.

5.3    ACRYLIC RESIN MANUFACTURE  BY WATER BASED PROCESSES

5.3.1   Water Based Process Description

       Both  emulsion and suspension  processes  use water  as a
       process  fluid and  require special steps to  achieve
       emulsification or suspension.   Most emulsion  process
       acrylics are sold as  a  latex product (paints,  adhesives
       etc.) and thus do not require complex recovery  systems as
       do suspension process  acrylics.   Figure  5-2,  Acrylic
       resins manufacture by emulsion/suspension  processes,  is a
       schematic showing both processes.  The left side of'Figure
       5-2 is common to both emulsion and suspension  processes.
       On the right side the upper train is for  emulsions  only
       and produces a latex  product.  The lower right  side  train
                             -34-

-------
                                                                                  [5]
I
U)
Ul
I
                                       SUSPENSION
                                       CATALYST
                                           T .
                                            N
                                                                              PROCESS EMISSIONS
                               MONOMER
                               MIX TANK
                  EMULSION
                  CATALYST, <-
                  EMULSIFIERS
                  OR SUSPENSION
                      AGENTS
SLURRY
SURGE
TANK
                                                                                     EXTRUDER-
                                                                                     PELLETIZER
                     FOR
                     CLEANING,
                     RINSING
                                         EMULSIONS
                                         TO PACKAGING
                                            OR SHIPPING
                                                       WWT
                                        RESINS TO
                                        PACKAGING OR
                                        BULK SHIPPING
                 FEED                               REACT                   .  RECOVERY/FINISH

         Figure  5-2.-  Acrylics  resins manufacture by  emulsion/suspension processes.

-------
        shows a brief suspension polymer-recovery  system.   Two
        process  descriptions  have  been developed, one  for
        emulsions  and one  for  suspensions; but  the other
        information is combined and only  one flowsheet,  VOC
        discussion, table  of  emissions, and  controls  section" is
        used.
5.3.1.1  Emulsion process.-

        A batch process for a methyl methacrylate/ethyl acrylate
        emulsion  co-polymer  latex with 40% solids  content is
        described in this  text, but it represents  a  variety of
        recipes and emulsion  products.  Reference  to  Figure  5-2
        will aid in following the discussion.

        Demineralized water is emulsified with  surfactants,
        catalyst, small amounts of monomers, and other additives
        in  the additive mix  tank.   This flows to  the reactor.
        Next, MMA  and EA  monomers flow to a  monomer mix  tank
        then through a filter to the reactor where  they join the
        emulsified water,  surfactant, catalyst, and  additives.
        The reactor is heated  to  initiate polymerization  and
        taken through a batch cycle resulting in  about  98-99%
        monomer  conversion.   The resulting   latex  is  vacuum
        stripped in the reactor to remove residual  monomers then
        discharged via a  cooling and  surge   tank to product
        storage.  The final step for latex is  packaging  or  bulk
        shipment.   Latexes are  difficult to purify  and
        emulsifiers, catalysts,  and other  additives  cannot be
        removed and are generally sold with  the product.

        Although no monomer  inhibitor removal steps  are shown
        (low-inhibitor grade  monomers are  assumed)  any  of  the
        three classic means  could be  used, ion-exchange ,
        distillation, and  caustic washing.
                            -36-

-------
5.3.1.2   Suspension process.-

         A  batch process for  a methyl methacrylate/ethyl  acrylate
         suspension  co-polymer resin  is described  in  this
         section.   There is an extruder-pelletizer  in  the
         finishing line, but   the process produces  resin powder
         without it.  A variety of recipes  and  resultant resins
         can  be  produced.  Low-inhibitor grade monomers  are
         assumed.

         Reference to Figure  5-2 shows  that the description for
         the  suspension process is the  same as  for  the emulsion
         process up to the cooling tank after the reactor - with
         two  exceptions.  One exception  is  that suspension or
         dispersion agents are used  in place of emulsifiers, and
         the  other is that catalyst  is  added directly to  the
         reactor rather than  the mix tank.   Suspension (slurry)
         leaving the cooling  tank is dewatered  in a centrifuge,
         the  resulting resin  powder  is dried  in a hot-air drier
         prior to  finishing.   Dried  resin powder can be the final
         product and either packaged or bulk shipped or it can be
         processed into pellets via  the  extruder-pel le ti zer .
         Suspension  products are low  in residual  additives as
         these are removed with the  water during dewatering and
         sent to wast'e water  treatment  (WWT, not shown) .

5.3.2     VOC  Emissions For The Water Based  Processes

         All significant  emissions  from  acrylic resin
         manufacturing  by water-based processes  are shown in
         Figure  5-2 and listed with bracketed  numbers in Table
         5-III.  The VOC values in the  table were calculated from
         industry data  assuming (55/65)  = 85% emulsion  and
         (10/65) = 15% suspension products.
                             -37-

-------
                 TABLE  5-III.-  VOC  EMISSIONS  FROM  ACRYLIC RESINS EMULSION/SUSPENSION PROCESSES*

                                     Uncontrolled
                                     (Bulk  Only)   Current  Practice  Well  Controlled
              Stream               it/10001  Product   #/1000# Product   fl/1000# Resin  Composition

          [1]  Monomer and Solvent
              Storage                    0.15             0.15              0.06       Pure Monomers
                                                                                       and Solvent

          [2]  Monomer Mix Tanks,
              Reactor/Stripper,                                                      Monomers and
              Surge/Cool                 0.48             0.48              0.05        Solvent VOC
                                                                                      in N2


          [3]  Dewatering, Drying*        0.42             0.42              0.04       Residual Monomers
 '                                                                                     in Air
OJ
oo
 I         [4]  Extrusion, Finishing,
              Packaging*                 1.26             0.00              0.00       Residual Monomers
                                                                                      in Air

              TOTALS                     2.31             1.05              0.15


         * Assumes that emulsions  are 85%, suspensions  15%, of  water based processes;  dewatering,
           drying, extrusion and finishing apply to  suspension  processes  only.

-------
Note that VOC emissions are based  on  pounds of actual
product which includes up to  60%  water  for emulsions
(latex)  but none for suspensions since the products are
resin powders or extrusions.

The major emission points  of these processes  are:

[1]  Monomer and solvent storage and handling  -  Emissions
    released  are working  and  breathing losses  from
    tankage as well as valve  and  pump  seal  and  line
    losses during loading  and transfer.   A solvent may
    be used for  clean up and for  ion-exchange bed
    regeneration (usually  methanol, not shown on Figure
    5-2) but only  storage  and  transfer  losses are
    included  here.   Emissions are pure monomer and
    solvent vapors,  primarily.
[2]  Mix  tanks, polymerizer/stripper  and  latex cooling
    tanks  - Emissions come  from working losses on
    tankage plus  residual  monomers  stripped.   All
    emissions (VOC)  are monomers in a flow of N2
    Both emulsions and  suspensions  can  have  these
    emissions.
[3]  Dewatering, drying  - For suspension processes only,
    because acrylic emulsions are used as  emulsions and
    not subjected to  recovery.    Suspension  process
    products  are recovered  by dewatering (screens,
    centrifuge)  and drying.   Emissions  are  residual
    monomers in air from these  operations.
[4]  Extrusion, finishing and packaging  -  Extrusion and
    finishing  emissions shown  are  for suspension
    processes only.  Some  emulsions  are  packaged into
    small cans and have a  very  small potential  VOC from
    packaging. Emissions are residual monomer vapors in
    ventilation air.
                    -39-

-------
            No data were  available  on  fugitive emissions from
            either emulsion or suspension processes.  However,
            water-based  processes  are  expected to have much
            lower fugitive VOC emissions  than hydrocarbon-based
            processes  because of the reduced opportunity  for VOC
            emissions  from leaks, spills  and cleaning.

5.3.3   Applicable Control  Systems (Water Based Processes)

       [1] Monomer  and  solvent  storage  and handling - As with
          hydrocarbon  based  acrylics,  present emissions are
          relatively  small and  existing controls usually are
          limited  to  conservation  vents on fixed  roof  tanks
          perhaps  with cooling  water  condensers for the more
          volatile substances.    Refrigerated  (ca  14F)
          condensers  are sometimes used  on  MMA  and  should
          achieve  about  90%  reduction  in VOC.  No additional
          controls seem presently warranted.
       [2] Monomer and  additive mix  tanks,  polymerizer/ stripper
          and latex cooling  tanks  - Presently there are few
          controls  on the mix  tanks and  cooling tanks and
          cooling  water  or refrigerated condensers  would be
          applicable and  could achieve  up to 90% VOC reduction.
          Most  polymerizer/strippers  presently have cooling
          water condensers for  economic  reasons.  High  (>90%)
          emissions reductions  have been achieved for  steam
          ejector  vacuum systems  in similar  service by  spray
          condensers.   This system  (spray  condensers for
          steam-jet evacuators) seems  attractive for control
          where applicable but creates  a  waste-water.
       [3] Dewatering and  drying - For suspension processes only.
          Emissions are machine  ventilation and dryer exhaust
          and are  presently  unabated.   Again, as in storage,
          controls do  not seem  warranted at present.   However
                             -40-

-------
    one means  of control  that  may be  available  is
    incineration in an existing boiler.   If  incineration
    is  used actual combustion efficiency of VOC reduction
    will exceed 90%.  However, recycle  of dryer air and
    purges  and/or flow splitting will  probably  limit
    reductions to <90%.
[4]  Extrusion,  finishing and packaging  - Extrusion and
    finishing  only  apply  to suspension  processes.
    Emissions of residual  monomer vapors are  collected by
    ventilation equipment.  If  uncontrolled,  these
    emissions can be the  largest VOC source in  water-based
    acrylics manufacture.  Tightly hooded or  enclosed (as
    in  an  extruder-  devolatilizer) equipment  can be
    evacuated and controlled by a steam-jet evacuator and
    spray condenser.  Well over 90%. VOC  reduction can be
    achieved; but, again,  a waste water will  be produced.
                      -41-

-------
                           SECTION 6
                         ALKYD RESINS
6.1  INDUSTRY  DESCRIPTION

     Alkyd  resins are a type of polyester resin (a condensation
     reaction product  of  polybasic acids  or anhydrides  and
     polyhydric  alcohols) .  Alkyds are  distinguished from  other
     polyester resins in that alkyds contain  fatty oils or  fatty
     acid as a third component.  The fatty acids are usually in
     the form  of naturally occurring oils,  such as linseed,  soya,
     and tung  oils.  Alkyds may be modified by co-reacting with
     other  synthetic resins or monomers,  and  may be blended with
     other  resin systems to expand their  range of properties.

     Alkyd  resins  are marketed  primarily as a liquid solution
     with an aliphatic or aromatic  solvent.   The resin  is used
     mainly for  surface coatings,  including oil based  paints.
     About  95% of alkyd resins produced are consumed in  surface
     coatings  with  most of the  remaining 5% being consumed in
     printing  ink vehicles (9_) .

     The most  common reactants are phthalic anhydride (polybasic
     acids  or anhydrides), pentaerthrito 1 and  glycerin
     (polyhydric alcohols), and linseed and soybean oils (fatty
     oils or fatty  acids).  Other polybasic  acids utilized are
     isophthalic, maleic and fumaric acid.
                             42-

-------
The popularity of alkyd coating resins  has  been due to
their low  cost,  ease  of application,  and  great
versatility.  Among  the more  important trade  sales
applications  of alkyd surface coatings  are  solvent-based
interior  and exterior enamels.  Typical  industrial end
uses include  finishes for metal furniture,  machinery and
equipment, wood furniture,  and general maintenance.

One of several methods for  classifying  alkyd  coating
resins is by  type and/or amount of oil (or fatty acid) in
the resin.  The type of oil determines  if  the alkyd will
be a drying  (polymerizable) or nondrying type.

No production capacity data  exist for  this  industry.
Capacity estimates may vary because, the same equipment can
be used to manufacture other products such as  plasticizers
like di-octyl phthalate (OOP) and  unsaturated polyester
resins. However, an historic utilization  factor of K =
0.68  (_!)  was combined with  an estimated  1%  annual
production shrinkage to provide a 1979  capacity estimate
of 1062 MM PPY for the model.

In  1976  over 265  million  gallons of  alkyd surface
coatings,  containing about 700 million  pounds of alkyd
resin solids, were produced in  the  United States.  The
sales  value of  these alkyd-containing  coatings was
estimated  at about 1.7 billion dollars.   The following
table summarizes the U.S.  supply/demand  situation for
alkyd  surface coatings in 1976.   Also,  Table 6-1  (JL.O)
gives  some  consumption   (demand) details  as  well as
estimates of  growth, and Table 6-II (11) gives details for
industrial alkyd consumption.
                      -43-

-------
             TABLE 6-1.- ESTIMATED CONSUMPTION OF ALKYD SURFACE COATINGS BY MAJOR MARKET, 1976 and  1981  (10)

                                   1976                                    1981
Trade Sales
 Exterior
 Interior
 Miscellaneous

Industrial
 Product Finishes 100
 Maintenance

Total
     Coatings
(millions of gals)

             135
                                          Alkyd Resin
                                         Solids Content
                                       (millions of Ibs)

                                                   365
                             Alkyd Resin
            Coatings        Solids Content
       (millions of gals) (millions of Ibs)
                                                                       110
                                       300
40
40
55

00
30
140
115
110
130
245
85
30
30
50
330
95
30
105
90
105
125 315
230
85
-5.5
-5.0
-1.0

-1.0
0
                               265
695
235
                                                                                          615
                             Average Annual
                              Growth Rate
                               1976-198la
                               (percent)

                                       -4.0%
                                                                                                              -1.0%
                                                                                            -2.5%
a.   Growth rates are rounded to nearest one-half percent.

-------
                           TABLE 6-II.-ESTIMATED CONSUMPTION OF INDUSTRIAL ALKYD SURFACE COATINGS
                                       1976
Ul
 I
    End Uses
                       Coatings
                  (millions of gals)
   Alkyd  Resin
  Solids  Content
(millions of Ibs)
                 1981

                      Alkyd  Resin
     Coatings        Solids  Content
(millions  of  gals)  (millions of  Ibs)
Product Finishes                 100
 Machinery and
  Equipment                16
 Metal Furniture
  and Fixtures             13
 Factory-Finished
  Wood                     15
 Wood Furniture
  and Fixtures'3             25
 Automotive, OEM           11
  Topcoat             <1
  Primer               4
  After-Market and
   Miscellaneous       7
 Trucks and Buses           4
 Containers and
  Closures                  5
 Insulation Varnishes       3
 Sheet Strip and Coil       2.5
 Other Trans., OEMC          2
 Appliances                 1.5
 Other Product Finishes^     2.5
    Maintenance Coatings
     Exterior
     Interior
     Marine

    Total6
                           15
                           12
                            3
                                             0.5
                                            13

                                            17
                                  30
                                  130
                                                         245
                                                     46

                                                     35

                                                     35

                                                      35
                                                     30
                                                     15

                                                     14
                                                      9
          42
          35
           8
               85
               330
                          18

                          15

                          13

                           25
                           7
       16
       12
        2
                                  95
                                                                         30
                                                                         125
                          50

                          40

                          30

                           35
                          23
                                             10

                                             13
                                              6
                                              6

                                             15
45
35
 5
                                                    230
                Average Annual
                 Growth Rate
                  1976-19813
                  (percent)

                      -1.0%
                                                     85
                                                     315
                                                                                                           -1.0%
    a.   Growth rates are rounded to the nearest one-half percent.
    b.   Includes nitrocellulose lacquers plasticized with alkyd resins.
    c.   Includes coatings for railroad equipment, aircraft, and miscellaneous transportation equipment.
    d.   Includes miscellaneous products such as toys, sporting goods, and gym equipment.
    e.   Totals may not equal the sums of the categories due to rounding.

-------
             STATUS OF ALKYD SURFACE COATINGS - 1976 (10)

                                             ALKYD RESIN
                          COATINGS          SOLIDS CONTENT
                    (Millions of Gallons)  (Millions of Pounds)

Production                       267                  700
Domestic Consumption              265                  695
  Trade Sales         135                   365
  Industrial  Products  130                   330
Exports                            2                    5

       Alkyd  formulations are  the  predominant types of  surface
       coatings  currently in use.  They can be tailored to meet a
       variety of end-use requirements through the choice and
       ratio  of  reactants and/or modifiers.  However,  in  recent
       years  some of the advantages of alkyds have diminished and
       the trend away  from  solvent-based  coatings  toward
       water-based systems has intensified.  The demand for alkyd
       coatings  declined steadily from 1973  through 1975; but  in
       1976 alkyds still made up about 30%  of the resins consumed
       in surface coatings.

       Consumption of alkyd  surface coatings  is expected  to
       decrease  about 2.5% annually between 1976 and 1981  (10).
       By 1981 an estimated 235 million gallons of alkyd  systems
       (615  million pounds of alkyd resin  solids)  will  be
       consumed  domestically,  compared with approximately 265
       million gallons  (695 million pounds  of solid resin)
       consumed  in 1976.  The  major reason for the diminishing
       demand for alkyd systems will be intensified antipollution
       regulations regarding  solvent use and emissions  (as
       requiring  the removal of solvents from coating  systems) .
       Beyond  1981  the  rate  of  decline  for conventional
                            -46-

-------
solvent-based  alkyd  formulations will probably  begin to
accelerate.   (See Table 6-1).

The manufacture of an alkyd resin involves  such reactions
as esterification,  polymerization of unsaturated fatty
acid chains,  and  ether ification  of hydroxyl  groups.
Ester ification  is the  major  reaction  used.   Batch
processing is  most commonly used with  the reaction  taking
place in  a  jacketed,  agitated  reactor  equipped  with a
condenser  and  a decanter.

Processes  for  alkyd  resin manufacture may  be  categorized
by the following two systems:

1. Fusion  and  solvent - by the methods by  which  fluidity
   and water  removal  are achieved in the  reactor.   The
   fusion  and  the solvent (or azeotrope) processes  are the
   important processes  in this system and  are described
   briefly below:

   o  When the reaction is carried out by  heating  in the
      presence of an inert gas it is called  the fusion
      process  (fluidity of the mass is achieved by  heat).
      In this  case,  the water produced by the  reaction is
      swept out with  the  inert  gas and vented  to
      atmosphere or  collected in a fume scrubber  system.
   o  When the reaction is carried out by  heating  in the
      presence of a  solvent it is called the  solvent (or
      azeotrope) process.  The solvent process  involves
      addition of another liquid (e.g., ethylbenzene or
      xylene at a level of 3-10% of the batch charge)  to
      aid  in the removal  of water.
                      -47-

-------
   Although the trend is  in  the  direction  of solvent
   processing  techniques,  there  will still be  a
   considerable volume of alkyds made  by  the fusion
   process because;

   -  There is a large investment  in existing plant
      installations,

      Certain alkyds, such as  the isophthalic types,
      are more easily made by the fusion  process,

    - Investment  cost  is  lower  on  new alkyd
      installations,

      Safety requirements  are less stringent than with
      solvent processing equipment.

Fatty acid and alcholysis methods - by  the nature of
the  ester ification reation  (direct  one-step  or
two-step)  which  is controlled  by  the  order  of
ingredient addition  to the reactor  and  the source of
ingredients.  Four basic methods are  recognized within
this  category;  the fatty  acid method,  the  fatty
acid-oil method, the oil-dilution method,  and  the
alcoholysis method.   The fatty  acid and  the  alcoholysis
methods  are most  important  today, and  these  are
described below.

o  Fatty Acid Method - The  entire charge  of  fatty
   acids,  polyhydric alcohols,  and dibasic acids is
   heated to reaction temperature  (usually  210-250C,
   but as  high as 230C  may be  used) and  maintained
   until product specifications are met.
                  -48-

-------
    o  Alcoholysis Method - A large proportion of alkyd
       manufacture  is accomplished  by  alcoholyzing
       triglyceride oils,  such as soybean and linseed oil,
       with pentaerythritol or glycerol as  the additional
       polyol.   After redistribution of the  fatty acid
       groups,  the partial esters, which  now have free
       hydroxyl groups,  are esterified with dibasic acids
       such as phthalic anhydride. The general alcoholysis
       method proceeds as follows:  The oil is heated  to
       230-250C; the sublimed litharge (lead oxide) and
       then  the polyol  are added;  and the  mixture  is
       reheated to 230-250C. One way to  follow the course
       of  the  alcoholysis reaction  is   by  noting the
       solubility of  the mixture  in  anhydrous  methyl
       alcohol.

Any  of the  four  methods can  be modified  further  by
manufacturing technique during the esterification cycle.
The  ester ification is a condensation reaction  with
elimination of water.

Producers of alkyd  coating resins  can be divided into
groups of  companies whose product is for  sale .only, for
sale and captive use, or  for captive use  primarily  (little
or no merchant  sales).  Eighteen  companies in the first
category produced approximately one-third  of  total alkyd
coating resins (solids basis)  in 1976. Ashland Chemical,
Cargill, and Reichhold Chemicals are the three largest  in
this category.   Twenty companies in the second category
also produced approximately  a  third of the  total alkyd
coating resins  (solids basis)  made in 1976.  Celanese,
Cook Paint  and Varnish, McCloskey  Varnish,  Reliance
Universal, and Syncon Resins are believed to be the  largest
of these.  Thirty-four  companies  in  the  third  category
accounted  for  approximately  the  remaining   third
                      -49-

-------
       of  the total alkyd coating  resins (solids basis)  produced
       in  1976.  The relative production of  these  companies and
       specific types of  alkyd resins  produced by  them are
       unknown.

6.2    ALKYD RESIN MANUFACTURE BY  SOLVENT PROCESS

6.2.1   Process Description

       The process  described here is a one-step  solvent batch
       process for the production  of a resin containing  phthalic
       anhydride and glycerine and  soybean oil  and dissolved in
       toluene.  Figure 6-1 is the  process schematic for such a
       process.  A fusion batch process description, schematic,
       and equipment  would be very similar  but without xylene
       solvent reflux, azeotropic  distillation,  and recovery or
       recycle.

       The process consists of two  main operations  -  poly-
       ester if icat ion and  thinning.   In  pol yes ter i f ica t ion ,
       molten phthalic anhydride,  glycerine,  and soybean oil are
       charged into the reactor from storage tanks.  The mixture
       is  agitated and heated (batch) while  the  reactor and the
       overhead condensation system are purged with an  inert gas.
       Then xylene is added.  The  polyester if ication is carried
       out at  250C.   When the polyesterification  reaction
       becomes vigorous the water  of reaction  evolves  rapidly.
       The temperature at  the top of  the column is  kept at
       100-120C  by refluxing xylene from  the  decanter of the
       solvent recovery system to  minimize the loss of reactants.
       As  the reaction approaches  completion  the  evolution of
       water from the reaction mixture begins to diminish.  The
       reflux of  xylene  is stopped  and all  the xylene is
       distilled from the reactor.  An inert gas sparge   is then
                            -50-

-------
VAPOR
RETURN
           PHTHALIC
          ANHYDRIDE
          STORAGE
                                                                                                          STACK
                                                                                                         GASES
                                                                                                      TO DRUM AND
                                                                                                      BULK LOADING
   FEED
                           REACT
                                                           RECOVERY
                                                                                       FINISH
                      Figure  6-1.-  Alkyd resins by  a batch  solvent process.

-------
       used  to remove residual water and  unreacted reactants.
       When  the polyesterification has reached the desired acid
       number, the alkyd resin product is pumped to the  thinning
       vessel.  During the reaction and  thinning, some of the
       reactants are carried  out  of the reactor with the water
       and thereby lost from the product.   After most of the
       volatiles  are condensed, the vapor  exhausted from the
       reactor is scrubbed  with water  before it leaves the
       process vent.

       In  the  thinning operation  the thinning vessel containing
       the required amount of toluene (solvent)  is purged with
       inert gas and then partially cooled alkyd resin is added
       at  a  rate  such that  the  resin  temperature is  kept at
       about 66C.  The resin is  checked for color or  refractive
       index (or  both),  acid number, viscosity, and specific
       gravity while in the thinning vessel.  Additives such as
       filter  aids, etc., are also  added before  the  thinned
       resin is pumped out through the  filter to the storage
       tanks.

6.2.2   VOC Emissions

       All  significant emission rates  and  sources  for this
       product are shown  on  Table 6-III.  Figure 6-1  is the
       schematic flowsheet for this product.   It includes the
       emission streams and their sources.

       The following paragraphs describe  the  emission streams
       that  are encountered:

       [1]   Raw material,  solvent, and modifier storage tanks -
            Fixed roof  storage tanks are  used  in  existing
            facilities (except for a  floating  roof  tank for
                            -52-

-------
    TABLE 6-III.-VOC EMISSIONS FROM ALKYD RESIN -  SOLVENT  PROCESS


                                       Current
                      Uncontrolled     Practice    Well  Controlled
Stream                #/1000# Resin  #/1000#Resin   #/1000# Resin

[1]  Raw Material,          0.14           0.14           0.06
     Solvent and
      Modifier Storage
      Tanks

[2]  Reactor                7.05           0.40           0.10

[3]  Thinning Vessel        0.26           .0.09           0.01

[4]  Product Storage Tanks  0.13           0.13           0.01

[5]  Product Drum and Bulk  0.11           0.11           0.01
     Loading Operations

[6]  Product Filter         0.01           0.01           nil
     Operations            	           	          . 	

Totals                     7.70           0.88           0.19
                               -53-

-------
     toluene).   Emissions are vapors of the substances
     stored  (and  blanket gas if used), and they  result
     from  vapor  displacement (working losses) and  tank
     breathing.   Phthalic anhydride (a solid at ambient
     conditions)  is stored at elevated temperatures- in
     heated,  insulated tanks.  Toluene, glycerine,  and
     soybean oil  are stored at ambient  conditions.
[2]   The reactor vent -  This  stream is  the largest
     potential emission source in the process.  The  flow
     rate and stream composition vary as the batch  goes
     through its  cycle  (as  is true for  most batch reaction
     flows) .  The stream carries unreacted monomers  and
     volatile impurities  from the feeds along with  inert
     gas.   Inert gas is added to the reactor  to  strip
     residual volatiles  from  the product after  the
     reaction is  complete,  to aid in water removal,  and to
     prevent  atmospheric oxygen  from contacting  the
     reaction mixture which would result  in product
     discoloration.  The  system  through which  the
     resulting emission travels includes the  overhead
     condenser and aqueous  or caustic scrubber the  system
     also collects small  emissions,  normally xylene,  from
     the reactor  solvent  recovery system.
[3]   Thinning vessel - This stream consists of toluene
     (solvent) vapor from the overhead condenser  in an
     inert  gas resulting from an inert gas  purge  flow
     maintained  to exclude  oxygen from  the product.   Some
     of  the  vapor is from displacement losses when  the
     vessel is filled from  the reactor.
[4]   Product storage tanks - Fixed roof storage  tanks  are
     utilized.  Emissions are vapors of the solvent  (i.e.
     toluene) used  in the product resin solution  and
                      -54-

-------
           result  from  tank breathing and vapor  displacement
           (working losses).
       [5]   Product drum and  bulk loading operations -  The
           emissions are vapors of the solvent  (i.e.   toluene)
           used  in  the  product  resin  solution  and emitted
           through  vapor displacement  when filling product
           drums, tank trucks  or tank cars.
       [6]  Product filter operations - Emissions are  primarily
           vapors  of  the solvent (i.e. toluene)  used  in  the
           product resin solution.  The emissions result  from
           filter operations and maintenance,  primarily opening
           the  filter to  clean  plates  or leaves.  They  are
           fugitive and  diluted highly by air.

6.2.3   Applicable Control Systems

       The  following control technologies are recommended  for the
       emission  streams  described in Section 6.2.2 and  in  the
       schematic flowsheet for  this product.

       [1]  Raw material, solvent,  and modifier storage  tanks - A
           floating roof  storage tank  is used  for toluene
           solvent.  Glycerine and  soybean  oil  have vapor
           pressures below the range generally considered to be
           VOC.   Other  tanks  in  this category should utilize
           vapor return  lines  to the loading tank trucks  or cars
           in order to eliminate all vapor displacement working
           losses occuring  during  tank filling.   This  results in
           an efficiency level of  approximately  58% of  the total
           tank losses.   (Modifiers or reactants  used in  some
           locations  or for some special  product runs might
           require  an inert gas  blanket/flare or incinerator
           systems  or floating  roofs because  of  higher vapor
           pressures.) Conservation valves should also be used;
           they are justified  adequately by process  economics

                            -55-

-------
    alone.   Aqueous scrubbers also should  be used  on
    phthalic anhydride  storage tank vents, primarily for
    housekeeping  purposes.   Phthalic anhydride  is a
    crystalline solid at ambient conditions  that  causes
    sublimed solids  buildup on the cool  surfaces adjacent
    to tank vents.   Quite high VOC removal efficiencies
    have  been  reported for this  scrubber  application
    (.12), (.13).
               /
[2]  Reactor - An overhead condensing system is  used   for
    process and economic reasons regardless of  emissions.
    Normally this  system consists of a direct condensing
    partial condenser or a distillation  column  and total
    condenser. Emissions from  the condensing  system
    should  be  reduced  by aqueous or caustic  scrubbing
    followed  by incineration (thermal or  catalytic) .
    Minimum efficiencies of 85% for the  scrubber  and 90%
    for  the incinerator should  be readily obtained.
    Various vents  from the reactor solvent  recovery
    system, such as  from the decanter, will also  use the
    reactor  scrubber  and  incinerator,  both   for
    housekeeping purposes and  to prevent plugging.
[3]   Thinning vessel  -  A refrigerant cooled
    after-condenser with 40F coolant can  be used  to
    yield a significant reduction without  moisture
    freeze-up;  however,  this condenser would  normally be
    provided anyhow  for process economic reasons.   The
    non-condensibles from the  condenser are  sent  to the
    incinerator (thermal or  catalytic) which is  also
    required  for  the reactor.   A  minimum  of 90%
    efficiency is  assumed for  this system.
[4]   Product storage - An  inert  gas blanket/flare  or
    incinerator system,  or equivalent should  be utilized
    on  the tanks  involved  here.  A  minimum  of 90%
                     -56-

-------
     reduction  efficiency is  assumed  with  these
     provisions.
[5]   Product drum and bulk loading operation -  Use hoods
     over  all relevant  points that are connected  to the
     incinerator through ducts equipped  with  fans.   Also,
     where applicable and  practicable, u'se  vapor  return
     lines. Mininum efficiencies of 90%  are assumed here.
[6]   Product filter operations - A hood  is  used that is
     designed  for the  filter area and connected  to the
     incinerator through ducts equipped with fans.  (The
     system may tie into and use the duct/fans system for
     stream  [#5] above).  A mininum incinerator  efficiency
     of 90% is assumed.
                      -57-

-------
                           SECTION  7
                MELAMINE - FORMALDEHYDE RESINS
7.1  INDUSTRY DESCRIPTION

     Melamine-formaldehyde resins (MF resins)  are aminoplasts,
     which are a class  of  thermosetting resins made  by the
     reaction of formaldehyde with the amino (-NI^) group  of
     compounds including melamine, urea, or urea derivatives  (one
     of these, Urea-formaldehyde  Resins, is discussed more fully
     in Section 20).  The polymerization of melamine-formaldehyde
     is analogous to  that of  urea and formaldehyde  with
     exceptions related  to  the different reactivity  of the
     -NH2  groups in melamine.  MF resins are generally made
     by a  batch reaction in an aqueous medium  with the primary
     reactions being addition,  condensation and polymerization.
     The first products of the  addition reaction between melamine
     and formaldehyde  are  methylolmelamines  and these  begin
     further  (condensation and cross linking)  reactions almost
     immediately.  When  sufficiently  reacted to provide the
     product properties  desired the condensation and  cross-
     linking  are stopped by cooling or by  chemical means.

     MF resins have many properties that are similar to those of
     the urea-formaldehyde (UF)  resins described in Section 20,
     and they are made using a  similar technology.  Frequently in
     fact,  they use the same equipment.  Like the UF resins, the
     MF resins are clear  and  colorless,  and  have  outstanding
     electrical properties.   MF resins  also provide  better
     chemical, water, and heat  resistance  than  UF resins, which
     justifies their higher price for specialized applications.
                             -58-

-------
The resin  product  can be shipped as  an  aqueous  syrup
(approximately  50%  of  sales  poundage), a powder  made by
first impregnating  syrup into  a solid  filler,  or as a
spray-dried powder.   (All types of powder make up the
remaining  50% of  sales poundage).  The  final stage' of
polymerization-cross-linking of linear chains does not take
place,  usually,  until the resin is cured to its final shape
- an insoluble  thermoset product.  Resins for  molding
powders  are generally polymerized further  than resins for
syrup applications such as adhesives.  Aqueous syrups  may be
mixed with  other coating formulations, or used to impregnate
fillers,  paper,  or textiles.

The solution stability of methylolmelamines can be  improved
by etherfying the methylol groups  formed  when formaldehyde
reacts with melamine,  usually  with an  alcohol  such as
methanol  or butanol.  The reaction  can  also take place on
melamine  condensates that have unreacted  methylol  groups.
Methylated MF resins  are water  soluble, and  the  aqueous
syrups  are  useful for  treating  textiles  to impart  crease
resistance.  Butylated  MF resins  are  hydrophobic,  and are
soluble  in  organic solvents such  as  toluene;  they are  widely
used in  surface coatings,  such  as varnishes  and baking
enamel,  because  they are  compatible  with  alkyd resins and
epoxy resins.   A  typical product of a batch  process for
making  butylated MF resin is a syrup containing 58.7% -resin
solids  in xylene solvent.

Production  of MF resins in 1976 was  188  MM  Ibs (dry  basis)
(2^, and  average market growth rate of 3.5%/yr is projected.
Little  production capacity data exist.  Production equipment
can be used interchangeably  to  manufacture  MF resins or
urea-formaldehyde resins, and  usually  phenol-formaldehyde
resins  also.
                        -59-

-------
       Approximately 60 manufacturers are  known  to produce MF
       resins  in the United States.   These producers are shown in
       Table 7-1, which also includes the  producers of  phenolic
       (phenol- formaldehyde) and urea-formaldehyde resins  (the
       latter  is the other major amino resin).

7.2    MANUFACTURE OF MELAMINE-FORMALDEHYDE RESIN AND A BUTYLATED
       MF RESIN

7.2.1  Process Description

       Melamine-formaldehyde syrup is made by  the batch  reaction
       of melamine and aqueous formaldehyde solution.   In  a
       simple basic recipe,  the  two ingredients  are mixed
       together and the pH is  adjusted with NaOH to about  8.5.
       Melamine is not soluble  in aqueous formaldehyde  at  room
       temperature, but as the mixture is  heated, the melamine is
       slowly  converted to  the  soluble methylolmelamines.  No
       catalyst  is  necessary,  and  the addition reaction  takes
       place easily and more completely than it does with  urea.
       Condensation  between methylolmelamine molecules  begins
       immediately and as it proceeds hydrophobic intermediates
       appear.  After about 3 hours,  the  syrup  is  tested  for
       miscibility with water.  When the test  indicates  that the
       desired degree of condensation has  been reached, the batch
       is cooled  and impurities  are filtered out.  Figure 7-1
       shows a schematic for making  both MF syrup and  butylated
       MF resin.  Some of the equipment shown  is needed  only for
       the butylated MF resin.  Both  processes  are  described
       further below (17) .   Emission data  were available only for
       butylated MF resin.
                              -60-

-------
TABLE 7-1.- PRODUCERS OF AMINO AND PHENOLIC RESINS
COMPANY AND PLANT
     LOCATION

ALLIED CHEMICAL CORPORATION
 Specialty Chemical Division
  South Point, Ohio
  Toledo, Ohio
Phenol-
Formal-
dehyde
  X
AMERICAN CYANAMID COMPANY
 Formica Corp.,.subsidiary
  Columbia, South Carolina
  Evendale, Ohio                 X
 Industrial Chemicals and
 Plastics Division
  Azusa, California
  Longview, Washington
  Wallingford, Connecticut

ASHLAND OIL, INC.
 Ashland Chemical Co., div
  Foundry Products Division
  Cleveland, Ohio                X
  Hammond, Indiana               X
 Resins and Plastics Division
  Calumet City, Illinois         X
  Fords, New Jersey              X
  Pensacola, Florida             X

AURALUX CHEMICAL ASSOCIATES, INC.
  Hope Valley, Rhode Island

THE BENDIX CORPORATION
 Friction Materials Division
  Green Island, New York         X

BORDEN INC.
 Borden Chemical Division
 Adhesives and Chemicals Div., East
  Bainbridge, New York           X
  Demopolis, Alabama             X
  Diboll, Texas
  Fayetteville, NC               X
  Louisville, Kentucky
  Sheboygan, Wisconsin           X
RESIN TYPE
   Urea-
   Formal-
   dehyde
      X
      X
                X
                X
                X
                X
                X
                X
                X
                X
                X
Melamine-
  Form al-
  dehyde
                            X
                            X
                  X
                  X
                  X
                  X
                  X
                  X
                  X
                  X
                  X
                              -61-

-------
TABLE 7-I.-PRODUCERS OF AMINO AND PHENOLIC RESINS (Continued)
COMPANY AND PLANT
     LOCATION
Phenol-
Formal-
dehyde
RESIN TYPE
   Urea-
   Formal-
   dehyde
BORDEN INC.
 Borden Chemical Division
 Adhesives and Chemicals
  Division - West
  Fremont, California            X
  Kent, Washington               X
  La Grande, Oregon              X
  Missoula, Montana              X
  Springfield, Oregon            X

BRAND-S CORPORATION
 Cascade Resins, Inc., div.
  Eugene, Oregon                 X

THE CARBORUNDUM COMPANY
  Wheatfield, New York           X

CARGILL, INC.
 Chemical Products Division
  Carpentersville, Illinois
  Philadelphia, Pennsylvania

CELANESE CORPORATION
 Celanese Coatings and Specialty
 Chemicals Co., sub., Celanese
 Resins Division
  Charlotte, North Carolina
  Louisville, Kentucky

CHAMPION INTERNATION, CORP.
 U.S. Plywood Division
  Redding, California            X

CLARK CHEMICAL CORPORATION
  Blue Island, Illinois          X

CNC CHEMICAL CORPORATION
  Providence, Rhode Island

COMBUSTION ENGINEERING, INC.
 C-E Cast Industrial Products Div.
  Muse, Pennsylvania             X
                X
                X
                X
                X
                X
                X
                X
                X
                X
                X
Melamine-
  Formal-
  dehyde
                  X
                  X
                  X
                              -62-

-------
TABLE 7-1.-PRODUCERS OF AMINO AND PHENOLIC RESINS  (Continued)
COMPANY AND PLANT
	LOCATION

COMMERCIAL PRODUCTS COMPANY
  Hawthorne, New Jersey

CONCHEMCO INCORPORATED
  Baltimore, Maryland
  Kansas City, Missouri

CONSOLIDATED PAPERS, INC.
  Wisconsin Rapids, Wisonsin

CONWED CORPORATION
  Cloquet, Minnesota

COOK PAINT & VARNISH CO.
  Detroit, Michigan
  North Kansas, Missouri

CORE-LUBE, INC.
  Danville, Illinois

CPC INTERNTIONAL, INC.
 Acme Resin Co., division
  Forest Park, Illinois

DAN RIVER, INC.
  Danville, Virginia

DE SOTO, INC.
  Berkeley, California
  Garland, Texas

THE DEXTER CORPORATION
  Waukegan, Illinois

DOCK RESINS CORPORATION
  Linden, New Jersey

THE DUPLAN CORPORATION
 Cap-Roc Incorporated, sub.
  Capital Plastic Division
   Brodhead, Wisconsin
Phenol-
Formal-
dehyde
  X
  X
RESIN TYPE
   Urea-
   Formal-
   dehyde
                X
                X
                X
                X
                X
                X
                X
                X
                X
Melamine-
  Formal-
  dehyde
                  X
                  X
                  X
                  X
                            X
                            X
                               -63-

-------
TABLE 7-1.-PRODUCERS OF AMINO AND PHENOLIC RESINS (Continued)
 COMPANY  AND PLANT
 	LOCATION

 EASTERN  COLOR &  CHEMICAL CO.
   Providence, Rhode  Island

 EMKAY CHEMICAL COMPANY
   Elizabeth,  New Jersey

 EXXON CORPORATION
  Nevamar Division
   Odenton,  Maryland

THE  FIBERITE  CORPORATION
   Winona,  Minnesota

 FORD MOTOR COMPANY
   Mt. Clemens, Michigan

 GAF  CORPORATION
  Chemical  Division
   Chattanooga, Tennessee

 GENERAL  ELECTRIC COMPANY
  Chemical  and Metallurgical
  Div., Laminated and Insulating
  Materials  Business  Department
   Cosocton,  Ohio
   Schenectady, New York
  Engineering  Plastics Product
  Department
   Pittsfield, Massachusetts

 THE  P.O.  GEORGE CO.
   St. Louis,  Missouri

 GEORGIA-PACIFIC CORPORATION
  Chemical  Division
   Albany,  Oregon
   Columbus,  Ohio
   Conway,  North Carolina
   Coos Bay,  Oregon
   Crossett,  Arkansas
   Louisville, Mississippi
   Lufkin,  Texas
   Russellville,  SC
   Savannah,  Georgia
   Taylorsville,  Mississippi
   Tewkesbury, Massachusetts
   Ukiah,  California
   Vienna,  Georgia
                               Phenol-
                               Formal-
                               dehyde
RESIN TYPE
   Urea-
   Formal-
   dehyde
                                 X
                                 X
                                 X
                                 X
                                 X
                                 X
                                 X
                                 X
                                 X
                                 X
                                 X
                                 X
                                 X
                                 X

                                 X
                                -64-
                                               X
                                               X
      X
      X
      X
      X
      X
      X
      X
      X
      X
      X

      X
      X
Melamine-
  . Formal-
  dehyde
                  X
                                                           X
    X
    X
    X
    X
    X
    X
    X
    X
    X
    X

    X
    X

-------
TABLE 7-1.-PRODUCERS OF AMINO AND PHENOLIC RESINS (Continued)
COMPANY AND PLANT
     LOCATION

GETTY OIL COMPANY
 Chembond Corp., sub.
  Andalusia, Alabama
  Spokane, Washington
  Springfield, Oregon
  Winnfield, Louisiana

GILMAN PAINT & VARNISH CO.
  Chattanooga, Tennessee

W.R. GRACE & CO.
 Agricultural Chemicals Group
  Alliance, Ohio
  Charleston, South Carolina
  Columbus, Ohio
  Finley, Ohio
  Fort Pierce, Florida
  Henrietta, Illinois
  Lansing, Michigan
  Memphis, Tennessee
  San Juan, Puerto Rico
  Statesville, North Carolina
  Tampa, Florida
  Tulsa, Oklahoma
  Wilmington, North Carolina

GUARDSMAN CHEMICALS, INC.
  Grand Rapids, Michigan

GULF OIL CORPORATION
 Gulf Oil Chemicals Co., div.
 Adhesives & Resins Dept.
  Alexandria, Louisiana
  High Point, North Carolina
  Lansdale, Pennsylvania
  Shawano, Wisconsin
  Valleyfield, Quebec
  West Memphis, Arkansas

HANNA CHEMICAL COATINGS CORP.
 Hanna Chemical Coatings Co.,
  Subsidiary
  Birmingham, Alabama
Phenol-
Formal-
dehyde
  X
  X
  X
  X
  X
  X
  X
RESIN TYPE
   Urea-
   Formal-
   dehyde
      X

      X
                X
                X
                X
                X
                X
                X
                X
                X
                X
                X
                X
                X
                X
      X
      X
      X
      X
      X
      X
Melamine-
  Formal-
  dehyde
    X
    X
    X
                X
                              -65-

-------
TABLE 7-1.-PRODUCERS OF AMINO AND PHENOLIC RESINS (Continued)
COMPANY AND PLANT
     LOCATION

HART PRODUCTS CORP.
  Jersey City, New Jersey

HERCULES INCORPORATED
 Organics Department
  Chicopee, Massachusetts
  ,Hattiesburg, Mississippi
  Milwaukee, Wisconsin
 Haveg Industries Inc., sub.
  Marshallton, Delaware

HERESITE & CHEMICAL COMPANY
  Manitowoc, Wisconsin

H & N CHEMICAL COMPANY
  Totowa, New Jersey

E.F. HOUGHTON & COMPANY
  Philadelphia, Pennsylvania

INLAND STEEL COMPANY
  Alsip, Illinois

INMONT CORPORATION
  Anaheim, California
  Cincinnati, Ohio
  Detroit, Michigan
  Greenville, Ohio
Phenol-
Formal-
dehyde
  X
  X
  X
  X
INTERNATIONAL MINERALS & CHEMICAL
 CORPORATION  Aristo Intl. Corp.
  Detroit, Michigan              X
THE IRONSIDES CO.
 Ironsides Resins, division
  Columbus, Ohio

KNOEDLER CHEMICAL COMPANY
  Lancaster, Pennsylvania

KOOPERS COMPANY, INC.
 Organics Materials Division
  Bridgeville, Pennsylvania

KORDELL INDUSTRIES
  Mishawaka, Indiana
  X
  X
  X
-66-
RESIN TYPE
   Urea-
   Formal-
   dehyde
Melamine-
  Formal-
  dehyde
                X
                X
                X
                            X

-------
TABLE 7-1.-PRODUCERS OF AMINO AND PHENOLIC RESINS (Continued)
                               Phenol-
                               Formal-
                               dehyde
                                 X
COMPANY AND PLANT
     LOCATION

LAWTER CHEMICALS, INC.
  South Kearney, New.Jersey

MAGNA CORPORATION
  Houston, Texas

THE MARBLETTE CORPORATION
  Long Island City, New York

MASONITE CORPOTATION
 Alpine Division
  Gulfport, Mississippi

MILLMASTER ONYX CORPORATION
(a subsidiary of Kewanee Ind.)
 Refined-Onyx Division
  Lyndhurst, New Jersey
MINNESOTA MINING AND MANUFACTURING
  Cordova, Illinois              X
  Cottage Grove, Minnesota       X

MOBIL OIL CORPORATION
 Mobil Chemical Company, division
 Chemical Coatings Division
  Kankakee, Illinois

MONSANTO COMPANY
 Monsanto Plastics & Resins Co.
  Addyston, Ohio                 X
  Alvin, Texas                   X
  Eugene, Oregon                 X
  La Salle, Quebec
  Santa Clara, California        X
  Springfield, Massachusetts     X

NAPKO CORPORATION
  Houston, Texas                 X

NATIONAL CASEIN COMPANY
  Chicago, Illinois
  Tyler, Texas
RESIN TYPE
   Urea-
   Formal-
   dehyde
Melamine-
  Formal-
  dehyde
                                               X
                                               X
                                               X
                                               X
                                               X
                  X
                  X
                  X
                  X
                                               X
                                               X
                             -67-

-------
TABLE 7-1.-PRODUCERS OF AMINO AND PHENOLIC RESINS (Continued)
Phenol
Formal
dehyde
COMPANY AND PLANT
_ LOCATION

NATIONAL CASEIN OF CALIFORNIA
(affiliate of National Casein)
  Santa Ana, California

NATIONAL CASEIN OF NEW JERSEY
(affiliate of National Casein)
  Riverton, New Jersey
NATIONAL STARCH AND CHEMICAL CORP.
 Proctor Chemical Company, sub.
  Salisbury, North Carolina
OCCIDNETAL PETROLEUM CORP.
 Hooker Chemical Corp., sub.
 Hooker Chemicals and Plastics
 Corporation, subsidiary
  Kenton, Ohio
  N. Tonawanda, New York
                                         RESIN TYPE
                                            Urea-
                                            Formal-
                                            dehyde
                                               X
ONYX OILS & RESINS INC.
  Newark, New Jersey

OWENS-CORNING FIBERGLAS CORP.
 Resins and Coatings Division
  Barrington, New Jersey
  Kansas City, Kansas
  Newark, Ohio
  Waxahachie, Texas

PAT CHEMICAL INCORPORATED
  Greenville, South Carolina

PATENT PLASTICS COMPANY
  Knoxville, Tennessee

PERSTORP U.S. INC.
(subsidiary of Perstorp AB
 [Sweeden] )
  Florence, Massachusetts

PIONEER PLASTICS CORPORATION
 Chemical Division
  Auburn, Maine
                                 X
                                 X
                                 X
                                 X
                                 X
                                 X
                                 X
                                                       Melamine
                                                         Formal
                                                         dehyde
                                                           X
                                               Xa
                                               X
                               -68-

-------
TABLE 7-1.-PRODUCERS OF AMINO AND PHENOLIC RESINS  (Continued)
COMPANY AND PLANT
	LOCATION

PLASTICS ENGINEERING CO.
  Sheboygan, Wisconsin

PLASTICS MANUFACTURING CO.
  Dallas, Texas

POLYMER APPLICATIONS INC.
  Tonawanda, New York

POLYREZ COMPANY, INC.
  Woodbury, New Jersey

PPG INDUSTRIES INC.
 Coatings and Resins Div.
  Circleville, Ohio
  Oak Creek, Wisconsin

RAYBESTOS-MANHATTAN, INC.
  Stratford, Connecticut

REICHHOLD CHEMICALS, INC.
  Andover, Massachusetts
  Azusa, California
  Carteret, New Jersey
  Detroit, Michigan
  Houston, Texas
  Kansas City, Missouri
  Malvern, Arkansas
  Moncure, North Carolina
  Niagara Falls, New York
  South San Francisco, CA
  Tacoma, Washington
  Tuscaloosa, Alabama
  White City, Oregon

RIEGEL TEXTILE CORPORATION
 H.I.T. Chemicals Division
  Ware Shoals, South Carolina

ROGERS CORPORATION
  Manchester, Connecticut
Phenol-
Formal-
dehyde
  X
  X

  X
  X
  X
  X

  X
  X
  X
  X
  X
  X
RESIN TYPE
   Urea-
   Formal-
   dehyde
                X
                X
                X
      X
      X

      X
      X

      X
      X

      X
      X
      X
      X
Melamine-
  Formal-
  dehyde
                  X
                  X
    X
    X
    X
    X
  X
                              -69-

-------
TABLE 7-1.-PRODUCERS OF AMINO AND PHENOLIC RESINS (Continued)
                               Phenol-
                               Formal-
                               dehyde
                                 X
                                 X
                                 X
COMPANY AND PLANT
	LOCATION

SCHENECTADY CHEMICALS INC.
  Oyster Creek, Texas
  Rotterdam Junction, NY
  Schenectady, New York

SCHER BROTHERS, INC.
  Clifton, New Jersey

SCOTT PAPER COMPANY
 Packaged Products Division
  Chester, Pennsylvania
  Everett, Washington
  Fort Edward, New York
  Marinette, Wisconsin
  Mobile, Alabama
SHANCO PLASTICS & CHEMICALS INC.
  Tonawanda, New York            X

THE SHERWIN-WILLIAMS COMPANY
  Chicago, Illinois
  Cleveland, Ohio
  Morrow, Georgia
  Newark, New Jersey
RESIN TYPE
   Urea-
   Formal-
   dehyde
SIMPSON TIMBER COMPANY
  Arcata, California
  Portland, Oregon

SOUTHEASTERN ADHESIVES COMPANY
  Lenoir, North Carolina

SPAULDING FIBRE COMPANY, INC.
  De Kalb, Illinois
  Tonawanda, New York

SUN CHEMICAL CORPORATION
 Chemicals Group
  Chester, South Carolina

SYBRON CORPORATION
 Jersey State Chemical Co., div
  Haledon, New Jersey
                                 X
                                 X
                                 X
                                 X
                                               X
                                               X
                                               X
                                               X
                                               X
                                               X
                                               X
                                               X
                                               X
Melamine-
  Formal-
  dehyde
                  X
                  X
                                               X
                             -70-

-------
TABLE 7-1.-PRODUCERS OF AMINO AND PHENOLIC RESINS (Continued)
                               Phenol-
                               Formal-
                               dehyde
 COMPANY  AND  PLANT
 	LOCATION

 SYNTHRON,  INC.
   Ashton,  Rhode  Island -
   Morganton, North  Carolina

 THOMASON INDUSTRIES INC.
  Southern  Resin  Division
   Fayetteville,  North  Carolina
   Thomasville, North Carolina

.TRW  INC.
  IRC Division
   Dowington, Pennsylvania
UNION CAMP CORPORATION
  Valdosta, Georgia              X

UNION CARBIDE CORPORATION
 Chemicals and Plastics Division
  Bound Brook, New Jersey        X
  Elk Grove, California          X
  Marietta, Ohio                 X
  Sacramento, California         X
  Texas City, Texas              X

UNITED-ERIE, INC.
  Erie, Pennsylvania             X

UNITED MERCHANTS & MANUFACTURERS
 Valchem-Chemical Division
  Langley, South Carolina

U.S. OIL COMPANY
 Southern U.S. Chemical Co., Inc. sub.
  East Providence, Rhode Island
  Rock Hill, South Carolina

UNIVAR CORPORATION
 Pacific Resins & Chemicals, Inc.
  Eugene, Oregon                 X
  Newark, Ohio                   X
  Portland, Oregon               X
  Richmond, California           X
RESIN TYPE
   Urea-
   Formal-
   dehyde
                                               X
                                               X
                                               X
                                               X
Melamine-
  Formal-
  dehyde
                  X
                  X
                                                X
                                                X
                                                X
                                                X
                                                X
                  X
                  X
                  X
                              -71-

-------
TABLE 7-I.-PRODUCERS OF AMINO AND PHENOLIC  RESINS  (Concluded)
COMPANY AND PLANT
	LOCATION

USM CORPORATION
 Crown-Metro, Inc., sub.
  Greenville, South Carolina

VALENTINE SUGARS, INC.
 Valite Division
  Lockport, Louisiana

WEST COAST ADHESIVES COMPANY
  Portland, Oregon
Phenol-
Formal-
dehyde
  X
  X
WESTINGHOUSE ELECTRIC CORPORATION
 Insulating Materials Division
  Manor, Pennsylvania            X
 Micarta Division
  Hampton, South Carolina        X

WEST POINT-PEPPERELL, INC.
 Griftex Chemical Co., sub
  Opelika, Alabama
WEYERHAEUSER COMPANY
  Longview, Washington
  Marshfield, Wisconsin
  X
  X
RESIN TYPE
   Urea-
   Formal-
   dehyde
Melamine-
  Formal-
  dehyde
                            X
      X
                            X
a Plant to be owned by Libby Owens  Ford
                             -72-

-------
U)
 I
       VAPOR
       RETURN
                                              REFLUX
                                              CONDENSER
             BUTANOL
             STORAGE
            (100%)
                                              A     V
                                              ^rC,
                                                            DECANTER
        VAPOR
        RETURN
                                                         TO PROCESS SEWER
                                                         OR ALCOHOL RECOVERY
FORMALDEHYDE  SOLUTION
37?  or 52$, @ 138F
(IN  BUTANOL FOR BUTYLATED)
               XYLENE,
            (SOLVENT)'
                                                                                   TO FLARE
                                                                           * COULD MAKE M-F SYRUP,
                                                                             M-F FILLED POWDER, OR
                                                                             BUTYLATED M-F SYRUP AS
                                                                             SHOWN
                                                             RESIN
                                                          IMPREGNATOR
                                                            (MIXER)
                                                                                  MOLDING POWDER PRODUCT
                                                                                 TO FURTHER SIZE
                                                                                  PROCESSING &  PACKAGING
                          RESIN SYRUP STORAGE

             FEED                         REACT

             Figure  7-1.-  Melamine-formaldehyde resin  - Batch process,
                                                                          STM

                                                                      RECOVERY/FINISH

-------
MF Manufacture
       The  first process described is a simple one  that  makes  a
       concentrated MF syrup widely  used  for decorative
       laminates,  surface  coatings,  or filled  powder.   The
       following operating  steps are followed:
       1.   Charge  the reactor with 37% or 52%  formaldehyde
           aqueous  solution, melamine  crystals,  and aqueous
           sodium hydroxide.
       2.   Heat the mixture to  the desired reaction  temperature
           with heating jacket  steam, and reflux under  vacuum at
           reaction temperature (typically 175F).
       3.   Monitor the reaction progress by sampling  the reactor
           contents for miscibility with water.
       4.   At the  desired  miscibility, cool  the batch  and
           concentrate the syrup by evaporating  water under a
           vacuum.  (This step may not be required,  since 63%  (wt)
           solids syrup is  made without concentration).
       5.   Adjust the pH (8.5-9.0) as required  and  pump out  the
           syrup through a  filter to the holding tank.

       At  this point resin syrup can  be   stored  or further
       concentrated  for use or for sale  in  varnishes, surface
       coatings, adhesives, or textile  treating  or  laminating
       preparation or it can be further processed  into  a powder.
       Procedures  for making  MF molding compounds  are also
       followed in UP molding compound manufacture  (Section 20).
       An  unfilled  powder  can be made by spray drying aqueous
       syrup  and a filled powder can be made by  impregnating a
       solid  filler  with aqueous syrup.  A  batch  process  for
       filled powder is described below:

       1.   Filler (such as  kraft paper)  is impregnated with resin
           syrup and mixed  to a wet paste in  a mixer.
       2.   Water is removed in a tunnel dryer  to  form  a  dry
           cake.
                             -74-

-------
       3.   The cake (popcorn)  is pulverized to a coarse powder in
           a micro-pulverizer.
       4.   This powder is milled in a ball mill with  additives to
           form a blended fine  powder.
       5.   The fine  powder is deaerated  and  compressed into a
           corrugated ribbon, which is  then  cut  into  molding
           granules for storage and sale.

7.2.1.1 Process variations.-

        Additional  ingredients  that  are  used  in  recipe
        variations include other  monomers, pH  control  agents,
        viscosity control agents, and catalysts.

        Product formulations  of MF resins are  varied by adding
        less  expensive monomers, such  as  urea or  phenol,  to
        produce a mixed polymer that has  many  of  the desirable
        features  of MF  resins.   Up  to 25% of  the melamine
        monomer in MF resins  is replaced by other  compounds that
        react  with  formaldehyde.    Compounds  that  form
        aminoplasts, such as  those containing  amino groups are
        preferred (e.g., urea  and substituted ureas, carboxylic
        acid  amides, toluenesulfonamides, and other reactive
        compounds).  Other additives such  as  colors, fillers,
        stabilizers, and lubricants are usually added at a  later
        stage of manufacture,  a practice  which  avoids handling
        and storing many grades of resin  syrup  and  also avoids
        contamination of the  syrup  reaction  kettle  with
        additives that are not required.

        The  F/M mol ratio is usually  about  2-3  for  molding
        compounds and about  3 for liquid casting resins.   For
        making  syrups to be  etherified as discussed belo.w,
                            -75-

-------
         higher mol ratios are frequently used, for example,  3.3
         for methylated resins,  and  5.8  for butylated resins.

         The initial product of  the  reaction  is always a  liquid
         syrup, which can be sold in this  form (with or without
         concentration) or further processed  and converted to  a
         dry powder, either filled  or  unfilled, for molding  or
         adhesive applications.

         No  information  is available  regarding the  relative
         importance of filled and  unfilled  powder manufacture
         although it is believed  that spray drying is favored  by
         process economics while  filler  impregnation (unfilled)
         gives a more acceptable  product.

7.2.1.2   Butylated MF manufacture.-

         Butylated MF resins are  hydrophobic,  soluble in organic
         solvents, and widely used  in  surface coatings such  as
         baking enamel.

         Formaldehyde, butanol,  melamine,  and catalyst are  all
         charged together to the  reactor at the beginning of each
         batch.

         The batch  is heated  to  the atmospheric boiling  point,
         about 204F.  Methylolation of  melamine and butylation
         of  me thylolme 1 amine take  place  more  or  less
         simultaneously, along with  some oligomer formation.  The
         vapors  are condensed in the  reflux condenser and  the
         subcooled condensate is  separated  into two layers  in  the
         decanter.   The  upper  layer   (79.9% wt, butanol)  is
         returned  to the  reactor.   The lower layer  (7.7% wt,
         butanol)  is stored for  butanol  recovery,  and the
                            -76-

-------
         withdrawal of this stream removes  water from  the  batch.
         Some  unreacted formaldehyde also leaves in this  stream.
         As  the  reaction proceeds the viscosity increases, and as
         the water is removed  the batch temperature rises  to
         about 230F in 5 hours.   Solids  content reaches about
         52-55%  (wt).

         When  the reaction has proceeded  to  the desired point,  a
         sample  is miscible with six volumes of mineral spirits.
         The rest of the water,  unreacted formaldehyde, and  some
         of  the  butanol are  removed by vacuum distillation.
         Pressure is reduced to  250 mm Hg or less and  this vacuum
         reduces the batch boiling temperature to about 190F
         slowing the reaction.   Water and butanol are  removed
         until the viscosity increases to the desired  value.  The
         batch is finished by  diluting with  xylene solvent,
         stirring, and filtering the cool  syrup as it is  pumped
         to  a  rundown tank for  final tests and adjustments of
         solids  content.  Storage  tanks  and drums are provided
         for the product group.
7.2.2    VOC  Emissions
         All significant emission rates and sources for  this
         product are shown  on  Table 7-II.  Figure  7-1 is  the
         schematic flowsheet for  this  product;  it includes the
         emission streams and their sources.

         The only  emission data  available are presented  here.
         They are for a process making  a butylated MF resin syrup
         rather  than for an MF resin syrup  or powder.  The equip-
         ment and flowsheet for these products are quite  similar
         but the emission data presented for butylated MF may not
         be  representative of the basic MF  resin industry.   The
                            -77-

-------
 TABLE 7-1I.- VOC EMISSIONS FROM BUTYLATED MELAMINE-FORMALDEHYDE
                      RESIN BY BATCH PROCESS
                                       Current
                      Uncontrolled     Practice   Well Controlled
Stream                #/1000# Resin  #/1000#Resin   #/1000#  Resin

[1]  Storage of Monomers,
     Alcohol, Solvents     0.10           0.10           0.04

[2]  Reactor                2.66           2.66           0.13

[3]  Blend (Thinning) Tank  0.05           0.05           0.01

Totals                     2.81           2.81           0.18
                               -78-

-------
process is  related to that of MF somewhat  in  the nature of
a co-polymer  of MF.  In the butylated  MF process, an ether
linkage (etherification) is brought about  by  reacting
butanol with  the N-methylol groups (maximum of six) formed
when formaldehyde is reacted with melamine.
There  are  such considerable differences  in  emission
components  that any attempt to relate  MF process emissions
to butylated  MF  process emissions  is of questionable
value.  Also  the  absence of a dryer in the  butylated
process is significant because it is a  large  potential
source of emissions.  The dryer  is  present in  MF
filled-powder manufacture  (filled and unfilled  powders
make up approximately 50% of the MF resin  sold).

The major  emission points of this process  are:

[1]  Liquid monomer  (and  comonomer)  and  solvent  storage
    tanks  (fixed roof)  -  Causes of emissions are  normal
    breathing  and filling.   Formaldehyde tanks -  37% or
    52% aqueous solution kept at 138F by internal  steam
    coils.  Emission streams contain  air drawn in the tank
    from atmosphere, formaldehyde and water vapor  from
    stored  solution  and small amounts of methanol  vapor
    (small percent  of  methanol allowed  by  formaldehyde
    specification).  Formaldehyde in  butanol  may be stored
    for use in the butylated MF  process.

    Butanol and xylene  (or similar organic solvent)  tanks
    will be present  for the butylated  MF process  and  will
    emit these substances,  respectively, along  with air
    drawn  in  from the  atmosphere.  Emission causes are
    breathing and filling.   All  of  the above storage
    emissions  are relatively small with butanol  emissions
                      -79-

-------
           the largest of the three  and  xylene and formaldehyde
           next, in that order.

       [2]  Reactor overhead vacuum system - Largest VOC emitting
           source in the plant.   Actual  flow  rates vary because
           process  is batch.  VOC  components are butanol  and
           formaldehyde diluted  with air  (approximate composition
           in wt% is - butanol,  55%;  formaldehyde, 5%; air,  40%).
           Emits  through vacuum  pump  (or  steam jet ejectors).
           Steam is obviously also  present if jet ejectors  are
           used.

       [3]  Blend tanks - Approximately  5% (wt) xylene solvent  (or
           other solvent used such as butanol) in air.  Vents
           from  blend (rundown)  tank,  which discharges blend to
           resin syrup storage tanks.

7.2.3  Applicable Control Systems

       The  following control technologies are  recommended  for  the
       emission  streams described  in  Section 7.2.2 and in  the
       schematic  flowsheet for  this product.  The  same stream
       numbering system is followed.

       [1]  Formaldehyde solution,  butanol,  and xylene storage
           tanks  -  Utilize pressure-equalizing, vapor-return
           lines to the tank cars or trucks to eliminate working
           losses from storage tank  filling (approximately 58% of
           total  potential storage  emissions).  Conservation
           vents will  also  be  required.   Since   they  would
           normally  be installed   for  economic  reasons,   no
           pollution control credit  is  given them.
                            -80-

-------
                           SECTION 8
                         NYLON 6 FIBER
8.1    INDUSTRY DESCRIPTION

8.1.1  General

       Nylon  is  the  common name  given  to any  of a group of
       commercially  important synthetic linear polyamides of  high
       molecular weight. Polyamides are synthetic  resins having
       recurring amide groups in the polymer chain;  these resins
       may be formed  into  fibers, bristles, moldings,  sheets, and
       coatings.  The U.S.  International Trade  Commission has
       divided the class of  polyamide fibers  into  two groups -
       nylon fibers  and aramid fibers based on the percentage of
       amide linkages attached directly to two aromatic rings.

       Nylons are identified by the number of carbon atoms  in the
       monomers used; hence  nylon 6 is a homopolymer of a six
       carbon compound - caprolactam.  Nylon  66  indicates that
       the polymer  is made from two monomers,  each having a
       six-carbon chain.   Nylon 66 was the first major  fiber made
       entirely  of  synthetic polymer.  Nylon  66  and  nylon 6
       accounted for  98% of all domestic nylon  fiber production
       in 1976.  Other commercial nylon fibers include  nylon  610,
       612, 11, 12 and Qiana nylon.  Less commercially  attractive
       nylons include nylon 3, 5, and 8.  Nylon  66  is  discussed
       more thoroughly in  Section 9 of this report.
                              -81-

-------
       today.  Nylon also exhibits elastic  properties;  it will
       return  to  its original  length after stretching  up to 8 %.
       This  characteristic  is used  advantageously  in
       manufacturing clothing  with  satisfactory dimensional
       stability.  Nylon is not  attacked by  insects, mildew, or
       perspiration.

       Differences between nylon 6 and nylon 66 are slight.  The
       principal  difference between the two is that nylon 6 has a
       lower  softening  and melting point.   The  minor property
       differences between nylon 6 and nylon  66 give one or the
       other the advantage  in  given  applications,  and  they
       compete in many applications (18) , (19 ) .
8.1.2  Nylon  6
       The primary market  for  nylon  6  is  in fibers  with
       applications in all  major  fiber markets, including
       carpeting, hoisery,  wearing  apparel, and tire  cord.   There
       is a much smaller market in  thermoplastics applications.
       High tenacity nylon  6  is used  in industrial applications,
       including fabrics, and  for  home furnishings.

       Most  domestic nylon  6 is manufactured  by the  "chip"
       process in which fiber spinning is  carried out  as a
       separate operation after  remelting the  "chips".   Two
       polymerization processes are  of industrial  importance -
       hydrolytic or water-catalyzed  polymerization  and  anionic
       or base-catalyzed polymerization.   The  water-catalyzed
       process  is the overwhelming  choice  for  fibers because it
       is more  suitable for large-scale operation and because it
       is easier to control.
                            -82-

-------
       General  consensus  in the industry is that nylon  6 develops
       by a reaction mechanism involving opening the  lactam ring
       by heat,  hydrolyzing by water, and chain growth  by  joining
       the exposed functional  groups by polycondensation (two
       polymer  chains  react and combine)  with elimination of
       water and with polyaddition (a molecule of monomer  adds on
       to a polymer chain) .   Special reagents  in  the reaction
       mix, such as acetic acid or amines, serve to  control  chain
       length.   The polymerization is an  equilibrium reaction
       with approximately 10% water extractable at completion.
       These are  lower molecular weight compounds,  including
       monomer  and oligomers.

       About 70% of all nylon 6 polymer is produced  by  continuous
       polymerization.   The subsequent chip extrusion,  extraction
       (to remove the  10%  water extractables remaining), and
       drying operations  are carried out normally on  a  continuous
       basis regardless of whether continuous or batch  polymeri-
       zation is used.   Emissions data per pound of  nylon  6  chips
       produced  are believed to be very similar for both the
       continuous and  batch manufacturing processes.   Future
       plants are expected to have approximately the  same 70/30%
       split between continuous and batch processing.

       Ten to twenty percent of nylon 6 production uses a method
       known as  "direct spinning" to make fibers.   The hot melt
       polymer  is vacuum-stripped to remove  unreacted monomers
       and oligomers before it is sent directly to spinning.
       Chip extrusion is  eliminated.

8.1.3  Production Levels  for Nylon and Aramid

       In 1976,  U.S.   production of  nylon and  aramid  fibers
       amounted  to 2,169 million pounds, a quantity  equal to 27%
                              -83-

-------
  of the total U.S.   man-made  fiber  production.   On a
  poundage basis, nylon ranked  second  of the  six most
  important man-made fibers  consumed  domestically.  Of the
  total  nylon and aramid fiber produced in 1976, nylon 66
  fiber  accounted for 1,360  million pounds (63%wt); nylon 6
  accounted for 667 million  pounds  (31%wt);  other types of
  nylon accounted for  26 million pounds (l%wt);  aramid
  fibers accounted for 23 million pounds (l%wt); and all
  types  of nylon and aramid  waste  accounted for 93 million
  pounds (4%wt).

  Data  concerning consumption  of nylon 66 and nylon 6  by end
  use are  not  available, but estimates in the percentage
  split  of major markets can be  made  from the amounts of
  production capacity designated for various products.  The
  following table presents  these estimated percentages for
  1976:

ESTIMATED CONSUMPTION OF NYLON 66  AND NYLON 6 BY END USE
        1976 (Percent)

Total Yarn and Staple
Total Yarn
Total Staple
Textile Yarn and Staple
Textile Yarn
Textile Staple
Carpet Yarn and Staple
Carpet Yarn
Carpet Staple
Industrial Yarn and Staple
Industrial Yarn
Industrial Staple
NYLON 66
67
70
61
79
78
100
60
60
60
76
78
45
NYLON 6
33
30
39
21
22
0
40
40
40
24
22
55
                         -84-

-------
       Nylon  6  demand is projected to grow  from  652  MM#/Yr in
       1976 to 880 #MM/Yr in 1982, an average  rate  of 5.1%/Yr.
       As  of  October 1977 there were eleven  U.S.  producers of
       nylon  6  fiber (yarn, staple,  and  tow)  with  a total of
       fourteen plants and total  nylon 6 production  capacity of
       919 million  pounds  per  year.   (Nylon  6  capacity
       represented 33% of  total  nylon  capacity  and nylon 66
       accounts  for 64%.   Monofilaments  and  other  nylons
       accounting for the remainder, or approximately 3%.   Three
       of  the eleven manufacturers,  Allied,  Akzona, and  Dow
       Badische, have 84% of the  total spinning  capacity.

       The capacity  data given in Table 8-1 refer  to spinning
       capacity, not polymerization capacity.   Only  five  of the
       manufacturers listed  (Akzona,  Allied,  Dow Badische,
       Firestone,  and  Rohm  and  Haas)  have  polymerization
       capability.  The others  purchase merchant  chip  for their
       spinning operations (18).

8.2    NYLON  6 MANUFACTURE BY THE  CONTINUOUS CHIP  PROCESS

8.2.1  Process Description

       This process uses a tower  or vertical tube  reactor, strand
       die pelletization,  a  continous  countercurrent  chip
       extraction  column, and  a recirculating nitrogen  drying
       system.  Figure 8-1 describes the process schematically.

       Caprolactam monomer is stored with agitation  and  under a
       nitrogen blanket at approximately 175F.   It is  metered
       continuously into the reactor along with  catalyst (water),
       the chain terminating agent  (acetic  acid),  and  additives
       such as delusterants and antistatic agents.  The reactants
       flow  down through  the  reactor  at  approximately  500F
                              -85-

-------
                                                    TABLE 8-1.- NYLON 6 - YARN, STAPLE, AND TOW
              PRODUCING COMPANY AND
 I
00
                ANNUAL CAPACITY AS OF OCTOBER 1977
                       (Millions of Pounds)
 CONTINUOUS FILAMENT YARN                          STAPLE AND TOW
TEXTILE  CARPET  INDUSTRIAL                 TEXTILE  CARPET  INDUSTRIAL   TOTAL
                                                 36
AKZONA  INCORPORATED
  American Enka Company,
   division Central,  SC
  Enka, North  Carolina               X
  Lowland, Tennessee                 X

ALLIED  CHEMICAL CORP.
  Fibers Division
   Columbia, SC
   Hopewell, Virginia

CAMAC CORPORATION
  Bristol, Virginia                  4
COURTAULDS NORTH AMERICA,  INC.
(100% owned subsidiary of
Courtaulds, Limited (United
Kingdom)
  Le Hoyne (Mobile),  Alabama         5
DOW BADISCHE COMPANY
(jointly owned by  Dow Chemical
U.S.A.  and BASF AG [Federal
Republic of Germany))
  Anderson, South  Carolina         23
THE FIRESTONE  TIRE &  RUBBER CO.
  Firestone Synthetic Fibers
   Company, division
    Hopewell, Virginia               0
GULFORD MILLS, INC.
  Gainesville Division
   Gainesville, Georgia              4
HANOVER MILLS, INC.
(100% owned subsidiary of Falk
Fibers  & Fabrics,  Inc.)
  Yanceyville, North Carolina        4
ROHM AND HAAS CO.
 Fibers Division
  Fayetteville, NC                   0
STAR FIBERS, INC.
(100% owned subsidiary of Star
Textile and Research, Inc. a
subsidiary of Dayco Corporation)
  Edgefield, South Carolina          0
SUNBURST YARNS, INC.
(100% owned subsidiary of Tulex
Corporation)
  Afton, Virginia                    1

TOTAL                             115
                                                          X
                                                          X
                                                          X
                                                         106
                                                          X
                                                         105
                                                          55



                                                           0


                                                           0



                                                           0


                                                          50
                                                           0

                                                         322
                      X
                     64
                     48


                      0



                      0


                      0
                      0

                    112
       X

      l8~5

        0
X
8
       55



        0


        0



        0


        0




       25
000

0     358        12
 I3T




. 309

  10
         135



          48


           4



           4


          50




          25



           1

         919

-------
TO

FLARE

\2\


Q











. . REFLUX
V 	 \ 	 	 CONDENSER
y^N T^A WASTE WATER
(^ ( ) 	 1 r~i TO TREATMENT
I ^V ^
t VENTN
1 1 C;DDVI
VENT ^ CONDENSER
TANK J
TO 1 ACETIC ACID>-J
RECOVERY - . ',



TO
1

VAPOR 	 iv
RETURN r

1
00
\ B


WH i c*n j  ^
ADDITIVES V-

FLARE
	 1 1

02
/!
 HOT H20
-X
p- 




















\
s
Jk


s.










REAC
(TUBE




^M


TOR
TYPE)
































W








DOWTHERM
-H






\^~~-^
^~^T-^ UNDERWATER
CAPROLACTAM
MONOMER
STORAGE

f lAlfl SYSTEM* PELLETIZER

EXTRUDER
1
QUENCH BATH
I


ET CHIPS f










H20
T

^-
jU




















N2 COOLER
sS



CHIP
EXTRACTION
COLUMN





re
.
*FOR DIRECT SPINNING USE BRINKS










NTRIFUGE

1

-J
n nvn













DEMISTER (WET FILTER) & FLARE








PRODUCT










*
I
WASTE WATER
TO TREATMENT

CHIP
DRYER


II U C1 * T C1 O


i TO SPINNING

(CHIPS)
TO STORAGE
FEED REACT
RECOVERY
FINISH
Figure 8-1.- Nylon 6 - Continuous chip process.

-------
during a residence time of approximately 18  hours.  Under
these conditions the polymer  approaches equilibrium.  The
molten polymer flowing out of the bottom of  the  reactor is
extruded, water quenched,  and pelletized to  a  proper
physical form for  extraction of residual monomer  and
oligomer.  The top  of the  reactor contains  a  boiling
polymerization reaction  mixture.   The  reflux  condenser
serves to return caprolactam  and other vaporized reactants
to the  reactor, while excess water  taken overhead is
removed.

Oligomer and  unreacted monomers are removed  from  the
chips, by continuous countercurrent extraction with water,
at approximately 200F.   The  extraction process reduces
the content of oligmers plus  monomers (mainly caprolactom)
from 10% to 3%, yielding a product with approximately  0.5%
residual monomer.   The  chips  are  centrifuged  next,  but
they  still contain  10 to 12% internal  moisture.  The
moisture remaining  in  the chips is removed in a
continuous, circulating, hot-nitrogen dryer.  The cool wet
nitrogen exhausted from  the  dryer  is cooled further to
condense out the  water, and then  it  is compressed,
reheated, and returned to  the dryer.  The dried nylon
chips are transferred to silo storage for subsequent sale
or remelt and  spinning.

Several variations of  the process  described above exist
(20^) , (2) .  They use  different  types of reactors, chip
extraction  equipment,  and/or  dryers.   Examples of such
variations are:

o  Using three, stirred-tank reactors  in series (one
   plant).
                       -88-

-------
       o   Using  stirred tanks  in  series  rather  than
          countercurrent extraction.
       o  Using  vacuum drying instead of  inert gas.
       o  Using a thin-film evaporator  for   monomer/ol igmer
          removal when direct spinning is carried out.
8.2.2  VOC Emissions
       All significant  emission  rates and  sources  for  this
       product  are shown on Table 8-II.   The schematic  flowsheet
       (Figure  8-1) for  the product includes the emission streams
       and their  sources, and the same stream  number  is  used for
       a given  stream throughout these discussions.  Nylon 6 chip
       dryer  and  storage have not  been included because  no VOC
       emissions were reported from these sources.   Emission
       figures include both  continuous  and batch  process
       emissions  -  prorated according to  the reported  nylon 6
       production poundage.  The estimated U.S. production  split
       was 70%  continuous and 30% batch.  VOC  emissions  from the
       two types  of processes are believed to  be nearly  equal on
       a per  pound of nylon 6 produced basis.

       The largest emissions from  nylon  6  manufacturing  plants
       actually  come from the  fiber  spinning  facilities
       downstream from the chip manufacturing  facilities
       described  here.   However,  these  spinning emissions are
       outside  the scope of this study.   Conversely, this  study
       does include spinning emissions when evolved from  "direct
       spinning", where  fibers are spun directly from the reactor
       hot melt without  a separate or intermediate  chip-making
       step.  The estimates are that 10 to  20% of U.S.   nylon 6
       fibers are manufactured by "direct spinning".

       A description of  the emission streams follows:
                              -89-

-------
TABLE 8-1I.- VOC EMISSIONS FROM NYLON 6 MANUFACTURE BY THE CONTINUOUS
                            CHIP PROCESS
                                       Current
                      Uncontrolled     Practice   Well Controlled
Stream                f/lOOOft Resin  #/1000#Resin   #/1000# Resin

[1]  Caprolactam Monomer
      Storage              0.01           0.01          nil

[2]  Polymerization
      Reactor              0.02           0.01          nil

[3]  Extrusion/Pelletizing  0.65           0.22          nil
      Sections (includes
      spinning if direct
      spinning)

Totals                     0.68           0.24          nil
                              -90-

-------
[1]  Caprolactam monomer storage  tanks - This stream emits
    vapor with blanket nitrogen  from the fixed roof tanks
    or  from cylinders storing  molten caprolactam.  Normal
    breathing, filling, and  withdrawing of monomer are the
    emission causes.  Caprolactam  is kept molten  by water
    heated  internal coils  and  agitators or mixers are
    generally provided.  Internal  pressure in the tanks  is
    either atmospheric or slightly positive and a nitrogen
    blanket is required.   Storage  temperature normally  is
    160 to  170C.  The  same  tanks  can serve  batch and
    continuous processes, if both  are present.

[2]  Polymerization reactor - This  stream emits caprolactam
    vapor diluted by blanket nitrogen and traces  of water
    vapor which taken overhead from  the polymerization
    reactor.  This reactor  typically  is a continuous  UK
    vertical  tube vessel  heated  by Dowtherm  in  the
    jackets.  The stream normally  passes through  a reflux
    condenser, a vapor condenser, and  a K.O. drum,  from
    which it is emitted directly.

    In  the  less common  batch process  case, the  reactor
    usually is an autoclave  with an overhead condenser.  A
    vacuum is drawn during part  of the reaction cycle and
    part of  the cycle proceeds  as a  closed  system  at
    elevated  pressures.  The stream  components  are the
    same as  for continuous processing but  in  somewhat
    different proportions.

[3]  Extrusion/pelletizing sections  -  This  stream  is
    potentially the largest  VOC  emission source from a
    nylon 6 plant.  Molten nylon 6 polymer from the bottom
    of  the reactor is extruded through a die to form  heavy
                      -91-

-------
           strands which are quenched  in  water,  and pelletized.
           Pellets  are  slurried  with  water  for  further
           processing. Vapors are produced  by  the extrusion,
           quenching, and pelletizing  operations  and normally are
           collected  by hoods.   Steam or  a water  spray  is
           commonly added to the  exhaust  vapor stream to prevent
           crystallization.
           The  stream is composed  of  caprolactam  and water  vapors
           in  a large volume of air.   These  operations are
           usually continuous and this emission  is essentially
           unaffected by the type  of  upstream process  (batch or
           continuous).   Additional  caprolactam  emissions are
           generated by the  direct spinning process and included
           in  this stream, but direct  spinning is  only used for
           an  estimated 10 to 20%  of  production.

8.2.3  Applicable Control Systems

       The  following control technologies are recommended for the
       emission streams that are  described  in Section  8.2.2 and
       shown on the schematic flowsheet.

       [1]  Caprolactam monomer  storage  tanks -  This monomer
           requires  a nitrogen blanket  on  the  storage  tanks
           regardless of VOC emission  considerations.   A pressure
           equalizing vapor return  line to  the  tank cars  or
           trucks should be  used  to eliminate working losses from
           storage  tank filling.  This  represents 58% of the
           total potential  storage  losses or emissions.  The
           inert gas blanket system should  exhaust tank vapors,
           on  pressure control,  to a  flare.  A minimum  reduction
           of 90% in the remaining VOC emissions  from  breathing
           is  assumed for  either case.  Any  tank or vessel
           pressure relief valves utilized for  either emission
                             -92-

-------
   control or safety should  also be tied into a flare.
[2]  Polymerization  reactor  -  Use a spray condenser to
    wash  emission  stream and  follow it by  bubbling
    through a seal pot.  The  result is an extremely low
    concentration of caprolactam  vapor in  nitrogen.
    Route  the  resulting  stream to the flare.   (If no
    flare  is  available,  atmospheric emission would be
    acceptable  because  the  condenser effectiveness is
    high and the resulting VOC  emission level is low).

[3]   Extrusion/pelletizing sections - All non-direct
    spinning continuous  and  batch processes should use
    the newly  demonstrated  "underwater pel le t ization
    system"  to  eliminate  nearly all VOC fumes.  This
    system also has  noise reduction  and process economics
    advantages.   For direct spinning, hoods are  to be
    used to collect  extrusion emissions and the take-off
    exhaust  from the spinning room air recirculation
    system.  Both should be sent to  wet-filter demisters
    then to flare.
                     -93-

-------
                            SECTION 9
                        NYLON  66 FIBER
9.1    INDUSTRY DESCRIPTION

       Nylons (polyamides) are  identified by the number of carbon
       atoms in the monomers  from which the particular product is
       synthesized.   Hence  nylon 66  is  a  copolymer of  the  two
       six-carbon  compounds,  adipic acid and hexamethylene
       diamine.  Together  nylon 66 and nylon 6 accounted  for  98%
       of the domestic nylon  fiber produced in 1976.  The primary
       market for nylon 66 is in fibers, with major applications
       in carpeting, hoisery, wearing  apparel, and tires.  A much
       smaller market exists  in thermoplastics applications.

       U.S. production of  nylon 66 was 1375 MM Ibs in 1976.   The
       projected growth rate  for U.S.  consumption for 1976-1981
       is 4.2% per year.

       The significant domestic producers of  nylon 66 are  shown
       on Table 9-1.  Du Pont and Monsanto  have 89%  (wt) of  the
       total capacity of the  six manufacturers listed (18).

9.2    BATCH OR CONTINUOUS POLYCONDENSATION OF NYLON 66

9.2.1  Process Description

       The commercial process for manufacturing nylon 66 starts
       with  the production  of a water solution  of  nylon salt
                               -94-

-------
                                                 TABLE 9-1.-  NYLON 66 FIBERS - PRODUCERS
 I
vo
     PRODUCING COMPANY AND
        PLANT LOCATION

     CHEVRON  CHEMICAL COMPANY
      OF PUERTO RICO
     (100%  owned subsidiary of
     Standard Oil  of  California)
       Guayama,  Puerto Rico

     E.I.  DU  PONT  DE  NEMOURS &
      COMPANY,  INC.
      Textile Fibers  Department
       Camden,  South  Carolina
       Chatanooga,  Tennessee
       Martinsville,  Virginia
       Richmond, Virginia
       Waynesboro,  Virginia
FIBER INDUSTRIES, INC.
(62.5% owned by Celanese Corp.
and 37.5% owned by ICI, Ltd.
(United Kingdom)
  Greenville, South Carolina
  Shelby, North Carolina
    KAYSER-ROTH  CORPORATION
     Yarn  Processing  Division
      Creedmoor,  North  Carolina
                                                     NYLON 66 - YARN, STAPLE AND TOW
                                                ANNUAL CAPACITY AS OF SEPTEMBER 1977
                                                       (Millions of Pounds)
                                    CONTINUOUS FILAMENT YARN
                                Textile    Carpet    Industrial
    MONSANTO
     Monsanto  Textiles  Company
       Decatur,  Alabama
       Greenwood,  South  Carolina
       Pensacola,  Florida
    WELLMAN,  INC.
     Wellraan  Industries,  Ir.c.  sub.,
     Man-Made  Fiber  Division
      Johnsonville,  South  Carolina

    TOTAL
                                   50
                                   X
                                   X
                                   X
                                       2AQ
                                   10
                                   X
                                   X
                                   94
 21
 X
344
 X
 X

To"
 X

 X

TT~O
                                                             ~
 X
115
                                  STAPLE AND TOW
                          Textile    Carpet    Industrial
                                                                         28
                                                                             0
                             X
                             X
                             16
                                       X
                                       X

                                      210
                                       X
                                       X
                                      ~55
                                  394
475
385
                             44
                           X

                          T7~5




                           40

                          480
                                                      Total
                                                                                                                 71
                                                      1,098
                                                                     10
                                                                                                0

                                                                                               10
                                                                                                                    494
                                                                    40
1,788

-------
       (hexamethylenediammonium-adipate).   The process described
       is shown on  Figure 9-1.  The polymerization reaction  takes
       place in the following three stages:

         o  Evaporation  of part of the  water with some  poly-
            condensation.
         o  Polycondensation with removal  of all but  a  small
            quantity of water.
         o  Polycondensation  to the desired degree and removal of
            the residual quantity of water.   Unlike the nylon 6
            reaction, which  is  of the equilibrium type,  this
            reaction goes to  completion.

         The nylon  66 process  described  here can be  entirely
         continuous and make  either chips, flakes, or  pellets for
         later spinning.  Also  it can  be  combined with direct
         spinning  to produce  yarn, staple, or  tow.   The current
         trend  appears to be  toward direct spinning.  Continuous
         nylon salt  preparation may be  integrated with  batch
         Polycondensation,  in which case either chips,  flakes, or
         pellets must be made.  The diagram depicts all of  these
         operations,  but  the  process as built would have separate
         trains or  items of equipment and  control for batch and
         continuous operations (22) , (23 ) .

9.2.1.1  Nylon  salt production.-

         Adipic acid is  dissolved in  hot water at 40C  in a
         jacketed,  agitated vessel in a nitrogen atmosphere, and
         HMD (hexamethylene-diamine)   is  dissolved in another.
         The two solutions  are  brought together  in a jacketed,
         agitated  reactor and nylon salt (hexamethylenediammonium
         adipate)  is formed.  This aqueous solution of nylon salt
         is transferred to  a  surge vessel and  stored for  later
         use in the nylon 66  polycondensation reactor.
                              -96-

-------
0
                                                                    H20<,
VAPOR
RETURN
 I
vo
J f[2]
"" ~& SPRAY
CONDENSER

I CUTTEB
WASTE f~"\
TREATING ^
ATION / h^
/AIR rf


12]

_
WAS1
_ NYL(
                                                                                                          TO
                                                                                                          CATALYTIC
                                                                                                          INCINERATOR
                                                                                       BLEND/DRYER


                                                                                          [2]j
                                                                                                       FLAKES,OR PELLETS
                                            OVERHEAD
                                          CONDENSER
                                     (HEAT RECOVERY
                                                                                                     [3]
                                                                                                               CONTINUOUS
                                                                                                                FILAMENT
                                                                                                                YARN
                                                                                                                       FIBER
                                                                                                                 TOW
                                                                                                  MELT(DIRECT)
                                                                                                   SPINNING
                 FEED
                              REACT
                                                   REACT
                                                                                  RECOVERY
                                                                                                               FINISH
                   Figure 9-1.- Nylon  66  by  batch or continuous  polycondensation.

-------
9.2.1.2  Nylon salt  purification and concentration.-

         The 48% nylon  salt  solution  is concentrated  in an
         evaporator to a  concentration of 65%.  After passing
         through a  clarifier (typically  a cartridge  type) to
         remove  the  trace  of  solid,  it  is  ready  for
         polycondensation.

         The evaporator can be run for either  batch or  continuous
         operation,  and generally it will be operated in the  same
         mode as  the polycondensation reactor.

9.2.1.3  Polycondensation  by a batch process.-

         The operation typically requires a cycle of five hours
         consisting  of the following steps:

         A.   One  and one-half  hour  charging and heating of the
             65%  nylon salt solution from the  surge  or day  tank
             to 230C; at  the  same time, the pressure is built up
             to 250  psig.  Viscosity stabilizer is added.

         B.   One  hour heating, up to 245C, while the pressure is
             maintained  at  250 psig.   During   this  time,
             delusterant,  stabilizer, and other  ingredients are
             added.

         C.   One  and one-half  hour heating with gradual release
             of pressure  from  250 to 0 psig at  270C.

         D.   One-half hour heating at 270-275C with pressure
             still at 0 psig.

         E.   One-half hour discharging,  with some  nitrogen
             pressure utilized to facilitate discharge.

                              -98-

-------
         Two jacketed  reactors, each provided with an agitator
         and nitrogen  blanketing are normally used (only  one  is
         shown in the  diagram).

9.2.1.4  Polycondensation  by  a  continuous tank process.-

         Although only one reactor  is shown on the schematic, the
         two stage polycondensation described here is more common
         than single  stage.

         The nylon salt solution from  the  surge or day  tank  is
         pressurized  to 290 psig, preheated to 530F, and charged
         to a first-stage tank reactor, which is regulated  at
         530F and 265 psig.  Additives, prepared separately  in
         small vessels, are  added under nitrogen pressure.   In
         the normally  agitated first-stage  reactor,  the  major
         part of  the  water  is evaporated  and a part of the
         adipate is polycondensed to a  low degree.  This material
         is then pumped and sprayed into a  second-stage  reactor
         together with a larger quantity of liquor re-circulated
         from that reactor.   A  stream of hot nitrogen flows
         countercurrent to the  liquid spray and carries away the
         water vapor  in a  manner preventing congelation of the
         polyamide.  Nylon 66 formed in this reactor, still
         containing some water, is  partially recirculated and the
         remainder is  conveyed  to a finisher where the residual
         water is removed  and the molecular weight is increased
         to the desired degree.  The mass in the second-stage
         reactor is viscous and requires agitation.

         Typical additives used at  this stage are acetic  acid  as
         a viscosity  stabilizer  and  titanium dioxide as  a
         delusterant.
                             -99-

-------
         Other additives may include  phenylphosphonate  or
         kaolinite as a nucleating agents,  various  substances
         as stabilizing agents, and  glycol  as an anti-static
         agent.   The total amount of additives  often comes to
         about 2-3% (wt) of the nylon  66 polymerized.   Some
         additives may be added to the finished  nylon 66 after
         the  polycondensation step, but viscosity stabilizer and
         delusterant  should  be  added  only  during  the
         polycondensation.

9.2.1.5  Formation of nylon 66  chips.-

         Nylon 66  may be used  in molten  condition (direct
         spinning process)  for processing  into fiber, or chips
         may  be  formed  and later remelted for spinning  (chip-
         remelt, spinning process).  Where  nylon  66 is produced
         for  plastic use, it  must be made in a pellet  form.

         The  process described here,  with  minor  modifications,
         can  be used to produce either nylon 66 chips,  flakes, or
         cylindrical pellets. Molten nylon  66 from the finisher
         is charged  to a casting wheel (chilled with cold  water),
         and  solidified and quenched by water  sprays,  then  cooled
         and  dried with a flow of inert gas.   The nylon  ribbon
         that forms  is loosened from the wheel  by a scraper and
         fed  to a cutter which reduces  it  to small chips or
         flakes.   These fall  into the blend/dryer for  further
         drying and  an inert  gas purge is taken to the catalytic
         incinerator.  The  chips or  flakes  go to storage for
         shipment  or later remelt  spinning on site.,   Heat
         treatment in the solid state increases the molecular
         weight and  melt viscosity for certain desired  blends,
         such as those for plastic resins.
                             -100-

-------
9.2.1.6  Fiber spinning.-
         Fiber spinning is  accomplished either directly  from  the
         hot melt (direct spinning) or by first remelting  chips
         or pellets made previously and stored.  Direct  spinning
         is  only practiced  in  conjunction  with  continuous
         polycondensation.

         Nylon 66 and  nylon 6 are quite similar in their melt
         spinning  and drawing  capabilities.  However, VOC
         emissions from direct spinning is less  for nylon 66 than
         for  nylon  6 manufacture because no residual  monomer
         remains in nylon 66 at this  stage.   The  absence  of
         residual  monomer in nylon 66  reduces fuming at  the
         spinneret.   Minor  handling differences result between
         the  two because of nylon 66's higher melting point  and
         lower thermal stability.
9.2.2    VOC  Emissions
         All  significant emission rates and  sources  for this
         product are  shown on  Table 9-II.   The schematic
         flowsheet,  Figure 9-1, includes the  emission streams  and
         their sources.

         The  plants studied employ a  spectrum of  technology
         (improved  over 40  years) and make a  wide  variety  of
         products such that  exact defining of (emission) sources
         and  compositions is  impossible  and arriving at  a
         representative  model is difficult.  The differences  in
         common  source  emissions between batch and continuous
         operations are  minor in composition but significant  in
         amount.
                             -101-

-------
o
NJ
I
    TABLE 9-II.-   VOC  EMISSIONS  FROM NYLON 66 FIBER - BATCH OR CONTINUOUS PROCESS


                                   Uncontrolled   Current Practice  Well Controlled
        Stream                     t/1000t Resin   #/1000# Resin     #/1000# Resin

    [1]  Nylon salt  preparation
        Section                       0.77             0.44             0.12

    [2]  Polycondensation  Section      2.10             0.29             0.01

    [3]  Fiber Spinning  Section        0.76             0.17             0.08

        Totals                        3.63             0.90             0.21

-------
It is possible  that a significant  portion of nylon 66
plant emissions  also  fall  into  the  category  of
particulates  (primarily as aerosols).  The extent  of such
emissions  and  the affect of particulate  controls  and
regulations  in  reducing VOC emissions  should be  given
further  consideration  in a detailed study.

A description of  the designated emission  streams follows:

[1]  Nylon salt preparation section - The  significant VOC
    emissions come  from the evaporators which  concentrate
    the  aqueous  solution of nylon salt  prepared and  stored
    upstream  of  the  evaporators.    Evaporation
    (concentration)  can be either batch or continuous.  In
    either case,  the  stream will be composed  largely of
    water  vapor  (99+%  by  wt)  with  small  amounts  of
    hexamethylene  diamine, ammonia, and C02  and with
    traces of hexamethylene imine and cyclopentanone.  The
    temperature  (before control)  will typically be 212F.

    Monomer storage  losses which could  be  included here
    were reported to be  negligible.   Adipic acid is
    supplied as  a powdered crystalline  solid and is
    typically dissolved in water in a closed,  N2
    blanketed dissolver vessel.  The hexamethylene diamine
    storage tanks  are  inert gas blanketed and  have  vapor
    displacement  lines back to the shipping  tank car.

[2]  Polycondensation section - The  polycondensation VOC
    emissions are  primarily those accompanying  the  water
    vapor exhausted  overhead from  the  polycondensation
    reactors. They  can be from either  batch or continuous
    operations.   This  is potentially the  largest  nylon 66
    VOC  emission  source.  Although the  relative quantities

                      -103-

-------
   will  vary  somewhat,  the composition of  the  exhaust
   stream  is  similar with either type of  operation  -
   typically water  vapor (99+% by wt water  of  solution
   and  of polymerization),  hexamethylene diamine,
   ammonia, and CC^1  and traces of volatile,  water-
   soluble, ingredient impurities (i.e.  hexamethylene
   imine, and cyclopentanone) .  Temperature  is  212F or
   somewhat above depending on the pressure  used.

   This  stream  also includes  the  exhaust from  the
   finisher and the  blend/dryer.  The  finisher completes
   the water  removal  by  an  inert  gas purge  and  the
   composition is largely  nitrogen, typically 95+%  (by
   wt) , 4 to 5% by  wt water vapor, and small amounts of
   hexamethylene  diamine  and  cyclo,pentanone_.   The
   blend/dryer (for  chip or flake processing) exhaust has
   a  composition similar to that for  the finisher  (blend/
   dryer data  were commonly included  in the  fiber
   spinning  exhaust data received  and appear to be
   relatively small) .

[3]  Fiber spinning section -  This stream,  the  second
   largest potential  nylon  66  VOC  emission  source,
   includes both emissions from direct  (melt) spinning of
   filament yarn and  from  the casting  and blend-drying of
   nylon 66 made into chips, flakes, or pellets.  In  the
   latter  case,  the fiber spinning is done later  in a
   separate step when the  chips are remelted.  This  step
   could  be  done either at the  same or at a  separate
   plant location,  and the related VOC  emissions for  this
   step are not included here.  Direct spinning  is  only
   used  with  continuous polymerization, but  indirect
   spinning via chips, flakes, or pellets can use  either
   batch or continuous polymerization.
                    -104-

-------
       The VOC  exhausted  in direct  spinning  is composed,
       primarily  of small  amounts of  oil  based  finishes
       (mineral/vegetable oils applied  to the  fiber  in  the
       process to provide lubrication and static suppression)  and
       hexamethylene diamine  in  water vapor.

       In the case where chips,  flakes, or pellets  are  made,  the
       composition is small  amounts of hexamethylene  diamine  and
       cyclopentanone  in water vapor  and inert gas (air  or
       nitrogen).

9.2.3  Applicable Control Systems

       The following control  technologies are recommended  for the
       emission  streams described in Section  9.2.2 and  on  the
       schematic flowsheet  for this product.  The  same  stream
       numbering  system is followed  here.  VOC reduction
       efficiencies  given are based on calculated  values from
       reporting producers and on estimates.

       [1]  Nylon salt preparation section - Send overhead  vapors
           from  the evaporator to a spray  condenser  using water
           as a  condensing medium.  VOC reduction  efficiency is
           approximately 85%.  (No  credit was given for  the
           condensation occuring in the preheat  exchanger, a unit
           which would be justified on  the basis  of process
           economics) . The HMD storage tank  would  have an inert
           gas blanket system with vapor displacement back to the
           tank  car for unloading.

       [2]  Polycondensation  section - Send  overhead  vapors from
           the  polycondensation reactor  to a  spray condenser
           using water as a condensing medium.   VOC  reduction
           efficiency is approximately 95%.   (Typically heat
                            -105-

-------
    recovery  and  condensation occur here which  involve
    preheat of the reactor feed stream).
    No pollution control credit was given because of  the
    process  economics  justification.  The  remaining
    non-condensibles from the spray condenser would  be
    sent  to  the catalytic incinerator. VOC  reduction
    efficiency is  approximately 90% for  this operation.

    Pass  the  finisher exhaust through a vent condenser
    (95% efficiency)  and then to the catalytic incinerator
    using platinum catalyst.  90% reduction efficiency  is
    assumed for the latter. The blend/dryer exhaust will
    go  to the  catalytic  incinerator, again  with  a
    reduction efficiency of 90%.

[3]  Fiber spinning  section -  Send this stream to  a
    catalytic oxidizer  using a platinum catalyst.   VOC
    reduction efficiency is approximately 90%.  (Demisters
    often will be used  for particulate  or aerosol
    control).
                     -106-

-------
                          SECTION 10
             PHENOL-FORMALDEHYDE (PHENOLIC) RESINS
10.1  INDUSTRY DESCRIPTION

      Phenol-formaldehyde or phenolic  resins are condensation
      products of phenol with formaldehyde.  They are produced  in
      the  largest quantities of  any thermosetting resins and are
      considered a work-horse of the plastics  industry.   They are
      used primarily for plywood and fiberglass lamination, for
      insulation, varnishes,  industrial laminates,  binders,
      electrical devices  and components, and for appliance
      housings.  They  were  the first synthetic  thermosetting
      polymer discovered and were trademarked  early as "Bakelite"
      in reference to the discoverer,  Dr. Leo  Baekland.

      "Resols" and "novolacs" are the  two main  types of phenolic
      resin made. ResolLs are most often made as an aqueous syrup
      in a one step process.   Another common  "resol"  form  is
      varnish, where the  resin is dissolved  in  an  alcohol  or
      other organic solvent.  Novolacs are most commonly made  in
      the   form  of molding powders in a  two step process.
      Equipment for the  two processes is similar  through the
      polymerization reaction.

      Production  of  phenolic resins  was 1660 MM Ibs for 1977.
      The  projected growth  rate for U.S.  consumption  for the
      period of 1977-1982 is 3.5 to 4.5% per year (24) ,(25) .
                             -107-

-------
      Approximately 60 manufacturers are known to produce
      phenolic  resins in the U.S.  These producers  are shown  in
      Table 7-1,  Melaraine-Formaldehyde Resins.

10.2   MANUFACTURE OF PHENOL-FORMALDEHYDE (PHENOLIC)  RESINS

10.2.1 Process  Description

       The two  processes described here are  both  simple batch
       processes  and together are believed to represent more  than
       75% of  the total phenolic  resin production  in the  U.S.
       Figure  10-1  shows a  schematic for both  processes.  The
       resol process is considered a one-step process (the  curing
       is done  by heat only, and  there is no  requirement for a
       second  addition of cross-linking reagent)  The reaction
       uses a base catalyst.   It is  used  most  often  to make
       either a concentrated aqueous syrup or a varnish (resin  in
       an organic  alcohol  solution).   The novolac process
       discussed  in this section is considered a  two-step process
       (the curing is done by adding a curing agent  that requires
       a separate step) using an acidic catalyst,  and it is  used
       normally to make a filled powder for  compression molding
       (iZ)' (!_>' (M)-

       A. One Step Process - Syrup or Varnish -

          The following operating steps are  carried  out in  this
          batch process.  One batch cycle normally takes up  to 8
          hours.

          1. Charge  liquid  phenol,  37  or 50%  aqueous
            formaldehyde solution, and aqueous sodium hydroxide
            catalyst to the reactor.
                             -108-

-------
                                                                                      TO INCINERATOR
O
vo
                     ORGANIC SOLVENTS
                     STORAGE (SEPARATE
                     TANKS AS SHOWN,
                     TYPICALLY FOR
                     HETHANOL, ETHANOL,
                     & BUTANOL)
 RIBBON
BLENDER
                                                                              SYRUP, VARNISH,  OR MOLDING POWDER
                                                                              CAN  BE MADE BY PROCESSES SHOWN
                                                                                    HOLDING POWDER
                                                                                        PACKAGING
                                                                          PELLETIZER
                     FEED
                                             REACT
                                                                         RECOVERY/FINISH
            Figure  1C-1.-  Phenol-formaldehyde  resr.n  using  one-step or two-step processes

-------
   2.  Heat  the mixture to the desired  reaction temperature
      under agitation and allow it to  reflux under vacuum.
      Temperature is typically 140-210F.  Overheating
      from  the highly exothermic reaction  is prevented by
      utilization of internal cooling  coils.
   3.  Monitor the  reaction progress by  sampling  the
      reactor contents for viscosity and/or gel  time (set
      up time).
   4.  Neutralize  the mixture with  an  acid.   Formic,
      acetic, phosphoric, and sulfuric acids are  commonly
      used.
   5.  Concentrate the syrup by water evaporation under a
      vacuum to  the concentration desired.
   6.  Cool  (this must be done quickly),  filter,  and  store
      as a  concentrated syrup  product (50%  solids,
      normally) .  If the product is to be held  for  later
      use,  stabilizers  often must be used  to prevent
      premature  curing.
   7.  Alternately, if a  varnish is to be made,  complete
      the dehydration  step, add  solvent  (usually an
      alcohol such as methanol)  cool, filter,  and  store
      the varnish product.

B. Two Step Process - Molding Powder-

   The following operating steps are carried out  in  batch
   operation.

   1.  Liquid phenol is charged to the  reactor and heated.
      Acidic catalyst (e.g., oxalic acid) and surfactant
      are added.
   2.  When  reaction temperature is reached (approximately
      220F) formaldehyde solution addition is  begun  and
      continued  over a period of several  hours.
                      -110-

-------
   2.  Heat  the mixture to the desired  reaction  temperature
      under agitation and allow it to  reflux  under vacuum.
      Temperature is typically 140-210F.  Overheating
      from  the highly exothermic reaction  is  prevented by
      utilization of internal cooling  coils.
   3.  Monitor the  reaction progress by  sampling  the
      reactor contents for viscosity and/or gel time (set
      up time).
   4.  Neutralize  the mixture with  an  acid.  Formic,
      acetic, phosphoric, and sulfuric acids  are commonly
      used.
   5.  Concentrate the syrup by water  evaporation under a
      vacuum to  the concentration desired.
   6.  Cool  (this must be done quickly),  filter, and  store
      as a  concentrated syrup  product (50%  solids,
      normally) .  If the product is to be held for  later
      use,  stabilizers  often must be used to prevent
      premature  curing.
   7.  Alternately, if a  varnish is to be made,  complete
      the dehydration  step, add  solvent  (usually an
      alcohol such as methanol)  cool, filter, and  store
      the varnish product.

B. Two Step Process - Molding Powder-

   The following operating steps are carried  out in  batch
   operation.

   1.  Liquid phenol is charged to the  reactor and heated.
      Acidic catalyst (e.g., oxalic acid) and  surfactant
      are added.
   2.  When  reaction temperature is reached (approximately
      220F) formaldehyde solution  addition  is begun and
      continued  over a period of several  hours.
                      Ill-

-------
          3. After formaldehyde  addition is complete,  the mixture
            is allowed to react for an additional hour  or  two.
          4. The temperature is  increased to approximately 270F
            (at  atmospheric  pressure)   to  allow  water  and
            unreacted phenol to distill off.
          5. Application of a  vacuum,  a  further temperature
            increase to 320F, and  injection  of live  steam
            strip residual volatiles  from the melt.
          6. The resin melt is  fed  to  a chilled drum flaker.  The
            flake  is then fed to a  grinder  and ground to a
            powder.
          7. The powder resin is blended with wood flour filler,
            lubricants, curing agent,  (e.g.,  hexamethylene
            tetramine) and other additives in a ribbon  blender.
          8. The filled resin is pelletized  and stored  prior to
            shipment or use.
10.2.2  VOC  Emissions
       All  significant emission rates and  sources  for  this
       product are shown in Table 10-1.   Figure  10-1,  which is
       the  schematic  flowsheet for this  product,  includes the
       emission streams and their  sources.

       [1]  Liquid monomer,  solvent, and organic additive storage
           tanks - Causes of emissions are  normal breathing and
           filling (fixed roof  tanks).

           Formaldehyde tanks - 37% or  50%  aqueous solution is
           kept at 120F by internal steam  coils.  The  emission
           stream contains  air  drawn  into  the  tank  from
           atmosphere, formaldehyde and  water  vapor  from the
           stored solution and  a  small amount  of  methanol vapor
                            -.112-

-------
     TABLE 10-1.-  VOC EMISSIONS FROM PHENOL-FORMALDEHYDE RESIN
                            MANUFACTURER
                                       Current
                      Uncontrolled     Practice   Well Controlled
Stream                #/1000# Resin  #/1000#Resin   #/1000#  Resin

[1]  Storage for Monomers,
     Solvents, & Organic
     Additives             0.14           0.14           0.01

[2]  Polymerization Reactor 0.22           0.22           0.00+

[3]  Product Storage and
     Blending (Liquid)     0.24           0.24           0.01+

     TOTALS                0.60           0.60           0.02+
                              -113-

-------
(small percent  of  methanol allowed by formaldehyde
specification).

Phenol tanks - Liquid phenol is maintained above  the
108F melting point by internal steam coils.   The
emission  stream  contains air,  drawn  into the tank from
the atmosphere,  and phenol vapor.

Tanks for  organic  solvents  (typically  methanol,
ethanol, and  butanol),  organic additives and/or
catalysts (aniline is  a  typical basic  organic
catalyst)  are  at ambient conditions.  Emission  causes
for these,  and for phenol, are the same as described
for formaldehyde breathing and filling.  The exhaust
emitted  will contain vapor of  these  substances,  along
with air  drawn into the tanks  from atmosphere.

All of the above  storage emissions are relatively
small separately but together  they are  in the range of
the other main streams in these plants.  Although  the
types and relative amounts of  each solvent used  will
vary, a  typical  ranking of emissions  from these  tanks
would show  methanol as the largest emitter,  followed
by ethanol, phenol and formaldehyde, all in  the  same
general  range, and with aniline emissions considerably
smaller.  With  respect to  weigh tank operations,  a
small  amount of  VOC  emissions are  generated  by
charging  these tanks from the  phenol  and formaldehyde
storage  tanks with  the weighed charge fed  directly
into the  reactor.  The substance charged is  the  only
VOC component of  the  exhaust stream  in each case.
Explosive range  considerations may require  nitrogen
blanketing  on  some or all of the  tanks  venting  to  the
incinerator (organic solvents  and  formaldehyde).

                 -114-

-------
[2] Overhead emissions  from polymerization  reactor  -  This
   stream is actually  a composite of two reactor  related
   vents.   The  first vent exhausts  from the overhead
   (reflux) condenser  during charging (phenol  and
   formaldehyde  discharged with air and water  vapor)  and
   during  the  atmospheric dehydration portion  of  the
   cycle (phenol,  formaldehyde, solvent such as methanol,
   and  water vapor discharged).   The  temperatures
   typically are 35C  and 25C, respectively.

   The  second  vent exhausts downstream  of  the  vacuum
   equipment that is connected to the overhead  condenser
   during dehydration under vacuum  and refluxing.   The
   composition is largely formaldehyde,  air,  and water
   vapor with some phenol and other  reaction  products.
   These  streams  together are  of  the  same order of
   magnitude as  the  total product storage emission
   streams (the  vacuum system vent stream  VOC  content is
   several times the quantity of the  atmospheric  vent) .
   The  temperature of this stream  is typically  25-35C
   (depending on cooling  or treatment beyond  the  reflux
   condenser).   Emission  rates and composition  vary over
   the  complete  batch  cycle.  The vacuum may sometimes be
   provided by steam jets rather than a vacuum  pump.

[3] Liquid  resin syrup and varnish  product and  product
   blend tanks - There are normal breathing and  filling
   losses.  Tanks are normally  fixed roof  at ambient
   temperatures although  some resins  or  resin
   intermediates are stored at elevated  temperatures.
   The  emission stream  normally -contains  phenol,
   formaldehyde, and vapor of the solvent  used for that
   resin (water  or organics such as methanol, ethanol, or

                     -115-

-------
          butanol).   When  combined  these  emissions are
          potentially (uncontrolled)  significant and as large  or
          larger  than  any  other emission stream  in  these
          plants.

10.2.3  Applicable Control Systems

       The following control technologies are recommended for the
       emission streams described  in  Section 10.2.2 and  in the
       schematic flowsheet for this product.

       [1] Liquid monomer, solvent, and organic additive storage
          tanks - For streams venting  tanks other than  phenol
          (typically formaldehyde, and methanol,  ethanol, and
          butanol solvents and aniline as a basic catalyst) use
          incineration.   95%  reduction efficiency is assumed for
          these streams.   For phenol  tanks -  use a vent
          condenser with discharge to  atmosphere.  Calculated
          reduction efficiency is  87%.  Sending this  stream  to
          incinerator is not feasible because of coating  of
          ducts when phenol cools  and freezes.

       [2] Overhead emissions  from  polymerization reactor  - The
          atmospheric vent should  be  discharged directly  to the
          incinerator.  (Reduction efficiency of 95% assumed for
          this discharge).  The  stream exhausting during  vacuum
          portions of the batch cycle  should  be scrubbed  in a
          baffled, aqueous scrubber after  the  reflux  condenser
          but ahead of the vacuum  pumps.  The discharge from the
          vacuum  pumps  should  then  be incinerated.    (Where a
          steam jet system is used, either in place of  a  vacuum
          pump  or  in parallel  for the high vacuum end  of the
          cycle, the same system  would be  employed except for
          adding a barometric condenser after  the  final  stage.
                            -116-

-------
    The estimated efficiency of  the  aqueous scrubber is
    90%  and  the incineration  is  assumed  to be  95%
    efficient.

[3]  Liquid  resin syrup and varnish  product and product
    blend tanks - Incinerate these streams.  95%  reduction
    efficiency is assumed.
                     -117-

-------
                          SECTION 11
                       POLYESTER FIBERS
11.1  INDUSTRY  DESCRIPTION

      Polyester fibers (P.P.) are defined  as  a manufactured fiber
      in which  at least 85% weight  of the fiber polymer is an
      ester of  a dihydric  alcohol and a  substituted aromatic
      carboxylic acid.  In commercial  practice essentially all
      P.P.  polymer  is produced  from  ethylene glycol  and  either
      dimethyl  terephthalate (DMT) or  terephthalic  acid  (TPA).
      The fiber polymer is produced using  the intermediate bis-
      (2-hydroxyethyl)-terephthalate  (BHET) monomer  with  either
      of the  two processes.  DMT is the older and more entrenched
      process making up about 77% of  the existing capacity,  but
      the TPA process is now preferred  and  most  new- construction
      is built  for  it.

      Polyester is  the largest of the synthetic  fibers.   In 1978
      polyester fiber production  in the  United States  reached
      3,800 million pounds and it continued to  show  significant
      market  strength through the first quarter  of 1979, (2^).

      Current polyester fiber capacity in the  United  States is
      estimted  at  approximately 5050 million pounds divided
      almost  equally between continuous filament yarn,  staple,
      and tow.   In  1976, capacity utilization for textile-grade
      filament  yarn at 62% (based on  November 1976 capacity)  was
      particularly  depressed, (21_) .  However, low capacity growth

                             -118-

-------
(about 2%  actual  per year for  1977  and  1978)  and  good
markets have  increased utilization to  an estimated  80% for
1979.  Sufficient  capacity exists to satisfy  anticipated
demand to  1980/1981.  Projected  demand  until  1982  is
essentially equivalent to  the planned  capacity.

Polyester fiber  polymer manufactured directly  from TPA is
preferred since  the recovery and purification of  byproduct
methanol  is avoided.  However,  much existing  capacity is
based on  DMT  because  polymerization grade TPA has only been
available  since 1963.    Table  11-1  lists  the  domestic
polyester fiber manufacturers.  Of the  18 manufacturers
listed, four  - DuPont, Fiber Industries  (Celanese) , Eastman
Kodak, and  American Hoechst - have approximately 80% of the
total capacity.  Most fiber manufacturers  purchase either
DMT or TPA as well  as  ethylene  glycol.   Only  American
Hoechst,  E.I. DuPont, and Eastman Kodak  have  captive raw
material  producing facilities, and all  three produce  DMT,
not TPA.

P.P. polymer  manufacture  is dependent  on aromatic feedstock
supplys because  DMT and TPA produced in  the United States
are derived from paraxylene.

The DMT  process consists of the  catalyzed  exchange  of
ethylene glycol groups  for methyl alcohol to yield  the
intermediate, BHET. The liberated methyl alcohol  is removed
from  the system by  distillation  in  order  to drive  the
exchange  to completion. Significant VOC  emissions can occur
from methanol recovery.

The TPA  process produces the  intermediate  BHET by  the
reaction  of ethylene  glycol with TPA and,  since there is no
byproduct methanol, VOC emissions are  lower.
                       -119-

-------
                 TABLE 11-1.-  POLYESTER YARN, STAPLE, AND TOW PRODUCING COMPANIES
to
o
 I
PRODUCING COMPANY AND
PLANT LOCATION

AKZONA INCORPORATED
(owned 64.5% by Akzo N.V.
(The Netherlands) American
Enka Company, division
 Central (Clerason), SC
 Lowland, Tennessee

ALLIED CHEMICAL CORP.
Fibers Division
 Columbia, South Carolina
 Moncure, North Carolina

AMERICAN CYANAMIDE COMPANY
Fibers Division
 IRC Fibers Co., subsidiary
  Panesville, Ohio

AVTEX FIBERS INC.
 Front Royal, Virginia
 Lewistown, Pennsylvania

BEAUNIT CORPORATION
 Elizabethton, Tennessee

DOW BADISCHE COMPANY
(jointly owned by Dow Chemical
U.S.A. and BASF AG)
 Anderson, South Carolina

E.I. DU PONT DE NEMOURS & CO.,
Textile Fibers Department
 Caraden, South Carolina
 Cape Fear, North Carolina
 Chattanooga, Tennessee
 Cooper River, South Carolina
 Kinston, North Carolina
 Old Hickory, Tennessee
                                                       ANNUAL CAPACITY AS OF SEPTEMBER 1977
                                                                (Millions of Pounds)
                                                  CONTINUOUS
                                                FILAMENT YARN           STAPLE AND TOW
                                                                                      TOTAL
                                                      X
                                                      X
                                                     130
                                                      X
                                                      X
                                                      70
                                                      55
                                                      20
                                                      X
                                                      X
                                                      X
                                                      X
                                                      X
                                                      X
                                                     7F5
                                                                             10
                                                                              45

                                                                              20
 X
 X
 X
840
                       140




                        70



                        55



                       115


                       60




                       20

-------
                   TABLE 11-1.-  POLYESTER YARN, STAPLE, AND TOW PRODUCING COMPANIES (continued)
NJ
M
I
PRODUCING COMPANY AND
   PLANT LOCATION

EASTMAN KODAK COMPANY
Eastman Chemicals Division
Eastman Chemicals Products, Inc.
subsidiary, Carolina Eastman Co.
division
 Columbia, South Carolina
Tennessee Eastman Co., division
 Kingsport, Tennessee

FALK FIBERS & FABRICS INC.
Universal Polymer Products Co.
subsidiary
 Fuquay-Varina, North Carolina

FIBER INDUSTRIES INC.
(owned 62.5% by Celanese Corp.
and 37.5% by Imperial Chemical
 Industries Limited (UK)
  Greenville, South Carolina
  Palmetto (Darlington), SC
  Salisbury, North Carolina
  Shelby, North Carolina

 THE FIRESTONE TIRE & RUBBER CO.
 Firestone Synthetic Fiber Co., div
  Hopewell, Virginia

 THE GOODYEAR TIRE & RUBBER CO.
 Chemical Division
  Scottsboro, Alabama

 CLARENCE L. MEYERS & CO.
 Meyers Fibers, Inc.
  Ansonville, North Carolina

 MONSANTO COMPANY
 Monsanto Textiles Company
  Decatur; Alabama
  Sand Mountain (Lake
   Guntersville), Alabama
                                                    ANNUAL CAPACITY AS OF SEPTEMBER 1977
                                                            (Millions of Pounds)
                                              CONTINUOUS
                                            FILAMENT YARN           STAPLE AND TOW
                                                                                                TOTAL
                                                  10
 X
 X
450
                                                  30
                                                  30
                                                  10
                                                  X
                                                 TTD"
                                                                           X
                                                                          405
                                               520
                                                10
 X
 X
 X
705
1,155


   30



   30



   10
                                                                                                  240

-------
           TABLE 11-1.-  POLYESTER YARN, STAPLE, AND TOW PRODUCING COMPANIES  (concluded)
PRODUCING COMPANY AND
   PLANT LOCATION

PHILLIPS FIBERS CORP.
(owned 90% by Phillips Petroleum
Company and 10% by Phone-Poulenc
SA [France])
 Rocky Mount; North Carolina

ROHM AND HAAS COMPANY
Rohm and Haas Carolina Inc., sub.
 Fayetteville, North Carolina

TEXFI INDUSTRIES, INC.
Texfi Yarn and Fibers Group
 Asheboro, North Carolina
 New Bern, North Carolina
WELLMAN, INC.
Wellman Industries Inc., sub.
Man-Made Fiber Division
 Johnsonville, South Carolina

TOTAL
        ANNUAL CAPACITY AS OF SEPTEMBER 1977
                 (Millions of Pounds)
  CONTINUOUS
FILAMENT YARN           STAPLE AND TOW
       50
      140
       X
       X
  40

2445
       0

     2295
TOTAL





    50



   140





    45




    40

 4,740

-------
11.2     P.P. MANUFACTURE  BY DIMETHYL TEREPHTHALATE PROCESS

11.2.1    Process Description

         Polyester fiber is manufactured from DMT  in either batch
         or  continuous processes. (Only  a batch  process  is
         described.)   The  three basic changes required  between
         batch and continous  operations are;  1) Replacing  the
         kettle-reactor in  batch operations for a column-type
         reactor in the ester exchanger, 2)  "No-back-mix" reactor
         designs  are  required  for continuous processes  at  the
         polymerizer,  and  3)  Differing additives and  catalysts
         are required  to  make  a product with proper  molecular
         weight, molecular weight distribution, etc.   The  batch
         process described here is a two-reaction-step  process
         which begins  with  an  ester exchange between ethylene
         glycol  and  DMT.   The  products  of this reaction  are
         methanol vapor (MeOH)  and BHET monomer.   The monomer is
         polymerized  to polyethylene terephthalate (PET)  in a
         second reaction step in the presence of heat,  catalysts,
         and vacuum.    The  major polymerization by-product is
         ethylene glycol with smaller amounts of methanol.   The
         ethylene glycol and methanol  are condensed  and
         transferred  to storage  tanks for reprocessing  by  others
         (28_), (29,).

         Fibers are  produced  from PET by spinning,  either
         directly from the  polymer melt,  or indirectly from
         chips.  Staple fiber  is wetted, drawn,  crimped,  dried
         with indirect heat, and may be cut  before baling.   Yarn
         fiber may be  dryed and  heat set before  it is tube wound

         Referring directly to Figure  11-1, Polyester  fiber
         manufacture  by the DMT/TPA process, molten  dimethyl
                           -123-

-------
                                                            TO SPENT
                                                            EG STORAGE
                                                         N2  & RECOVERY
                                         POLYMERIZATION I
                                            REACTORS    I
                                                                          FIBER
                                                                          'PRODUCT
-$FROM EG SPRAY CONDENSER
                                                   ALTERNATIVE
                                                      CHIP
                                                     FORMING
    TO EG RECOVERY

FEED              ESTER REACT
                                       POLY REACT .
                                                                 FINISH
 Figure 11-1.-  Polyester  fibers using  DMT/TPA processes,

-------
terephthalate  (DMT) and ethylene glycol  (EG)  are drawn
from storage  tanks  [1]  and sent to the  first step, or
ester exchange,  reactor.  The EG goes  first  to a small
mix tank where  catalysts and additives are  stirred in,
and then to the  reactor.  About 0.6 Ib EG and  1.0 Ib DMT
are  used  for  each 1.0  Ib PET  product.   The ester
exchange reaction is conducted to  start  at  170 and end
at 230C  with  atmospheric pressure,  and  the major
products are  BHET monomer and methanol.   Methanol has to
be removed from the  reactor as a vapor to  shift the
reaction to increase  the  formation of BHET.   Methanol
vapor overhead  (OHD) from the ester exchange  reactor is
controlled by  cooling  water  (CW) and  refrigerated
condensers, and  the vent stream [2] is the  first major
process emission source.  Condensed byproduct methanol
is sent  to methanol  storage  for export  to  the DMT
supplier for  reuse, and the tank vent  for this methanol
storage tank  is  another major emission source,  [5]

Bottoms  from  the  ester exchange  reactor contain the
desired BHET  intermediate or monomer.   They  are sent to
the second step, the  polymerization  reactors.  In the
first polymerization reactor, the  pressure is  lowered to
the range of  1-760 mm Hg absolute  and  the temperature is
increased to  230-285C to remove residual methanol and
the EG forming  from BHET polymerization to PET.  In the
second polymerization  reactor, to further  reduce
methanol and  EG  residuals, the pressure is lowered  below
1 mm Hg, and  the temperature is raised to 260-300C.  A
metallic catalyst is employed.  The vapor streams  from
the polymerization reactors are combined  and  controlled
by various systems designed to avoid plugging  or  fouling
from  PET  solids.   These systems include EG spray
condensers or contactors and the vacuum systems  shown in


                    -125-

-------
         Figure 11-1.  The vent  from these  vapor  systems is the
         third major process emission point, stream [3].   Systems
         that  use steam jet ejectors  for vacuum produce VOC
         contaminated contact waters,  and  they  will  have
         substantially greater VOC emissions if these  waters are
         cooled  with atmospheric cooling  towers (atmospheric
         contact) than if once-through f^O or mechanical
         vacuum pumps (non-atmospheric contact) are used.

         The two polymerization  reactors are operated in series
         with the (product)  bottoms from the second reactor  being
         sent  either to melt  spinning  or to  a chip  forming
         machine for later spinning.   Chip  forming  is not
         discussed in this report.  Oil base finishes  are  applied
         to  the  filaments  made in melt  spinning  to  provide
         lubrication and static  suppression for fiber  processing.
         The bulk of the oil base (finish)  is  recovered and
         recirculated.  A small  quantity is  emitted through the
         spinning machine  vents and  constitutes  the  fourth
         emission stream,  [4].  The  oil exits the spinning
         machine vents in the form of a "smoke".

11.2.2    VOC Emissions (DMT Process)

         All significant emissions for this product are shown on
         Table 11-11.  The schematic flowsheet for this product,
         which includes the emission streams and  their sources,
         is Figure 11-1.  The same stream  number is  used  for  a
         given stream throughout, but note  that the DMT process
         has streams  [1] through [5] and TPA only has  [1]  through
         [4].  The designated streams for the DMT process  are:

         [1] Raw and recovered  materials  storage tanks, except
            recovered methanol  (MEOH) - Fixed roof storage  tanks
            are  used  throughout  in existing  facilities.
                             -126-

-------
TABLE 11-11.-  VOC EMISSIONS FROM POLYESTER FIBER MANUFACTURE  BY  DIMETHYL
                                TEREPHTHALATE PROCESS

                            Uncontrolled   Current Practice  Well  Controlled
     Stream                 #/1000 Resin   #/1000# Resin      #/1000#  Resin




H
NJ
1
[1]
[2]
[3]
[4]
[5]

Raw and Recovered
Material Storage
Ester Exchange Reactor
Polymer izers*
(a) non-atmos contact
(b) atmos contact
Spinning Machines
MEOH Storage - DMT
Process Only
Subtotals*
(a) Non-atmos contact
(b) Atmos contact

0.15
0.04
3.65
3.83
0.29
4.31 ,
7.96

0.15
0.04
3.65
1.28
0.09
1.56
5.21

0.05
0.04
0.19
0.03
0.31
0.31
     Weighted Total - DMT      6.07              3.32              0.31
     51.8% (a) , 48 .2% (b)

*Emissions subtotals are given assuming polymerizer vents  [3] are  controlled  by
(a) non-atmos contact condensers and  (bj non-atmos contact + atmos contact
(cooling tower) condensers.

-------
    Emissions are vapors of EG and DMT and  result from
    vapor displacement  (working  losses)  and tank
    breathing.  The bulk of dimethyl terephthalate (a
    solid  at ambient conditions) is stored  in  hopper
    bins until needed.  Then it  is  melted  at elevated
    temperatures in heated, insulated tanks.   Fresh  and
    spent ethylene glycol  are stored at ambient
    conditions.  Recovered methanol  (MEOH)  storage is
    treated as emission stream [5].
[2]  The ester exchange reactor -  This stream  is  one of
    the larger  potential emission sources in this
    process.  The flow rate and stream composition vary
    as  the batch goes through its  cycle.   The  stream
    carries  methanol byproduct  vapors  primarily  and
    steam, and it is processed  through  both cooling
    water  and refrigerated condensers.
[3]  The polymerization reactors  - This  stream carries
    large  quantities of steam  and ethylene glycol
    vapors, small amounts of MEOH vapors,  volatile feed
    impurities, and inert gas.   Inert gas  is added to
    the  reactor to strip  ethylene  glycol vapors,
    residual volatiles, and steam from the  polymer  and
    prevent product discoloration   from oxygen
    contamination.  The resulting emissions  pass through
    a  system that includes glycol  and  water contact
    condensers (spray).  There are two types  of contact
    condensers;  (a) non-atmospheric contact  or
    once-through, and (b) atmospheric-contact.  Although
    type (a) produces a flow of contaminated  water, it
    has low VOC emissions compared  to type  (b) .   Type
    (b)  systems use a cooling tower  to  cool  the
    contaminated water for reuse  in the spray  condenser,
    and  the  cooling tower  itself  becomes a  large
    potential VOC emission source.
                    -128-

-------
[4]  The spinning machines - A fume or smoke  of  oil  and
    moisture is emitted  from various vents.    Usual
    controls include  catalytic  incinerators and mist
    eliminators.
[5]  Recovered methanol  storage  tank ventilation (DMT
    process only) - This  stream is large  due  to  the
    volatility of MEOH, and refrigerated condensers  are
    used to  control it.

VOC emissions from the DMT process can be summarized as
follows:

o   Polymerizer vent gas treatment exhaust,  stream [3],
    is a potentially large emission source, depending on
    the following process  variation.  Spray condenser
    bottoms, largely  warm contaminated water, can be
    handled  in either  of  two ways - Type (a) process,
    once through or recycle without atmospheric  contact
    and - Type (b), recycle through a cooling tower with
    atmospheric contact.   Type (a) emissions  are
    estimated to be 0.044 lb/1000 whereas Type  (b)  are
    estimated to be 3.65 lb/1000.

o   Spinning machine vents, stream [4] are another large
    emissions source, and they are the largest  for  the
    Type  (a) variation,  second  largest for Type (b).
    Current  practice puts  stream  [4] at 1.28 lb/1000.
    Thus  the total emissions of a non-contact  plant
    [type (a)], with current practice, are estimated to
    be 1.56  lb/1000 and those for a contact  plant  [Type
    (b)] are 5.21 lb/1000.  Table 11-11 summarizes  the
    emissions for polyester fibers manufacture by  the
    DMT process.
                    -129-

-------
11.2.3   Applicable Controls  (DMT Process)

        (Section  11.2.3  has been combined  with  11.3.3 that
        follows  since  the controls are  the same  for both
        processes.)

11.3     P.P.  MANUFACTURE  BY TEREPHTHALIC  ACID  (TPA) PROCESS

11.3.1   Process Description  (TPA)

        Polyester fiber  is manufactured from TPA in either batch
        or  continous  processes, but only a batch process  is
        described.  The process  is  a two-step process exactly
        analogous to the DMT process described  in Section  11.2.
        The products of  the  first,  or esterification, reactor
        are t^O vapor  and  BHET.  BHET is polymerized in the
        second step reactors just as in the DMT process.  The
        absence  of MEOH vapor  as a first  step byproduct
        eliminates  the  need for the byproduct, MEOH, storage
        tank, vent  [5],  and the VOC in major emission  stream
        [2].  For the  purposes of this study, these are the only
        significant differences between  the two processes.
        Figure 11-1, therefore, represents  the  process flow for
        the TPA  process  provided the MEOH  storage  tank and
        emission  stream  [5]  are deleted.  Of course process
        conditions for TPA differ from DMT, but the objectives
        are the same - short reaction time,  low polymer  ether
        linkage  content, good  polymer  color  and thermal
        stability.

11.3.2   VOC Emissions  (TPA Process)

        The emission  streams for this process correspond  to
        those  for the DMT process except that there  are  no
        byproduct methanol emissions.  Again, Figure 11-1  can  be

                            -130-

-------
used minus  stream  [5] and the  MEOH storage tank.    Table
ll-III summarizes  the emission rates and sources  for  the
TPA process.  The major streams are:

[1]  Raw and recovered materials storage tank -  Fixed
    roof  storage tanks and bins are used throughout  the
    process and they have  conservation vents  on  the
    tanks.  The emisssions are vapors of EG, TPA  and  TPA
    dust;  and  they  result from  working  (vapor
    displacement)  and breathing losses.  Terephthalic
    acid  is stored in bins at  ambient conditions  until
    needed,  and  then  it  is melted  and  stored   in
    insulated tanks at  elevated temperatures until
   i
    charged.  There are no emissions.
[2]  Esterification reactor  -  This  stream  consists
    primarily of steam and EG  vapors, with small  amounts
    of feed impurities and volatile side products.   For
    economic reasons (EG recovery) it is controlled with
    condensers, and exits at about 220F.
[3]  Polymerization  reactors  - Like stream  [2] , this
    stream  consists  of steam  and EG vapors with  small
    amounts  of volatile  impurities.   It is  well
    controlled by  CW condensers exiting at about  120F.
[4]  Melt spinning - A fume or smoke of oil and  water
    droplets is emitted from various vents.  This is  the
    largest single source of hydrocarbon emissions from
    PET manufacture by  TPA.   Usual  controls  include
    catalytic incinerators and mist eliminators.

The polyester  fibers by TPA process is  relatively
non-polluting  because  it does not produce  byproduct
methanol  with attendant recovery and storage emissions.
Like the  Type (a)  variation of the DMT process,  spinning
machine vents,  Stream  [4],  are the  largest  single
emissions  source  at 1.28  lb/1000  (current practice).

                  -131-

-------
TABLE ll-III.-  VOC EMISSIONS FROM POLYESTER FIBER MANUFACTURE  BY  TEREPHTHALIC
                                          ACID PROCESS
     Stream
Uncontrolled    Current Practice   Well Controlled
#/1000# Resin    #/1000# Resin      #/1000# Resin
[1]

[2]
[3]
[4]
Raw and Recovered
Material Storage
Ester Exchange Reactor
Polymerizers
Spinning Machines

Nil
0.039
0.042
3.83

Nil
0.039
0.042
1.28

Nil
0.039
0.042
0.191
     Totals
   3.91
1.36
0.27

-------
         Total emissions are estimated  to  be 1.36 lb/1000 with
         current practice.  Table  ll-III summarizes emissions  for
         polyester fiber manufacture  by  the TPA process.

11.3.3    Applicable Control Systems  (DMT and TPA Processes) (See
         paragraph 11.2.3)

         Because the DMT and TPA processes are similar, differing
         only in that DMT produces byproduct  methanol  and has  a
         control  option  with  atmospheric  contacting  of
         contaminated cooling water,  and TPA  produces  byproduct
         water  and does  not have such  an  option, the control
         systems  for the  two are  discussed  together.   The
         following controls are  recommended  for the streams
         described in Sections 11.2.2  and  11.3.2 and shown on
         Figure 11-1. The same  stream numbering system is used
         throughout.

         [1] Emissions from fresh  and recovered materials storage
            tanks - Fixed  roof tanks are  satisfactory for
            ethylene glycol since  its vapor  pressure is low.
            Other tanks with more volatile  or  hazardo.us vapors
            should use vapor return  lines to loading tank  trucks
            or cars, thereby  eliminating  working  losses or
            approximately 58%  of  total  (working plus breathing)
            tank  emissions.  Conservation  vents should be used
            on all tanks not equipped  with  more sophisticated
            vent  control and they are almost always economically
            justified.    Inert  gas   blanketing  and
            flare/incinerator  systems may  be required for some
            storage  tanks, or  CW  or  refrigerated condensers.

            Water scrubbers may be applicable on DMT and TPA
            tank  vents primarily  for housekeeping purposes.   DMT
            and TPA are crystaline  solids at ambient conditions

                            -133-

-------
    and  can cause  sublimed  solids  buildup  on  cool
    surfaces adjacent to  tank vents.   High VOC removal
    efficiencies have been  reported  when scrubbing
    phthalic anhydride (12^) , (13); a material physically
    similar to DMT.   No control efficiency was  assumed.

[2]  Emissions from the ester exchange or esterification
    reactors -

    o  DMT process - With the DMT  process,  byproduct
      methanol  vapor must be removed  to  enhance the
      reaction and recovered for economic reasons; the
      reactor vent is a  major process emission source.
      Presently  economic  controls  include  a  C.W.
      condenser and provision for refluxing part of the
      MeOH  for  continuous or column-type reactors.
      BDCT will include  a  refrigerated condenser on the
      K.O. drum vent. 90% reduction of MeOH vapors was
      assumed.

    o  TPA Process - With the  TPA  process  the  main
      byproduct is H20 vapor, not MeOH; however,
      ethylene glycol vapors and volatile feed impuri-
      ties and side  products are  all  present and the
      ethylene glycol must be recovered.  Present con-
      trols  are C.W.  condensers  with  the exit  vent
      temperature about  220F.

[3]  For  the polymerization  reactors -

    o  DMT process - The  polymerization of  BHET is
      conducted under vacuum to  remove EG vapors and
      shift  the  reaction  toward  completion.
      Temperatures are high  (520-560F) and an N2
      inert gas  blanket is  used  in  all equipment

                   -134-

-------
      downstream  of  the  polymerization reactor  feed
      tank  (not  shown  in Figure 11-1) .  For  the
      continous process a pre-polymerization  reactor
      proceeds  polymerization.  The major emission
      point  [3] is  the vacuum system  discharge  (at
      least  two separate  vents for the  continuous
      version) . Cooling water  condenser controls are
      used for EG  recovery  for economic  reasons and the
      exit temperature  is about 100F.   Polymer solids
      content of the vapor streams  is  high enough to
      foul surfaces  and plug jet nozzles so some  type
      of prevention  is  commonly practiced.   One method
      sprays hot  EG vapors into the vacuum lines  to
      reduce deposition.  The  scheme shown in Figure
      11-1 shows spray contact  condensing  the vapors
      with cold EG liquid to avoid  solids clogging the
      vacuum system  nozzles.  The contactor  bottoms are
      saponfied before EG purification.   The well-
      controlled value assumes  discontinuance  of
      atmospheric-contact, cooling  water.

   o  TPA process  -  Essentially the same as  for the DMT
      process.

[4] Melt  spinning  -  DMT and TPA processes  -  Spinning
   lubricant and water  vapor are emitted as  an  aerosol
   or smoke from various spinning vents. This  stream,
   [4], is the major  emission source for these  plants.
   Common controls include  mist  eliminators  and
   catalytic incinerators, and  expected efficiencies
                   -135-

-------
    are 70 and 80%, respectively.   Improved  control can
    be obtained by controlling a higher percentage of
    the total number of spinning machines and  by using
    more efficient control devices  such as electrostatic
    precipitators.  An  overall  (from uncontrolled)
    control efficiency of 95% was  assumed.

[5]  MeOH storage - DMT process only - Byproduct methanol
    is  produced from  the  DMT process only.   Controls
    include a refrigerated condenser  system.  An overall
    efficiency of 90% was assumed.
                    -136-

-------
                          SECTION 12
                   HIGH DENSITY POLYETHYLENE
12.1  INDUSTRY DESCRIPTION

      High-density polyethylene (HOPE)  resins  are  linear
      thermoplastic polymers of ethylene  with densities  higher
      than  0.94 g/cm^.

      HOPE resins are  typically produced by  low-pressure
      processes operated at 100-1500  psi.   In these processes,
      generally, organic solvents  are used  and the ethylene  is
      dissolved in them; the solid  catalyst  is  in suspension;  and
      the polymer forms a slurry (e.g.,  the  processes originated
      by Phillips Petroleum  Company, and  Solvay  &  Cie, sa) .
      Amoco Chemicals Corporation  and  Union  Carbide Corporation,
      however, have new gas-phase  processes  that do not  require
      solvents.  The solvent processes have  higher potential VOC
      emissions than the new gas-phase processes.

      Although there are  various  solvent  processes  used, the
      variations do not affect emissions except with respect  to
      the solvent recovery methods  used.

      The  1978 U.S. production of  HOPE was 4200 MM PPY and
      capacity was 5300 MM PPY (2:) , (50) .  These figures
      represent increases of 15% and  21% respectively over 1977.
      Overall  utilization of capacity was 79%  in 1978 and
      increasing, but resin supply  is  expected  to be adequate
      through  1983.
                           -137-

-------
        Capacity  in 1979 is estimated  to  be  5480 MM PPY (jj) , (51)
        and  utilization, K, will rise  to  0.83 if 8% growth (50)
        is assumed from 1978 to 1979.

        There  are eleven U.S. producers of HDPE and the market is
        not  particularly dominated  by any one or a few.   Table
        12-1 lists the U.S. manufacturers of HDPE and gives their
        location  and capacity (52).

        Current over-capacity  for ethylene  (greater than 30%  )
        ensures  adequate raw  material  supplies  to HDPE
        manufacturers since  ethylene  makes  up over 97%  of HDPE
        resin  production.  Typically,  about  1.05 Ib ethylene  are
        required  to produce 1 Ib of  HDPE  resins, and about 40% of
        all  production  is homopolymer.   The remaining  60%
        copolymer resin is usually greater than 95% ethylene  and
        has  less than 5%  of such comonomers  as 1-butene  and
        propylene.

        Classically HDPE has been  made  using low-pressure
        technology, (500-1500 psig)  and LDPE has been using high
        pressure.  New low pressure  technology using Zeigler
        catalysts can produce  LDPE  also, and so, not  only does
        the  classic pressure distinction  not exit, but  also some
        equipment can be used for both of the major resin  types.
        For  example, 38%  of  the 855 MM PPY  (1978)  Phillips
        Petroleum Company capacity at  Pasadena, Texas,  can swing
        between HDPE and LDPE (see Table  12-1).

12.2    HDPE MANUFACTURE BY LIQUID PHASE  PROCESSES

12.2.1  Process Description (Liquid  Phase Processes.)

        Various solution, suspension  or  "diluent" liquid-phase
        HDPE processes have been produced commercially (j^3_,j>4_) ,

                            -138-

-------
                          TABLE 12-1.-   U.S. MANUFACTURERS OF HOPE RESINS AND THEIR LOCATIONS
                                              AND CAPACITYS (52)
                                                              ANNUAL CAPACITY
                                                              AS OF OCTOBER 78
U)
UD
 I
COMPANY AND PLANT LOCATION

ALLIED CHEMICAL CORPORATION
 Specialty Chemicals Division
  Baton Rouge, Louisiana

ATLANTIC RICHFIELD COMPANY
 ARCO/Polymers, Inc., subsidiary
  Port Arthur, Texas

CHEMPLEX COMPANY
(jointly owned by American Can Company
and Getty Oil Company)
  Clinton, Iowa

CITIES SERVICE COMPANY
 Chemicals Group
  Columbian Chemicals, division
   Texas City, Texas

DOW CHEMICAL U.S.A.
   Freeport, Texas
   Plaquemine, Louisiana

E.I. DU PONT DE NEMOURS & COMPANY, INC.
 Plastic Products and Resins Department
   Orange, Texas
   Victoria, Texas

GULF OIL CORPORATION
 Gulf Oil Chemicals Company
  Plastics Division
   Orange, Texas
                                                        THOUSANDS OF
                                                       METRIC TONS
                                                          272
                                                           68
86
                                                           82
                                                          136
                                                          125
                                                          104
                                                          102
                                                          200
                 MILLIONS
                OF POUNDS
                   600
                   150
190
                   180
                   300
                   275
                   230
                   225
                                                                              440
        PROCESS
        Phillips, Ziegler
        Ziegler, Koppers
Phillips
        Ziegler
        Own
        Own
                           Phillips,
                           Union Carbide

-------
              TABLE 12-1.-  U.S. MANUFACTURERS OP HOPE RESINS AND THEIR LOCATIONS
                                 AND CAPACITYS  (Continued)

                                                 ANNUAL CAPACITY
                                                 AS OF OCTOBER 78
                                           THOUSANDS OF        MILLIONS
COMPANY AND PLANT LOCATION                METRIC TONS         OF POUNDS  PROCESS

HERCULES INCORPORATED
 Polymers Department
  Lake Charles, Louisiana                       7                  15

NATIONAL PETRO CHEMICALS CORPORATION
(jointly owned by National Distillers and
Chemical Corporation and Owens-Illinois, Inc)
   La Porte, Texas                            227                 500    Phillips, Solvay,
                                                                          US I

PHILLIPS PETROLEUM COMPANY
 Plastics Division
  Pasadena, Texas                             388                 855    Own

SOLTEK POLYMER CORPORATION
  Deer Park, Texas                            270                 595    Phillips, Solvay

STANDARD OIL CORPORATION (INDIANA)
 Amoco Chemicals Corporation, subisidiary
  Chocolate Bayou, Texas                      159                 350    Own, Solvay, USI

UNION CARBIDE CORPORATION
 Chemicals and Plastics, division
  Seadrift, Texas                             181                 400    Own
TOTAL                                       2,406               5,305

-------
including Phillips'  original solution  and  also their
particle-form  processes, Solvay1s hexane  slurry,  and
various proprietary systems like  those of Dow  Chemical.
Conventional  Zeigler catalysts require recovery  systems
and, therefore, have higher potential  VOC emissions.   The
high-efficiency Ziegler  catalysts and supported metal
oxide catalysts such as those used in  UCC's liquid-phase,
Phillips-particle-form process do not require  recovery,
so they have  lower potential VOC  emissions.   The  process
shown  here  (diluent) could be  either  solution  or
suspension  and  is assumed to be  of the high-efficiency
catalyst type that does not require  catalyst  recovery.

The Phillips  particle-form process serves as  the basis
for this description but  it is intended to represent  all
other  liquid  phase processes  with high-efficiency
catalysts.

Referring to  the schematic for this  process,  Figure 12-1,
the "Feed" section also  depicts catalyst preparation.
Silica  gel is  impregnated with  chromium;  then it  is
dried,  dehydrated and activated.   Thus prepared, catalyst
is fed  to the reactor  by  being slurried in  a  stream of
process  solvent  (pentane) .  Ethylene monomer and a
suitable comonomer (butene-1) are also fed to the reactor
where polymerization takes place  in pentane.   There  are
diluent VOC emissions from both storage [1] and  catalyst
preparation [2].

Product polyethylene is recovered,  see  "Recovery"
section -  Figure 12-1, by flashing from a low  pressure
(500 psig)  to a vacuum and by steam  stripping, [3].  Heat
                     -141-

-------
to
I
                                 [3] FROM DILUENT RECOVERY,
                                    VENTS, PURGE GASES,  WAX
  FLARE/
INCINERATOR ,
 SYSTEMS       [5]
           FRESH
           FEED
           FRESH
            AIRV
                 ^   "I
                                A
                              X]"-TO SAFETY FLARE
            FRESH
                            FEED                        REACT           RECOVERY

             Figure  12-1.-  HDPE~ by "liquid-phase  (diluent)  processes.
                         FINISH

-------
         is  supplied by circulating  pentane  vapor  through  a
         heater and mixing hot vapor with  reactor effluent and by
         steam.  The diluent purification  and recovery system is
         not  shown.  The main streams  leaving the flash drum  and
         stripper are taken  to  this  system from which  both  a
         light ends bleed, [3]/  and bottoms  (wax) purge,  [3],  are
         made.   Finally polymer  solids  are blended  with
         antioxidant  (A.O.)  and  pelletized   in  an
         extruder-pelletizer.  Conditions  in  the steam strippers
         leave the polymer  solids wet  so  that they  must  be
         dewatered by rolls or centrifuges and dried,  [4], prior
         to extrusion.   Phillips particle-form solids  require
         solvent drying (sections shown  in dotted box) and  this
         produces associated potential VOC emissions.

         An ethylene safety flare is always  a part of each system
         and  some plants may use it for VOC  emissions control.  A
         special  flare or  incineration  system may  also  be
         provided especially for the diluent  recovery light  ends
         bleed [3] .   A wax  incinerator   (low molecular  weight
         polymer) is also provided  sometimes  and may only be  9 5%
         efficient  for VOC removal.  Thus  the wax incinerator
         vent, [5], may have a VOC  emission.

12.2.2   VOC Emissions (Liquid Phase Processes)

        All significant emissions for  liquid-phase HOPE are  shown
        in Figure 12-1 and listed in Table 12-11 using bracketed
        numbers to indicate the emission streams (8_) , (55) .

        The major emission points of this  process are:

        [1] and [2] Diluent and  comonomer storage and catalyst
           makeup - Diluents are usually stored in fixed  roof
                            -143-

-------
                          TABLE 12-11.-  VOC EMISSIONS FROM HOPE MANUFACTURED BY SOLVENT PROCESSES

                                        Uncontrolled   Current Practice  Well Controlled  Composition
                 Stream                 #/1000g Resin   /1000 Resin     fl/lOOOt Resin      Vol  %

            [1]   Diluent and Comonomer
                 Storage                   0.20              0.20               0         15 -  70% VOC

            [2]   Cat Makeup                0.01              0.01               0         90% VOC

            [3]   Product Recovery Flash
                 Drum Purge, Including
                 Strip Decanter &
                 Centrifuge                23                0.50              0.2        Approx. 50% VOC

          [4]   Polymer Drier              8                 8                0.4        0-5%  VOC
>
 I           [5]   Wax Incinerator           0.40              0.04              0.04       0.2%  VOC

            [6]   Fugitive                  1.53              1.53              1.53

                 TOTAL                    33.14             10.28              2.17

-------
    tanks with conservation vents.  Some diluent is also
    used in catalyst preparation and addition.   Emissions
    are from tank breathing and working losses and from
    catalyst slurrying.

[3]  Product recovery -  (Flash  drum purge,  stripper-
    decanter, and dewater rolls or centrifuge)  - From  the
    reactor, polymer and associated  gas are blown down
    into the flash drum.  Vapors  from  the drum [3] are
    sent to distillation (diluent recovery) from which a
    light ends bleed is  sent  to flare or incineration to
    purge  impurities  and ethylene.   From  the  drum,
    polymer with absorbed and adsorbed diluent  is sent to
    the  steam stripper  for  diluent recovery.   Steam
    stripped diluent  is condensed and decanted for
    separation into water-rich and diluent-rich streams.
    The  decanter vapors  [3]  are  flared or burned in a
    boiler  or incinerator.  VOC  are emitted  from the
    diluent-recovery, distillation,  overhead  purge and
    from  the stripper-decanter vapors and are sent to
    flare or to incineration.
[4]  Pellet  Dryer/Stripper - Pellet  dryers are usually
    required for systems that steam  strip polyethylene
    fluff or powder. Dryers remove residual diluent from
    the polymer and emit it to the atmosphere and are  the
    major emission point for the  process. Some systems
    produce pellets from a melt  and thus do  not have
    water-wet pellets to dry.  These  systems  produce
    pellets with entrained or dissolved  diluent that must
    be steam-stripped.    The amount  of  VOC emitted from
    drying or pellet stripping depends  on the  residuals
    from the polymers in the preceeding processes.  It
    varies widely.
                    -145-

-------
        [5] Flare/Incinerator Systems - One or more  flares  will
           be in use at most  HOPE plants.  Some manufacturers
           use new or existing boilers to recover fuel values as
           well as dispose  of  certain VOC containing  streams.
           Figure 12-1 is meant  to  show both flare  and
           incinerator systems vents as indicated by stream  [5].
           A low  molecular weight wax  is removed  from still
           bottoms  in diluent  recovery,  and  it  too  is
           incinerated, usually in  a  special  incinerator.
           Emissions are  usually small  because  flares  and
           incinerators can achieve high emissions reductions.

        [6] Fugitive - This  includes leaks,  samples and equipment
           entry  losses mostly from feed,  reactor,  and  diluent
           recovery sections.

12.2.3   Applicable Control Systems (Liquid Phase Processes)

        The following controls  are recommended for  the  streams
        described in Section 12.2.2 and shown  in Figure  12-1  and
        Table 12-11. The same numbering system  has been used.

        [1] and [2]  Diluent and comonomer storage and  catalyst
           preparation - Most present-day  diluent  and  some
           comonomer storage  is  fixed-roof tankage and  may or
           may not have an  N2~pad to flare.   Catalyst
           preparation VOC losses are  from  tankage  and  from
           activation- solution  drying, but  they are  minimal.
           Future tankage will be floating  roof and/or inert-pad
           or condenser protected.  Control was assumed 100%.
        [3]  Product recovery including  flash  drum  purge,
           stripper-decanter  vapors, and dewatering  rolls or
           centrifuge ventilation -  Flash  drum   and
           stripper-decanter vapors bleeds  or purges  are
           controlled  effectively  now by  flare or  boiler

                            -146-

-------
           incineration.   As the cost of energy  and solvents
           rises, more  attempts will be made to  recover  these
           materials  before flaring.   Improved  control will
           result both from VOC  recovery before flaring  and  from
           increased  use  of flaring  for  those not  presently
           practicing  it.   Sixty percent control efficiency  has
           been demonstrated.
       [4]  Pellet drying/stripping -  Dryer/stripper exhaust
           conditions vary widely  and  essentially  are
           uncontrolled  at present.  Boiler or other incineration
           is recommended but adsorption/recovery may also  be
           feasible especially for those processes  using N2
           gas dryers and/or  practicing dryer  recycle.   An
           efficiency  level of 95% was assumed.
       [5]  Flaring  and  incineration.  Well controlled  flares,
           incinerators, and boilers can achieve  greater than 99%
           reduction of  the VOC  in the inlet.  Wax incinerators
           were assumed  to be 95% efficient for both VOC and wax.
           Wider  use  of flares and incinerators at existing
           plants could greatly reduce all HOPE  VOC  emissions
           except for  drying.  Control efficiency of 95% has been
           demonstrated.
       [6]  Fugitive - Distributed  fugitive leaks can only  be
           reduced by  good housekeeping  and by  equipment
           replacement.   No efficiency estimate was made.

12.3     HOPE MANUFACTURE BY GAS  PHASE PROCESSES

12.3.1   Process Description (Gas Phase Processes)

        Union  Carbide Corporation's  (UCC)  silica-supported ,
        chromium-oxide-catalyst, gas-phase  process  was  the  first
        ever commercialized.   The original  UCC plant was built at
        Seadrift, Texas in 1968 (30 MM PPY capacity).   BASF's
                           -147-

-------
gas-phase  process is somewhat similar and is assumed to
have similar VOC emissions.   Major  differences between
the UCC and BASF processes,  besides catalyst systems,
include use of fluid-bed  technology for UCC's reactors
and use of mechanically  stirred dry/reactor  beds for
BASF.   Because the BASF process  uses a higher pressure
and temperature (500 psig, 100-110C) than UCC (300  psig,
93C),  it would be  somewhat higher  in potential VOC
emissions.

The UCC fluid-bed gas phase process  serves as the basis
for this description, but  it is intended to represent
other  gas  phase processes  as well  (52), (54) , (55) .

Referring  to Figure  12-2,  HOPE by gas  phase processes,
the "Feed"  section of the  flowsheet  also depicts catalyst
preparation.   Silica gel  is  impregnated with chromium
oxide via metallo-organic compounds,  and water, and
hexane solvent.  Impregnated catalyst is dried with warm
inerts (N2) and the resulting VOC  stream, [3],  is
flared.  Dried catalyst is  conveyed into the reactor bed
fluidized  in N2  Gas-phase processes do not require
catalyst  recovery systems since  the high-activity
catalyst  is left  in the  product  polymer.   Ethylene
monomer and suitable comonomers  (such  as butene-1) are
fed to  the reactor along  with the  catalyst where
polymerization  takes place around  small  catalyst
particles.

With UCC technology, the  reactor is fluidized and the
polymerization reaction is controlled by recirculating a
large  flow of gas and  fines through a  circulation
compressor and coolers.   Compressor  seal-oil (saturated
with ethylene) vents and  gas  sample analyzer vents are

                    -148-

-------
FRESH,
 FEED
            BUTENE-1
           CO-MONOMER
      RECYCLE
FRESH
      ETHYLENE MONOMER
A
                       A
             CAT  SUBSTRATE
                                                                                 FROM _ _
                                                                                  CAT  [3]
                                                                                DRYER
                                                                               POLYMER
                                                                                PURGE
                                                                                 TANK
        LAJ

       T
                                                                                                    FLARE &
                                                                                                  INCINERATOR
                                                                                                    SYSTEMS
                 CAT ACTIVATION
                      SOLVENTS
                                             ETHYLENE
                                                  CIRCULATION    CW
                                                    COMPRESSOR   COOLER
                                          -SMETALO-ORGAHICS

                                                 TO
                                                 FLARE
                                                                                  POLYMER
                                                                                  DISCHARGE
                                                                                  TANK
                                                                                             SAFETY
                                                                                             VENTS
                                                                                                 VENT
                                                                            VENT
                                                                            GAS COMPRESSOR
                                                                                   -TO
                                                                                   FLARE
fflP
                                                                          N2^-ST7

                                                                                 TPOLYMER
                                                                                   PURGE
                                                                                 I   TANK

                                                                          AIRS-*-   	
                                                                                      AIR-CONVEYING
                                                                                                          A.O.
                                                                                                   EXTRUDER-PELLETIZER
                                                                                                     TO PELLET  STORAGE
                                                                                                   GRANULE SALES
                                          FEED
                                                                      REACT
                                                                               RECOVER
                        FINISH
                                Figure  12-2.-  HOPE by gas-phase processes.

-------
        taken  from  the reactor [2],  From the reactor,  product
        polymer  is  blown down to a polymer discharge  vessel and
        purge  tank system  for  product recovery.  The  polymer
        discharge vessel vent  is  picked up by  a  separate vent
        compressor and returned  to the reactor.  The  polymer
        purge  tank  is purged with N2 and this  stream  is
        flared  [3].  Product fluff or powder is  air conveyed to
        the  powder  polymer bins for storage and  is captured by a
        baghouse.   Baghouse air is vented to the atmosphere [4].
        A conventional  extruder-pelletizer  finishing  line
        follows  the powder polymer bin storage.

12.3.2  VOC  Emissions (Gas Phase Processes)

        All  significant emissions for gas phase  HOPE  are  shown in
        Figure  12-2 and  summarized  in  Table  12-III0   VOC
        emissions streams are indicated by bracketed  numbers on
        both Figure 12-2 and Table 12-111.

        The  major emission points for gas phase  HDPE processes
        are:

       [1] Comonomer and solvent storage and loading  - Comonomers
          like  butene-1 will be stored under pressure  or with
          inert gas to avoid  oxygen contamination  and safety
          hazards.  Solvents  are  used in  small  quantities for
          catalyst impregnation.  Total emissions are  estimated
          to  be less than 0.01 lb/1000 and are  negligible.
       [2] Compressor Seal-Oil vents; Gas Sample Analyzer Vent -
          Compressor seal oil  becomes saturated with reactor
          contents, primarily ethylene.  These  dissolved gases
          bubble out in the  seal  oil recirculation surge tank
          and  are  vented.  The reactor is controlled by  sampling
          and  analyzing the reactor recirculation flow.  The Gas
                             -150-

-------
                 TABLE  12-111.-  VOC EMISSIONS FROM HOPE MANUFACTURED BY GAS PHASE PROCESSES
 I
M
Ui
             Stream

        [1]   Co-Monomer  and  Solvent
             Storage  and Loading
        [2]   Compressor  Seal-Oil  Vents?
             Gas  Sample  Analyzer  Vent

        [3]   Product  Receiver;  Catalyst
             Dryer
        [4]   Product  Handling-Collect,
             Compound,  A.O.  Feed,
             Pelletizer,  Storage
        [5]   Flare

        [6]   Fugitive

             TOTALS
Uncontrolled
#/1000ft Resin
Neg
0.02
No Data
0.09
0.02
0.13
Current Practice
S/lOOOfl Resin
Neg
0.02
Neg
(Flared)
0.09
0.02
0.13
Well Controlled
/1000# Resin
Neg
0.02
Neg
(Flared)
0.09
0.02
0.13
Composition
Vol %
72% Propylene
18% Butene-1
10% Isopentam
100% Ethylene
Ethylene,
Isopentane
<0.1% VOC
+99% N2



-------
           Sample Analyzer samples a small portion of  the sample
           flow and vents it to the atmosphere;  the bypassed flow
           is  sent to flare.
       [3]  Product  Receiver;  Catalyst Dryer - Potentially the
           largest VOC stream  for  the process, this  stream [3]
           from  the  Polymer Purge Tank  is  flared  in  the  UCC
           version of the process.  The catalyst dryer VOC are
           those volatiles from the organo-metallic compounds and
           solvents used in catalyst impregnations.   Drying is
           accomplished by jacket heat and an N2 purge.   The
           N2  Purge stream bearing catalyst drying VOC  is
           flared.
       [4]  Product Handling Including Collecting, Compounding,
           Anti-Oxidant (A.O.)  Feed, Etc. -  Residual  dissolved
           monomer and other hydrocarbons are stripped from the
           polymer by the flow of conveying air.  Some volatile
           A.O.  material is lost during feeding and  compounding
           and is picked up by machine ventilation.   These are
           large very dilute (about 700 ppm, VOC) streams.
       [5]  Flare - The flare controls the largest potential VOC
           stream, [3], from the product receiver, as well as the
           catalyst drying VOC,  the Gas Sample Analyzer bypass
           flow, and miscellaneous vents.  No data are  available
           concerning inlet or outlet conditions.  It  is assumed
           that outlet VOC is  negligible.
       [6]  Fugitive - Calculated value.

12.3.3   Applicable Control Systems (Gas Phase Processes)

        Controls are discussed for  the  streams described in
        Section 12.3.2 and shown in Figure 12-2  and Table 12-111.

        [1]  Storage and loading VOC emissions for comonomer and
            solvent are less than 0.01 lb/1000,  and controls are
            not warranted.

                             -152-

-------
[2]  Compressor Seal-Oil Vents  and  Gas Sample Analyzer
    Vent  -  VOC emissions are small  and control is not
    warranted at present.   Future  controls  could use
    either local carbon cannister adsorption or piping  to
    flare or  incinerator.
[3]  Product Receiver; Catalyst Dryer -  These are
    potentially large  sources of VOC emissions but are
    completely controlled  by  existing flare systems.   No
    additional controls are needed.
[4]  Product Handling  and Collecting;  Compounding with
    Anti-Oxidant, A.O.   Feed; Pellet Storage - Residuals
    stripped  from the  polymer by conveying air make  up
    most of this VOC emission.   Emissions are low  (0.09
    lb/1000)  and dilute (<700  ppmv)  at present.   If
    controls are needed, some  form  of conveying air
    recycle should be investigated, or incineration in  a
    boiler  may be feasible  if  a capacity match can  be
    made.  Presently no controls are warranted.
[5]  Flare - Well designed  and well-controlled flares can
    achieve greater than 99%  reduction of gaseous VOC  in
    the inlet. The major VOC  bearing  stream (stream [3]
    from  the  Polymer Purge Tank) is flared.  No controls
    are needed for flare exhaust.
[6]  Fugitive - No applicable  controls are known.
                    -153-

-------
                          SECTION 13
                   LOW DENSITY  POLYETHYLENE
13.1  INDUSTRY DESCRIPTION

      Low  density polyethylene (LDPE) resins  are  thermoplastic
      polymers of ethylene produced by free radical addition
      reactions.  They have densities below 0.94  g/cm^.   The
      lower density (compared  to HOPE)  results  from their more
      amorphous  (i.e.   less crystalline) molecular structure.
      Most LDPE resins are homopolymers  but some   are copolymers
      and  these have potential VOC emissions of the comonomers as
      well as ethylene*  The most important  comonomer is vinyl
      acetate; some  others  include  acrylic  acid and  ethyl
      acrylate.

      LDPE resins  are  the largest volume thermoplastic resins
      produced in the U.S.  and  worldwide with U.S.   production
      passing the 7 billion ppy  mark  for the first time  in  1978.

      The  1978  U.S. production of  LDPE was 7110 MM  PPY and
      capacity  was 8245 MM  PPY.   These  figures  represent
      increases of about 9%  for  production and  capacity over
      1977.  Utilization of capacity, K, remained about the same
      for  1978 as for 1977 at  85%, but was climbing at  year's end
      (1978).   K was expected  to reach 91% in 1979, based  on
      anticipated growth and no  new capacity (2), (5).
                             -154-

-------
There are 14  U.S.  manufacturers of LDPE,  counting Phillips
Petroleum's  swing capacity (300-350 MM LDPE),  the  bulk of
which presently also make  HDPE.   Although  UCC  is  the
largest  with  18% of the capacity and DOW  second  with 12%,
there is a wide  distribution of the remaining 70%.  Thus
the market  is  not  particularly dominated by just  a  few
large producers.  Tables 13-1(a) (56)  and  (b)  (57) list the
U.S.  manufacturers of  LDPE and  Table  (b)  gives  the
location and  capacity.  Table 13-1  (a)  is  a simple  summary
of Table 13-1  (b) for size comparison.   Phillip's capacity
is not counted  in these tables although Phillips  is  listed
in Table 13-1  (b).

Current  over-capacity for ethylene  (greater than  30%)
spells  adequate  raw materials  supplys  to  LDPE  resin
producers.  Usually about 1.05 Ib ethylene  is  required to
produce  a pound of product resin.   Conditions  in  the
reactors are  such that ethylene is  a liquid and no solvents
are used except  for naptha to dissolve  the organic peroxide
initiators.   Co-monomers used in some  resins include vinyl
acetate, acrylic acid and  ethyl acrylate.  Potential VOC
emissions are  primarily ethylene due to the high  pressures
used in  the  reactors, but  naptha, organic  iniators,  and
various  co- monomers may also be emitted.

Classically  LDPE was made by high-pressure (15,000 - 50,000
psig)  technology and HDPE  by low (500 -  1500  psig).   New
low pressure  technology (example UCC's  catalyzed  fluid bed
gas phase process) can produce LDPE as  well as  HDPE  so the
classic  distinction no longer exists.   Phillips Petroleum's
Pasadena, Texas, plant is an example with  300 MM  PPY (1978)
HDPE that can  swing to make  LDPE.  It  is  currently  making
HDPE and so  is  listed in Table 13-I(b)  but the  capacity is
not included  in  the total.
                       -155-

-------
  TABLE 13-1(3).-  SUMMARY OF U.S. MANUFACTURERS OF LDPE RESINS
                      AND THEIR CAPACITIES (56)

                 LOW-DENSITY POLYETHYLENE RESINS
                         Major Producers

                 ANNUAL CAPACITY AS OF MID YEAR
                              1978

                 Thousands of Metric         Millions Of
                         Tons                   Pounds

Union Carbide            674                    1,485
Dow                      463                    1,020
Northern Petrochemical   295                      650
Gulf                     386                      850
USI                      324                      715
Du Pont                  320                      705
Cities Service           159                      350
Exxon                    299                      660
Others                   821                    1,810

Total                  3,740                    8,245
                              -156-

-------
    TABLE 13-I(b).-  U.S. MANUFACTURERS OF LDPE RESINS
            AND THEIR LOCATIONS AND CAPACITIES
                                   ANNUAL CAPACITY
                                 AS OF OCTOBER 19 78
CO. & PLANT LOCATION

ATLANTIC RICHFIELD COMPANY
 ARCO/Polymers, Inc., sub.
  Houston, Texas

CHEMPLEX CO. (jointly owned
by American Can Co. & Getty
Oil Company)
  Clinton, Iowa
Thousands of
Metric Tons
    181
Millions of
   Pounds
    400
    141
    310
CITIES SERVICE COMPANY
 Chemical Group
  Columbian Chemicals, division
   Lake Charles, Louisiana       159

DART INDUSTRIES INC.
 Chemical-Plastics Group
  Plastic Raw Materials Sector
  Rexene Polyolefins Company
   Bayport, Texas                 68
   Odessa, Texas                 181
                    350
DOW CHEMICAL U.S.A.
   Freeport, Texas
   Plaquemine, Louisiana
    299
    163
E.I. DU PONT DE NEMOURS & CO., INC.
 Plastics Products and Resins Dept.
  Orange, Texas                  211
  Victoria, Texas                109

EASTMAN KODAK COMPANY
 Eastman Chemical Products, Inc.
 subsidiary, Texas Eastman Co.
  Longview, Texas                113

EXXON CORPORATION
 Exxon Chemical Co., division
 Exxon Chemical Co., USA
  Baton Rouge, Louisiana         299
                    150
                    400
    660
    360
                    465
                    240
                    250
                    660
                              -157-

-------
    TABLE 13-I(b).-  U.S. MANUFACTURERS OF LDPE RESINS
            AND THEIR LOCATIONS AND CAPACITIES (Continued)

                                   ANNUAL CAPACITY
                                 AS OF OCTOBER 1978
CO. & PLANT LOCATION

GULF OIL CORPORATION
 Gulf Oil Chemicals Company
 Plastics Division
  Cedar Bayou, Texas
  Orange, Texas

MOBIL CORPORATION
 Mobil Oil Corporation
 Mobil Chemical Co., div.
 Petrochemicals Division
  Beaumont, Texas

NATIONAL DISTILLERS AND
 CHEMICAL CORPORATION
 Chemicals Division .
 U.S. Industrial Chemicals
 Co., division
  Deer Park, Texas
  Tuscola, Illinois
Thousands of
Metric Tons
Millions of
   Pounds
    249
    136
     550
     300
    136
     300
    249
     75
     550
     165
NORTHERN NATURAL GAS COMPANY
 Northern Petrochemical Co., sub.
 Polymers Division
  Morris, Illinois               295

PHILLIPS PETROLEUM COMPANY
 Plastics Division
  Pasadena, Texas                f

UNION CARBIDE CORPORATION
 Chemicals and Plastics, div.
  Seadrift, Texas                336
  Texas City, Texas              125
  Torrance, California            73
Union Carbide Caribe, Inc., sub.
  Penuelas, Puerto Rico          141
                     650
           Total
  3,740
     740
     275
     160

     310

   8 ,245
                              -158-

-------
13.2     LDPE MANUFACTURE  BY  LIQUID  PHASE (HIGH PRESSURE)
        PROCESSES

13.2.1   Process Description  (Liquid Phase Processes)

        Two primary variations of the high-pressure  liquid-phase
        processes have emerged.  They are based on reactor  type,
        either tubular or autoclave.  For the purposes  of this
        report, these two types and all high-pressure  variations
        of them will  be  treated  as one process.   Reactors are
        operated  continuously with initiator  solution  being
        injected upstream or  directly into the reactor.   Reactor
        effluent  is flashed through separators with ethylene
        recyled.   Melted polymer is  cooled,  blended   with
        antioxidants, and pelletized.   The  polymerization  is
        highly exothermic so  product cooling  is  used  as  well  as
        jacket cooling for tubular reactors.

        A tubular reactor version of this process  is described
        but  it is intended  to apply to  the  autoclave reactor
        version too.

        Referring to  Figure  13-1,  LDPE  by liquid-phase
        (high-pressure)  processes, fresh and.  recovered  ethylene
        streams  are  dried  and  fed  to  the suction  of the
        multi-stage "primary"  compressor where  the  pressure  is
        raised to about 4000 psig.  Co-monomers and  some  recycle
        gas from the high pressure separator  wax K.O. drum join
        the primary compressor  discharge at  the suction  to the
        "hyper" compressor.   The  "hyper" compressor  raises the
        pressure to the 40,000-50,000 psig reactor pressure.  The
        feed  section also  contains  the  initiator (organic
        peroxide, catalyst-like  materials),  initiator  diluent,
        mix  tank,  and  injector pumps.   Prepared initiator
        solution is injected  directly into the reactor downstream

                            -159-

-------
cr>
o
I
                                  TO
                                  SAFETY
                                  FLARE
           FRESH
           FEED
                                                                     PROCESS
                                                                     FUGITIVE
                                                                     EMISSIONS
                  FROM
                  OLEFINS
                  RECOVERY
                                                                           EXTRUDER-
                                                                           PELLETIZER
                          FLARES AND
                          INCINERATION
                          SYSTEMS

                            A.
                            T/WAX FROM K.O.'S
                            "*} SAFETY FLARES,
                               WASTE RESIN,
                               OLEFINS BOTTOMS
                               RESIDUES
                                                                                                  TO WAX
                                                                                                  INCINERATOR
                                                                                      TO  PELLET
                                                                                      STORAGE
                                          VENT/RECYCLE   RECOVERY
                                          COMPRESSOR
                                                          *REACTOR MAY BE AUTOCLAVE
                          FEED
REACT/RECOVERY
                                                                                        FINISH
                   Figure' 13-1.- LDPE by liquid-phase  (high-pressure)  processes

-------
        of  the hyper compressor discharge.   The  tubular reactor
        shown is actually jacketed  and  supplied  with both steam
        (for "light off" or start-up) and cooling water.   Reactor
        effluent is throttled into  the  high  pressure separator.
        High pressure separator overheads  are cooled  for wax
        condensation and returned to  the hyper compressor suction
        via the  high pressure  wax K.O.   drum.   High pressure
        separator bottoms are throttled down to the low pressure
        separator.  The low pressure  separator overheads  are  also
        cooled  for wax removal  and  routed  through  the low
        pressure  wax K.O.   drum to the  vent/recycle  gas
        compressor  and thence to the  olefins recovery unit  (not
        shown) .   The low pressure separator  bottoms  are the
        product  resins still containing residual ethylene
        monomer.   These  product resins  are  routed  to  the
        finishing line where anti-oxidants (A.O.)  are added and
        they  are pelletized  in an extr uder-pelle t i zer .   Hot
        extruded pellets are  water  cooled and  conveyed  to  a
        hot-air dryer.  Most residual ethylene monomer is driven
        from the product resins by  the  extruder - pelleti zer and
        dryer  (vent [3]).   Dried  pellets are air conveyed to
        pellet storage (_55) , (J58_) ,  ( 59 ) .

13.2.2  VOC Emissions (Liquid Phase)  Processes

        All significant emissions from  high  pressure LDPE resin
        manufacture are shown in Figure 13-1 and listed in Table
        13-11 with  bracketed numbers.

        The major emission points of  this process are:

        [1] Additives, initiator systems and hydrocarbon  storage-
           Various liquid hydrocarbon  additives may actually be
           co-monomers like vinyl  acetate or  1-butene, or  they
           may be  modifiers, etc., that are either lost as VOC
           or actually recovered and reused.  Initiator systems
                            -161-

-------
            TABLE 13-11.-  VOC EMISSIONS FROM LDPE MANUFACTURED BY LIQUID PHASE  (HIGH  PRESSURE)  PROCESSES
                 Stream
                            Uncontrolled   Current Practice  Well Controlled
                            /1000# Resin   ft/10008 Resin     fl/lOOOft Resin   Composition
            [1]   Additive Initiator
                 Systems Storage
                               2.10
0.50
0.00
Ethylene; VOC
            [2]   Reactor Slowdown; Reject
                 System Scrubber and Vent
                 Tank                      1.60
                                                 0.70
                 0.00
            Ethylene only
to
 I
[3]   Polymer Extruder;  Dryer;
     Storage                   0.90

[4]   *Wax;  Safety Flares;
     Incinerator for Waste
     Residues                  0.40
0.80
                                                             0.04
                 0.20
                 0.04
            Ethylene; VOC
            0.2% VOC in
            combustion gases
            [5)   Fugitive
                               7.60
1.65
1.65
100% ethylene
                 TOTALS
                                          12.60
                                                 3.69
                 1.89
            'Assumed same as wax incinerator values for HDP3 by Solvent Processes.  See Section  12

-------
    involve the special  organic-peroxide initiators as
    well  as  initiator solvents  such as isopropanol,
    acetone or  naphtha. Various other  hydrocarbon
    additives and solvents are used and stored and stream
    [1]  includes  them.  Emissions are  working  and
    breathing  losses from  tankage and  mixing  tank
    ventilation as well as  valve and pump seal leaks,
    etc.

[2]  Reactor blowdowns; reject system scrubber and reject
    system  vent tank -  Reactor  blowdowns occur when
    pressure surges from the reactor must be relieved.
    Blowdowns are routed to a wetted cyclonic separator
    where  resin fluff is  scrubbed from the gas with
    water.  The resin-water,  separator bottoms slurry is
    routed to a vent  tank where a nitrogen purge  removes
    degassing  ethylene  vapors.   VOC are nearly pure
    ethylene.

[3]  Polymer extruder-pelletizer and dryer, pellet storage
    bins -  Organic liquid additives  especially
    anti-oxidants (A.O.) are incorporated into the resin
    in the extruder and are the major non-ethylene VOC.
    Emissions  arise  from  extrusion,  pelletizing, A.O.
    addition, pellet  drying before storage, and  from the
    pellet  storage bins.   VOC is ethylene and  organic
    (A.O.).

[4]  Wax, waste and  residue incinerator, safety flares - A
    low molecular weight polyethylene  wax is removed  from
    both high and low pressure separator vapor  streams
    after  cooling.  A special incinerator  is  used to
    destroy  this material as well as the waste resin
    (contaminated  or off-spec)  and residues  from the
    olefins  recovery unit (not shown on Figure 13-1).
    Since  the special  incinerator  will not  achieve
                     -163-

-------
            complete  combustion, VOC  will be  various feed
            impurities, low molecular  weight  polymer and residual
            volatiles, and some vaporized  wax or  combustion
            gases.  Data given  in  Table  13-11,  stream  [4],  are
            for  HOPE wax incinerators.   Safety flares  will be
            (primarily) burning ethylene from various relief
            valves,  etc.,  and are  assumed to have complete
            combustion and thus no  VOC.

        [5]  Fugitive process emissions -  Most of these  emissions
            are  reactor cell  (high pressure ethylene) leaks.
            Values shown in Table  13-11 are estimated by industry
            for  LDPE by high pressure  processes.

13.2.3  Applicable Control Systems  (Liquid Phase Processes)

        The  following  controls are  recommended for  the  bracketed
        streams  shown  in Figure 13-1 and  listed  in  Table 13-11.

        [1]  Additives,  initiator systems  and  hydrocarbon storage-
            tankage losses may be  reduced to  nearly zero with
            inert gas  safety padding and  venting to incinerators
            or flares  or to recovery  systems. The  major VOC
            source in  this stream  is  the  uncontrolled  catalyst
            (inititator) system, mix-tank vent.  This  tank should
            be provided with an N2  pad and be vented to  the
            flare or recovery systems.  Demonstrated efficiency
            is nearly  100%.

        [2]  Reactor blowdowns; reject  system  scrubber  and  reject
            system  vent  tank - Although  cyclonic  scrubber-
            separators  have been used to remove resin,  gaseous
            emissions  have been uncontrolled for  these safety-
            related emissions.  Newer  plants  route  these gases to
            special safety flares  and  efficiency of VOC removal
            is essentially 100%.
                             -164-

-------
[3]  Polymer extruder-pelletizer and dryer; pellet storage
    bins - Although older plants do not always have  them,
    applicable controls  for  the extruder-pelletizer
    include collection and flaring or recovery and reuse.
    Pellet storage bin emissions could be greatly reduced
    by  hotwater soaking  after pelletizing  and before
    drying  or  by other  devo1 ati 1 ization means
    demonstrated efficiency is 75%.

[4]  Wax, waste and residue incinerator;  safety  flares -
    Unburned wax was assumed  to  be  50%,  low-molecular-
    weight, polyethylene wax and 50% various hydrocarbons
    (based on industry data for HOPE).   About 0.8 Ib of
    wax was  produced per  1000 Ib  of HDPE and  this 0.8
    lb/1000 Ib was arbitrarily assumed for high  pressure
    LDPE.  The "uncontrolled"  value in Table 13-11 is 50%
    (0.8) = 0.4 lb/1000 (wax was  assumed  not volatile),
    and the  "controlled"  value (95%  efficiency wax
    incinerator) is 5%  (0.8)  =  0.04  lb/1000.  These
    values  were obtained  by  assuming  the incinerator
    makes an aerosol VOC of the unburned wax and  that the
    95% efficiency applies to  waste  resin and residues.
    No  controls are needed for  incinerator  effluent.
    Safety flares were assumed  100%  efficient  in
    combustion and so have no VOC or need for controls.

[5]  Fugitive process emissions - High  pressure reactor
    cell leaks account for most fugitive  emissions in a
    high pressure LDPE unit.   No applicable controls are
    known.  Generally,  newer  units  have  lower  fugitive
    emissions  probably  due  to  better   seals  and
    construction techniques.   In a well-controlled older
    plant,  fugitive emissions are  the  major source of
    VOC.
                     165-

-------
13.3     LDPE MANUFACTURE BY GAS  PHASE PROCESSES

13.3.1   Process Description (Gas Phase Processes)

        Union Carbide Corporation's (UCC) low pressure  gas phase
        LDPE process serves as the basis for  this  description,
        but it is intended  to represent others also.   Although
        UCC does not now have a  commercial gas phase  LDPE unit,
        they are making market-test quantities of product resin
        in a converted  HOPE gas-phase unit  of  similar
        construction.  The VOC emissions  in  Table 13-111  are
        projections for a UCC planned, 300 MM PPY  unit.

        The process description  below is the same as  that given
        under Table  12-111,  HOPE manufacture  by gas  phase
        processes, except for the  chapter number headings  and for
        the process schematic, Figure  13-2,  and Table  of  VOC
        emissions, Table 13-111.

        Reference  to Figure  13-2, LDPE  by gas  phase  (low
        pressure) processes,  indicates that the "Feed"  section of
        the flowsheet also  depicts catalyst preparation.  Silica
        gel  is   impregnated  with  chromium  oxide via
        metallo-organic compounds  and water  and hexane solvent.
        Impregnated catalyst  is  dried with warm inerts  t^)
        and  the  resulting VOC  stream,  [3],  is  flared.   Dried
        catalyst is conveyed  into the  reactor  fluidized  in
        N2  Gas phase processes do not require catalyst
        recovery systems because the  high-activity  catalyst
        remains with the product polymer.
        Ethylene  monomer  and  suitable comonomers (such as
        butene-1) are fed to the reactor along with  the catalyst


                            -166-

-------
 FRESH
 FEED
            BUTENE-1
            CO-KONOMER
       RECYCLE
FRESH
      ETHYLENE MONOMER
                       A
             CAT SUBSTRATE
AIRfr-
                CAT ACTIVATION
                                             ETHYLENE^         _
                                                  CIRCULATION   CW -
                                                   COMPRESSOR   COOLER
                                          SMETALO-ORGANICS
                                                 FLARE
                     SOLVENTS 9-i
                                                                                     CAT  f3")
                                                                                   DRYING LJ
                                                                                   POLYMER
                                                                                    PURGE
                       FLARE &
                     INCINERATOR
                       SYSTEMS
                                                                                          SAFETY
                                                                                           VENTS
                                                                                 POLYMER
                                                                                 DISCHARGE
                                                                                 TANK
                                                                                                 VENT'I (V):
  |VBNT
   GAS COMPRESSOR
           FLARE
 N2$~-S~7

        TPOLYMER
A.O. f-*J  PURGE
    "^n  TANK

 AIRJ-*
                      SHIPPING
                      PACKAGING
                      LINE
                                                                                     AIR-CONVEYING
CO
                                          FEED                        REACT         RECOVER

                       Figure  13-2.-  LDPE by gas-phase (low pressure)  processes,
                             FINISH

-------
                   TABLE 13-111.- VOC EMISSIONS FROM LDPE MANUFACTURED BY GAS PHASE (LOW PRESSURE) PROCESSES
00
 I
               Stream

               [1]   Co-Monomer and Solvent
                    Storage and Loading
               [2]   Compressor Seal-Oil Vents;
                    Gas Sample Analyzer Vent

               [3]   Reactor Slowdown;  Product
                    Receiver;  Catalyst Dryer
               [4]   Product Handling-Collect,
                    Compound,  A.O.  Feed,
                    Pelletizer,  Storage
               (5)   Flare*

               (6)   Fugitive

                    TOTALS

               *99.8%  combustion efficiency claimed.
Uncontrolled
#/1000# Resin
0.01
0.01
34.6
0.10
H /i
IM/ /*
0.02
34.7
Current Practice
#/1000# Resin
Neg
(Flared)
Neg
(Flared)
Meg
(Flared)
Neg
(Flared)
OA7
. U /
0.02
0.09
Well Controlled
#/1000# Resin
Neg
(Flared)
Neg
(Flared)
Neg
(Flared)
Neg
(Flared)
Om
. u /
0.02
0.09
Composition
Vol %
5% Butene-1
95% Isopropanol
100% Ethylene
N2,
Isopropanol
<0.1% VOC
+99% N2
100% Ethylene


-------
        where polymerization takes place  around  small catalyst
        particles.

        After fluid-bed polymerization  (UCC  technology)  in the
        reactor,  product polymer  is  blown down to  a polymer
        discharge vessel and  purge  tank system for product
        recovery.  The reactor  is  fluidized and the reaction
        controlled by recirculating a  large flow of gas and  fines
        through a circulation compressor and coolers.  Compressor
        seal-oil  (saturated  with  ethylene)  vents  and  gas sample
        analyzer  vents are  taken  from  the reactor  [2] .   The
        polymer discharge vessel  vent  is picked up by  a separate
        vent compressor and  returned to the reactor.   The  polymer
        purge tank is purged with N2 and this stream is
        flared.  Antioxidant (A.O.) is metered  to the line and
        product granules are blown  to  the powder polymer  bin via
        air and are captured there  by  a baghouse.  Baghouse air
        is vented  to the  atmosphere  [4] .   A  conventional
        packaging line follows  the  powder polymer  bin  storage.

13.3.2   VOC Emissions (Gas Phase  Processes)

        All significant emissions for  gas phase LDPE are shown  in
        Figure 13-2  and summarized in  Table  13-111.   VOC
        emissions streams are indicated by  bracketed  numbers  on
        both the figure and  the table.

         The major emission  points  for gas-phase  LDPE processes
         are:

         [1]  Comonomer and  solvent storage  and  loading  -
            Comonomers like  butene-1  will  be stored  under
            pressure  or  with inert gas  to  avoid  oxygen
            contamination and  safety  hazards. Solvents are used
                             -169-

-------
    in  small quantities for catalyst  impregnation. Total
    emissions are estimated to  be  less than 0.01 lb/1000
    and are negligible.

[2]  Compressor Seal-Oil vents;  Gas Sample Analyzer Vent-
    Compressor seal oil becomes saturated with  reactor
    contents, primarily ethylene.   These dissolved gases
    bubble out in the seal oil  recirculation surge  tank
    and  are vented.  The reactor  is controlled  by
    sampling and analyzing  the  reactor recirculation
    flow.   The Gas  Sample Analyzer samples a small
    portion of the  sample flow  and vents  it to  the
    atmosphere; bypassed flow is  sent to flare.

[3]  Reactor Slowdown; Product Receiver; Catalyst  Dryer-
    Potentially the largest VOC stream for the  process,
    this stream [3]  from the Polymer Purge Tank  arises
    from product charges and from shutdown/startup.  It
    is  flared in the UCC  version of the process.   The
    catalyst dryer VOC are  those volatiles  from  the
    organo-metallic compounds and  solvents used  in
    catalyst impregnations.  Drying is accomplished  by
    jacket heat and an N2  purge.   The N2 purge
    stream that  bears catalyst drying VOC is  also
    flared.

[4]  Product Handling Including  Collecting, Compounding
    Anti-Oxidant (A.O.) Feed, Etc. - Residual dissolved
    monomer and other hydrocarbons are stripped from the
    polymer by the flow of conveying  air.  Some volatile
    A.O.   material  is   lost during  feeding  and
    compounding and is picked up  by machine ventilation.
    These are large very dilute (hundreds of  ppm,  VOC)
    streams.

                    -170-

-------
        [5] Flare - The flare  controls the largest potential VOC
           stream, [3],  from  the product receiver as  well as the
           catalyst drying VOC, the Gas  Sample  Analyzer bypass
           flow, and miscellaneous vents.   It  is assumed  that
           outlet VOC  is only 0.07 lb/1000  since  claimed
           efficiency is 99 .8%.

        [6] Fugitive - Same as for HDPE by gas phase  processes.

13.3.3   Applicable Control Systems and Efficiency for Gas Phase
        LDPE Processes

        Controls are discussed for the  streams described  in
        Section 13.3.2 and shown in Figure 13-2  and Table  13-111.

        [1]  Comonomer and solvent  storage and loading VOC
           emissions are less than 0.01 lb/1000, and  controls
           are not warranted.

        [2] Compressor Seal-Oil Vents and  Gas  Sample  Analyzer
           Vent - VOC emissions are small and flare  control is
           provided.  No additional controls are needed.

        [3] Reactor Slowdown;  Product Receiver;  Catalyst Dryer -
           These are potentially large sources  of VOC emissions,
           but they are completely controlled by existing flare
           systems.  No additional controls are  needed.

        [4] Product Handling  and Collecting; Compounding  with
           Anit-Oxidant,  A.O.  Feed;  Pelletizer and Storage -
           Stripped  residuals from  the  polymer removed  by
           conveying air make up most  of  this VOC emission.
           Emissions are low  (0.10 lb/1000), dilute (<1000 ppmv)
                            -171-

-------
    at  present, and are flared.  No  additional controls
    are needed.

[5]  Flare - Well-designed and well-controlled flares  can
    achieve greater than 99% reduction of gaseous VOC  in
    the inlet.   It was  assumed  this  flare was 99.8%
    efficient.  The major VOC bearing stream (Stream  [3]
    from the Polymer Purge Tank) is flared.   No controls
    are needed  for flare exhaust.

[6]  Fugitive -  No applicable controls known.
                     -172-

-------
                          SECTION  14
                         POLYPROPYLENE
14.1  INDUSTRY DESCRIPTION AND STATUS

      The  principal characteristics of polypropylene that have
      contributed to its rapid growth and acceptance are:

      o   Comparatively low density;
      o   Improved stiffness, deflection  temperature, clarity,
          stress-crack resistance, chemical  resistance, and
          electrical  insulating properties  as  compared  to
          low-density polyethylene;
      o   Mechanical strength properties  sufficient to compete
          with more  costly engineering plastics in  many
          applications;
      o   Good injection-molding  characteristics;
      o   Ability to be drawn and oriented  -  this  is the basis
          for  the  production of  polypropylene fibers,  and  of
          oriented film and bottles.

      Polypropylene  of commercial value  could, not be produced
      until  the stereospecific catalysts were  discovered in the
      1950's.  Because  of  the  methyl  group it  contains, a
      molecular unit of  polypropylene is  asymmetric  and can
      assume either of these two  regular geometric arrangements;
      isotactic, with all methyl  groups aligned on the same side
      of the chain, or  synd iotactic,  with the methyl  groups
      alternating.  All other forms, in which this positioning is
      more or less random, are called atactic.   First prepared by
                              -173-

-------
Giulio Natta  in  1954,  only the isotactic form  is of
commercial  interest.

Because  it is  linear and  stereoregular,  isotactic
polypropylene  is capable of crystallization when cooled
from  the melt.   Typically, commercial  samples of
polypropylene contain  about 70% crystalline material
(isotatic), with the remainder  amorphous (atactic).  A
significant drawback  of polypropylene  is  its
comparatively  low, low-temperature  impact strength.  To
improve this property, blends  with  ethylene-propylene
elastomers, and copolymers containing 5 to 20%  ethylene,
were  introduced.   Other  drawbacks  of  polypropylene
include its narrow melt  range  and  its  tendency to sag
when hot.   These weaknesses have  prevented it from making
deep  penetration  of some  large thermoplastic  resin
markets.  The  major current uses  of polypropylene are:
                                         Wt%
       Fiber  products                   30%
       Car and Truck Parts              15%
       Packaging                        15%
       Toys,  housewares                  5%
       Appliance Parts                   5%
       Other                            30%
                            Total       100%

The automotive market for polypropylene has been growing
at  a  rate  faster  than has  the  to'tal  demand  for
polypropylene, mainly  because  of its displacement of
steel (due  to  its lighter weight).  Fiber products of all
kinds actually  make  up  the largest  single use of
polypropylene. These uses account for nearly a third of
domestic  U.S.  consumption, and they  grow  at close  to or
slightly  above the rate for all  polypropylene (an average
rate  of  8% annually) .   Packaging  ranks  close to

                     -174-

-------
automotive  use  in importance as  a polypropylene outlet.
Most  attention  in packaging  uses  goes  to  oriented
polypropylene  films, which are  cutting  into use of
cellophane dramatically.   Other  uses - for  example,
bottles,  certain wire and cable  coverings, and appliance
parts -  have  small market bases,  large  growth rates,  and
big potential.

Polypropylene resins  are supplied in  many grades  for  a
variety  of  uses.  There  are major distinctions between
homopolymer,  intermediate-impact copolymer, and  high-
impact copolymer, the grades may also differ in  specific
formulation.  New super-active  catalyst systems of  the
type that have been  successfully used in high-density
polyethylene  production for some  time are beginning  to be
used in  polypropylene production.

Polypropylene  resins are  converted  to end  products
through  injection molding and through  variations of  the
extrusion  process.  Filament  extrusion  is- the  most
important of  the latter.

Key data showing  the 1977 supply/demand picture of
polypropylene in the United States (2), (60)  are
tabulated below:

POLYPROPYLENE RESINS - U.S.  SUPPLY/DEMAND, 1977
             (Millions of  Pounds)

 ANNUAL  PRODUCTION CAPACITY (year-end)        3,658
 ESTIMATED  PRODUCTION                        2,750
 ESTIMATED  DOMESTIC CONSUMPTION               2,470
 ESTIMATED  EXPORTS                             280
                     -175-

-------
        Demand levels  and  corresponding  U.S. polypropylene
        capacities  are tabulated,  as follows,  for  the period
        1978-1980 with projections for  both the  basic  and
        extraordinary set  of demand  assumptions,  (j>) , (60) .

             U.S.   POLYPROPYLENE  CAPACITY VERSUS  DEMAND
                              1978          1979           1980
                         Basic  Extra*  Basic  Extra*  Basic  Extra*

Average Annual Demand       8%  .    10%     8%     10%     8%     10%
 Growth Rate

Total Demand (Millions   2,973   3,028  3,.214    3,333   3,474  3,670
 of Pounds)

Effective Capacity,  (90%      4,325          4,795           4,795
 of Nameplate, Millions
 of Pounds

Capacity Utilization      69%      70%     66%    69%    72%     76%

*Extra = Extraordinary
        Polypropylene demand  is  projected  to grow at an average rate
        of 8.0% per year.  This  assumes  a GNP growth on the  order of
        3.5% and one year  of  very low or zero growth in five years.

        U.S. producers of  polypropylene are listed in Table 14-1,
        and this includes  the new capacities already announced for
        completion through 1979,  (61).
                             -176-

-------
      TABLE 14-1.- U.S. PRODUCERS OF POLYPROPYLENE  RESINS  (61)
COMPANY AND PLANT
   LOCATION
START-UP     ANNUAL YEAR-END CAPACITY
  YEAR         (MILLIONS OF POUNDS)
             1977               1979
ATLANTIC RICHFIELD CO.
 ARCO/Polymers, Inc.
  subsidiary
    La Porte, Texas3         1962
DART INDUSTRIES, INC
 Chemical Group
  Plastic Raw Material
  Sector, Rexene Poly-
  olefins Company
    Bayport, Texas          1976
    Odessa, Texas           1966
EASTMAN KODAK CO.
 Eastman Chemical Prod.,
 Inc., subsidiary Texas
 Eastman Company
    Longview, Texas         1960
EXXON CORPORATION
 Exxon Chemical Co.
 division Exxon Chemical
 Company, U.S.A.
    Baytown, Texas          1960
GULF OIL CORPORATION
 Gulf Oil Chemicals Co.
 division, Plastics Div.
    Cedar Bayou, Texas      1978
HERCULES INCORPORATED
 Polymers Department
    Bayport, Texas          1974
    Lake Charles, LA        1961
               280
 400
              150
              150
150
150
              140
140
              500
550
              400
              750
                                 400
400
750
                              -177-

-------
       TABLE 14-1.- U.S.  PRODUCERS OF POLYPROPYLENE  RESINS  (17)
                             (Continued)
 COMPANY AND PLANT
    LOCATION
START-UP     ANNUAL YEAR-END CAPACITY
  YEAR         (MILLIONS OF POUNDS)
             1977               1979
 NORTHERN NATURAL GAS CO.
 Northern Petrochemical Co.
  subsidiary, Polymers Div.
     Morris, Illinois        1978
 NOVAMONT CORPORATION
     Kenova, West Virginia   1961
     La Porte, Texas         1979
 PHILLIPS PETROLEUM CO.
  Plastics Division
     Pasadena, Texas         1970
 SHELL CHEMICAL COMPANY
     Norco, Louisiana        1977
     Woodbury, New Jersey    1963
 SOLTEK POLYUMER CORP.
     Deer Park, Texas        1978
 STANDARD OIL CO. (IND)
  Amoco Chemicals Corp.,
  subsidiary.
     Chocolate Bayou, Texas  1971
     New Castle, Delaware    1960
              160
              180

              150
              300
  200

  160
  265


  180

  300
  300

  200
              275
              250
  575
  250
 TOTAL
            3,685
5,370
aPlant was acquired from Diamond Shamrock Corporation  in  April  77.
                               -178-

-------
14.2     POLYPROPYLENE MANUFACTURE

14.2.1   Process Description

        Commercial  polypropylene resins are characterized by
        having a controlled content of isotactic material.  They
        are  obtained  through  coordination  polymerization,
        employing a  heterogeneous Ziegler-Natta type catalyst
        system,  which  typically is a combination of  titanium
        tetrachloride and  aluminum alkyls.

        The  process  described  here is a  continuous  slurry
        process;  it  is  the most widely used commercially.   Figure
        14-1 shows a schematic  for the process.  The major raw
        material, propylene, is stored in pressure vessels while
        methanol solvent and  hexane diluent are  stored in
        vertical floating  and fixed roof  storage tanks.

        The  process steps consist of mixing and metering  the
        catalyst system, manufactured  on  site,  into  the
        polymerization reactor along with  propylene  and  the
        diluent hexane,  which acts as a heat  transfer agent and
        polymer-suspending medium.  A portion of the mixture of
        polymer/monomer/diluent  is continuously fed to a flash
        tank where  volatile components, mostly propane  and
        unreacted propylene, are vaporized,  withdrawn,  and
        recovered.   Slurry  from the flash tank is fed  to  the
        deactivation/decanting section for washing with methanol
        to remove most of the  catalyst residues.   The  light
        hydrocarbon  crude product slurry  is decanted from the
        heavy methanol-water phase; the latter is fed to methanol
        recovery.   The  light crude  product  slurry, containing
        isotactic  polymer product  solids  and  an atactic
        polymer-hexane  solution,  is  fed  to  a centrifuge, where
        the  two  phases are  separated.  The isotactic  polymer
                            -179-

-------
                                                                                                         TO FLARE
OD
O
 I
                                                          cn
                                                     CHILLER I    J
                                                                                       TO WASTE WATER TREATMENT

                                                                                       TO WASTE OIL TREATMENT
                                                                                     . ATATIC  POLYMER  TO
                                                                                       RECOVERY OR LANDFILL
                                                                                          EXTRUDER/PELLETIZER
                                                            DEACTIVATION/DECANTING
                                                                  SECTION .
                                                                                                            PELLET
                                                                                                           STORAGEl
EXAU,ST AIR
   ii
                                                                                                                          CYCLONE
                                                                                                                             PRODUCT
                                                                                                                        (TO HOPPER CARS)
    PELLET PRODUCT
  (TO BAGS,CARTONS,
    OR HOPPER CARS)
                                               INCLUDES VIRGIN, RECOVERED
                                                AND SPENT MATERIAL
               FEED
                                    REACT
                                                                         RECOVERY
                                                                                                                 FINISH
                                Figure  14-1.-  Polypropylene  - Continuous slurry  process,

-------
solids layer  is  fed to  the product drier  while the
atactic-hexane  solution phase is  fed  to diluent recovery.
Dried polypropylene/ containing less  than 0.5% volatiles
by weight,  is extruded, pelletized and sent  to product
storage.

In the methanol  recovery section,  the crude methanol
streams are refined and recycled  and  the bottoms streams,
mostly water and  catalyst  metals  are  sent to  sewer.   In
the hexane  recovery section,  hexane is purified and dried
for recycle, and the  atactic solids are recovered  or
landfilled. The  water stream containing small amounts  of
hexane is sent  to sewer or recycled for cooling water.

Methanol,  a polar materal,  is  a catalyst deactivation
agent when  intermixed with the flash  tank slurry.   Highly
corrosive products are formed  by catalyst residues  so
that  construction  materials exposed to them  must  be
designed  accordingly and special  efforts must  be made  to
minimize  such residues in  the process.  Catalyst residues
also  affect the resins  processing characteristics
adversely.

While  all  of the installations  for which  data were
received use the process  described, continuous  slurry
with  a Zieg 1er-natta type catalyst,  a few  process
differences were  noted.  One  producer used a  mixture  of
aliphatic hydrocarbons with  10  to 12 carbon  atoms as  a
process  diluent  rather  than hexane.  In another case
isopropyl  alcohol replaced methanol  as  a washing/
deactivation agent.  Minor differences exist,   in certain
processes,  in  equipment  used  (in  the  deactivation/
decanting section) for removing  catalyst residues from
the polymer and diluent from  the  slurry.
                     -181-

-------
        Besides the common method of  extruding and pelletizing
        product, some facilities may also  send it to storage  in
        flake  form.  Polymer dryers vary  with the facility but
        the  fluid bed dryer with hot nitrogen or air is now the
        most common.  Most plants use  nitrogen blanketing to  some
        degree on  process  systems  and/or  storage,  and one
        facility reported nitrogen blanketing of essentially the
        entire system.
14.2.2   VOC  Emissions
        All  emission rates  and  sources for  this product are
        listed on Table 14-11,  and  the  sources are shown on the
        flowsheet,  Figure  14-1.   Numbers  for  the streams
        discussed  below  are  consistent with  the numbers
        designating the same streams  used on the table and on the
        flowsheet.

        [1] Alcohol  and process diluent  storage tanks - These
           streams  vent organic  vapors  in  nitrogen (used for
           inert blanketing) during normal  tank breathing and
           filling.  The VOC portion of each  stream is composed
           only of the alcohol  or  process  diluent stored.  The
           numbered stream represents  the  total emissions from
           all such tanks.

        [2] TiCl^ and aluminum  alkyl  liquid storage tanks
           (catalyst raw materials)  -  These streams vent  organic
           vapors  from  the catalyst manufacturing  section
           storage during normal breathing and filling.  VOC  is
           process diluent (i.e.,  hexane)  in  blanket nitrogen.
                            -182-

-------
     TABLE 14-11.- VOC EMISSIONS FROM POLYPROPYLENE  MANUFACTURE
                   BY A CONTINUOUS SLURRY PROCESS
                                       Current
                      Uncontrolled     Practice   Well  Controlled
Stream                #/1000# Resin  #/1000#Resin   #/1000#  Resin
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
Liquid Storage:
Alcohol; Diluent
Aluminum Alkyl and
TiCl4 Storage
Catalyst Manufacturing
Section
Polymerization Reactor
Deactivation/
Decanting Section
Alcohol Recovery
Section
Diluent Recovery
Section
Product Dryer;
0.18
0.01
0.13
4.07
21.30
Nil
11.40
8 .02
0.08
Nil
0.01
0.00
0.06
Nil
0.32
2.99
0.00
Nil
0.00
0.00
0.00
Nil
0.00
0.15
     Extruder/Pelletizer
     Section

[9]  Fugitive. Primarily    0.39           0.39           0.39
     API Separator
Total                     45.50           3.85           0.54
                              -183-

-------
[3]  Catalyst manufacturing  section -  This stream is
    similar  to [2] .   It vents volatile organic vapors
    dispersed  in  blanket  nitrogen but with  an
    approximately equal  amount of ethane (not within VOC
    definition).  One of the relatively small  emission
    streams,  [3]  is  effectively controlled in  current
    practice.'

[4]  Polymerization reactor - This  stream vents  organic
    process  off-gases,  mostly  propane and unreacted
    propylene with some  diluent vapors.   A  large amount
    of blanket nitrogen  from  the reactor accompanies the
    organic off-gases.

[5]  Process deactiyation/decanting section -  This stream
    is process diluent and wash alcohol  vapors in blanket
    nitrogen.  It is  the largest source  of VOC emissions
    in  the  typical plant before  control   but  is
    effectively controlled in current practice.

[6]  Alcohol  recovery section - VOC, primarily  process
    alcohol vapors and traces of by-product  organics such
    as  cyclohexane, are vented  with inert  blanket
    nitrogen.  Venting occurs when  the  recovery  section
    is in (normally continuous) operation and emissions
    are small.

[7]  Diluent recovery  section - This  stream  vents  inert
    blanket  nitrogen with small  amounts  of volatile
    organic  compounds.   VOC are  composed  of  diluent
    (hexane)  and alcohol (methanol) vapors and  other
    organics such as  ethane (not considered  a VOC).  This
    stream is the second largest VOC emission stream in a
    typical  plant (prior to  control)  and the  third
    largest source of VOC emissions  in  current  practice
    (after control).
                     -184-

-------
        [8] Product dryer  and extruder/pelletizer section -  This
           stream vents the  product dryer near the end of the
           production  train.   Emissions  from the  extruder/
           pelletizer are included.  The dryer emission is the
           largest VOC  stream emitted to the atmosphere from  a
           typical  plant  as  currently practiced.   The
           extruder/pelletizer stream  is much  smaller  both
           potentially  (uncontrolled)  and controlled  (current
           practice) .   A single  vent system  and  control
           technology could serve both sections in some process
           design  schemes.   Emissions  consist  of  vapors of
           hexane, methanol,  and propane,  and (possibly)  some
           propylene diluted  by a large  quantity  of drying
           medium, commonly, hot N2

        [9] Fugitive -  Most  fugitive emissions arise  from the
           waste  organic/water separator (API) serving  the
           section.  VOC  are  mostly process alcohol with  some
           diluent and  other organic solvents.   Fugitive
           emissions  are the  second  largest source of  VOC
           emissions from a typical plant with current practice.

14.2.3   Applicable Control Systems

        The following control  technologies are recommended for
        the emission streams described in Section  14.2.2 and on
        Figure 14-1. Flaring with or without refrigerated vapor
        condensation is  the control system recommended for the
        majority of emissions.   This system has a high control
        efficiency (90% assumed) and is  commonly practiced.
        Sale, or use as  a  boiler fuel, now common for some  of the
        emission streams,  constitutes complete abatement (100%
        abatement) and  is  equivalent to any recommended control
        technology.  Actual  flare  systems used are subject to
        normal design considerations such as available pressure,
        required line sizes and  materials,  cross  contamination
                            -185-

-------
        (within  a process section) flammability,  etc.
        [1]  Alcohol and  process diluent storage  tanks  -
            Refrigerated vent condensers on each  vent  followed by
            flaring.3  100% control efficiency was  assumed.
        [2]  TiCl4 and aluminum alkyl liquid storage tanks -
            Refrigerated vent condensers on each  vent  followed by
            seal pots.  No additional  controls are  needed.
        [3]  Catalyst manufacturing section - Refrigerated vent
            condenser followed by flaring.  100% efficiency was
            assumed.
        [4]  Polymerization reactor -  Flaring vent stream.  No
            additional controls are required.
        [5]  Process deactivation/decanting section  - Flowing vent
            stream.  100% efficiency was assumed.
        [6]  Alcohol recovery  section  -  Refrigerated  vent
            condenser.  No additional  controls are  required.
        [7]  Diluent recovery  section  -  Refrigerated  vent
            condenser followed by flaring.  100% efficiency was
            assumed.
        [8]  Product dryer  and  extruder/pelletizer  section  -
            Flaring of vent streams preceded by refrigerated vent
            condenser on dryer  vents  only. 95% efficiency was
            assumed.
        [9]  Fugitive - Enclose separation vessel with necessary
            control systems.  The organic phase should be   piped
            to waste or slop oil treatment arid the  water phase to
            waste  water treatment.  An acceptable alternative
            control scheme would  be an enclose.d tank or  vessel
            with a vapor recovery system.  No  control  was
            assumed.
aprocess economics  frequently dictate use  of  cooled  and/or
 refrigerated  vent  condensers in these services.
                             -186-

-------
                          SECTION 15
                      POLYSTYRENE RESINS
15.1  INDUSTRY DESCRIPTION

      Polystyrene offers  a  combination of excellent physical
      properties and processability at  a  relatively low price for
      thermoplastic materials.   It is crystal clear and  has
      colorability, rigidity, good electrical properties, thermal
      stability, and high flexural  and tensile strengths.   The
      family  of polymers and copolymers from styrene monomer and
      its  modifications ranks third in  all  plastics consumption
      in this country.

      Products made of polystyrene include  packaging materials,
      refrigerator linings,  major and small  appliance parts,
      containers, radio  and  television housings,  housewares,
      toys, insulation for lighting and signs,  insulating  boards
      and  cups, automotive components, telephones, and machine
      parts.

      The  demand for polystyrene  did not  grow rapidly until after
      World War II, when the many plants  built  during  the  war to
      supply  styrene monomer for  GR-S synthetic  rubber production
      began to make a large quantity of  relatively inexpensive
      styrene monomer available.   Polystyrene resins are marketed
      in general  purpose  (styrene homopolymer) and rubber
      modified impact grades (typically homopolymer plus   5-10%
      of polybutadiene rubber).   Slightly more   than one half of

                             -137-

-------
        the  polystyrene sold  is  impact grade.   Polystyrene is
        often  marketed  in pellet or bead form; however,  some is
        captively  converted to film, sheet,  and  foam.

        There  are  approximately seventeen major  manufacturers of
        polystyrene  resins in the U.S.  These producers are  shown
        in Table 15-1 as follows (65).

        Production of polystyrene  resins in  the  U.S.   for 1978
        (2)  was 3823 MM pounds including exports.   The  projected
        U.S. consumption growth rate for the period of  1977-1982
        is 3 .9-5.9%/year.    Using  5% growth  and  the  1978
        production,  a 1979 capacity estimate (jj)  of  5373 gives
        utilization, K = 0.75.

15.2     MANUFACTURE  OP' POLYSTYRENE  RESIN BY  BULK  (MASS),
        SUSPENSION,  OR BULK-SUSPENSION PROCESSES

15.2.1  Process Description

        The  processes described here and shown on  Figure  15-1 are
        the  most  widely  used today for producing polystyrene
        resins.  The equipment shown can be  used   to make either
        general purpose grade or impact grade polystyrene by the
        suspension  process,  the bulk  (mass) process,  or the
        bulk-suspension process (63 ) , (66).

        The  suspension process is,  alone or  in .conjunction with
        bulk prepolymerization (the bulk-suspension process), the
        most widely used process  for polystyrenes today.  The
        bulk or mass process was formerly the most widely used.
        Suspension polymerization  is  essentially mass
        polymerization  taking place in small  spherical  droplets
        of monomer suspended  in  water;  each  droplet  acts as an
                             -188-

-------
       TABLE 15-1.- U.S. PRODUCERS OF POLYSTYRENE RESINS (65)

                                    ESTIMATED ANNUAL CAPACITY AS OF
COMPANY AND PLANT LOCATION          JULY 1, 1977 (in Millions of Ibs)

 A & E PLASTIK PAR CO., INC.
 A & E Plastics Division
  City of Industry, California                             45
AMERICAN HOECHST CORPORATION
 Foster Grant Company, Inc., sub.
  Plastics Division
    Chesapeake, Virginia                   210
    Leominster, Massachusetts              120             610
    Peru, Illinois                         280
AMERICAN PETROFINA, INCORPORATED
 Cosden Oil & Chemical Co., subsidiary
    Big Spring, Texas                      150
    Calumet City, Illinois                 270             420
 Polymer Research Inc., subsidiary
    Orange, California                      60
    Windsor, New Jersey                    120             180
ATLANTIC RICHFIELD COMPANY
 ARCO/Polymers, Inc., subsidiary
    Beaver Valley, Pennsylvania                            440
BASF WYANDOTTE CORPORATION
 Polymers Group
  Styropor Division
    Jamesburg, New Jersey                                   95
DART INDUSTRIES INC.
 Chemical Group
  Plastic Raw Materials Sector
   Rexene Styrenics Company
    Holyoke, Massachusetts                 60
    Joliet, Illinois                       40              130
    Santa Ana, California                  30
DOW CHEMICAL U.S.A.
    Allyn's Point, Connecticut            150
    Ironton, Ohio                         180"
    Joliet, Illinois                      130              920
    Midland, Michigan                     260
    Torrance, California                  200
CARL GORDON INDUSTRIES, INC.
 Gordon Chemical Company Division
    Oxford, Massachusetts                 110
 Hammond Plastics Division
    Worcester, Massachusetts               75              265
 Hammond Plastics - Midwest, Inc.
    Owensboro, Kentucky                    80
                              -189-

-------
TABLE 15-1.- U.S.  PRODUCERS OF POLYSTYRENE RESINS (continued)

                                   ESTIMATED ANNUAL CAPACITY AS OF
COMPANY AND PLANT LOCATION         JULY I, 1977 (in Millions of Lbs)

HUNTSMAN CHEMICAL AND OIL CORPORATION
    Troy, Ohio                                              30
MONSANTO COMPANY
 Monsanto Plastics & Resins Company
    Addyston, Ohio                        300
    Decatur, Alabama                      100              800
    Long Beach, California                 50
    Springfield, Massachusetts            350
PLASTIC SERVICES AND PRODUCTS INC.
 S.P. Polymers, Inc., division
    Los Angeles, California                                 20
POLYSAR GROUP
 Polysar Plastics Inc.
  D.C. Division, Polystyrene Plant
    Forest City, North Carolina                             40
 Polysar Resins Inc.
    Copley, Ohio         '                 120              235
    Leominster, Massachusetts             115
THE RICHARDSON COMPANY
 Plastics Group
  Polymeric Systems Division
    Channelview, Texas                     50
    West Haven, Connecticut                40
SHELL OIL COMPANY
 Shell Chemical Company, division
    Belpre (Marietta), Ohio                                220
STANDARD OIL COMPANY (INDIANA)
 Amoco Chemicals Corporation, subsidiary
    Joliet, Illinois                      250
    Medina, Ohio                           45              320
    Torrance, California                   35
    Willow Springs, Illinois               35
UNION CARBIDE CORPORATION
 Chemicals and Plastics, division
    Bound Brook, New Jersey               125
    Marietta, Ohio                        225  '            350
UNITED STATES STEEL CORPORATION
 USS Chemicals, division
    Haverhill, Ohio                                        225

TOTAL                                                    5,345
                              -190-

-------
                                                                   VACUUM
                                                                    PUMP
                                                                              DEMISTER
                                                                                       CENTRIFUGE.   |	,


                                                                                                   (D^FER)'  I
                                                                                         FAN/DEMISTERI  I

                                                                                                   A  n
                                                                                                   Mil 11II'  \/
                                                                                                         ^TO FLARE
            DISSOLVER    PREPOLYMERIZER
             (MIXER)     (BULK  REACTOR)
FEED/DISSOLVE
                        EITHER GENERAL PURPOSE
                        GRADE OR IMPACT GRADE
                        POLYSTYRENE .CAN BE HADE
PREPOLY/REACT
                                                                     EXTRUDER-PELLETIZER
                                                                     (WITH QUENCH BATH)
                                                                                               PRODUCT OUT
                                                                  RECOVERY
                                                                                      FINISH
    Figure  15-1.- Polystyrene  by  suspension,  bulk,  or  bulk-suspension  processes.

-------
individual  mass  polymerization  system.   Suspension
simplifies  heat  transfer with  the heat  of reaction
dissipating  into water.  The process allows  better rate
and temperature  control than in mass  polymerization.
Separation of  the polymer from water and  the  suspending
agents is not  difficult.  A typical  reaction  formulation
for this process is  deionized and deaerated  water (68
parts),  deoxygenated  styrene monomer (100  parts), hydroxy
apatite  (0.77  part),  dodecyl benzene sulfonate (0.00256
part), and benzoyl peroxide (0.204  part).

The bulk-suspension process is a natural  evolution from
the bulk and the suspension processes, combining  some of
the advantages of each.  The equipment shown  can  be used
either for continuous or batch processes.  The  finishing
and separation steps  downstream of  the suspension reactor
and devolatilizer a're normally run  continuously in  either
case.

All of the equipment  shown would  be  used  if making  impact
grade  polystyrene by  the bulk-suspension  process.   Impact
grade  resin  requires  monomer modification by  dissolving
chopped  butadiene rubber into the styrene.   For  general
purpose  grade  resin,  the manufacturer simply  skips this
elastomer predissolving step.  The suspension  process
could be  used alone  by deleting the bulk  prepolymer-
ization step.  Either  grade of polystyrene,  impact or
general  purpose, could be made by the suspension process.
A medium impact resin  is  made by blending  the  general
purpose  and  high impact polystyrenes.

Specific  equipment  configurations  and  the  number  and
types of  process  trains vary widely depending on  the
product  grades and dominant process.


                     -192-

-------
Typically the  following operating  steps are performed  to
make impact grade  polystyrene by the bulk-suspension
process:

Step 1.   Rubber elastomer dissolving.

     o    Styrene  is charged and heated  in the dissolving
         tank.
     o    Rubber  bales  are chopped  and added to hot
         styrene  in the dissolving tank.
     o    The  mixture  is agitated  for 4-8  hours  to
         complete rubber dissolution.   Rubber/styrene
         solution  is  transferred  to  the  bulk
         prepolymerizer.

Step 2.   Bulk  (Mass) Prepolymerization

     o    The rubber/styrene solution  heated to  reaction
         temperature in the prepolymerizer.
     o    Catalyst is added, and the mixture is allowed  to
         react to 30-40% conversion of styrene  monomer.
         The resulting suspension  is  transferred  to  the
         suspension reactor.

Step 3.   Suspension Polymerization

     o    The reactor  is  evacuated.  Demineralized  water
         and  suspending  agents  are  charged  and the
         reactor  evacuated a second time.
     o    The  prepolymerized  suspension from Step 2  is
         transferred into  the  suspension  reactor with
         agitation to ensure satisfactory particle size
         is made.

                     -193-

-------
     o   After the  mixture  is  heated  to  reaction
         temperature, additional catalyst (usually an oil
         soluble peroxide)  is added as  required by the
         formulation  and the mixture is allowed  to react.
         The  reaction temperature may be increased and/or
         catalyst additions made to ensure  a  high percent
         conversion of styrene.  Three  to eighteen  hours
         total  reaction time may be required.
     o   The product suspension of beads in water is
         cooled, devolatilized, and transferred  to slurry
         storage tankage.

Step 4.   The  beads  produced  in  the suspension
         polymerization reactor are washed  and  dewatered
         with a solid bowl centrifuge.   Surface  water and
         suspending  agent removals  are  accomplished in
         this step.

Step 5.   Bead form polymer may be sold  as  is,  but  it is
         more commonly converted  to pellet form.   For
         pellet production, dyes, pigments,  lubricants,
         antistatic  agents, and  other  additives  are
         mixed  with  the  beads  and then  melt extruded
         through a die.   Extruded polymer is  cooled  in a
         quench bath  and, finally,  pelletized.

There are a number of variations on the process  described
in addition  to the  reaction process  variations noted
above.  Some  of these include:

    o   The residual  monomer level  in  the beads may be
        reduced by steam stripping  of the slurry.
    o   Increased bead washing efficiency may be  obtained
        by first  vacuum  filtering the  slurry,  then


                     -194-

-------
               reslurrying  in  fresh  water,  and  then
               centrifuging.
           o   Various hot air dryers,  such as rotary, fluid bed
               or  flash,  may be used  after  the centrifuging
               step.
15.2.2   VOC  Emissions
        All  significant emission  rates and  sources  for this
        product  are shown  on Table  15-11.   The  schematic
        flowsheet for this product,  which  includes the emission
        streams and their sources, is Figure 15-1.   The same
        stream  numbering system is  used  throughout.

        [1]  Styrene monomer,  reactor feed, and mixing/ dissolving
            tanks - All of these sources are fixed roof tanks  or
            kettles operating at atmospheric  pressure.  The VOC
            emission is essentially styrene with traces of other
            organics.  The emission cause is normal breathing  and
            filling for all sources  so  atmospheric air will  be
            part of the emission.   Operation of these sources  can
            be  either batch or continuous.   Together they are  a
            relatively small  source of VOC emissions.

        [2]  Reactor atmospheric vent - This emission results  from
            charging the reactor  in a batch  operation.  The
            stream is primarily styrene  vapor in air or nitrogen.
            It  is typically  at  110F and  potentially of  a
            moderate quantity.

        [3]  Devolatilizer  overhead  condenser -  These  are
            non-condensibles  from  this  condenser,  and typically
            exhaust through a vacuum pump.   An oil demister  is
            often used downstream  of the vacuum pump primarily  to
                             -195-

-------
             TABLE 15-11.-  VOC EMISSIONS FROM POLYSTYRENE RESIN MANUFACTURE
a\
           Stream
Uncontrolled   Current Practice  Well Controlled
#/1000# Resin   #/1000# Resin     #/1000# Resin
[1]
[2]
[3]
[4]
[5]
[6]
Styrene monomer, reactor
feed, and feed mixing/
dissolving tanks
Reactor atmospheric vent
Devolatilizer overhead
condenser
Styrene recovery tower
overhead condenser
Recycle Styrene storage
and intermediate hold tanks
Extruder-pelletizer vent
TOTALS
0.11
0.12
3.10
0.10
nil
0.19
3.62
0.11
0.12
2.07
0.10
nil
0.14
2.54
0.06
0.01
0.17
0.01
nil
.00+
0.25+

-------
    separate out organic mist.   The  stream  is largely air
    with styrene, the  main  VOC component,  along  with
    traces of other volatile  organic components  from the
    reaction melt.  The  temperature will  normally  be
    moderate, typically 80F, unless steam  jets  are  used
    instead of a vacuum pump,  in which case it will  be
    much hotter, perhaps 212F.   This is potentially the
    largest VOC stream in the  plant, but  it   is not a
    particularly large quantity.  It would be present
    regardless of which basic process was being  utilized
    in  the  plant equipment.  This part  of  the plant
    normally runs as a continuous operation regardless of
    how  the polymerization section is run.

[4]  Styrene recovery  section  ove'rhead condenser - The
    noncondensibles from this condenser usually  are  also
    exhausted through a vacuum  pump, and this is similar
    to the stream discussed  in  [3] above except that  it
    is  smaller.  This  stream is  composed  of a small
    percent of styrene in  air,  normally at  nearly ambient
    temperature.  If stream ejectors are used instead  of
    the  vacuum pump, it will  contain water vapor  and  be
    at  about 212F.   This  is  normally  a  continuous
    emission stream.

[5]  Intermediate hold tanks  (other than for reactor) and
    recycle styrene storage  tank - These sources are all
    fixed roof tanks and constitute  a minor source of VOC
    emissions (the least quantity of any of  the streams
    listed).  The recycled styrene hold tank and the hold
    tank for the styrene recovery tower feed are the main
    sources in this stream.   Normal  breathing and filling
    are  the causes of emissions  for  these  and the
    emission composition in both cases  is air drawn  from

                     -197-

-------
           the  atmosphere and styrene vapor  from the liquid
           stored.   Other hold tanks have essentially no VOC
           emissions.   These tanks are all in  the  continuous
           section of the plant.
        [6] Extruder-pelletizer  section vent -  This stream is a
           continuous  emission,  but it  is  typically  of a
           fugitive  type.   The emission results when  hot,
           extruded, polystyrene-product strands from the
           dieplate contact  the  cold  quench bath  water.
           Typically, it is  composed of 5-7 ppm styrene  in  water
           vapor and air at  approximately ambient  temperature.
           Though small, this stream is potentially  the second
           largest VOC  emission source from the plant.

15.2.3   Applicable Control Systems

        The following control technologies  are  recommended for
        the emission streams described  in  Section 15.2.2 and
        shown on the schematic flowsheet for this product.  The
        same stream numbering system is followed here.

        [1] Styrene monomer,  reactor feed, and mixing/dissolving
           tanks - Use  a pressure equallizing vapor return line
           to the tank  cars  or  trucks from  the  styrene  monomer
           tank to eliminate working losses from  tank  filling
           (reduces styrene  tank VOC emissions  by approximately
           58%).   No other  controls are required,  except for
           conservation valves, where usable,  and those  would
           be justified for  economic reasons.

        [2] Reactor atmospheric  vent - Flare this stream.  A 90%
           reduction efficiency is assumed for this  mode of
           control.
                            -198-

-------
[3]  Devolatilizer overhead condenser  -  Flaring is the
    primary control to be  used here.   90% reduction
    efficiency is assumed  for this  mode of control.  An
    oil  demister is also recommended,  primarily for
    elimination of organic mist.   However, it  should
    effect  some VOC reduction and a conservative  estimate
    of 20%  reduction has been assumed.

[4]  Styrene recovery  overhead  condenser - Flare  this
    stream.  A 90% reduction efficiency is assumed for
    this mode of control.

[5]  Intermediate hold tanks  and  recycle styrene storage
    tank -  These are very low VOC  emission sources and
    require no control  other than .conservation valves.

[6]  Extruder-pelletizer section  vent - F],are this  stream.
    A 90%  reduction efficiency is  assumed.   As  this
    emission  is of the  fugitive  type, a hood and  fan will
    be required for area pick-up.   An oil demister is
    also recommended, primarily for  elimination of the
    mist created.
                     -199-

-------
                          SECTION 16
                       POLYVINYL ACETATE
16.1  INDUSTRY  DESCRIPTION

      Polyvinyl acetate  (PVAc)  in this  report includes  vinyl
      acetate homopolymer and all the  copolymers  in  which vinyl
      acetate  is the major  constituent.   Polyvinyl  acetate is
      marketed  as an emulsion and as a solid  resin.   Homopolymer
      and copolymer emulsions are the  predominant  form of PVAc,
      with  paints and  adhesives   accounting  for  about
      three-quarters of total consumption. PVAc is also produced
      as an  intermediate in  the manufacture of  polyvinyl  alcohol
      (PVA), polyvinyl butyral,  and  polyvinyl  formal but such
      production will not be included  here.   (See  Section 17 of
      this report for  polyvinyl alcohol  production) .  The
      predominant copolymers are those with n-butyl acr.ylate and
      2-ethylhexyl  acrylate.

      Polyvinyl  acetate and  its important  copolymers  are  largely
      thermoplastic.  An unplasticized vinyl  acetate  homopolymer
      film of medium molecular weight  is clear  and  quite hard and
      tough at  room temperature,  but its softening  point lies
      only several  degrees higher.  Depending on  their chemical
      structure, comonomers may have a plasticizing or hardening
      effect, thus  altering  both  the  softening  temperature and
      the mechanical properties of the resin  considerably.  PVAc
      and its copolymers generally exhibit good  light  stability.
                             -200-

-------
Most vinyl  acetate  horaopolymers and copolymers are used  in
the form of aqueous emulsions.  Major  applications are  in
paints,  adhesives,  textile treatments,  paper coatings and
other uses. Emulsions  for paints and for adhesives commonly
have a solid resin  content of 55%; most PVAc emulsions for
paper coatings  have a  solids content of 48% (^8_) .   Adhesive
uses  include packaging and labeling, construction, and
other miscellaneous uses.   The largest single segment  in
the latter  category is  textile treating (including textile
sizing), which  involves mostly finishing,  fabric coating,
and laminating.   Some  homopolymers and  copolymers come  as
solid resins in the form of powders or  beads, among  which
certain  types are especially designed to be redispersed  in
water, while others are redispersed in  different solvents
(e.g., ethyl acetate in the case of 'a homopolymer).

About 80%  of the PVAc  (excluding  that  produced  as  an
intermediate) is manufactured by emulsion polymerization
usually  by  batch processes.  Polymerization is carried out
in water in the presence of surfactants and a free-radical
initiator,  e.g., a  suitable peroxide,  persulfate, or  diazo
compound.  PVAc homopolymer and  copolymer  emulsions are
produced by varying recipes for different end uses.   Solid
polyvinyl acetate  resins  are usually  made by suspension
polymerization  (similar to emulsion polymerization except
that a suspension agent is used rather  than emulsifiers) .

The estimated U.S.  demand  and growth  rates for  polyvinyl
acetate  are shown below for the period of 1976 to 1981.   No
manufacturing capacity data are available for this product.
A 1979 capacity estimate  of  999 MM PPY was made based  on
1976 sales  (69), 6% annual growth, and 0.85 utilization.
                       -201-

-------
      Paints  are expected to remain the  largest market, but
      growth  should be modest as the penetration of  this  market
      is quite high.  The  use of PVAc emulsions  (especially
      copolymers)  in  adhesives  will  grow somewhat  faster  than
      paints.  PVAc demand for  paper coatings will grow  at
      similar rates as adhesives, as a result of the  replacement
      of natural  binders.   Some  sources  feel that PVAc
      consumption  for paper coatings will  grow at an average  of
      at least 6%  per year.

    ESTIMATED U.S. DEMAND FOR POLYVINYL  ACETATE, 19 76-1981*( 69_.)

                               DEMAND
                           MILLIONS OF  LBS   AVERAGE ANNUAL
                           1976       198'1   GROWTH RATE, (%)

Polyvinyl Acetate  (dry base) 713     926-985      5.4-6.7%
    Paints                  250       319            5
    Adhesives               259     347-381         6-8
    Paper Coatings           90     115-126
    Other Uses               98     125-137         5-7
    Exports                   16      20-22

      Historically, production of PVAc emulsions has  been  low  in
      capital  costs and  therefore many  companies have built
      facilities  to produce  it.   Today,  more spohisticated
      product requirements and stricter  pollution controls impose
*Includes homopolymers and copolymers with more  than  60%  vinyl
acetate content.
                             -202-

-------
        demands which cannot be met  by  many small producers.
        However,  the producers can be  subdivided into  three
        groups:

        o   Producers of merchant PVAc emulsions  and  resins 'for
           multiple uses, i.e., merchant suppliers of  paint
           and/or  of emulsions, emulsions and  resins  for all
           other uses;

        o   Paint companies which produce most  or  all of their
           PVAc emulsions captively;

        o   Producers of PVAc emulsions  primarily for  captive
           compounding (other than paint  production), although
           many of  these producers occasionally sell emulsions to
           other compounders,  distributors, or users.

        Tables 16-1 and  16-11 list  U.S.   manufacturers of
        polyvinyl acetate.

16.2    POLYVINYL ACETATE BY EMULSION POLYMERIZATION

16.2.1   Process Description

        The process  described  here  is  a batch  emulsion
        polymerization followed  by batch stripping and  resulting
        in  an  emulsion product (latex) (7_0) ,  (^1).  Figure  16-1
        is  the process schematic.  The following  process  steps
        are the principal ones carried out:

        o    Apply vacuum to reactor to remove residual  oxygen,
            break vacuum with inert gas, and  re-evacuate.
        o    Charge  water, monomers, emulsifiers and  modifier.
            (Monomers are  usually vinyl acetate with  small
            amounts of acrylic monomers or ethylene.)

                             -203-

-------
TABLE 16-1.- PRODUCERS OF MERCHANT PVAc EMULSIONS AND RESINS (68)
COMPANY
PLANT LOCATION
AIR PRODUCTS AND CHEMICALS, INC,
 Polymer Chemicals Division
Calvert City, Kentucky
AIR PRODUCTS AND CHEMICALS, INC,
 Polymer Chemicals Division
City of Industry, CA
Cleveland, Ohio
Elkton, Maryland
South Brunswik, NJ
BORDEN, INC.
 Borden Chemical Division
  Thermoplastic Products
Bainbridge, New York
Compton, California
Illiopolis, Illinois
Leominster, MA
CELANESE CORPORATION
 Celanese Polymer Specialties Co.,
  subsidiary Celanese Resins Division
Louisville, Kentucky
Newark, New Jersey
CIBA-GEIGY CORPORATION
 Dyestuffs and Chemicals Division
  Chas. S. Tanner Company, subsidiary
Greenville, SC
E.I. DU PONT DE NEMOURS & CO., INC.
 Plastic Products and Resins Department
Seneca, Illinois
W.R. GRACE & CO.
 Industrial Chemicals Group
  Dewey and Almy Chemical Division

                              -204-
Owensboro, Kentucky
South Acton, MA

-------
TABLE 16-1.- PRODUCERS OF MERCHANT PVAc EMULSIONS AND RESINS
                           (Continued)
COMPANY
PLANT LOCATION
H & N CHEMICAL COMPANY
Totowa, New Jersey
MONSANTO COMPANY
 Monsanto Plastics and Resins Company

NATIONAL STARCH AND CHEMICAL CORP.
REICHHOLD CHEMICALS, INC.
 Reichhold Polymers Inc., subsidiary
 (formerly Standard Brands Chemical
  Industries, Inc.)
Springfield, MA

Meredosia, Illinois
Plainfield, New Jersey

Charlotte, NC
Kansas City, Kansas
Morris, Illinois
South San Francisco, CA
Stamford, Connecticut
Cheswold, Delaware
Clifton, New Jersey
STANCHEM, INC.
East Berlin, CT
UNION CARBIDE CORPORATION
 Chemicals and Plastics, division
Alsip, Illinois
Garland, Texas
Somerset, New Jersey
South Charleston, WVA
Torrance, California
Tucker, Georgia
UNION OIL COMPANY OF CALIFORNIA
 AMSCO Division
                             -205-
Charlotte, NC
La Mirada, California
Tacoma, Washington

-------
     TABLE 16-11.-PRODUCERS OF PVAc EMULSIONS AND RESINS FOR
                        COMPOUNDING (68 )
COMPANY AND PLANT LOCATION
ADHESIVES
TEXTILE
TREATING
AZS CORPORATION
 AZS Chemical Company Division
  Atlanta, Georgia
CELANESE CORPORATION
 Celanese Resins Division
  Bridgeview, Illinois
  Charlotte, North Carolina
  Newark, California
    X
    X
    X
   X
   X
   X
 Wica Chemicals Division
  Charlotte, North Carolina
COLLOIDS, INC.
 North Chemical Company, Inc., subsidiary
  Marietta, Georgia
                 X
DAN RIVER, INC.
 Chemicals Products Division
  Danville, Virginia

DIAMOND SHAMROCK CORPORATION
 Process Chemicals Division
  Cedartown, Georgia
DOBBS-LIFESAVERS, INC.
 Beech-Nut, Inc., subsidiary
  Canajoharie, New York
(chewing gum)
                             -206-

-------
     TABLE 16-11.-PRODUCERS OF PVAc EMULSIONS AND RESINS FOR
                     COMPOUNDING (Continued)

                                                        TEXTILE
COMPANY AND PLANT LOCATION                ADHESIVES     TREATING

EMKAY CHEMICAL COMPANY
  Elizabeth, New Jersey                                    X

FRANKLIN CHEMICAL COMPANY
  Columbus, Ohio                              X

H.B. FULLER COMPANY
 Polymer Division
  Atlanta, Georgia                        .    X
  St. Bernard, Ohio

GULF OIL CORPORATION
 Gulf Oil Chemicals Company, division
  Industrial and Specialty Chemicals Div.
   Lansdale, Pennsylvania                     X

KEWANEE INDUSTRIES, INCORPORATED
 Milmaster Onyx Group
  Refined-Onyx Division
   Lyndhurst, New Jersey                                   X

PHILIP MORRIS, INCORPORATED
 Polymer Industries, Inc., subsidiary
  Greenville, South Carolina                  X            X
  Springdale, Connecticut                     X
                             -207-

-------
     TABLE 16-11.-PRODUCERS OF PVAc EMULSIONS AND RESINS FOR
                     COMPOUNDING (Continued)

                                                        TEXTILE
COMPANY AND PLANT LOCATION                ADHESIVES     TREATING

QUAKER CHEMICAL CORPORATION
  Conshohocken, Pennsylvania                               X

RAFFI AND SWANSON, INC.
 Polymeric Resins Division
  Wilmington, Massachusetts                   X

SCHOLLER BROTHERS, INC.
  Elwood, New Jersey                      .                 X

A.E. STALEY MANUFACTURING COMPANY
 Chemical Specialties Division
  Corning, New Jersey                         X
  Lemont, Illinois                            X            X

SYBRON CORPORATION
 Jersey State Chemical Company, division
  Haledon, New Jersey                         X            X

UNITED MERCHANTS & MANUFACTURERS, INC.
 Valchem - Chemical Division
  Langley, South Carolina                                  X
                              -208-

-------
O
>>
 I
                 VAPOR
                 RETURN
                                                            VACUUM STEAM JET
                               .V.       WATER

                                   EMULSIFIER
                                     CATALYST

                                     MODIFIER

                                    INITIATOR
                    VINYL ACETATE
                  MONOMER  STORAGE
           AFTER
 REFLUX  CONDENSER
CONDENSER
                                    CW OR STM
                                      POLYMERIZATION
                                             REACTOR
                                                                          V.AC.
                                                                       TO RECOVERY
                                                                                                TO  FLARE
                         TO W.W.
                         TREATMENT
                                                                               PRODUCT OUT
                                                                   P.V.AC.
                                                                LATEX STORAGE
                        FEED
                                                  REACT
                                                                   RECOVERY/FINISH
                         Figure 16-1.- Polyvinyl  acetate  - Emulsion polymerization,

-------
o    Heat  reactor  contents to  desired  reaction
    temperature,  typically 120-140F, by  circulation of
    hot water  through reactor jacket.
o   Initiate reaction by charging  catalyst,  activator and
    reducing agent,  which  may be  potassium persulfa'te,
    ferrous  sulfate, and sodium bisulfite, respectively.
    Heat of  reaction  is removed by cold  water circulation
    through  jacket.
o   After reaction  goes  to completion, batch  is vacuum
    stripped  to  remove  residual monomer  and  to
    concentrate latex.  Heating is accomplished  again by
    circulating hot water through  jacket.
o   Cool product  latex and discharge reactor contents to
    storage.

A number of  variations to this basic scheme exist,  some
of the more  significant are:

o  Oxygen removal may  be accomplished by  inert  gas
   purging rather  than application of  vacuum.
o  Monomers  may be  added in several  increments  or may be
   metered into  reactor while reaction  is proceeding
   rather than being  added as single  charge, prior to
   initiation.
o  Jacket cooling  may  be  augmented by overhead reflux
   condenser.
o  Stripping may  be carried out in separate  vessel.
o  Residual  monomer may be removed by  gas  sparging (with
   air or preferably  inert gas) or by  steam  distillation
   or by one of  these  operations  combined with vacuum
   stripping.
o  It may be advisable  or  necessary to screen  emulsion
   upon discharge  to  receiving vessels  for  removal of
   small amounts  of agglomerates.

                   . -210-

-------
16.2.2  VOC Emissions
       All  significant emission rates and  sources  for this
       product are  shown  on  Table  16-111.  The flowsheet  for
       this product which includes the emission  streams and
       their sources is Figure 16-1.  No emissions were reported
       for  product  storage.   A  description of the designated
       emission streams follows:

       [1]  Monomer storage  tanks - These streams vent  the  fixed
            roof storage  tanks for  vinylacetate (VAc)  liquid
            monomer  at  ambient conditions.  Pure VAc monomer
            vapor with air  is  the only emission unless an  inert
            blanket gas  is  used.  Normal  breathing, filling,  and
            emptying  are  the  causes of the  emissions.   This
            stream  is the  second largest  significant emission
            stream from  this process as currently controlled.
       [2]  Reactor-safety  relief valves  and rupture discs  - This
            stream  carries  materials vented under  emergency
            conditions from  the  polymerization  reactor.
            Relieving  this  stream  occurs  very  rarely,
            approximately  one batch per year per  plant, and
            generally results  from reactor jacket and/or reflux-
            condenser, cool ing-water  failure   while  the
            (exothermic)  reaction step is  in progress.  The
            constituents of  this  stream vary with time but  are
            primarily VAc  monomer vapor (the VOC component),
            water vapor, PVAc  product (solids), and some  other
            vaporized  liquids  from  the   reactor  including
            initiator and  various emulsifying and other  agents
            present in the  reaction mix.  The  emission  stream  is
            the smallest  emission stream  from the  process  as
            currently practiced.  Note that  mid-batch conditions
            are reflected  in Table 16-111.   The quantity  of VOC


                             -211-

-------
     TABLE 16-III.-VOC EMISSIONS FROM POLYVINYL ACETATE LATEX -
                       EMULSION POLYMERIZATION
                                       Current
                      Uncontrolled     Practice   Well Controlled
Stream                #/1000# Resin  t/1000#Resin   #/1000#  Resin
[1]  Vinyl Acetate           2.02           2.02           0.85
     Monomer Storage

[2]  Reactor Safety Relief   0.05           0.05           0.01

[3]  Reactor Vacuum System   5.37         '  5.37           0.54


 TOTAL                      7.44           7.44           1.40
                             -212-

-------
            released varies widely between early and late  in  the
            batch.

        [3]  Polymerization reactor through overhead vacuum system
            -  This stream carries non-condensibles vented through
            the vacuum-steam jet system.  The composition  varies
            with  time; however, upon leaving the jets, the stream
            will  be  composed  of  steam  with some VAc  and air.
            This  stream is the  largest  source  of VOC emissions
            from  the process,  both  potentially and in   current
            practice.   The air  emitted enters the  system  by
            leakage into the vacuum conditions  in the reactor.

16.2.3  Applicable Control Systems

        The  following control  technologies  are recommended  for
        the emission streams  described  in  Section  16.2.2.
        Equivalent systems to  those  recommended here should  be
        available and would be acceptable alternatives.   Actual
        flare systems used  would  be subject to  normal good
        engineering practice considerations, including maximizing
        recovery  of both liquid and vapor organics and designing
        for  pressure levels available.

        [1]  Monomer storage tanks  -  A vapor return line  to  the
            tank  truck loading  area  will eliminate all  working
            loss  emissions  from  tank  filling (58%  of total
            current emissions  from these tanks).   Conservation
            valves will also be required  on  these tank vents,  but
            these would be installed for  economic reasons  and  no
            pollution control  credit is  given  them (Vapor  loss
            prevention efficiency of these valves is quite low.)
            This  minimum abatement system  should be quite  cost
            effective.
                            -213-

-------
[2]  Reactor safety relief  system  -  To plant flare
    systems.  Flare efficiency of 90% is assumed.

[3]  Polymerization reactor  through overhead vacuum system
    -  Exhaust from the vacuum  steam  jets goes to an
    after-condenser cooled  by 90F  water,  the remaining
    non-condensibles are  sent  to  plant flare.   Flare
    efficiency of  90%  is assumed.   Insufficient
    information was available to calculate an efficiency
    for the  after-condenser.  The wel1-contro 11 ed
    emission figure for  this stream as shown in Column 2,
    Table  16-111 reflects  the  effect of flaring only.
    Use of the after-condenser would lower this emission
    figure somewhat and  would be quite cost effective.
                   -214-

-------
                          SECTION 17
                       POLYVINYL ALCOHOL
17.1    INDUSTRY DESCRIPTION

        Du Pont introduced polyvinyl alcohol (PVAL)  commercially
        into  the U.S.  in 1939.   PVAL includes all  resins made by
        the  alcoholysis  of  polyvinylacetate  (PVAc).   It is
        characteristically a white to cream colored  powder which
        is  water  soluble.  PVAL cannot  be prepared by direct
        polymerization because  vinyl  alcohol  is  an  unstable
        liquid.

        U.S.  production of polyvinyl alcohol  was  127 MM Ibs in
        1978  (2J .  Imports from Japan are  expected  to remain at
        the 1976 level of 10 MM despite the fact that excess  U.S.
        production capacity  existed  and some was exported.
        (Japan is the world's largest producer  and'  had  been
        exporting more to  the U.S. before U.S.  capacity was
        increased substantially around  1973.)  The projected
        growth rate for U.S.  consumption  for 1976-1981  is 6.7 to
        8.6%  per year (69).

        There are only three major producers of polyvinyl alcohol
        in  the U.S.   These producers  are shown on Table  17-1
        (68).
                            -215-

-------
       TABLE 17-1.- U.S.  PRODUCERS OF POLYVINYL ALCOHOL (68)
Company and Plant Location
 Annual Capacity
 As Of July 19.77
(Millions of Lbs)
AIR PRODUCTS AND CHEMICALS, INC.
 Polymer Chemicals Division
  Calvert City, Kentucky
        40a
E.I. DU PONT DE NEMOURS & CO., INC,
 Plastic Products and Resins Dept.
  La Porte, Texas
       125b
MONSANTO COMPANY
 Monsanto Plastics & Resins Company
  Springfield, Massachusetts

                        Total
        45'
       210 (160)c
aExpansion to an estimated total of 55 million pounds  is
 planned.

^portion of capacity (on the order of 25 million pounds per
year  for each company) is used to produce PVA1 for captive
polyvinyl
 butyral production.

cDatum in parentheses  indicates capacity for PVA not
including
 that used captively for polyvinyl butyral production.
                             -216-

-------
17.2    MANUFACTURE OF POLYVINYL ALCOHOL

17.2.1   Process Description

        The  process described here and  shown in Figure 17-1  is
        entirely continuous and  utilizes  solution polymerization
        with methanol as the solvent  and a hydrolysis reaction
        catalyzed by a base (8_) , (T0_) .   The molecular weight  of
        PVAL polymer and the degree of hydrolysis are controlled
        by the processing  conditions.   These characteristics
        greatly influence the properties  (and uses) of the  PVAL
        made.  The two significant commercial  grades of the  latter
        are  partially hydrolyzed  (87 to 89%)  and  completely
        hydrolyzed (+99%).

    A.   Raw  Material Storage and Purification

        Inhibitor in vinyl acetate monomer  (VAM) is removed  in a
        stripping column, and purified uninhibited VAM is  stored
        in a daytank. Initiator solution, along  with  VAM,  is
        charged into the polymerization  section by pump.

    B.   Polymerization and Hydrolysis

        Special properties may  be obtained by treatment  of the
        PVAc during polymerization  before  hydrolysis,  or  by
        giving special  treatment   in  finishing  the  PVAL.
        Polymerization of vinyl  acetate  usually is carried  out in
        two  stages at 140F (60C).   Polymer solution from the
        second reactor is collected in a  polymer solution  surge
        tank.   An inhibitor  is added into  the surge  tank  to
        prevent polymerization in the  monomer stripping column.
        Methanol  vapor  from  the evaporator is used  to  strip
        unconverted monomer in the polymer  solution.  Additional
        liquid methanol  is  added  to  the  stripping  column  to
                            -217-

-------
                                                                                          NC1NERATOH
OO
I
                Figure  17-1.- Polyvinyl alcohol  -  Solution polymerization.

-------
    control the viscosity of the polymer solution in  the
    column.  Essentially all the VAM is removed in  methanol
    solution from the overhead of the  column and recycled to
    the  polymerization reactor section.  The polymer product
    from the bottom of the monomer stripping column is  a 35
    wt%  PVAc solution in methanol.

    This solution is hydrolyzed continuously in two  parallel
    reactors.   The  reaction is catalyzed  with  sodium
    hydroxide-methanol solution (charged intermittently  from
    a feed tank once  every  5 minutes).   PVAL  slurry is
    withdrawn continuously from the hydrolysis reactors and
    collected  in a  surge tank.  Surge  tank  slurry  is
    neutralized with acetic acid from  storage.

C.  Solvent Separation and Product Drying

    Neutralized PVAL slurry is sent to the  centrifuge where
    PVAL is separated from the mother  liquor and washed  with
    methanol.   Mother liquor and  washing methanol  are
    collected in a crude solvent storage tank.  Washed PVAL,
    usually containing 10 wt%  methanol,  is dried in  a rotary
    dryer.  Close-looped nitrogen gas is  used to. dry PVAL,
    and  part  of the methanol  vapor in the nitrogen stream
    from the dryer is condensed and sent to the crude solvent
    storage tank.

D.  Bulk Handling

    Dried PVAL  from the  rotary dryer  is transferred to the
    storage bins.  PVAL product from the storage  bins is
    loaded  in railroad cars or trucks  from  transportaion to
    purchasers.
                        -219-

-------
E.   Solvent and By-product Recovery

    Crude solvent  from the  crude storage tank  contains
    methanol, methyl acetate,  some  sodium acetate, and water.
    Methanol  and  methyl acetate are  recovered as overhead
    from  the  mixed solvent column and pass into the  ester
    hydrolyzer where methyl acetate is  hydrolyzed to methanol
    and acetic acid.  A stream of water is added near the top
    of the column  for  hydrolysis  and  to  condense rising
    vapor.  Essentially all the methyl  acetate is hydrolyzed,
    and the stream  from the bottom  of  the column is comprised
    of methanol,  acetic acid and water.   Methanol  is
    separated from  the acetic  acid  and  water in the methanol
    column,  and  sent  to the  methanol  storage  tank  for
    recycle.  The dilute acetic acid  from the bottom of  the
    methanol column is sent to crude acetic  acid storage (not
    shown)  until  needed for  the acetic acid extractor  and
    column.

    Sodium  acetate  is converted to acetic acid by reaction
    with  sulfuric  acid  in the acetic  acid reactor.    The
    reaction product is combined with  the dilute acetic acid
    from  the methanol  column  and extracted wi.th methyl
    acetate for acetic acid recovery.   Recovered acetic acid
    is separated from  methyl  acetate  in  an acetic acid
    recovery column and sent to storage.  Part of the acetic
    acid  is used to  neutralize  the  hydrolysis  reaction
    product, and the remainder is sent  to a VAM plant or sold
    as a  by-product.  The dilute methyl acetate solution from
    the acetic  acid column overhead  is sent to the methyl
    acetate recovery column  for recovery.  The  recovered
    methyl  acetate  is used in  the extractor  for acetic acid
    extraction.  The bottom stream from the methyl  acetate
    recovery column is sent to waste treatment.
                        -220-

-------
17.2.2   VOC Emissions
        All  signifacant emission  rates and  sources  for this
        product  are shown  on Table  17-11.   The  schematic
        flowsheet, Figure 17-1,  includes the emission streams'and
        their sources.  The major emission points are:

        [1]  Vinyl acetate monomer (VAM)  storage tanks -  The cause
            of  emissions  is normal breathing and  filling
            associated with fixed roof storage tanks.  The  tanks
            are normally blanketed  with  nitrogen.   The
            composition (weight) is greater than 50%  nitrogen  the
            remainder is principally VAM vapor.  The  temperature
            is  ambient.
        [2]  Methanol storage tank - The.cause  of emissions  is
            normal  breathing and filling.   The composition  is
            approximately 25% (by  wt) methanol and  75% air
            (N2 if the tank is blanketed).  The temperature
            is  ambient.
        [3]  VAM purification section - This  stream vents  inerts
            from a VAM inhibitor stripper  column and associated
            surge tank (breathing and filling losses)  treating
            the VAM before  it is charged  to  the polymerization
            reactor. The overall composition  is largely  inerts
            (N^) with less  than 1% VOC,  typically acetatalde-
            hyde  and vinyl  acetate,  in approximately equal
            amounts.  The temperature is ambient.
        [4]  VAM recovery column - This column  is part of  the VAM
            recycle  system  following  polymerization  of the
            monomer.  The stream vents  inerts from  the  system.
            The composition is primarily nitrogen accompanied  by
            vinyl acetate and traces of acetaldehyde.    Most  of
            the vinyl acetate is condensed in the  overhead
            condensing system provided for process reasons.  The
            temperature is  about 95F.
                            -221-

-------
    TABLE 17-II.-VOC EMISSIONS FROM POLYVINYL ALCOHOL MANUFACTURE
                                       Current
                      Uncontrolled     Practice   Well Controlled
Stream                #/1000# Resin  #/1000#Resin   #/1000# Resin

[1]  VAM Storage Tanks        0.35        0.07          0.00+

[2]  Methanol Storage
     Tanks                   0.47        0.07          0.00+

[3]  VAM Purification
     Section                 0.04        0.04          0.00+

[4]  VAM Recovery Column      1.67        0.25          0.01

[5]  Intermediate Process
     Storage Tanks           0.22        0.03          0.00+

[6]  Hydroylsis, Solvent
    Separation and Product
     Drying Sections         48.0        0.27          0.01

[7]  Storage for Solvent and
    By-product Recovery
     Areas                   6.07        1.34          0.07

[8]  Solid Resin Conveying
     Section                 0.24        0.24          0.00+

[9]  Truck and Hopper Car
    Loading and Unloading    0.04        0.04          0.02

[10] Solvent and Distillate
     Recovery Section        1.00        0.02          0.00+

                TOTAL        58.1        2.37          0.11+
                             -222-

-------
[5]  Intermediate process storage  tanks - Causes of  the
    emissions here are normal  breathing and filling  of
    the  fixed roof tanks  holding the reacted polymer  for
    hydrolysis.  This also  includes  such  losses from
    storage tanks as reaction inhibitor.  The stream  is
    nitrogen, from displacement in the  tanks, with 10  to
    20%  (by wt) methanol as the  VOC  component.   This
    intermittent stream is usually at  or slightly above
    ambient temperature.
[6]  Hydrolysis, solvent separation and product drying
    sections - These streams  exhaust inerts  under normal
    process conditions.  They also include the hydrolysis
    area catalyst storage tank breathing  and  filling
    emissions (methanol in  nitrogen  at 160F).  The
    overall uncontrolled  stream composition is methanol
    and  methyl acetate in nitrogen.  The resultant  stream
    temperature is 110 to 115F. Treatment of this  stream
    by a water scrubber will  knock out  most of the  VOC.
[7]  Storage for solvent and by-product recovery areas -
    These storage tanks include the  crude solvent tanks
    and  other intermediate  tanks serving  the solvent,
    distillate, and by-product recovery area.  All  of  the
    tanks are atmospheric, fixed-roof tanks at ambient
    temperature.  Emissions  are caused by normal
    breathing and filling (the recovery columns operate
    continuously).  Composition of  the exhausts vented
    from these tanks are methanol,  methyl  acetate,  and
    vinyl acetate vapors  and  blanket nitrogen in varying
    amounts depending on the  particular service.   The
    combined stream is 45% nitrogen, 30% methyl acetate,
    20%  methanol, and  5%   vinyl  acetate (weight) .
    However, these tanks  will generally have refrigerated
    exhaust vent condensers with the non-condensibles
    combined for further  treatment.   The composition  of
    such a  composite stream  would be  approximately  10%
    methanol, 10% methyl  acetate,  1% vinyl acetate  and
                    -223-

-------
           79% nitrogen (weight  ).
        [8] Solid resin conveying  section - This stream exhausts
           inerts and volatile organics during various cycles of
           material conveying,  classification,  and packaging.
           Pneumatic conveying  is often  used  and  flow rate is
           intermittent because different  powders are made at
           different times.   Composition  is  mostly inerts with
           about 2 to 3% (by wt)  methanol and methyl acetate in
           approximately equal quantities.   The  streams are
           usually ambient vents from powder storage bins or
           silos.
        [9] Truck  and hopper car loading and  unloading - This
           stream  is intermittent, varying  with  the  type of
           powder and the amount  being handled.  Composition is
           typically inerts  (air  or N2> with approximately
           1/2% by weight each, of methanol and methyl acetate.
           Emissions are caused by displacement and  are at
           ambient temperature.
       [10] Solvent and distillate recovery section  - This  stream
           is the normal overhead process vent from the recovery
           towers.   The composition  is  about 50% nitrogen by
           weight,  with  large amounts  of methyl  and  vinyl
           acetate  and lesser  amounts  (a few  percent)  of
           methanol  and acetaldehyde.   The  methyl acetate is
           from the acetic acid  column while  the vinyl acetate
           comes off the mixed  solvent column.

17.2.3   Applicable Control Systems

        The following control technologies  are recommended for
        the emission streams described in Section  17.2.2.  VOC
        reduction efficiencies given for various controls in  this
        section  are based on calculated  values  from reporting
        resin  producers  unless otherwise designated.
                            -224-

-------
Efficiencies said  to  be  assumed  have been estimated.
Reduction  efficiency for  all streams  recommended to be
incinerated  is 95% (Pullman Kellogg estimate).

[1]  VAM  storage tanks - Use refrigerated  vent  condenser
    (20F refrigerant) and  incinerate  the non-
    condensibles.  Condenser reduction  efficiency is
    approximately 80%.
[2]  Methanol storage tank -  Use refrigerated  vent
    condenser (20F refrigerant) and incinerate  the  non-
    condensibles.  Condenser reduction  efficiency is
    approximately 85%.
[3]  VAM purification  section  -  Incineration only is
    recommended because  of low initial  (uncontrolled)
    levels of emissions.   A refrigerated condenser would
    normally be provided  on the column here for process
    reasons  (no VOC emission reduction credit  was given
    this condenser).
[4]  VAM recovery column -  Use  a refrigerated  vent
    condenser (20F refrigerated) on the column  overhead
    vent and incinerate the non-condensibles.   Condenser
    reduction efficiency  is approximately 85%.
[5]  Intermediate process storage  tanks  -  Use  separate
    vent  condensers  (70F  water)  on  these  tanks.
    Incinerate the non-condensibles  from all  such  vent
    condensers.  Condenser VOC reduction efficiencies are
    approximately 90%.
[6]  Hydrolysis, solvent  separation  and  product  drying
    sections -  Send  component  streams  to  a  single
    scrubber  using water  as a  scrubbing agent  and
    incinerate the overhead from the scrubber.   Scrubber
    VOC  reduction efficiency  is  approximately  99.6%.
    There  will  also be a vent condenser on  the  rotary
    dryer  exhaust for process reasons (No credit is taken
    for  this reduction) .
                    -225-

-------
 [7] Storage for  solvent and by-product recovery areas -
    Use a  separate  refrigerated  vent condenser  (20F
    refrigerant)  on these tanks.   Incinerate the non-
    condensibles  from  all such vent condensers.  Vent
    condenser VOC reduction efficiencies range from
    approximatley 70%  to  90%.   The average  condenser
    efficiency  for the composite stream is 78%.
 [8]  Solid resin  conveying  section -  This  is  an
    intermittent  stream  and incineration is  not
    recommended.  Scrubbing  with  water as a  scrubbing
    agent should be  used.  A 98% VOC  reduction  efficiency
    is assumed  for such scrubbing.
 [9] Truck and hopper car loading and  unloading  - Because
    these  are  intermittent  emissions (during  loading
    operations)  and  relatively  small, they will not be
    incinerated.  Filling losses could be substantially
    reduced by  using vapor return lines to source  storage
    bins or tanks.   Assume  60% VOC reduction for this
    means of control.
[10]  Solvent and distillate recovery section -  Use a
    single scrubber  with  water  as  the scrubbing agent,
    and incinerate the  overhead  from the  scrubber.
    Scrubber VOC reduction efficiency is approximately
    98%.
                     -226-

-------
                          SECTION 18
                    STYRENE BUTADIENE LATEX
18.1  INDUSTRY  DESCRIPTION

      Styrene-butadiene  (S/B)  latex is a high-styrene-content
      resin sold  in emulsion  form.   S/B is  a  copolymer of
      polystyrene  (covered in Section 15), one of  the principal
      commodity thermoplastics.  Acrylonitrile-butadiene-styrene
      (ABS)  and styrene-acrylonitrile (SAN)  resins  are the other
      important copolymers (3_) .  The major markets  for S/B latex
      are carpet and upholstery backing, and paper  coating which
      account for  over 80% of domestic consumption.

      The copolymer latexes, also known as S/B emulsions or high
      styrene emulsions,  usually have a resin content of about
      50-65%.   The styrene/butadiene ratio varies  from 54:46 to
      80:20.  The  bulk are carboxylated (achieved through  the  use
      of such acids  as maleic,  itaconic, fumaric,  acrylic, or
      methacrylic).  The  type and degree of carboxylation  have an
      effect on adhesion, compound stability during  application,
      and cross-linking ability.   Small amounts of  co-monomers
      other  than styrene  and butadiene may be used,  depending on
      the application.

      These  styrene-based polymers have a wide range  of physical
      properties.  Generally, they all have excellent resistance
      to water  and are very good electrical insulators,  but  their
      mechanical properties  and  resistance  to  weathering vary
                             -227-

-------
widely,  depending on the exact type of  resin.  Polystyrene,
especially in  the form of foam products,  burns when ignited
and to combat  this problem, special fire retardant  grades
are produced by  incorporating additives.

It  is believed  that  all  commercial  S/B  latex  is
manufactured by batch emulsion polymerization.  A free-
radical polymerization of  the copolymers  styrene  and
butadiene  is involved; this  reaction may be  initiated by
heating  or, more effectively, by heating  in the presence of
a free-radical initiator (such as benzoyl peroxide) .   The
polymerization of styrene-butadiene is highly exothermic,
and the  molecular weight and molecular- weight distribution
of the resins depend greatly on the conditions  of  their
manufacture.

Only S/B latexes with over 45% styrene are considered   in
this report.   The U.S. production of such S/B latexes  was
estimated  to be 660 million pounds (solids  content)  for
1977 (Tl) Of this amount 595 million  pounds  are  believed
to be carboxylated S/B latexes.  Production capacity data
for S/B latexes  are  not available,  but existing  total
capacity is believed to be ample for demand until  1982.  A
capacity estimate for 1979  of 856 MM pounds/year  was made
based on 1977  production, 5% growth and  0.85  utilization.
The processing equipment for S/B latexes also can be used
to make  acrylic or polyvinyl acetate emulsions.  (These
products are  discussed  in  Sections  5   and   16,
respectively).

S/B latex  demand  in its major markets is  generally expected
to grow at an average of 4  to  5%  annually  from 1977 to
1982.  This would lead to  a  consumption level of 790-830
million  pounds,  dry  basis, by 1982.    The mostly
                      -228-

-------
        modest  growth  projections for the major  styrene-based
        polymers  reflect  the  effects  of the  increasingly
        competitive interplay of  thermoplastic  resins  in  the
        extrusion, molding,  and emulsion markets.

        Table 18-1  lists U.S.  producers of  S/B  latexes (73) .
        The  largest four (probably accounting for  over 50% of
        total production in  1976) are Dow, Reichhold,  AMSCO,  and
        General Tire (71),  (74).

18.2    STYRENE-BUTADIENE BY EMULSION POLYMERIZATION

18 .2.1   Process Description

        The  batch  process  described  consists  of  emulsion
        polymerization followed by  stripping.   The  product is an
        emulsion (latex) and Figure 18-1 is a  schematic  for  the
        process.

        The  major process steps are:

        o  Apply  vacuum to  reactor to remove residual  oxygen,
          break vacuum with inert  gas, and re-evacuate..
        o  Charge water, monomers, emulsifier  and modifier.
          (Monomers are mixtures of styrenes  and  butadiene with
          small amounts of  other monomers).
        o   Heat  reactor contents to  desired  temperature,
          140-160F,  by circulation of hot  water through
          jacket.
        o  Initiate reaction by charging catalyst,  activator  and
          reducing agent  (typically  potassium persulfate,
          ferrous  sulfate,  and sodium bisulfite  respectively).
          Heat of  reaction  is removed by circulating  cold water
          in jacket.
                             -229-

-------
   TABLE 18-1.- U.S.  PRODUCERS OF STYRENE-BUTADIENE LATEXESa(73)
COMPANY
PLANT LOCATION
AMERICAN SYNTHETIC RUBBER CORPORATION
Louisville, Kentucky
ATLANTIC RICHFIELD COMPANY
 ARCO/Polymers, Inc., subsidiary
Beaver'Valley, PA
BORDEN, INC.
 Borden Chemical Division
  Thermoplastics Products
Illiopolis, Illinois
Leominster, MA
DART INDUSTRIES INC.
 Chemical Group
  Plastic Raw Materials Sector
   Southwest Latex Corporation
Bayport, Texas
DOW CHEMICAL U.S.A.
Allyn1s Point, CT
Dalton, Georgia
Freeport, Texas
Midland, Michigan
Pittsburg, California
THE FIRESTONE TIRE & RUBBER COMPANY
 Firestone Synthetic Rubber and Latex
 Company, division
Akron, Ohio
GAF CORPORATION
 Chemical Products
Chattanooga, Tennessee
                              -230-

-------
TABLE 18-1.- U.S.
PRODUCERS OF STYRENE-BUTADIENE LATEXES
          (Continued)
COMPANY
                         PLANT LOCATION
THE GENERAL TIRE & RUBBER COMPANY
 Chemical/Plastics Division
                         Mogadore, Ohio
THE B.F. GOODRICH COMPANY
 B.F. Goodrich Chemical Company, division   Louisville, Kentucky
THE GOODYEAR TIRE & RUBBER COMPANY
 Chemical Division
                         Akron Ohio
W.R. GRACE & COMPANY
 Industrial Chemicals Group
  Dewey and Almy Chemical Division
                         Owensboro, Kentucky
                         South Acton, MA
REICHHOLD CHEMICALS, INC.
 Reighhold Polymers Inc., subsidiary
 (formerly Standard Brands Chemical
  Industries, Incorporated)
                         Cheswold, Delaware
                         Kensington, Georgia
UNION OIL COMPANY OF CALIFORNIA
 AMSCO Division
                         Charlotte, NC
                         La Mirada, California
UNIROYAL, INC.
 Uniroyal Chemical, division                Scotts Bluff,
                                            Louisiana

aProducers of solid S/B copolymer resins are not included.  For
  example, Phillips Petroleum Company produces K-Resin, BDS Polymer,
  a clear, impact-grade butadiene-styrene copolymer for packaging, at
  Borger, Texas, in a plant with a capacity of 10 million pounds per
  year.                       _231_

-------
   VAPOR
   RETURN
     WATER

EMULSIFIER '

  CATALYST!

  MODIFIER !

 INITIATOR '
                                                JK.O.
                                                DRUM   VAC>  STM> jET

                                                   STM'
    STYRENE MONOMER STORAGE
    (OR CYLIMDRIC  TANKS)
 I
M
U)
K>
 I
                             CW OR STM
                                                                                                        TO  FLARE
                                                                                         [3]
                                                            K.O.
                                                           DRUM/
                                                                                CW
         POLYMER
         REACTOR
          BUTADIENE MONOMER STORAGE
     (PRESSURE TANKS OR MORTON SPHERES)
                                                                                        DISPOSAL
                              CW 55F
                                                            REFLUX
                                                              COND.'
                                                                         VAC. STM. JET
                                                                     STM

t

<=^r=



dr>
>
 1
^-
cw
^
                                                                            (OR VACUUM PUMP)
                                         CW 55F
                                                                 K.O.I
                                                                 DRUM
                                                                  DISPOSAL
                         VACUUM
                        STRIPPER
PRODUCT  OUT
                                                                      S/B LATEX  STORAGE
                                                    TUNNEL DRYER
                                                                          .SOLID RESIN
                                                                          PRODUCT (POWDER)
                  FEED                  REACT               RECOVERY                   FINISH

            Figure.18-1.- Styrene-butadiene  latex using emulsion polymerization.

-------
        o   After  reaction runs to completion,  batch is vacuum
           stripped in separate vessel  to remove residual monomer
           and  concentrate latex.   Heating  is  accomplished  by
           circulating hot water through jacket.

        A  number of variations are  possible and some of  the more
        significant ones are:

        o   Oxygen removal  may be accomplished by  inert gas
           purging rather than application of vacuum.
        o   Monomers may be added in several increments or may  be
           metered into reactor while reaction is proceeding
           rather  than added as a  single  batch  charge  prior  to
           initiation.
        o   Stripping may be carried out in.reactor rather than  in
           separate vessel.
        o   Catalyst may be added at the start or may be metered
           into reactor while  reaction  is proceeding.
        o   Residual  monomers may  be removed by either gas
           sparging   (with  air  or  inert  gas),  or steam
           distillation, or one of  these operations combined  with
           vacuum  stripping.
        o   The drying section  for producing solid resin,  (powder)
           may or  may not be present.
        o   The reactor and stripping vacuum  may be provided  by
           either  vacuum steam jets or  vacuum pumps.
18.2.2   VOC  Emissions
        All  significant emission  rates and  sources  for this
        product  are shown  in Table  18-11.   The  schematic
        flowsheet for this product,  which  includes the emission
        streams  and  their sources,  is  Figure 18-1.  Emissions
        were reported to  be nil  for  product  storage.    A
        description of the emission  streams follows:
                             -233-

-------
TABLE 18-II.-VOC EMISSIONS FROM  STYRENE-BUTADIENE  LATEX MANUFACTURE
                 BY EMULSION POLYMERIZATION  PROCESS
Stream

[1]  Styrene Monomer
     Storage

[2]  Reactor Safety
     Relief

[3]  Reactor Reflux
     condenser and
     vacuum system

[4]  Vacuum Stripper
     overhead

[5]  Solid Resin Dryer

TOTALS
                 Current
Uncontrolled     Practice   Well Controlled
#/1000# Resin  #/1000#Resin  #/1000# Resin
0.31
nil
20.41
nil
0.20
0.31
nil
20.41
nil
' 0.20
0.13
nil
2.04
nil
0.02
     20.92
20.92
2.19
                             -234-

-------
[1]  Styrene monomer storage tanks - This  stream vents the
    fixed  roof storage tanks  for styrene  monomer  at
    ambient conditions.  Pure styrene vapor  in  air (or
    inert blanket gas  if used) compose the gas  emitted.
    This  stream is one of the two primary  sources  of
    styrene emissions within the  typical S/B latex (by
    emulsion polymerization) plant.

[2]  Reactor safety relief valves and  rupture  discs -
    Under  emergency conditions,  this  stream  carries
    materials  vented from the polymerization  reactor.
    The main  emergency conditions causing  relief  are
    reactor jacket and/or reflux condenser cooling  water
    failures and agitator failures during the reaction.

    Steam  composition varies  with time as  the  batch
    proceeds  but is generally  butadiene  (the  most
    volatile VOC component), styrene monomer vapor  water
    vapor, inert gas or air, other vaporized liquids from
    minor constituents in the batch, and emulsified S/B
    product solids and entrained liquids.  Relieving this
    stream is extremely rare, only once  per 5  to 10 years
    per reactor.  Because of the great infrequency of
    relieving,  no average yearly quantity of VOC  emitted
    is considered.

[3]  Polymerization reactor  (reflux  condenser) -  This
    stream emits butadiene from the reactor  along with
    water vapor and non-condensibles.   It is the  largest
    source  of  VOC  emissions  from the process  (both
    potential and as currently practiced).  It  includes
    emissions  during the vacuum  cycle  of  the  reactor,
    through  the steam jets, and  emissions  during  the
                     -235-

-------
           pressure  cycle  of the reactor.   Water  vapor  (or
           steam) enters  from the reaction mix  and from  the
           steam jets (while  under vacuum) and air  enters  the
           system by leakage  when under vacuum.

        [4] Vacuum stripper  (stripper reflux condenser)  - This
           stream is  listed  for reference only  since no  VOC
           emissions are reported from it.   The  stream  consists
           almost wholly of steam and non-condensibles  removed
           by  vacuum jets.   VOC  is minute  quantities  of
           styrene.

        [5] Tunnel dryer  for  solid resin - This  stream is  the
           second major  source of styrene emissions  from  the
           process,  but  it  will only be present in plants that
           make the  alternate  solid resin product  in  addition to
           the normal emulsion product (estimated to be 1/2 of
           the plants) .  The  stream will consist  of  the drying
           medium (e.g.,  air or nitrogen), in addition with
           styrene vapor.

18 .2.3   Applicable Control Systems

        The following control  technologies are  recommended  for
        the emission  streams described in Section  18.2.2 and in
        the schematic flowsheet  (Figure 18-1) for  this  product.
        Several systems  equivalent  to  those recommended  are
        available and might prove preferable  after detailed
        study.  The actual plant flare system provided is subject
        to a number of considerations and the  guidelines  of good
        engineering  practice.  Stream  [3],  venting  butadiene
        monomer  from  the  reactor raises the question  of flare
        versus  incinerator, and  this  should  be resolved in a
        detailed study.   Control by  flare was  selected  for
                            -236-

-------
economic  reasons, but  it  raises  the question  of the
flammability of the mixtures.  A more  detailed  study
would determine both  flammability  and  explosive  limits.

[1]   Styrene monomer  storage  tanks  - A vapor  return line
     to the tank truck will  eliminate all working loss
     emissions or 58% of current emissions.   Conservation
     valves  should also be  used,  but these should be
     installed for  economic reasons.   No pollution
     abatement credit is given them.
[2]   Reactor safety relief  valves  and  rupture  discs  -
     These are routed to the  plant  flare  system  and  are
     preceded by the  knock-out vessel  (a  flare efficiency
     of 90% is assumed).
[3]   Polymerization reactor (reflux condenser) - Exhaust
     from either vacuum  steam jets  or  vacuum  pumps  to a
     water-cooled after-condenser  and  knock-out  vessel is
     sent to plant flare.  Flare efficiency of 90%  is
     assumed.  The after-condenser  has little  direct
     effect on VOC emissions  but condenses  water vapor so
     the flared mixture  can be burned  (within
     flammability limits).   An alternate  route for  this
     stream (for the  portion  of the batch cycle  when the
     reactor is under pressure)  by-passes the  vacuum
     equipment and after-condenser  but goes to the
     knock-out vessel and then to  the  flare.
[4]   Vacuum stripper  reflux condenser  - The reflux
     condenser can be justified for process reasons  but
     also serves as (nearly 100%)  abatement for  VOC
     (styrene) emissions.
[5]   Tunnel dryer for solid resin - This  is routed  to the
     plant flare system.
                      -237-

-------
                          SECTION 19
                 UNSATURATED POLYESTER  RESINS
19.1  INDUSTRY DESCRIPTION

      Unsaturated polyester (UP)  resins  are esters of diols  like
      propylene glycol (PG) and the  anhydrides of unsaturated and
      saturated dicarboxylic acids like  maleic (unsaturated)  and
      phthalic  (saturated)  acid.  UP  resins are supplied
      dissolved in a vinylic monomer,  usually styrene, with which
      they  are cross-linked during application or cure.   They are
      usually reinforced with fiberglass or  mineral  fillers,  as
      in  fiberglass reinforced plastics  (FRP).

      Unsaturated polyester resins  are  produced typically  by a
      batch polyesterification (polycondensation) reaction  in a
      jacketed, agitated reactor  fitted  with  a water condenser.
      A few newer plants  produce  the  resin  by a  continuous
      process.  Formulation variables  that affect the properties
      of  unsaturated polyester  resins  are  manipulated  with
      relative ease, so  that their exact composition varies
      widely.   Composition and  amount of VOC  emissions  will
      depend on the exact formulation.   As an example,  data for
      one halogenated specialty resin  indicate a high emission of
      a halogenated solvent with  that  formulation and no other.

      Unsaturated polyester resins are marketed  as liquid resin
      solutions in styrene monomer and  are  used to  make  FRP
      panels, bath fixtures and boat hulls.   U.S. production  in

                             -238-

-------
1978  was approximately  1210  MM pounds (2^) and  installed
capacity was  estimated to be 1600 MM pounds  (75) .  Based on
1977  data ( 7_6 ) , utilization,  K, was 0.71  and with  an 8%
average  annual growth  ,  1979 installed capacity  was
estimated to  be  1735 MM pounds (7_7) , (^78_) .   Adequate supply
seems assured for  the next five years.   Installed  capacity
figures currently  show an  excess capacity, but  estimates
for  this  industry can be  misleading  because  the same
equipment can be used for alkyd resins.

There were more  than 20 producing companies  in  the  U.S. in
1977, most of them operating  more than one plant.   Table
19-1  lists the  U.S. manufacturers and gives  plant locations
{7_5)  .  The four  largest, Reichhold,  W.R.  Grace,  Koppers,
and  Ashland  Oil,  have 52% of  the  capacity;  the top 12
manufactures  have  90% of it.

The most common  raw materials for these resins are maleic
anhydride (unsaturated) ,  phthalic anhydride  (saturated),
and propylene glycol (diol)  all of  which can  produce  VOC
emissions.   The thinning  and  crosslinking  monomer is
styrene (STY),  also a potential VOC  emission source.  Other
saturated and unsaturated acids and  higher molecular weight
glycols  are  substituted  in varying  amounts  to  yield
improvements  in  one property or another.  Table 19-11 lists
the most common  raw materials and their chemical  formulas
and molecular weights.

The common processes used  for U.S.  unsaturated  polyester
manufacture  may be  classified  either  as  "fusion"  or as
"solvent" processes.  Fusion processes use  inert gas to
remove the water of reaction, and the solvent processes  use
                       -239-

-------
TABLE 19-1.-  U.S. PRODUCERS OF UNSATURATED POLYESTER RESINS (75)

                                ESTIMATED ANNUAL CAPACITY AS OF
COMPANY AND PLANT LOCATION      JANUARY I, 1978  (Millions of Lbs)

ALPHA CHEMICAL CORPORATION                        90
    Colierville, Tennessee
    Kathleen, Florida
    Riverside, California

ASHLAND OIL, INCORPORATED                        130
  Ashland Chemical Co., division
   Resins and Plastics Division
    Calumet City, Illinois
    Los Angeles, California
    Newark, New Jersey
    Valley Park, Missouri

AZS CORPORATION
  AZ Products, Inc., division                     10
    Eaton Park, Florida

  Lancaster Chemical Corp., division
    Newark, New Jersey

CARGILL, INCORPORATED                             50
  Chemical Products Division
    Carpentersville, Illinois
    Forest Park, Georgia
    Lynwood, California

COOK PAINT & VARNISH COMPANY                      30
    Detroit, Michigan
    Milpitas, California
    North Kansas City, Missouri

W.R. GRACE & COMPANY                             225
  Hatco Group
  Hatco Polyesters Group
    Bartow, Florida
    Colton, California
    Jacksonville, Arkansas
    Linden, New Jersey
    Swanton, Ohio

ICI AMERICAS INCORPORATED                         25
  Specialty Chemicals Division
    Wilmington, Delaware
                               -240-

-------
     TABLE 19-I.-U.S. PRODUCERS OF UNSATURATED POLYESTER RESINS
                             (Continued)

                               ESTIMATED ANNUAL CAPACITY AS OF
COMPANY AND PLANT LOCATION     JANUARY I, 1978  (Millions of Lbs)

INTERPLASTIC CORPORATION                          75
  Commercial Resins Division
    Jackson, Mississippi
    Minneapolis, Minnesota
    Pryor, Oklahoma

KOPPERS COMPANY, INCORPORATED                    130
  Organic Materials Group
  Coatings and Resins Division
    Bridgeville, Pennsylvania
    Chicago, Illinoisb
    Redwood City, California
    Richmond, California

OWENS-CORNING FIBERGLAS CORPORATION              100
  Resins and Coatings Division
    Anderson, South Carolina
    Valparaiso, Indiana

PPG INDUSTRIES, INCORPORATED                      80
  Coatings and Resins Division
    Circleville, Ohio
    Houston, Texas
    Springdale, Pennsylvania
    Torrance, California

REICHHOLD CHEMICALS, INCORPORATED                350
    Azusa, California
    Detroit, Michigan
    Elizabeth, New Jersey
    Houston, Texas
    Jacksonville, Florida
    Morris, Illinois
    South San Francisco, California
    Tacoma, Washington

H.H. ROBERTSON COMPANY                           100
  Freeman Chemical Corporation, subsidiary
    Chatham, Virginia
    Marshall, Texasb
    Saukville, Wisconsin
                               -241-

-------
     TABLE 19-I.-U.S.  PRODUCERS OF UNSATURATED POLYESTER RESINS
                               (Continued)

                               ESTIMATED ANNUAL CAPACITY AS OF
COMPANY AND PLANT LOCATION    JANUARY 1, 1978  (Millions of Lbs)

ROCKWELL INTERNATIONAL CORPORATION                20
  Automotive Operations
  General Components Group-Plastics Division
    Ashtabula, Ohio

ROHM AND HAAS COMPANY                             30
    Philadelphia, Pennsylvania
  Rohm and Haas Tennessee Inc., subsidiary
    Knoxville, Tennessee

SCM CORPORATION                                   20
  SCM Coatings and Resins Division
    Chicago, Illinois
    Cleveland, Ohio
    Huron, Ohio
    Reading, Pennsylvania
    San Francisco, California

THE SHERWIN-WILLIAMS COMPANY                      20
  Coatings Group
    Cleveland, Ohio
    Emeryville, California

THE STANDARD OIL COMPANY (OHIO)                   75
  Vistron Corporation, subsidiary
  Chemicals Department
  Silmar Division
    Cowington, Kentucky
    Hawthorne, California

UNITED STATES STEEL CORPORATION
  USS Chemicals, division0
    Neville Island, Pennsylvania
                               -242-

-------
     TABLE 19-I.-U.S.  PRODUCERS OF UNSATURATED POLYESTER  RESINS
                           (Concluded)

                               ESTIMATED ANNUAL CAPACITY AS OF
COMPANY AND PLANT LOCATION    JANUARY 1, 1978  (Millions of Lbs)

WHITTAKER CORPORATION                             20
  Whittaker Coatings and Chemicals         .
  Mol-Rez Division
    Minneapolis, Minnesota

OTHERS                                            20

                       TOTAL                   1,600
 aCapacity estimates for this industry have limited value,
  since multipurpose reactors for condensation products  (e.g.,
  alkyd resins, plactizers) can be used.  Estimates listed are
  only for  condensa capacity dedicated to unsaturated polyester
  resins production.
 ^To begin operation in the second half of 1978.
 CA plant at Neville Island, Pennsylvania is expected to  start
  up in 1979 with a capacity of 9 0 million pounds per year.   Resin
  is produced at the Wallingford, Connecticut plant of American
  Cyanamid Company and will continue to be produced there until
  the new facility is opened.
                               -243-

-------
     TABLE 19-II.-COMMON RAW MATERIALS  FOR  UNSATURATED POLYESTER
                             MANUFACTURE
                          SYMBOL
            FORMULA
               MOL.  WT,
Maleic anhydride            MA
Phthalic anhydride          PA
Isophthalic acid            IA
Fumaric acid                FA
Hydrogenated bisphenol A    HBA
            C4H23
            C8H43
            C8H44
            C4H44
            C15H282
                 98.1
                148 .1
                166.1
                116.1
                240.4
Tetrahydrophthalic
  anhydride                 THPA
Tetrahydrobromophthalic
  anhydride                 THBA
Propylene glycol            PG
Diethylene glycol           DG
Styrene                     STY
            C8H83
            C8H3Br4
            C3H82
            C4H105
            C8H8
                152.1

                463.7
                 76.1
                106.1
                104.1
Methyl methacrylate
MMA
,H82
100.1
                            -244-

-------
        azeotropic distillation.  Although both  are  known to be
        produced  commercially in the U.S.,  there  is no  published
        information about  relative capacities.  Uncontrolled
        emissions levels from the fusion process  are  higher than
        from  the  solvent process because inert gas stripping is
        used  with it, and VOC are not recovered  (solvent recovery
        provides  some VOC  reduction for the solvent  process).
        Although  lower than the fusion process  in VOC emissions,
        the solvent process does have solvent -  usually xylene -
        as well as other emissions.  The xylene  or other  solvent
        is added  in the reactor and removes the  water of reaction
        by being  azeotropically distilled overhead  where it is
        condensed,  decanted,  and recycled.  A more detailed
        discussion of fusion and solvent processes is  developed
        in the sections that follow (79) . .

19.2    UNSATURATED POLYESTER RESIN MANUFACTURE

19.2.1  Process Description (Fusion and  Solvent  Processes)

        Both  the  fusion and the solvent  processes described below
        are batch operations and both can be  performed  either as
        one-step or as two-step processes, virtually without
        equipment changes.  The emission points  are the same for
        both processes.   Extra equipment  used  to  make  a
        fire-retardant specialty resin (shown in the dashed box
        of the schematic)  presumably could be used  with  either
        the fusion or the solvent process.  The  extra  equipment
        is bypassed during  normal resin  production.
                             -245-

-------
        The  process described first  is  a one-step fusion^
        process  for producing polyester resin made from phthalic
        and  maleic  anhydrides, and  propylene glycol,  and
        dissolved in styrene.  Figure 19-1, Unsaturated polyester
        resin manufacture by  fusion/solvent  processes,  is a
        schematic diagram of  the  process.

        The  process has two parts,  namely  reacting  (polyester-
        ification) , and thinning.  After the  polyesterif ication
        reactor  and its overhead  condensation system are purged
        with an  inert gas, molten maleic and phthalic anhydrides
        and  propylene glycol  are  charged into the reactor and  the
        mixture  is agitated and heated.  For  the fusion process
        the  overhead condensation system generally consists of a
        packed column, a  partial  and a  total condenser and
        various tanks,  lines,  and  a  caustic  scrubber.
        Polyesterif ication is  carried  out  at 200C, and as  the
        reaction proceeds, byproduct water is evolved.   The  inert
        gas  flow is increased to remove  this water,  and the
        temperature at the top of the  packed column is kept at
        100-120C  by  first  injecting  and  then refluxing water
        from the partial condenser.  As the  reaction approaches
        completion and the  volatiles  begin  to diminish, the
        temperature starts to rise in the reactor and fall  in  the
        column.   The inert  gas  rate  is  increased further to
        remove most  of the residual water  vapor and  unreacted
        materials.  When the  desired acid number is reached  in
IA variation  uses the same equipment  in a two-step process
wherein the  saturated  anhydride (PA) is  added  and esterified
first,  and  cooled slightly,  before  the  MA  is  added  and
esterified.   Because reactor temperatures are lowered for the
two-step process, VOC emissions of glycols  can be lessened.
                            -246-

-------
                                                            FOR THE SOLVENT PROCESS THIS . WATER TANK
                                                            REPLACED BY DECANTER AND TWO RECEIVERS
I
to
                                                                  EXTRA EQUIPMENT SPECIALTY RESINS
                         v>^^-
-------
         the  reactor,  the polymer is  cooled, blended with
         additives-'-, if  any, and pumped to the  thinning
         vessel.  During the reaction and thinning,  some  of  the
         reactants are carried out of the reactor  with  the water
         vapor  and  lost from the product.  After  most  of  the
         volatiles  are  condensed the  vapor exhaust  from  the
         reactor  is scrubbed with caustic  or  water before  it
         leaves the process vent.   The reactor vent [2]  is  the
         single largest  emission source in  the process  and  the
         only emission  point  for the  reactor.   The solvent
         process is similar,  basically, to  the fusion  process.
         The major  process difference  is that  a xylene-water
         azeotrope is formed in  the reactor  to remove  byproduct
         water  vapor overhead.  This  necessitates different
         equipment  to remove and reuse  the solvent.   Solvent
         process equipment  changes in Figure 19-1 are  indicated
         by asterisk and include a decanter and  two  receivers in
         place of a water tank/K.O. drum for  the  fusion process.

         In  the thinning operation,  the thinning  vessel
         containing the  required amount of styrene is purged with
         inert  gas  before the  partially cooled  unsaturated
         polyester  is added  at a rate  that keeps the  resin
         temperature  at about 66C.  Overhead vapors  from  the
         thinning  operation  are  controlled by a condenser.
         Thinning tank emissions are shown as emission point [3].
         They are VOC (mostly  STY) carried  out in  an  inert  gas
         flow.
^Additives may be added in the  reactor or in the  thinning
 vessel.  In the thinning vessel resin is checked for color, acid
 number,  and other physical  properties, and additives such as
 hydroquinone inhibitor,  and filter aids are added.
                              -248-

-------
         Certain specialty  resins are  made  by additional
         processing  after  the  reactor  but before  thinning.
         Figure 19-1  shows  extra equipment in the dashed  box  for
         making special (fire-retardant) halogenated resins.  The
         halogenation process has potential VOC emissions from
         two pieces of equipment - the halogen-reactor  scrubber
         vent, and the stripper  overhead vent.   Both vents  are
         identified as emission  stream [2]  and  their estimated
         emissions  are given in the  table with the  process
         reactor emissions, vent [2] .   Resin leaving  the
         specialty equipment flows back to enter the  thinning
         operations  and processing continues  as for  regular
         production resins.
19.2.2   VOC Emissions
        All significant emissions for this product  are listed in
        Table  19-111.   Emission points  are  indicated on  the
        flowsheet  by bracketed numbers.  Both  the  fusion  and
        solvent processes are represented by  the data.   The
        emissions streams  are:

         [1] Raw material storage,  except monomer  -  Fixed  roof
            storage tanks  are  used throughout  the operations in
            the existing facilities.  Emissions are  vapors of
            phthalic and  maleic anhydrides (PA  and MA)  and
            propylene glycol  which  result  from  vapor
            displacement (working) and tank breathing.   Both PA
            and MA are  solids  at room temperature  and  both  are
            stored in hopper bins until needed.   As needed, they
            are melted  at  high  temperatures^  (290 and 160F
            respectively)  in heated, insulated tanks.
 At these  temperatures PA and MA tend to sublime  and
 recondense causing solids deposits.
                            -249-

-------
TABLE 19-1II.-  VOC EMISSIONS FROM UNSATURATED POLYESTER  RESIN -  FUSION  OR SOLVENT
                                          PROCESSES
          STREAM
UNCONTROLLED   CURRENT PRACTICE  WELL CONTROLLED  COMPOSITION
#/1000# RESIN    #/1000# RESIN    #/1000# RESIN      VOL %
[1] RAW MATERIAL STORAGE 	


[2] PROCESS
NORMAL
REACTOR
RESIN
SPECIALTY RESIN

I
NJ
(Jl
o
1


[3] THINNING


[4] PRODUCT
[5] MONOMER

AND BLENDING


STORAGE
STORAGE
TOTALS - NORMAL :


- SPECIALTY:

12
22

0


0
0
12
23

.4
.8

.11


.05
.02
.6
.0
0

0
18

0


0
0
0
18
.04

.44
.0

.08


.05
.02
.6
.2
0

0
6

0


0
0
0
6
.0

.05
.3

.02


.05
.01
.1
.43
0
0
0

1
8
1
0


0
1


.97 PA,
.14 MA,
.01 PG

.0
.0
.0
.5


.2
.0



PG
MCI 2,
PG
STY


STY
STY



-------
[2]  From  the esterification reactor - This stream is the
    largest potential emissions source for either the
    fusion or  solvent  process.   The flow  rate  and
    composition vary, but  the  major VOC component is
    propylene  glycol.   The  reactor vent  carries
    unreacted monomers and volatile  impurities contained
    in  the monomers  in  a stream  of inert  gas.   The
    stream of inert gas serves  three  purposes:

    o   Assists in removal of  water  formed  in  the
       reaction and thus  pushes  the  reaction forward;
    o   Strips residual volatiles;
    o   Prevents oxygen contamination.

    The specialty resin has a vol-atile-  solvent  process
    that  greatly increases VOC  emissions.  Table  19-111
    shows the composition of all  the  streams.

[3]  Thinning vessel -  This vent  discharges styrene vapor
    in  an inert gas resulting from the purge  flow from
    the product.

[4]  Product storage  - Fixed roof tanks are  used, and
    small amounts of  VOC are emitted from working and
    breathing losses.   Almost all  emissions are  styrene
    vapors.

[5]  Monomer storage -  Styrene is  the  predominant monomer
    used  in thinning, and  it  is stored in fixed  roof
    tanks.   Due to styrene1s higher  vapor pressure (10
    mmHg  at 87F) it  is a larger  potential VOC  emission
    source,  [5], than the  other raw material  storage
    vents,  [1].

-------
19 .2.3    Applicable Control  Systems

         Because emissions from  the fusion and solvent processes
         are similar and arise from the same process  sources, .the
         control systems for the  two are discussed  together.  The
         following controls are recommended  for the streams
         described in section 19.2.2 and shown in Figure 19-1.

         [1]  Emissions from feed material  storage (except
            monomers)  - Fixed  roof tanks  are  satisfactory for
            PAf MA and propylene glycol since vapor  pressures of
            all three materials  are low at ambient temperature.
            However, both PA and MA have potential housekeeping
            problems  since they are heated prior to reactor
            charging and because they are  solids that  sublime
            and reform at vents.  Presently uncontrolled  in the
            unsaturated polyester industry,  these vents are
            controlled (12)  (13) by aqueous scrubbers  with  about
            95% VOC efficiency in  the  phthalic and  maleic
            anhydride producing  industries.

         [2] Reactor vent  emissions  -  For many unsaturated
            polyester manufacturers, the  reactor  vent  is the
            largest potential VOC emission  source even  through
            nearly all are  controlled by a combination of packed
            columns,  condensers,  and scrubbers  with perhaps
            90-95% reduction of VOC.  Several manufacturers use
            thermal incinerators or boilers for tail-gas  cleanup
            of the reactor vent and may expect 95% additional
            VOC removal efficiency.  For specialty resins, the
            volatile halogenated solvent used may be controlled
            by refrigerated (-30F)  condensers on both the
            halogen-reactor scrubber vent  (ice  traps  will be
            required)  and  the  stripper  vent.   Demonstrated
            control  is 90% for  normal  resins and  65%  for
            specialty resins.
                             -252-

-------
[3] Thinning vessel vent emissions - These emissions are
   primarily styrene  vapor in  an  inert gas  flow.
   Present controls vary from none to a cooling-water
   condenser.   Adequate control would  include  a
   refrigerated  brine  condenser.   Cooling  to  40F,
   gives an 80%  emissions reduction without moisture
   freeze-up. 80% control was assumed.

[4]  Product storage  - Emissions are almost  entirely
   styrene vapor.  Storage tanks have fixed roofs and
   should be equipped with conservation vents.
   Emissions are  low  and no controls are warranted.

[5]  Monomer storage  - Generally, styrene monomer is
   stored in fixed roof tanks with  conservation vents.
   Presently, most  tanks are uncontrolled.   Future
   tanks  will   use  f1oating-roof  tanks  and/or
   refrigerated-vent condensers.   50% control was
   assumed.
                    -253-

-------
                          SECTION 20
                   UREA-FORMALDEHYDE  RESINS
20.1  INDUSTRY DESCRIPTION

      Urea-formaldehyde resins (UP resins) are aminoplasts, which
      are  a  class of thermosetting resins made by the reaction of
      formaldehyde with the amino (-N!^) group of urea or
      urea derivatives (14) ,  (15).

      Desirable properties of urea-formaldehyde resins  include
      heat resistance, solvent and chemical  resistance,  extreme
      surface hardness,  and resistance to  discoloration  on
      exposure to heat or  light.   The largest end  uses  for
      urea-formaldehyde resins are  as  an  adhesive in particle-
      board  and medium-density fiberboard,  for other adhesives,
      and  in compression-molded plastic parts.  Other major
      applications  include textile  and  paper treating  and
      coating,  and  cross-1inkers   for  1 ess-expensive ,
      thermosetting, surface coatings.   One  or more properties of
      UF resins may be improved  by replacing part or all  of the
      urea with various urea derivatives.   The most widely  used
      example of  this  type - melamine  -  has been the base  of a
      separate branch  of the aminoplast industry.  Melamine was
      discussed in Section 7.

      The  reaction of  urea and formaldehyde  is complex,  involving
      stepwise condensation and  competing reactions.  The overall
      reaction is analogous  to PF  resol  formation (See  Section
      10). UF resins are generally made by a batch reaction in an
                             -254-

-------
aqueous medium.  A mixture  of low molecular  weight UP
polymers with  some methylolurea and  dimethylolurea is the
normal  commercial  resin.   The  resin product can be
shipped as  an  aqueous syrup (approximately 75%  of  sales
poundage) or as a powder produced  either by impregnating
the syrup on  a solid  filler,  or  by spray drying.   The
final stage of polymerization (cross linking) takes place
when the resin is cured to its  final form, an  insoluble
thermoset product.

Production of UF  resins was 1122  MM  PPY  in 1978  (2_) .
Although some  disagreement  exists, most market experts
expect  UF resin sales to  decline  at  a   rate  of
approximately  1.5% per year during  the next  five years.
Economic and  environmental conc.erns are  the  primary
reasons given. Particleboard is becoming less profitable
since  the  resin  costs are increasing  faster   than  the
price of the particleboard itself.  For  this  reason  some
plants  are closing,  and industry  sources  doubt  that
additional  capacity will  be  added  for quite some  time.
Also, urea-formaldehyde  is  not a  permanent  bond;  under
certain conditions, it breaks down releasing  formaldehyde
and the odor is obnoxious.   Little production  capacity
data for UF resins exist.   Production equipment can be
used  interchangably to  make melamine-formaldehyde
(another aminoplast) or UF resins,  and, in  many cases,
phenol-formaldehyde resins.

The 1978 production of 1122 MM PPY was  combined  with  1.5%
anticipated decline and a 0.8 utilization to  arrive  at a
1979 capacity  estimate of 1381.5 MM PPY.   Approximately
60 manufacturers are  known  to  produce UF  resins in the
United States. These producers are  shown in  Table 7-1 of
Section 7.

                      -255-

-------
20.2    UREA  FORMALDEHYDE SYRUP AND FILLED  POWDER MANUFACTURE

20.2.1  Process Description

        The process first described  is a  simple batch  process
        used  to make a  concentrated  syrup widely  used in  the
        manufacture of  partic1eboard  and  medium  density
        fiberboard.  Figure 20-1  shows  a  schematic for  the
        processes described here (17) ,  (21).

        The following operating steps  are carried out:

        o Charge 37 or 52% formaldehyde solution, solid  prilled
          urea, and  aqueous  sodium  hydroxide  in  correct
          proportions to the reactor  that  is being  agitated.
        o  Heat mixture  to  desired  reaction temperature  by
          utilizing steam in the jacket, and allow  it  to  reflux
          under vacuum at reaction temperature.
        o Monitor  reaction progress by  sampling reactor contents
          for viscosity.
        o  At desired viscosity,  cool  batch  to approximately
          140F, and then concentrate  syrup by evaporation of
          water  under vacuum  until  desired  degree  of
          concentration  is reached (typically  65% wt).
        o Adjust batch pH as required  and  pump out  syrup through
          filter to syrup holding  tank.

        At this  point the resin syrup  can be stored  for  sale.
        Also  it can be condentrated further, or processed further
        for sale as a solid powder.   An unfilled powder- can be
        manufactured by  spray  drying  the  aqueous  syrup,  and a
        filled  powder can be obtained  where a solid  filler is
        impregnated by the syrup and further processed.   A  batch
        process of  the latter type  is  described below:
                              -256-

-------
  VAPOR
RETURN
                      CAUSTIC
 FORMALDEHYDE SOLUTION,
 52? e  138F (FIXED ROOF)
    STM
       RESIN  SYRUP
        STORAGE
                                                               FORMALDEHYDE
                                                                 SCRUBBER
                                                                                TO
                                                                                INCINERATOR
                  SYRUP PRODUCT
                  -- TO DRUMS
                  OR TANK CARS
    RESIN
IMPREGNATOR1
   (MIXEJO
                                                    AIR
                                                (MAKE-UP)
PROCESS
 SEWER


  MOLDING POWDER
 ' PRODUCT TO FURTHER
  SIZE PROCESSING
  &  PACKAGING
                                                            FAN
                                                            *AN
            FEED
                                   REACT
                                                          RECOVERY/FINISH


        Figure  20-1.-  Urea-formaldehyde resin -  Batch process,

-------
        o   Filler  (such as kraft paper)  is  impregnated with resin
           syrup and mixed to wet paste  in  a mixer.
        o   Water is removed in tunnel  dryer to form dry cake.
        o   Cake ("popcorn") is pulverized in a Mikro- Pulverizer
           to  coarse powder.
        o   Coarse  powder is milled in  ball  mill with additives to
           form blended fine powder.
        o   Fine powder  is deaerated and  compressed  into
           corrugated ribbon, which is cut  into molding granules
           for storage and sale.
20.2.2  VOC  Emissions
        All significant emission rates and  sources  for  this
        product  are discussed  in  this  section.  Also  they are
        shown on Table 20-1.  Figure 20-1  is the  schematic
        flowsheet for the product,  which  includes the  emission
        streams and  their sources.   Emissions from  the
        impregnator and dryer (streams  [3] and  [4]) were prorated
        to  reflect  an estimated  conversion of only 25%  of the
        resin syrup to molding powder within the total  domestic
        UF  resin industry.

        [1]  Formaldehyde solution  storage  tanks - This  stream
            vents the fixed-roof  storage  tank for the  52%  (wt)
            aqueous  solution  of formaldehyde  (37%  is  also
            commonly used) kept at 138F by  internal steam coils.
            Normal  breathing and  filling  cause the emissions.
            The  stream is composed of air drawn  in the tank  from
            the  atmosphere, formaldehyde and water vapor from the
            stored  solution, and some methanol vapor (methanol is
            a common constituent of formaldehyde, functioning as
            an inhibitor - purchase  specification of 0.5 - 1.0
            wt%  methanol).


                              -258-

-------
TABLE 20-1.-VOC EMISSIONS FROM UREA-FORMALDEHYDE - BATCH  PROCESS
                                       Current
                      Uncontrolled     Practice   Well Controlled
Stream                #/1000# Resin  1/lMOJResin  I/IOOO* Resin

[1]  Formaldehyde
     Solution Storage

[2]  Resin Reactor

[*3]  Resin Impregnator
      (Mixer)

[*4]  Powder Dryer

    Totals
0
0
0
11
12
.01
.08
.02
.99
.10
0.01
0.07
0.02
2.83
2.93
0.01
0.00 +
0.00+
0.01
0.02 +
* Prorated to reflect estimated conversion of only 25% of  resin
  syrup to molding powder (filled and unfilled) within domestic
  UF resin industry.
                                -259-

-------
[2] Overhead emissions from  reactor - This stream  is  a
   relatively small potential  source of VOC emissions
   and  includes the fugitive emissions picked up  at  the
   reactor manhole when  reactants and various additives
   are  charged to the reactor.   The emission rate  and
   composition vary over the batch  cycle.  The average
   composition  includes  large  quantities of air;
   considerable water vapor  evolved  by the reaction  and
   from the  formaldehyde solution charged; unreacted
   formaldehyde; methanol  from the formaldehyde;  and
   traces of other reactants,  additives, catalyst,  and
   reaction products from the  reactor.  Most of the  VOC
   emissions here are exhausted  from the overhead  vacuum
   and  condensing system used  for each batch.
[3] Resin impregnator (mixer)  -.This stream is  also  a
   relatively small potential  source of VOC emissions.
   The  emissions are  of  a  fugitive  nature,  being
   generated by the impregnator or mixer in which  the
   solid filler is impregnated  with  resin syrup from the
   reactor and then mixed to a  wet paste.  The equipment
   is completely housed; operators also work within  the
   enclosed  space, which has  controlled ventilation.
   The  VOC constituents, formaldehyde and methanol,  are
   exhausted with large  quantities of air  and  water
   vapor.  A proration is made  in this stream to reflect
   only 25% of total syrup resins going to powder.
[4] Dryer for powder - Stream exhausts the tunnel dryer
   removing water from filled  powdered resin.  This is
   the  largest potential emission source of VOC from the
   plant even with the  proration that was  made  to
   account for only 25%  of total syrup resins going to
   powder.  The bulk of  the stream is air, the  drying
   medium, with water vapor  comprising under 5% (wt)  and
   the  main VOC components,  formaldehyde and methanol,
   less than 0.1% (wt).
                     -260-

-------
20.2.3   Applicable Control Systems

        The  following control technologies  are recommended  for
        the  emission streams described in Section 20.2.2 and
        shown  in the schematic flowsheet for this product.

        [1]  Formaldehyde  solution  storage  tanks -  Use the
            pressure equallizing  vapor  return  line to tank cars
            or trucks to eliminate working  losses from storage
            tank filling (approximately 58% of total potential
            storage emissions).   Conservation valves will also  be
            required; since they  would  normally be installed  for
            economic reasons, no pollution control credit  is
            given them.
        [2]  Overhead emissions from reactor -  This stream will
            include  both fugitive emissions  picked up at the
            reactor  manhole and emissions from the  overhead
            vacuum and reflux system for the reactor.  Controls
            for the former should utilize sufficient hoods and  a
            fan for gathering and containment.   Both this stream
            and emissions from  the  enclosed overhead
            vacuum/reflux system  (which  will  have  an
            after-condenser)  should be  sent  to  the incinerator.
            The  incinerator will be  required especially for
            Stream  [4], the dryer exhaust.   The VOC reduction
            efficiency of the incinerator applicable to  the  total
            reactor exhaust is assumed  to be 95%.
        [3]  Resin impregnator (mixer) - Recommended control here
            is  area  pick-up of  fugitive emissions and proper
            ventilation, much as  currently practiced.  Additional
            hoods or other pick-up aids should be added where
            needed.   Current practice reflects  the benefit  of  the
            overall process change  (increased conversion)  but  the
            reduction effect is considerably less here than  for
                              -261-

-------
    the  dryer (20% reduction  from the uncontrolled
    estimate).   The  emissions gathered here should be
    sent to the  incinerator ([4], dryer exhaust).  A VOC
    reduction efficiency of 95%  on this  impregnator
    stream is assumed  using the incinerator.

[4]  Dryer  for  powder  - A  very  important  control
    recommended  here  is already reflected  in  current
    practice figures.  It  is  the process  change
    increasing conversion of formaldehyde to resin.  An
    85% reduction in the formaldehyde content of  the VOC
    stream from  uncontrolled emission rates was  found to
    result  (by  measurement) from this change and is
    probably  the maximum reduction possible from this
    technique.   Further reduction by other  means (in
    series)  are  still  required for this stream.

    Water scrubbing of the dryer exhaust should  be used
    in conjunction with  dryer recycle.  This should be
    followed by  incineration of  a  purge   stream
    (approximately 10% by volume).  A relativley large
    flow of water (approximately 100 GPM) will be needed
    in  the  scrubber  but high  removal efficiencies,
    approximatley 99%  for methanol and  approximately 85%
    for  formaldehyde, can be achieved.  VOC reduction
    efficiency  for  the  incinerator is assumed to be
    approximately 95%  on the purge stream.
                     -2G2-

-------
                         REFERENCES
(!_)       The Research Corporation  of New England, "Impact of  New
         Source Performance Standards on 1985 National Emissions
         from Stationary Sources", Vol.  I, Contract No. 68-02-
         1382, Task 3, October 24, 1975.

(2)       Anon., Chemical and Engineering  News,  p.  43, Volume
         57, Number 24, June 11, 1979.

(3)       Pullman Kellogg, "Emission, Process  and Control Tech-
         nology  Study of the ABS/SAN,  Acrylic Fiber  and NBR
         Industries", Contract 68-02-2619,  Task 6, April  20,
         1979 .

()       Chemical  Economics Handbook,  "Plastics and Resins",
         Stanford Research Institute, 606.4031 E, April,  1979.

(J5)       Chemical  Economics Handbook,  "Plastics and Resins",
         Stanford  Research Institute,  580.0020 D-H,  April,
         1979 .

(jj)       Chemical  Economics Handbook,  "Plastics and Resins",
         Stanford Research Institute, 674.4521 D, May, 1976.

(T)       Fong, Wing Sien, "Polyacrylates", Report No.  65, Pro-
         cess Economics Program,  Stanford Research Institute,
         November, 1970.
                             -263-

-------
 (8_)       Pullman Kellogg,  Trip Report, E.  I.  DuPont Plastics
          Products  and Resin Department, Contract No.  68-02-2619
          Task  7, October 17, 1978.

 (9_)       Chemical  Economics Handbook, "Plastics  and Resins",
          Stanford  Research Institute, 580.0230 A-G,  May,  1979.

(10)       Chemical  Economics Handbook, "Surface Coatings", Stan-
          ford  Research Institute, 592.5821  A-E,  September, 1977.

(11)       Chemical  Economics Handbook, "Surface Coatings", Stan-
          ford  Research Institute, 592.5822  A-Z,  September, 1977.

(12)       Shreve, R. Norris, "The Chemical Process  Industries",
          3rd Edition, McGraw Hill Book Co.',  N.  Y.,  1967.

(13)       Monsanto Research Corporation,  "Phthalic Anhydride
          Plant Air Pollution Control", Contract No.   68-02-1320,
          Task  25,  September 1977.

(14)       Chemical  Economics Handbook, "Amino  Resins", Stanford
          Research  Institute, 580.0275 A-Z,  June, 1979.

(15)       Chemical  Economics Handbook, "Amino  Resins", Stanford
          Research  Institute, 580.0276 A-Z,  June, 1979.

(16)       Chemical  Economics Handbook, "Amino  Resins", Stanford
          Research  Institute, 580.0277 A-S,  June, 1979.

(11)       Schwaar,  Robert H., "Thermosetting  Resins",  Report No.
          93,  Process Economics Program,  Stanford Research
          Institute, March, 1976.
                              -264-

-------
(18)       Chemical Economics Handbook, "Fibers-Synthetic", Stan-
          ford Research Institute, 543.4122 B-E,  December,  1977.

(19 )       Smith, W. Mayo, "Manufacture of Plastics",  Volume.1,
          Reinhold Publishing Corporation, N.  Y.,  1964.

(20)       Russell, Grant E., "Nylon 6", Report No.  41A, Process
          Economics Program Stanford Research Institute, July,
          1976.

(21)       Pullman Kellogg, Trip Report, Allied Chemical,  Contract
          No. 68-02-2619, Task 7, 24 October 1978.

(22)       Yen, Yen-Chen, "Nylon 66", Report No.  54,  Process Eco-
          nomics Program, Stanford Research Institute,  November,
          19 69 .

(23)       Pullman Kellogg, Trip Report, E. I.  DuPont de Nemours,
          Contract No.  68-02-2619, Task 7, 17 October  1978.

(24)       Chemical  Economics  Handbook,  "Plastics  and Resins",
          Stanford  Research  Institute,  580.0931  A-D, 580.0932
          A-B, 580.0933 A-D, 580.0934 A-B, May,  1978.

(25)       Chemical Economics Handbook, "Formaldehyde", Stanford
          Research  Institute,  658.5031  A-H, 658.5033  L-M,
          658.5034 L,  September, 1979.

(26)       Pullman Kellogg, Trip Report, Union Carbide Chemicals,
          Contract No. 68-02-2619, Task 7, 9  November 1978.
                               -265-

-------
(27)       Chemical Economics Handbook, "Polyester Fibers", Stan-
          ford  Research Institute,  543.4821 D-J,  543.4822 A-M,
          February, 1978.

(28 )       Elkin,  Lloyd M., "Polyethylene Terephthalate" , Report
          No. 18, Process Economics Program,  Stanford Research
          Institute, November, 1966.

(29)       Elkin,  Lloyd M. and Soder, Sara L.,  "Polyethylene Tere-
          phthalate", Report No. 18A, Process  Economics Program,
          Stanford Research Institute, January, 1972.

(30)  -  (49)  Reserved and not used.

(50)       Chemical  Economics  Handbook, "Plastics and Resins",
          Stanford Research Institute, 580.1341 C,  April,  1979.

(51)       Anon.,  Chemical and Engineering News, p.  14,  Volume  56,
          Number  36, September 4th, 1978.

(52)       Chemical  Economics  Handbook, "Plastics and Resins",
          Stanford Research Institute, 580.1342 C,  April 1979.

(53)       Magovern, Robert L., "Linear Polyethylene and Polypro-
          pylene", Report Number 19B, Process  Economics Program,
          Stanford Research Institute, November, 1966.

(54)       Magovern, Robert L.,  "Linear Polyethylene  and Propy-
          lene, Report Number  19C, Process Economics Program,
          Stanford Research Institute, November, 1966.

(55)       Pullman Kellogg, Trip Report, Union  Carbide  Chemicals,
          Contract Mo. 68-02-2619, Task 7, 8  November  1978.
                              -266-

-------
(56)       Chemical Economics  Handbook, "Plastics  and  Resins",
          Stanford Research Institute,  580.1331  E, April 1979.

(57)       Chemical Economics  Handbook, "Plastics  and  Resins!',
          Stanford Research Institute,  580.1332  D, April 1979.

(58)       Magovern, Robert L., "Low Density Polyethylene", Report
          Number 36, Process Economics  Program,  Stanford Research
          Institute, April 1968.

(59)       Magovern, Robert L., "Low Density Polyethylene", Report
          No.   36A, Process Economics Program,  Stanford  Research
          Institute, March 1977.

(60)       Chemical Economics  Handbook, "Plastics  and  Resins",
          Stanford Research Institute,  580.1431  C and  G, February
          1978 .

(61)       Chemical Economics  Handbook, "Plastics  and  Resins",
          Stanford Research Institute, 580.1432  F-I, February,
          1978 .

(62)       Pullman  Kellogg, Trip Report, Amoco Chemicals  Corpora-
          tion  Contract No. 68-02-2619, 12  October,  1978.

(63)       Magovern, Robert L., "Linear  Polyethylene  and  Polypro-
          pylene", Report No.  19-A, Process Economics  Program,
          Stanford Research Institute,  October,  1969.

(64 )       Chemical Economics  Handbook, "Plastics  and  Resins",
          Stanford Research Institute,  580.1502,  F October,  1977.
                              267-

-------
(65)       Pong, Wing Sien, "Polystyrene", Report No. 39, Process
          Economics Program,  Stanford Research Institute, June,
          19 68 .

(66)       Pong, Wing Sien, "Polystyrene", Report No. 39A,  Process
          Economics Program,  Stanford  Research Institute, May,
          19 74 .

(67)       Chemical  Economics Handbook,  "Plastics and Resins",
          Stanford Research Institute,  580.1872 A and I, Septem-
          ber, 1977.

(68 )       Chemical  Economics Handbook,  "Plastics and Resins",
          Stanford Research Institute,  580.1871 C and D, Septem-
          ber, 1977.

(69 )       Chin, Yu-Ren, "Polyvinyl  Acetate & Polyvinyl Alcohol",
          Report  No.  57A, Process Economics  Program, Stanford
          Research Institute, September,  1976.

(70)       Pullman Kellogg, Trip Report, W.  R.  Grace & Co., Con-
          tract No. 68-02-2619,  Task 7,5  October 1978.

(71)       Chemical  Economics Handbook,  "Plastics and Resins",
          Stanford Research Institute,  580.1501 C, July, 1979.

(72)       Chemical  Economics Handbook,  "Plastics and Resins",
          Stanford Research Institute,  580.1502 B, July, 1979.

(73 )       Yen, Yen-Chen, " Styrene-Butadiene  Elastomer",  Report
          No.  64, Process Economics Program,  Stanford Research
          Institute, November,  1970.
                              -268-

-------
(74)       Chemical  Economics Handbook,  "Plastics and Resins",
          Stanford Research Institute,  580.1233 C, May, 1978.

(75)       Chemical  Economics Handbook,  "Plastics and Resins-",
          Stanford Research Institute,  580.1231 C, May, 1978.

(76)       Anon., Chemical and Engineering News, p. 11, Volume  57,
          Number 13, March 26, 1979.

(77)       Stinson,  Stephen C., Chemical  and Engineering News,
          pgs.  10-13, Volume 57,  Number 32,  August 6, 1979.

(73 )       Fong, Wing Sien, "Unsaturated Polyesters",  Report  No.
          26A,  Process Economics  Program,  Stanford Research
          Institute, January, 1977.
                             -269-

-------