-------
3. PRIORITY DECISION MODEL
The specific conclusions that follow are referenced to the systems analysis
factors assimilated in the Priority Decision Model presented in Section vn and
Sections V and VI discussed above.
The Priority Decision Model was developed from standardized evaluation
and comparison of the major polymerization processes including such factors and
sub-factors as:
Total potential population exposed
Population exposure potential of the average plant
Plastic production volume
Production growth trend
Emission potential index
Hazard potential index
Odor potential index
The model, depicted in Exhibits 1-1 and 1-2, was developed jointly with
EPA and features the factors discussed above. Major emphasis in this model is
directed to the hazard index.
The hazard potential is derived from published
occupational safety and health threshold limit values
(TLV) of most likely air contaminants.
Market and production data provided the information to
estimate the total potential population exposed in terms
of each sector, taking into account the average plant, growth
trends and production volume .
Emission potentials were based on process technology
assessment.
Odor potential was based on published odor threshold
data.
Exhibit 1-3 summarizes key findings related to the elements of the model.
1-4
-------
EXHIBIT 1-1
Environmental Protection Agency
SUMMARY OF FACTORS IN THE
PRIORITY DECISION MODEL
Broad Systems Analysis Factors For
Each Chemical/Plastics Industry Sector
A:
B:
C:
D:
Market and Production from
data in Section V
Emission Potential from
information in Section VI
Hazard Potential from
information in Section VI
Odor Potential from
information in Section VI
Sub-Factor
Sub-Factors Weight
Aj=Total Potential 0.4
Population Exposed
A =Population Exposure 0.2
Potential of the
Average Plant
A3=Plastic Production 0.2
Volume
A4=Production Growth 0.2
Trend
Process Technology 1.0
Assessment
Toxicity (TLV) of 1.0
Principal Likely
Emissions
Odor Threshold of 1.0
Principal Likely
Emissions
Priority Decision Formula
AC + BC + AD = R, where R is the overall rating
The formula has the following features:
The hazard factor, C, appears twice as a multiplicant and
is given significant emphasis , as required by EPA
The product of A x C emphasizes situations where the hazard
potential is high and the potential population exposure is great
The product of B x C emphasizes situations where hazard
potential and emission potential are high and, therefore, the
relative magnitude of potential concentrations of hazardous
substances at receptor locations are factored in qualitatively
The product of A x D emphasizes the relative magnitude of the
potential nuisance to the population from odorous substances
Source: Snell (and EPA and Snell in development of priority decision formula)
1-5
-------
EXHIBIT 1-2
Environmental Protection Agency
RANKING OF PLASTICS SECTORS
REGARDING AIR POLLUTION
SYSTEMS FACTORS
Selection formula:
AC + BC + AD = R
B
i
O9
Plastic
Vinyl Resins
Styrene Resins
Acrylics
Alkyds
Polyurethanes
Phenolic and Other Tar
Acid Resins
Polyethylene and
Copolymers
Polyesters
Amino Resins
Cellulosics
Polyamides
Polypropylene
Coumarone-Indene and
Petroleum Resins
Epoxy Resins
Production 5
Population
Exposure
Related Index
Number
10.0
8.5
8.5
8.0
8.0
Emission
Potential
Index
Number
7.0
7.4
5.0
4.8
2.6
Hazard
Index
Number
4.0(1)
2.8
4.5
6.6
9.3
Odor
Index
Number
2.3
7.4
9.0
5.0
7.7
Overall
Selection
Index
Number
91.0
107.4
137.3
124.5
160.2
Priority
Order
8
6
2
3
1
7.5
6.5
6.5
6.5
6.0
5.5
5.0
5.0
3.5
4.0
8.0
4.8
5.3
6.7
7.0
8.8
7.1
4.2
5.2
1.3
6.6
4.8
3.5
1.2
1.7
4.2
5.4
6.9
2.5
5.3
6.8
4.3
1.5
1.9
7.7
4.1
111.6
35.2
109.1
100.8
70.3
23.3
33.0
89.3
56.0
12
5
7
10
14
13
9
11
U)Based on 50 ppm TLV for vinyl chloride
Source:
Snell
-------
-EXHIBIT 1-3
Environmental Protection Agency
KEY FINDINGS FROM THE PRIORITY
DECISION MODEL
Production and Population Exposure
In terms of total potential population
exposed alkyds, polyurethanes, acrylics.
amino resins and phenolic and other tar
acid resins are most significant. This is
because there are numerous establish-
ments engaged in the manufacture of
these products, and are often located in
populated areas.
The population exposure potential of the
average plant is highest for cellulosics,
where establishments are located in high
population density areas. This index is
then most significant for alkyds as well
as coumarone-indene and petroleum resins.
Plastic production volume is highest for
polyethylene and copolymers. vinyl resins,
styrene resins, and polypropylene. These
account for approximately 78 percent of
total annual production volume. The next
four highest volume plastics and resins are
phenolic and other tar acid resins, poly-
esters, amino resins, and alkyds account-
ing for only approximately 16 percent.
The highest volume resins also exhibit
the most significant production growth
trend. Acrylics are also characterized by
rapid potential growth.
Emission Potential
The manufacture of the largest
volume products has the highest
emission potential both in terms
of process complexity and possible
emission quantity at individual plant
sites. These products include poly-
ethylene and copolymers, vinyl
resins, styrene resins and polypropylene.
Polyurethanes production, excluding
foam manufacture, which is not con-
sidered part of the chemical/plastics
industry, has the lowest emission
potential. Reasons include process
simplicity and use of almost closed
systems.
Hazard Potential
The hazard potential of the
principal chemical species
in manufacture is overwhelm-
ingly highest for polyurethanes
because of the use of isocya-
nates.
The next important categories
in this regard are alkyds and
polyesters.
The hazard index assigned to
vinyl resins is 4.0 versus 9.3
for polyurethanes based, in
part, on the use of a TLV of
50 ppm for vinyl chloride
versus 0.02 ppm for toluene
diisocyanate, respectively.
However, in the jight of
recent evidence* Blinking
polyvinyl chloride (PVC)
operations to cancer deaths,
this index may have to be
revised upward as new ex-
posure standards are set.
Odor Potential
. The odor potential of
the principal chemical
species is overwhelm-
ingly highest for acrylics.
. The next important
categories in this regard
are coumarone-indene
and petroleum resins,
polyurethanes and
styrene resins.
Source; Snell
-------
The system-, analysis of air emission in the chemical/plastics industry
identified polyurethanes, acrylics, and alkyds as the prime candidates for in-depth
study. However, it is possible that in the wake of the emerging concern with the
hazards associated with PVC, the hazard index associated with vinyl resins will
have to be raised from 4.0, for example, to 9.0. Then, vinyl resins will become
of highest priority concern from a systems viewpoint of air pollution control.
4. IN-DEPTH STUDIES
The specific conclusions that follow are referenced to the information presented
in Section VIII, dealing with
Emissions and their controls from the manufacture of
polyurethanes, acrylics and alkyds as well as other
selected high volume resins.
Emission control technology and costs.
The in-depth evaluations confirm the low emission potential index assigned
to polyurethanes manufacture (excluding foams). Although the hazard index is
high, emission factors are low - of the order of 3 x 10~7 Ibs isocyanates per Ib of
prepolymer. Effective control technology exists and is believed to be practiced.
Conventional scrubbing techniques can reduce appreciably the total emissions
from acrylic facilities but not easily eliminate odor nuisance.
From a solution polymerization process acrylic ester
emissions could be of the order of 1 x 10~3 Ibs per
Ib of product, while this could be 3 x 10~3 for solvent.
From an emulsion process emission of both acrylic
monomers and vinyl acetate could be of the order of
1 x 10~3 Ibs per Ib of product, respectively.
From a suspension process acrylic monomers emission
could be of the order of 5 x 10~4 Ibs per Ib of product.
The principal emission problem with the manufacture of alkyds is solvents.
Total emissions can be of the order of 0.01 Ibs per Ib of product.
1-8
-------
The in-depth studies also provide specific emission factor data for high
volume resins and control cost data for representative emission control devices.
The table below summarizes operating cost data for representative control
techniques.
Annual Operating Cost
Emission Control Device Per CFM of Capacity
Bag Filters $0.30 - 0.501
Compression/Refrigeration $3.00 - 6.00
Scrubbers $0.40 - 0.601
Flares $0.10 - 0.202
Regenerative Adsorption $2.00 - 6.003
1. Neglecting the value of recovered product.
2. Assumes no heating value for the stream itself, but does
include supplying the necessary air in case of an essen-
tially inert gas stream.
3. Excludes values of recovered material and assumes a
0.05 - 0.3% by weight concentration of absorbate. Also
excludes the cost of a pretreatment of the gas stream.
Source: Section Vin
1-9
-------
5. OVERALL CONCLUSIONS
The study indicates that plastics industry sources of air pollution which
require control technology development are:
Monomer emissions, particularly of materials of hitherto
unrecognized toxicity, e.g., vinyl chloride;
Solvent emissions, both from solution polymerization and
alkyd manufacture.
Currently, flaring, bag filtration and scrubbing are the most economical
techniques available for control, as compared to regenerative adsorption and
compression/refrigeration which are up to ten times as costly to operate. The
basic problem with all of these techniques, however, is that none currently ad-
dresses in a satisfactory manner the control of potentially significant absolute
quantities of air pollutants when dispersed in large volumes of vehicular air,
for example, from drying operations and general plant ventilation. Process
development and improvements probably represent a better approach to min-
imizing emissions at low concentration in large air volumes than development
of effluent cleanup techniques specifically addressing this problem.
The section that follows deals with recommendations.
1-10
-------
SECTION H
RECOMMENDATIONS
-------
SECTION II
RECOMMENDATIONS
Recommendations based upon the system analysis of air pollutant
emissions fall into two categories
engineering and scientific investigations
further system analyses
The discussion below details each recommendation, while Exhibit
II-l provides R&D project plans.
1. STUDY PROCESS MODIFICATIONS TO REDUCE GASEOUS AIR
EQLLUTANT EMISSIONS FROM LARGE AIR VOLUME SOURCES
Large air volume sources include dryers and
ventilation systems.
The removal of low concentration gaseous
emittants (mostly hydrocarbons) from dryer
exhausts can represent a major economic and
engineering undertaking because of the large
volumes of air utilized, if removal is to be
affected after drying.
It is recommended that various techniques of
stripping monomers and other potential gaseous
emittants be examined in-depth before the dry-
ing step.
For example, in the polyvinyl chloride industry
steam stripping is being studied.
In regard to ventilation, it is recommended that
combining of vents and ventilation exhausts into
a limited number of controlled emission points be
studied.
II-l
-------
Engineering studies with extensive industry con-
tacts and minimum dependence on literature
review are envisioned.
2. EVALUATE IN-DEETH THE USE OF LIQUID SCRUBBER SYSTEMS
FOR EMISSION CONTROL vs. COMBUSTION BASED SYSTEMS
Combustion type pollution control systems usually require fuel
enrichment to sustain combustion. With the present and continuing energy
crisis, fuels will remain short and scrubbing will conserve this commodity.
It may also provide recycling opportunities rather than destruction of valu-
able raw materials.
Conduct a technical and economic evaluation of
various liquid (water and oil) scrubbers and packed
columns for removing organic contaminants from air
streams.
Compare the cost and effectiveness of scrubber sys-
tems with thermal decomposition methods.
3. STUDY THE IMPACT OF AIR QUALITY IN THE VICINITY OF
POLYVINYL CHLORIDE PLANTS
In light of recent evidence linking poly vinyl chloride operations to
cancer deaths, measurements of atmospheric contaminants in the proximity
of producing plants should be made and used as a basis for the evaluation
of health effects on exposed populations and to set subsequent emission
standards.
Dispersion models of 8-10 sites under conser-
vative meteorological assumptions should be
made.
Ambient modeling of 8-10 residential and/or
residential zones near plants.
II-2
-------
4. REFINE THE PRIORITY DECISION MODEL FOR THE CHEMICAL/PLASTICS
INDUSTRY THROUGH COMPUTERIZATION AND CONTINUING INFORMATION
RETRIEVAL
The Priority Decision Model of Section VII provides
a systematic framework for considering basic tech-
nical as well as economic factors related to air
pollution control at the industry level.
It is recommended that the model be adapted to
computerization.
It is further recommended that a continuing infor-
mation retrieval program be maintained focusing
upon
updating information related to the
economic structure of the industry
(production, market and population
exposure data, etc.)
continuing study of the hazard poten-
tial of the chemicals used
continuing compilation of emission
factors as a function of changing tech-
nology, improved emission controls
and data availability
The next section introduces the details of the study.
II-3
-------
Exhibit II-1 (1)
Environmental Protection Agency
RECOMMENDED R&D PROJECT PLANS
Project Name
Control of Emissions From
Large Air Volume Sources
r
Evaluation of liquid Scrubber
vs. Combustion Based
Approaches
Project Definition
. Dryers and ventilation
systems can represent
large air volume sources
with low concentrations
of emittants
. Stripping of emittants
before drying is to be
studied
. Use of combined ventil-
ation and other exhaust
system is to be studied
with centralized air
pollution control
. Industry contacts are to
be emphasized
. Comparison of cost and
effectiveness of scrubber
systems versus thermal
decomposition methods
Expected Deliverable(s)
. Conceptual design and
cost estimates
. Recommended pilot plant
scale work
Time Frame Man-Years Principle Skills Needed
1 1 Experience in Polymer
Plant Design
Process Engineering
Drying
Ventilation
Technical and economic 3 months 1/4
evaluation of various liquid
(water and oil) scrubbers for
removing organic contaminants
from air streams.
Estimation of cost effectiveness
for recovering selected materials
for recycle purposes.
Literature review is to be the
study approach
Process Engineering
Air Pollution Control
-------
EXHIBIT II-l (2)
H
en
Project Name
Study the Impact of Air
Quality in the Vicinity of
Polyvinyl Chloride Plants
and Detailed Engineering
Study Regarding Emissions
Priority
Project Definition
Expected Deliverable(s)
Time Frame Man-Years Principle Skills Needed
Computerization of Priority
Decision Model and Continuing
Refinement
. In light of recent evidence .
possibly linking polyvinyl
operations to cancer deaths
in production plants, pollu-.
tant concentrations in the
atmosphere to which popu-
lation is exposed should be .
quantified and used as a
basis to evaluate health
effects.
. Perform detailed engineer-
ing study regarding extent
of emission, status of con-
trols and possible future
controls.
Same as Project Name
Dispersion model of 8-10
sites under conservative
meteorological assumptions
Ambient monitoring of 8-10
residential or populated
zones near these plants
Emission profiles
Control technology assess-
ment
Computer based model
Continuing information
retrieval regarding
- hazard aspects
- emission profiles
- controls
- industry structure
1 year
5 years 1 /3 per year
Meteorology
Air Pollution Chemistry
PVC Production
Process Engineering
Air Pollution Control
Systems Analysis
Computer Science
Engineering Knowledge of
Industry
Air Pollution Control
Engineering
Source: Snell
-------
SECTION ni
INTRODUCTION
-------
SECTION m
INTRODUCTION
The increase in public awareness of the need to prevent and control
air pollution resulted in the passage by Congress of the Clean Air Act of
1970. Under the provisions of Section 103 of the Act, the Environmental
Protection Agency (EPA) is required to conduct and promote the coordina-
tion and acceleration of research, investigations, experiments, training,
demonstrations, surveys. and studies relating to the causes, effects, ex-
tent, prevention and control of air pollution.
In pursuance of these mandates, EPA awarded Contract No. 68-02-
1068 to Foster D. Snell, Inc. (Snell) to undertake a System Analysis of
Air Pollutant Emissions in the Chemical/Plastics Industry. The study was
originally intended to deal with odors from the manufacture of plastic materials,
synthetic resins and non-vulcanizable elastomers (SIC 2821) . By EPA
request, the study emphasis was shifted to general air pollutant emissions
with attention to the hazard potential of likely emittants.
There are hundreds of products classified in SIC 2821. However,
over 97% of these can be categorized within 15 principal generic groups.
Polyethylene and Copolymers
Vinyl Resins
Styrene Resins
Polypropylene
Phenolic and Other Tar Acid Resins
Polyesters
Amino Resins
Alkyds
Acrylics
Coumarone-Indene and Petroleum Resins
Polyur ethanes
Cellulosics
Epoxy Resins
Polyamides
Rosin Modifications
III-l
-------
In Sections V and VI, these are broadly defined in regard to market,
production, plant location, process and potential emission characteristics,
etc. Using a weighting procedure, jointly developed with EPA, these data
are incorporated into a "priority decision model" to rank each group in
a priority order. This system model is presented in Section VII.
The priority plastics and resins are discussed further in Section VIII.
These include polyurethanes, acrylics and alkyds. In depth consideration is
also given, in that section , to emission characterization and controls from
the manufacture of polyvinyl chloride, polypropylene, polystyrene, nylon
and polyethylene. General control technology and costs are also treated in
Section VIII.
Recommendations from the system analysis appear in Section II and
deal with both technical steps, as well as proposed means of developing further
characterization of emissions, since the literature as well as the sources con-
tacted generally lacked this type of information.
III-2
-------
SECTION IV
STUDY APPROACH
-------
SECTION IV
STUDY APPROACH
The study undertaken by Snell is titled System Analysis of Air Pollutant
Emissions from the Chemical/Plastics Industry. • The study was originally
intended to deal with odors from the manufacture of plastic materials,
synthetic resins and non-vulcanizable elastomers. By EPA request,
the study emphasis was shifted to general air emissions, with attention
to the hazard potential of the likely chemical species in these emissions.
The principal system analysis steps included
• definition of the industry in terms of production volumes
and trends by major product, plant capacities and loca-
tions and average population densities at each plant site
(Section V).
• definition of the major processes of the industry in terms
of equipment, reaction conditions, specific process chemi-
cals and quantities, products, emission points, likely
emittants and general controls (Section VI).
• development of a "priority decision model" to select
industry sectors for further study and to segment the
industry in a possible priority order for further EPA
actions; decision factors include market and production
configuration by major product (total potential population
exposed, population exposure potential of the average
plant, plastic production volume, production growth
trend), emission potential of the manufacture of each
major product; and hazard potential as well as odor
potential of emittants (Section VII).
• in-depth study of priority sectors and description of
general emission control methods and costs (Section
VIII).
• development of research and development recommenda-
tions (Section II).
These work steps were completed during the period from March 1973
through March 1974.
IV-1
-------
The work scope required that primary means of generating the required
information be literature review. This was comprehensive and included a search
by EPA's Air Pollution Technical Information Center. The list that follows pro-
vides examples of other sources searched:
• Chemical Abstracts, 1967 - most recent
• Air Pollution Abstracts, Vol. 1 - most recent
• Environment Information Access, Jan. 1972 - most recent
• Government Reports Index,
• Odors and Air Pollution: A Bibliography with
Abstracts, EPA AP-113
• Environment Science and Technology, 1969 - present
• Pollution Engineering, 1971 - present
• Archives of Environment Health, 1967 - June 1970
• Journal of the Air Pollution Control Association,
1967 - present
• Plastics Technology, 1969 - present
• Card Catalog of the Snell collection, of the Engineering
Societies Library, and of the Chemists' Club
Either letters of inquiry were sent to or phone interviews were conducted
with a limited number (less than 10)of design engineering firms and states with a
high concentration of plastics producers. Through the cooperation of the Manu-
facturing Chemists Association, a symposium-sty led meeting was held with
major producers interested in polyurethanes and acrylics. Four of these con-
tacts submitted confidential detailed data. Both the literature and these contacts
were useful sources of general information, but only limited data was obtained
on the quantified characterization of emissions.
It is noted, particularly regarding emission data in this report, that
results are not based upon statistically sufficient surveys and serve only as
case illustrations.
We are grateful for the technical guidance of Dr. Belur Murthy, Project
Officer. Particularly thorough inputs were provided by the following industry
sources and their contribution is appreciated:
• Or. Kenneth D. Johnson of the Manufacturing
Chemists Association
• The DuPont Corporation
• The Union Carbide Corporation
• The Mobay Chemicals Corporation
• Rohm and Haas Company
• Blaw-Knox Chemical Plants, Incorporated
• Crawford & Russell, Incorporated
IV-2
-------
SECTION V
PROFILE OF THE CHEMICAL/PLASTICS INDUSTRY REGARDING MARKET,
PRODUCTION, PLANT LOCATION AND POPULATION EXPOSURE FACTORS
-------
SECTION V
PROFILE OF THE CHEMICAL/PLASTICS INDUSTRY REGARDING MARKET.
PRODUCTION. PLANT LOCATION AMD POPULATION EXPOSURE FACTORS
The work of this section was completed during mid-1973.
Plastics and resin materials can be classified broadly into two categor-
ies: (1) thermosets and (2) thermoplastics. Thermosets are materials which
solidify or set on heating and cannot be remelted or reshaped once they have
been fully cured. Thermoplastic resins can be softened by heat and regain
their original properties upon cooling.
Further, these resins are divided into some 15 generic groups, within
the above two categories, members of each generic group having similar chem-
ical structure.
There are literally hundreds of plastics and resin materials produced
in the United States. More than 97% of these can be categorized within the
15 principal generic groups. The remainder are either unique in structure
or are produced in such low volume or by only a few producers, that they
are not reported in order to keep company production data confidential.
1. OVER THE YEARS THE NUMBER OF COMPANIES PRODUCING
PLASTICS AND RESIN MATERIALS HAS BEEN INCREASING
(1) The Number Of Producers Has Increased By About 700%
Since 1947
According to the 1967 Census of Manufacturers, the number of
producers has increased from 97 in 1947 to 391 in 1963 and an estimated
500 in 1967 and probably close to 650 in 1972.
(2) Producer's Specialization Ratio Has Decreased
The Specialization Ratio indicates the proportion of product
shipments (both primary and secondary) of the industry represented
by the primary products - in this case, plastics and resin materials.
The Specialization Ratio has decreased steadily from 92% in 1947 to
83% in 1967 indicating that producers are diversifying and possibly
integrating either backward or forward into raw material production
or fabricated products.
V-l
-------
(3) - Establishment Size Has Decreased
There were more plants employing less than 20 employees in
1967 than in previous years. In 1947, only 36% of existing establish-
ments had less than 20 employees. But, by 1967, 49% of the plants
had less than this number of production workers. Companies are,
therefore, probably localizing production to service nearby markets.
2. GROWTH OF SYNTHETIC RESIN PRODUCTION HAS BEEN STEADY
Production of synthetic resins for the period 1967-1972 and forecasted
for 1977 is shown in Exhibits V-l and V-2.
(1) Both Thermosets and Thermoplastics Production Have Grown
Thermoset resin production has increased from 3.1 billion pounds
in 1967 to 4.1 billion pounds in 1972, a compounded annual increase
of 5.6% per year.
Thermoplastics production increased from 10.7 billion pounds
in 1967 to 20.4 billion pounds in 1972, a compounded annual increase
of 13.8% per year.
(2) Thermoplastics Comprised 83% Of All Synthetic Resins Produced
In 1972
Thermoplastics are expected to increase their share of resin
production by 1977 and at that time account for about 85% of the total
produced.
(3) Seven Resins Account For 90% Of Production
Exhibits V-3 and V-4 show the resin groups ranked in order
of descending production volume, and as can be seen, the following
seven products make up the bulk of production .
A - Polyethylene and copolymers
B - Vinyl resins
C - Styrene resins
D - Polypropylene
E - Phenolic and other tar acid resins
F - Polyesters
G - Amino resins
V-2
-------
EXHIBIT V - 1
i
u
1967
Alkyds 638
Polyesters 513
Epoxy Resins 135
Phenolic and Other Tar Acid Resins 983
Polyurethane 89
AminO Resins 690
Other 46
Total 3,094
Environmental Protection Agency
TOTAL PLASTICS AND RESIN MATERIALS
PRODUCTION (million pounds per year) (1,2,3,4)
Thennosets
Estimated
1968
692
615
158
1,097
71
816
27
3,476
1969
674
688
166
1,181
81
816
27
3,633
1970
636
569
165
1,186
95
746
92
3.489
1971
580
730
169
1,194
79
746
92
3,590
1972
695
862
174
1.413
116
804
-
4,064
1977
750
1,900
200
2,230
177
1.100
-
6,377
Acrylics
Cellulosics
Poly amides
Coumarone-Indene and
Petroleum Hydrocarbons
Polyethylene and Copolymers
Rosin Modifications
Polypropylene
Styrene Resins
Vinyl Resins
Other
Total
Thermoplastics
-
171
63
284
3,799
134
662
2,391
2,671
520
-
187
88
349
4,568
86
878
2,896
3,216
606
-
193
92
357
5,490
86
1,090
3,343
3,686
676
538
182
91
283
5,844
87
1,031
3,550
3,756
324
590
174
100
264
6,381
87
1.288
3,748
4,076
-
660
190
115
325
7,624
95
1,755
4,479
5,186
-
1,350
200
175
325
15,300
90
3,500
9,000
8,300
-
10,695
12,874
15,013
15,686
16,708
20,429
38,240
All Resins:
Grand Total 13,789
16,350
18,646
19,175
20,298
24,493
44,617
-------
EXHIBIT V-2
Environmental, Protection Agency
PLASTIC AND RESIN MATERIALS PRODUCTION
1964 - 1972 and 1977 (Projected)
• •• • , i
._;:_:J: .. iiLLti
lift; :: 'M?r ' •"
••
ffl
--. i-
;'! '! :
|
LH ;H:i
L; , : . ...J!.. .,:-,;
.,.;^,-, ,..^i—L ^j—Lj 4 ... -I- -
..-.
-------
EXHIBIT V - 3
Environmental Protection Agency
PLASTIC AND RESIN PRODUCTION
RANKED IN ORDER OF VOLUME
Resin
Polyethylene and Copolymers
Vinyl Resins
Styrene Resins
Polypropylene
Phenolic and Other Tar Acid Resins
Polyesters
Amino Resins
Alkyds
Acrylics
Coumarone-Indene and
Petroleum Resins
Cellulosics
Epoxy Resins
Polyurethanes
Polyamides (Nylon)
Rosin Modifications
Other
Total 19,175
Production
1970
5,844
3,756
3,550
1,031
1.186
569
746
636
538
283
182
165
95
91
87
416
(million
1971
6,381
4,076
3,748
1,288
1,194
730
804
580
590
265
174
169
79
100
87
-
pounds)
1972
7,624
5,186
4 ,'479
1,755
1,413
862
851
695
660
325
190
174
116
115
95
-
20,298
24,493
Source: Exhibit V-l
V-5
-------
EXHIBIT V - 4
Environmental Protection Agency
INDIVIDUAL RESINS AS PERCENT OF
TOTAL 1972 PRODUCTION
Percent of Accumulated
Resin Total Production Percent
Polyethylene and Copolymers 31.1 31.1
Vinyl Resins 21.2 52.3
Styrene Resins 18.3 70.6
Polypropylene 7.2 77.8
Phenolic and Other Tar Acid Resins 5.8 83.6
Polyesters 3.5 87.1
Amino Resins 3.5 90.6
Alkyds 2.8 93.4
Acrylics 2.7 96.1
Coumarone-Indene and 1.3 97.4
Petroleum Resins
CeUulosics 0.8 98.2
Epoxy Resins 0-7 98.9
Polyurethanes 0.5 99.4
Polyamides 0.5 99.9
Rosin Modifications 0.4
Other
Total 100.3* 100.3*
*Does not add to 100.0% because of rounding errors.
Source: Exhibit V-3 and Snell estimates
V-6
-------
(4) Raw_"MateriaL§ujppltes Are Coming Under Pressure
Many 'of tfre 'laxges't volume resins are based on petroleum,
and shortages 'will 'develop rars 'evi'denced toy .the present energy
crisis-. For %xample>, 'benzerTe is presently in 'critical -supply ;and
it is \Ke starting 'material for .rstyrene plastics.
le"om'petitioh for 'p'etroleum., ''as an 'energy source, vwi'H jprob.ably
cause some •sKbftage's ca!lso.
(:5) fB'.y-'l97.7L:itJ8_ExRectecl -That Production COf /fill :Plastics iWjill
''Reabh.i4.4 .'.6jBillib~n Pounds
Production'wiiLprbbably increased the rate'of. 12.:7% through
1972-1977.
3. ADDITIONAL PLANT CAPACITIES WILL BE REQUIRED FOR ALMOST
ALL RESINS'PRODUCED/AFTER 1974
(1) Most Producers Of Major Plastics Are Installing Additional
Capacity
Major producers of large volume resins are already installing
additional capacity, but this will not be sufficient to meet needs much
beyond 1977. This assumes that feedstocks will be available.
(2) Present Facilities Will Probably Be Enlarged
The large volume resins are being made at or close to a
source of raw materials.
Petroleum refineries and crackers will probably remain located
at'locations close to' ports or near pipe lines.
V-7
-------
V-A POLYETHYLENE AND COPOLYMERS
Polyethylene (PE) resins are themoplastics containing, predominantly,
repeating ethylene groups. The molecular weights of the PE resins varies over
a wide range, from wax-like materials of relatively low molecular weight
(10,000 - 25,000) to rigid and tough plastics of ultra-high molecular weight
(2,000,000 - 4,000,000) with densitites ranging from 0.91-0.93 (low to medium)
and 0.94-0.97 (high).
1. POLYETHYLENE IS THE LARGEST PRODUCED POLYMER
Domestic production of PE increased from 3.8 billion pounds in 1967
to 7.6 billion pounds in 1972, a compounded growth rate of 14.9% per year.
In 1972, however, production increased 19.5% over the previous year.
Yearly production for the period 1967-1972 is shown in Exhibit V-l.
PE Consumption Will Continue To Grow At Above Normal
Growth Rate
Increasing use in packaging, molding, and construction should
provide a growth of about 15% per year over the near term.
2. THERE ARE 18 PRODUCERS OF POLYETHYLENE
The 18 producers operate 25 plants. Exhibit V-A lists the locations
and plant capacities of the producers.
(1) PE Production Is Concentrated In Two States
The Gulf Coast area, more specifically the states of Texas and
Louisiana, produces over 80% of the PE at 20 plant locations. The
reason for this heavy concentration is that the raw material (ethylene)
is produced in this area. The remaining 4 plants are located rela-
tively close to consumers.
(2) Plant Capacities Vary Widely
Plant capacities range from a high of 1.2 billion pounds per
year to as small as 100 million pounds per year or less. The tendency
is to enlarge existing facilities, rather than build new grass roots plants,
V-8
-------
EXHIBIT V-A
Environmental Protection Agency
PRODUCERS: POLYETHYLENE (4.5)
Estimated Capacity (1975)
Producer and Location . High Density Low Density
(million pounds) (million pounds)
Allied Chemical Corp.
Baton Rouge, La. 225
Amoco Chemicals Corp.
Alvin, Tex. 100
Celanese Corp.
Pasadena, Tex. 375
Chemplex Co.
Clinton, Iowa 125 310
Cities Service Co.
Lake Charles, La. 220
The Dow Chemical Co.
Freeport, Tex. 100 300
Plaquemine, La. 225 500
E. I. Du Pont de Nemours & Co., Inc.
Orange, Tex. 200 520
Victoria. Tex. 150
Eastman Kodak Co.
Longview, Tex. 250
Exxon Chemical Co.
Baton Rouge, La. 400
Gulf Oil Corp.
Orange, Tex. 150 500
Cedar Bayou, Tex. 200
Monsanto Co.
Texas City, Tex. 180
National Distillers and Chemical Corp.
Deer Park, Tex. 300
Tuscola, m. 150
National Petro Chemicals Corp.
La Porte, Tex. 270
Northern Petrochemical Co.
Joliet. HI. 500
Phillips Petroleum Co.
Pasadena. Tex. 250 94
Rexene Polymers Co'.
El Paso. Tex. 310
Sinclair-Koppers Co.
Port Arthur, Tex. 200 100
Union Carbide Corp.
Seadrift, Tex. 400 750
Texas City,' Tex. 225
Torrence, Calif. 120
Whiting, Ind. 240
Total 2,800 6,139
V-9
Total Polyethylene Capacity.- 8,939
-------
V-B VINYL RESINS
PVC and its copolymers (vinyl chloride content varies from 85% to
97%) are the most important of the vinyl resins. They are produced by
emulsion or suspension polymerization of vinyl chloride alone or with a
comonomer such as vinyl acetate, vinylidene chloride, etc. They can be used
alone or as a highly plasticized (as much as 75% plasticizer) form.
Polyvinyl acetate (PVAc), and to a lesser extent polyvinyl alcohol
(PVA) are important resins included in the vinyl group. PVAc is made by
polymerizing vinyl acetate in a manner similar to vinyl chloride polymeriza-
tion. PVA is made by the hydrolysis of PVAc.
Other vinyl resins include PVC copolymers containing less than 50%
vinyl chloride, polyvinyl butyral. polyvinyl formal and small amounts of
polyvinyl ethers.
1. VINYL RESINS ARE THE SECOND LARGEST PRODUCED POLYMER
GROUP
Domestic production of vinyl resins for 1967-1972 increased from 2.7
billion pounds in 1967 to 5.2 billion pounds in 1972, a compounded growth rate
of 14.0% per year. In 1972, however, production increased 27.2% over the
previous year. Yearly production for the period 1967-1972 is shown in
Exhibit V-l.
Vinyl Resins Will Continue To Grow At Above Normal
Growth Rates
Vinyl resins are finding increased usage in the construction
industry and much of this growth will, therefore, depend upon total
economic growth. This anticipated growth will also depend upon resin
supply in 1973, but with new plant constructions underway, supply to
sustain this growth should be adequate by 1974.
2. THERE ARE ABOUT 22 PRODUCERS OF FOLYVINYL CHLORIDE
These 22 producers operate some 37 plants with a total capacity of
about 6 billion pounds per year. Exhibit V-B1 lists producers, plant locations
and company capacities by 1974. In some instances individual plant capacities
are unavailable.
V-10
-------
EXHIBIT V-B1
Producer and Location
The B. F. Goodrich Co.
Niagara Falls, N.Y.
Salem County. N.J.
Calvert City, Ky.
Avon Lake, O.
Long Beach, Calif.
Continental Oil Co.
Pawtucket, R.I.
Assonet, Mass.
Oklahoma City, Okla. (180)
Diamond Shamrock Corp.
Delaware City, Del. (220)
Deer Park, Tex. (300)
Union Carbide Corp.
Institute. W.Va.
Charleston, W.Va.
Texas City, Tex.
Borden Inc.
Leominster, Mass. (145)
niiopolis, m. (200)
The Firestone Tire & Rubber Co.
Pottstown, Pa.
Penyville, Md.
Tenneco Inc.
Environmental Protection Agency
PRODUCERS: POLYVINYL CHLORIDE
Estimated Capacity in 1974
(million pounds)
875
(6)
(100),
(4)
'(4)
(200)$
(250)
Fleming, N.J.
Burlington, N.J.
Pasadena, Tex. (300)' (by 1974)
The Goodyear Tire & Rubber Co. _
Plaquemine, La. (200X.
Niagara Falls, N.Y. (80)
Occidental Petroleum Corp.
Burlington Township, N. J.
Rublntech, Inc.
Gulf Coast
Painesville, O.
(former Allied)
Air Products & Chemicals, Inc.
Calvert City, Ky.
Pensacola, Fla.
Stauffer Chemical Co.
Delaware City, Del.
Ethyl Corp.
Baton Rouge. La.
Olln Corp.
Assonet, Mass.
Uniroyal, Inc.
Painesville, O.
380
520
320
345
400
520
300
420
450
170
50
150
150
150
130
V-ll
-------
Producer and Location
Pantasote Co.
Pt. Pleasant, W.Va.
American Chemical Corp.
Long Beach. Calif.
General Tire & Rubber Co.
Ashtabula, O.
Great American Chemical Corp.
Fitchburg, Mass.
Keysor-Century Corp.
Saugus, Calif.
Georgia-Pacific Corp.
Plaquemlne, La.
National Starch
Meredosla, HI.
EXHIBIT V-B1 (continued)
Environmental Protection Agency
PRODUCERS: POL WIN YL CHLORIDE(6)
Estimated Capacity In 1974
(million pounds)
120
ISO
100
70
50
220
10
Total
6.050
V-12
-------
(1) PVC Production Facilities Are Concentrated In The Midwest,
Gulf Coast And On The Northeast Coast
PVC producers have located plants either close to the market
place or close to raw material supply. The larger producers are also
basic in monomer production.
(2) Plant Capacities Vary Over A Narrow Range
While total company capacities vary considerably, the average
plant size is estimated to be about 200 million pounds per year.
3. THERE ARE OVER 100 PRODUCERS OF POLYVINYL ACETATE
There are 9 relatively large producers of PVAc operating 31
plants in the U.S. with an estimated capacity of 325 million pounds per year.
In most instances individual plant capacities are unavailable. Exhibit V-B2
lists major producers, plant locations and some company capacities. The
many smaller producers and plant locations are listed in Appendix 1.
(1) PVAc Production Facilities Are Scattered Throughout The U.S.
The preponderance of plants to make PVAc is due to its prime
end uses — in paints and adhesives. Many paint and adhesive manu-
facturers make their own PVAc and these industries are located to serve
local markets at population centers.
(2) Plant Capacities Are Relatively Small
Plant capacities can vary from about 40 million pounds per year
to about 1 million pounds. The larger manufacturers probably average
15-20 million pounds per year.
4. THERE ARE 3 PRIME PRODUCERS OF POLYVINYL ALCOHOL
The 3 prime producers operate plants at 4 locations and will have
an operating capacity of slightly over 272 million pounds per year by the end
of 1973. Exhibit V-B3 lists producers, plant locations and capacities where
available.
V-13
-------
EXHIBIT V-B2
Environmental Protection Agency
PRODUCERS: POLYVINYL ACETATE(7'8)
Producer and Location Capacities
(million pounds)
Air Products & Chemicals, Inc. 25
Cleveland, O.
Elkton, Md.
City of Industry, Calif.
CalvertCity, Ky. (20)
Borden Inc. 40
Bainbridge, N.Y.
Compton, Calif.
Leominster, Mass.
Dliopolis. ni.
Demopolis. Ala.
Celanese Corp. 25
Louisville, Ky.
Belvidere, N.J.
Newark, N.J.
W. R. Grace & Co. 25
Cambridge, Mass.
Owensboro, Ky. (10)
Acton, Mass.
E. I. Du Pont de Nemours & Co., Inc. 50
Toledo. O.
Niagara Falls. N.J.
National Starch and Chemical Corp. 55
Plainfield, N.J.
Meredosia, 111.
Reichhold Chemicals, Inc. 40
Charlotte, N.C.
Elizabeth, N.J.
Morris, m.
Kansas City, Kans.
South San Francisco, Calif.
Tacoma, wash.
Jacksonville, Fla.
Azusa, Calif.
Monsanto Co. 40
Springfield, Mass.
Union Carbide Corp.
Institute, W.Va.
S. Charleston W.Va. 25
Gardena. Calif.
Total 325
(8)
Other reported producers are listed in Appendix 1.
V-14
-------
EXHIBIT V - B3
Environmental Protection Agency
PRODUCERS: POLYVINYL ALCOHOL
Capacity (Million pounds)
Producers 1972 1973
E.I. Du Pont de Nemours & Co., Inc.
Niagara Falls, N.Y. 25
La Porte, Texas - 100
Air Products S Chemicals, Inc.
Calvert City, Ky. 30 30+
Monsanto Company
Springfield, Mass. 12 142+
Total Capacity 67 272+
Note: Borden.Inc. has a B million Ib/year plant on standby at
Leominster, Mass.
V-15
-------
PVA Plant Capacities Vary Considerably
Plant capacities have, in the past, been relatively small — on
the order of 15 -25 million pounds per year. The newest plant which
will be on stream in 1973, however, will have a rated capacity of 100
million pounds per year.
5. THERE ARE SEVERAL ESTABLISHMENTS PRODUCING OTHER
VINYL RESINS
The principal "other" vinyl resin produced is polyvinyl butyral. This
resin, and several others, is generally produced at the same locations as PVA
and/or PVAc. Prime producers are Monsanto Co., E .1. Du Pont de Nemours
Co., Inc., and Dow Chemical Co.
V-16
-------
V-C STYRENE RESINS
Polystyrene is manufactured by polymerizing styrene monomers, then
forming pellets by an extrusion process.
Polystyrene copolymers include aerylonitrile-butadiene- styrene (ABS),
styrene-aerylonitrile (SAN) , styrene-butadiene, styrene-divinyl benzene
and styrene-rubber.
For reporting purposes, the U.S. Tariff Commission has divided these
resins into two categories: (1) polystyrene and copolymers, and (2) ABS and
SAN.
1. STYRENE RESINS ARE HIGH VOLUME PRODUCTS
Domestic production of polystyrene resins increased from 2.4 billion
pounds per year in 1967 to 4.5 billion pounds in 1972, a compounded growth
rate of 13.4% per year. In 1972 production increased 19.5% over the previous
year. Yearly production for the period 1967-1972 is shown in Exhibit V-l.
Polystryene Resin'Production Grew At A Faster Rate Than
ABS-SAN Resins
Of the total 4,479 million pounds of styrene resins produced in
1972, 81% or 3,643 million pounds was polystyrene and its copolymers,
the remainder being ABS and SAN resins. Polystyrene growth in 1972
over the preceding year was about 22%, while ABS-SAN resins grew
9.7%. In anticipation of these growing markets, producers are plan-
ning major plant capacity expansions.
2. THERE ARE SOME 21 LARGE PRODUCERS OF STYRENE RESINS
Of these 21 producers, 4 produce both polystyrene and ABS-SAN
resins; 14 produce only polystyrene, and 3 produce only ABS-SAN resins.
These 21 producers have production facilities at some 42 locations throughout
the U.S. Major plant locations, producers and capacities are listed in
Exhibit V-C. Other reported producers are listed in Appendix 1.
V-17
-------
(1) Production Facilities Are Concentrated In Two Geographic
Regions
While a few plants are located in California and Texas, the major-
ity of the large plants are located in the Midwest and Northeastern regions
of the U.S. Major markets for these resins are located in these areas.
(2) Production Facilities Tend To Be Of Medium Size
The majority of the plants appear to be sized at about 100 million
to 200 million pounds per year. There are, however, a large number
of plants smaller than 50 million pounds.
V-18
-------
EXHIBIT V-C
Environmental Protection Agency
PRODUCERS: STYRENE RESINS <4• u •
Estimated Capacity, 1973 (million pounds)
Producer and Location ABS- SAN Polystyrene and Copolymers
The Dow Chemical Co. 980
Joliet, m. - x
Torrence, Calif. 20 x
Midland. Mich. 105 x
Ironton (Hungry Rock). O. x
Riverside (Pevaly). Mo. - x
Allyn's Point. Conn. 65 x
Monsanto Co. 400
Addyston, O. 270 x
Springfield, Mass. - x
Long Beach, Calif. - x
Foster Grant Co., inc.
Leominster. Mass. - 155
Peru, m. - 195
Cosden Oil & Chemical Co. 300
Calumet City, m. x
Big Spring, Tex. - x
Sinclair-Koppers Co.
Kobuta, Pa. - 300
Union Carbide Corp. 280
Marietta, O. - x
Bound Brook, N.J. 35 x
Amoco Chemicals Corp. 280
Medina, O. x
Willow Springs. 111. x
Leominster, Mass. - x
Torrence, Calif. - x
United States Steel Corp.
Haverhill. O. - 200
BASF Wyandotte Coip.
Jamesburg, N.J. - 130
Rexene Polymers Co. 130
Joliet. m. 50 x
Holyoke, Mass. - x
Ludlow, Mass. - x
Santa Ana, Calif. - x
Shell Chemical Co. 130
Marietta, O. x
-Belpre, O. x
Polysar
Leominster. Mass. - 100
Forest City. N.C. - 25
Uniroyal, Inc. 200+
Baton Rouge. La. x -
Scotts Bluff. La. x -
V-19
-------
Producer and Location
The B.F. Goodrich Co.
Louisville, Ky.
Borg-Warner Corp.
Ottawa, m.
Washington, W.Va.
Diamond Plastics, Inc.
Long Beach, Calif.
Gordon Chemical Co., Inc.
Oxford, Mass.
Worcester, Mass.
Petrochemical Investment Corp.
Houston. Tex.
The Richardson Co.
West Haven, Conn.
U.S. Industries
A & E Plastik Pak, Inc.
City of Industry, Calif.
Grand Total for Styrene Resins:
EXHIBIT V-C (continued)
Environmental Protection Agency
PRODUCERS: STYRENE RESINS(4' ' '
Estimated Capacity. 1973 (million pounds)
ABS - SAN Polystyrene and Copolymers
30
200
260
50
40
x
x
50
35
50
45
Total 1.235+
5,110+ million pounds per year
3,875
Note: x denotes production at this location, but capacity is not known.
Other reported producers *8* are listed in Appendix 1.
V-20
-------
V-D POLYPROPYLENE
Polypropylene resins (PF) are thermoplastic resins containing,
predominantly, repeating propylene units. PP is produced by hetero-
geneous polymerization of propylene dissolved in hydrocarbons. Occasion-
ally,-propylene is copolymerized with small amounts of ethylene to improve
low temperature impact properties.
1. POLYPROPYLENE IS BECOMING A COMMERCIALLY SIGNIFICANT
.PRODUCT
In 1972, PP production increased 36% over the previous year and almost
doubled the average growth rate of 21% for the period of 1967-1972. PP pro-
duction in 1972 was 1.8 million pounds as compared to 0.7 million pounds in
1967. Exhibit V-l shows yearly production volume for the period 1967-1972.
PP Growth Will Continue At Above Normal Growth Rate
While it is not expected that the.growth rate shown for the past
year will continue, industry sources believe that a 15% average growth
rate over the near future should not be discounted. It is also expected
that PP copolymers will take an increasing share of the market, and may
in time be dominant over homopolymers.
2. NINE PRODUCERS ACCOUNT FOR THE ENTIRE PRODUCTION
OF POLYPROPYLENE
These 9 producers presently operate at 10 locations. However,
one of these producers has been erecting a new plant to be on stream by
December 1974. Plant locations and production capacities are listed in
Exhibit V-D.
(1) The Majority Of Production Facilities Are Located On
The Gulf Coast
Over 70% of the production capacity is located in Louisiana
and Texas. Three producers, one each in W. Virginia, Delaware
and New Jersey, account for the remainder. The major share of the
new capacity will be coming on the Gulf and will increase this region's
capacity to just under 75% of the total.
V-21
-------
EXHIBIT V-D
Environmental Protection Agency
PRODUCERS: POLYPROPYLENE (12)
Producer
Hercules, Inc.
Amoco Chemicals Corp.
Exxon Chemical Co.
Shell Chemical
Rexene Polymers,Co.
Novamont Corp.
Texas Eastman Co.
Diamond Shamrock Corp.
Phillips Petroleum Co.
Total
Total Capacity by 1974
Plant Location
Lake Charles, La. 600
Bayport, Tex.
New Castle, Del. 250
Chocolate Bayou,Tex. 150
Increases
Capacity by.
Apr.'73 Dec. '74
(Million pounds/year)
Baytown, Tex.
Woodbury, N.J.
Odessa, Tex.
Neal, W.Va.
Longview, Tex.
Deer Park, Tex.
Pasadena, Tex.
150
200
100
300
250
130
120 40
100
90
85
2,075 490
2.565
V-22
-------
(2) Plant Capacities Vary Over A Wide Range
Plant size varies tremendously from the smallest with a capacity
of 85 million pounds per year to the largest with a capacity of 750 million
(when complete in 1974) . The majority, however, range from 100 to
300 million pounds per year.
V-23
-------
V-E PHENOLIC AND OTHER TAR ACID RESINS
Phenolic resins are thermosetting resins formed by the reaction of
phenol with aldehydes. The properties of the final product can be varied
widely by choice and ratio of reactants and by reaction conditions. Phenols
can be replaced by other tar acids to produce products with different proper-
ties , but these too result in insoluble, infusible thermoset products.
1. PHENOLIC PRODUCTION HAS INCREASED AT AN AVERAGE ANNUAL
RATE OF 7.5% FOR THE PAST 5 YEARS
As shown in Exhibit V-l, phenolic resin production increased from
983 million pounds in 1967 to about 1,413 million pounds in 1972, an average
compound growth rate of 7.5% per year. This growth rate has not been con-
sistent but has steadily been increasing so that 1972 production was 18% over
the previous year.
Overall Growth For The Next 5 Years Will Approach
That Of The Past 5 Year Period
The large growth exhibited by phenolics in 1972 was due
largely to growth in the appliance market and plywood industry.
Continued growth will depend upon the general economic climate
of the country and supplies of wood for the plywood industry. Growth'
is expected to continue at the rate of 10 - 12% over the next 5 years.
2. THERE ARE NUMEROUS PHENOLIC RESIN PRODUCERS
The major producers operate plants at 47 locations throughout the
United States and are shown in Exhibit V-E. An additional 71 companies
operate an additional 121 plants. These producers and plant locations are
listed in Appendix 1.
(1) Plants Are Concentrated In Areas Of Consumer Demand
The principal uses are molding, adhesives, thermal insulation
and plywood. As such, plants are located near plywood producers
(Oregon, California and the South), molders (Midwest and East Coast)
and adhesive producers (metropolitan or highly populated areas).
V-24
-------
Producer and Location
Ashland Oil, Inc.
Pensacola, Fla.
Thomasville, N.C.
Bethel, Conn.
Fords, N.J.
Newark, N.J.
Calumet City, 111.
Paramount, Calif.
Borden Inc.
Compton, Calif.
Fremont, Calif.
Kent, Wash.
La Grande, Ore.
Missoula. Mont.
Springfield, Ore.
Berkeley, Calif.
Sheboygan, Wise.
Bainbiidge, N.Y.
Diboli. Tex.
Fayetteville, N.C.
General Electric Co.
Schenectady, N.Y.
Pittsfield, Mass.
Occidental Petroleum Corp.
Kenton, O.
North Tonawanda, N. Y.
Monsanto Co.
Alvin (Chocolate Bayau),
Addyston (Port Plastics), O.
Eugene, Ore.
Seattle, Wash.
Capacity 1/172
(million Ibs)
60
40
90
300
110
EXHIBIT V-E
Environmental Protection Agency
PRODUCERS: PHENOLIGS C13)
Producer and Location
Plastics Engineering Co.
Sheboygan, Wise.
Reichhold Chemicals, Inc.
Charlotte, N.C.
Moncure, N.C.
Houston, Tex.
Tuscaloosa, Ala.
Andovei. Mass. /4\
Carteret, N.J. (20)
Elizabeth, N.J.
Niagara Falls, N.Y.
Detroit (Ferndale), Mich.
Kansas City, Kans.
Azusa, Calif.
South San Francisco, Calif.
Tacoma, Wash.
White City, Ore.
Simpson Timber Co.
Portland, Ore.
Union Carbide Corp.
Texas City, Tex.
Bound Brook, N.J.
Marietta, O.
Elk Grove, Calif.
Sacramento, Calif.
Capacity 1/1/72
(million Ibs)
75
360
40
190
(4)
(25)(4)
(25)
Total Capacity
1.265
(8)
Other reported Phenolic resin producers are listed In Appendix 1.
V-25
-------
(2) Plant Size Varies Widely
There are a few large plants with capacities of over 150 million
pounds per year. But judging from total company capacity, and the
number of producing locations per company, the average plant size
is probably in the order of 20 - 30 million pounds per year. Small
plants with capacities of less than 1 million pounds are also numerous,
V-26
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V-F POLYESTERS
Many different resins are called polyesters, including alkyds and
unsaturated polyester resins. This section is concerned with the unsatur-
ated polyesters.
These unsaturated polyester resins are based on unsaturated prepoly-
mers, which are made by the esterification of dihydric alcohols (glycols)
with unsaturated and modifying dibasic acids and/or anhydrides. The un-
saturated prepolymer is dissolved in an unsaturated monomer (e.g. styrene)
with which it cross-links to form the ultimate polymer.
1. POLYESTERS RANK SIXTH IN TOTAL VOLUME PRODUCED
Domestic production of polyester in 1972 increased a healthy 18% over
1971, although this growth was not as large as the increase observed in 1971.
Production has grown from 513 million pounds in 1967 to 862 million pounds
in 1972, a compounded growth rate of 10.9% per year, and is shown in Exhibit
V-l.
Polyester Consumption Is Expected To Grow At A Higher
Than Normal Rate
Growth of these resins is tied closely with the construction,
transportation and recreation industries. With the boom in the build-
ing trade, increasing use in truck body construction, modular building
fabrication and fiber-glass marine craft and accessories, production of
polyesters is expected to grow at a rate of 15 - 20% for the near future
period.
2. THE BULK OF POLYESTER PRODUCTION IS ACCOUNTED FOR
BY 33 COMPANIES
These 33 companies operate at over 80 locations as shown in Exhibit V-F,
V-27
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EXHIBIT V - F
Environmental Protection Agency
PRODUCERS: POLYESTERS t4-8,14)
Producer and Location
Plant Capacity
(million pounds)
Allied Chemical Corp.
Des Plaines, 111.
Los Angeles, Calif,
Toledo, O.
Whippany, N.J.
Moncuie, N.C.
Alpha Chemical Corp.
Colliersville, Term.
Kathleen, Fla.
American Cyanamid Co.
Azusa, Calif.
Penysville, O.
Wallingford, Conn.
Ashland Oil Inc.
Los Angeles, Calif.
Newark, N.I.
Pensacola, Fla.
Valley Park, Mo.
Atlas Chemical Industries, Inc.
Wilmington, Del.
Cargill, Inc.
Lynwood. Calif.
Cook Paint & Varnish Co.
Detroit, Mich.
Hialeah, Fla.
Mllpitas, Calif.
North Kansas City, Mo.
De Soto, Inc.
Berkeley, Calif.
Chicago Heights, HI.
Garland, Tex.
Diamond Shamrock Corp.
Oxnard, Calif.
Redwood City, Calif.
H. H. Robertson Co.
Saukville, Wise.
General Electric Co.
Mt. Vernon, Ind.
Schenectady, N.Y.
P. D. George Co.
St. Louis, Mo.
25
30
15
Producer and Location
Plant Capacity
(million pounds)
W. R. Grace & Co. 150
Bartow, Fla. 20
Linden, N.J. 20
Montebello, Calif. 10
Swanton, O. 50
Jacksonville, Ark. 45
Guardsman Chemical
Coatings. Inc.
Grand Rapids, Mich.
Inmont Corp.
Greenville, O.
Cincinnati, O.
Detroit, Mich.
Interplastic Corp.
Minneapolis, Minn. 70
Pryor, Okla. 30
Koppers Co., Inc.
Bridgeville, Pa. 30
Richmond, Calif.
Molded Fiber Glass Companies, 45
Inc.
Ashtabula, O.
Occidental Petroleum Corp.
North Tonawanda, N. Y.
Baton Rouge, La.
Owens-Corning Fiberglas Corp. 90
Anderson, S.C. 50
Valpariso. Ind. 40
PPG Industries, Inc.
Circleville. O.
Houston, Tex.
Springdale, Pa.
Torrence, Calif.
Reichhold Chemicals, Inc. 200
Azusa, Calif.
Detroit, Mich.
Elizabeth, N.J. 30+
Grand Junction, Tenn.
Houston, Tex.
Jacksonville, Fla.
South San Francisco, Calif.
Tacoma, Wash.
V-28
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EXHIBIT V - F (continued)
Environmental Protection Agency
PRODUCERS: POLYESTERS (4 •ff, 14)
Producer and Location Plant Capacity
(million pounds)
Resinous Chemicals, Corp.
Linden. N.J.
Rohm and Haas Co.
Knoxville, Term.
Philadelphia, Pa.
SCM Corp.
Chicago, m.
Cleveland, O.
Huron. O.
Reading, Pa.
San Francisco, Calif.
Schenectady Chemicals, Inc.
Schenectady, N.Y.
The Sherwin-Williams Co.
Cleveland, O.
Emeryville. Calif.
The Standard Oil Co. (Ohio) 42
Hawthorne, Calif. 30
Covington, Ky. 12
Stepan Chemical Co.
Anaheim, Calif.
United Merchants & Manufacturers,
Inc.
Langley. S.C.
VWR United Corp.
Newark, O.
Portland, Ore.
Richmond, Calif.
Westinghouse Electric Corp.
Manor, Pa.
WMttaker Corp.
Lenoir, N.C.
Minneapolis, Minn.
Colton, Calif.
V-29
-------
(1) Five Producers Reportedly Account For 50% Of Production
Producer, and more specifically individual plant capacities are
confidential. Where possible we have indicated plant or producer capa-
city based on industry and literature references. According to Chemical
Economics Handbook 1*4) f industry concentration in 1968 was approxi-
mately as follows:
Percent of 1968 Production Accounted For By ...
3 largest producers 40%
5 largest producers 50%
10 largest producers 70%
15 largest producers 85%
20 largest producers 95%
The three largest producers are believed to be W.R. Grace 6 Co.,
PPG Industries, Inc. and Reichhold Chemicals, Inc.
(2) Individual Plant Capacities Are Highly Flexible
Production economics are such that plants operate on a 24 hour
basis, processing 2 batches per day per reactor. The smallest econom-
ically feasible batch size would be about 500 gal., while several of the
larger plants have multiple 5,000-6,000 gal. reactors. Plant capacities
could, therefore, vary from about 1 million pounds to over 70 million
pounds per year.
Another consideration that must be taken into account is the
inter changeability of products produced. For example, alkyds and
polyesters can be made in the same equipment. Comparing polyester
plant locations with alkyd plant locations confirms this.
(3) Plants Are Geographically Widely Dispersed But Tend To
Locate Near Populated Areas And Markets
A rough estimate of the geographic distributions of the markets
is as follows <14):
Midwest States 40%
Far Western States 20%
Southwestern States 15%
New England and Middle 13%
Atlantic States
Southeastern States 12%
V-30
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V-G AMINO (U-F and M-F) RESINS
Amino resins are principally resins made by condensing formaldehyde
with urea or melamine. Other amino resins include: aniline-formaldehyde,
guanamines and ethylene-urea-formaldehyde condensation products.
1. AMINO RESIN PRODUCTION HAS INCREASED STEADILY OVER THE
PAST 5 YEARS
Amino resin production has increased from 690 million pounds in 1967
to 851 million pounds in 1972. This is an average annual growth of 4.4% per
year. Growth for 1972 was slightly better than this at 5.8%. Production for
the period 1967-1972 is shown in Exhibit V-l.
Amino Resin Consumption Is Expected To Grow 5-6%
Over The New Term
Amino resin usage has benefited by the increases in bonding
and adhesives markets, which in turn have benefited from high levels
of activity in the building industries. Molding applications, however,
declined somewhat.
2. THERE ARE 82 AMINO RESIN PRODUCERS
i
These 82 producers operating at 165 locations in the United States are
listed in Exhibit V-G. It is interesting to note that these amino resin plants
operate at the same locations that phenolic resins are produced. This is
typical since their major end uses compete.
We Believe Amino Resin Production Capacity To Be
Similar To Phenolic Resin Capacity
In many instances, literature refers to construction of phenolic/
urea-formaldehyde resin plants. Both products are produced in similar
manners, and equipment would probably be interchangeable. Therefore,
average plant production capacity for amino resins would probably be
in the range of 20-30 million pounds per year, with many small plants
having capacities of less than 1 million pounds per year.
V-31
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EXHIBIT V - G
Environmental Protection Agency
PRODUCERS: AMINO RESINS W
Allied Chemical Corp., Toledo, O.
American Alkyd Industries, Carlstadt. N. J.
American Cyanamid Co., Wallingford, Conn.
Evandale, O.
Charlotte, N.C.
Azusa, Calif.
Apex Chem. Co., Inc. Elizabethport, N. J.
Ashland Oil, Inc., Fords, N.J.
Calumet City, HI.
Thomasville. N.C.
Paramount, Calif.
The Bendix Corp., Troy, N.Y.
Borden, Inc., Bainbridge, N.Y.
Compton, Calif.
Freemont, Calif.
Kent, Wash.
La Grande, Ore.
Missoula, Mont.
Springfield, Ore.
Sheboygan, Wise.
Deboli, Tex.
Fayeneville, N.C.
Brown Co., Gorham, N. H.
CPC International, Inc., Forest Park, m.
Charlotte, N.C.
Cargill, Inc., Carpentersville, m.
Philadelphia, Pa.
Lynwood, Calif.
Celanese Corp., Newark, N. I.
Louisville, Ky.
Chemical Prods. Corp., E. Paterson, N. J.
Clark Oil & Refining Corp., Blue Island, El.
Tewksbury. Mass.
Commercial Products Co., Hawthorne, N.J.
Cook Paint & Varnish Co., Detroit, Mich.
N. Kansas City, Mo.
Dan River Mills, Inc.. Danville. Va.
De Paul Chem. Co., Inc., Long Island City, N.Y.
De Sow. Inc., Chicago Heights, HI.
Garland, Tex.
Berkeley, Calif.
The Duplan Corp., Brodhead, Wise.
Eastern Color & Chem. Co.. Providence, R. I.
Emkay Chem. Co., Elizabeth. N.J.
FMC Corp., Fredericksburg, Va.
GAF Corp., Chattanooga, Tenn.
General Electric Co., Pittsfield. Mass.
Georgia-Pacific Corp., Coos Bay. Ore.
Columbus, O.
Crossett, Ark.
Louisville. Miss.
Lufkin, Tex.
Conway, N.C.
Savannah, Ga.
Guardsman Chem. Coating Inc., Grand Rapids, Mich.
Gulf Oil Corp., Shawano, Wise.
Alexandria, La.
High Point, N.C.
W. Memphis, Ark.
Lansdale. Pa.
H & N Chem. Co., Totowa. N.J.
The Hanna Paint Mfg. Co., Inc., Columbus, O.
Hart Products Corp., Jersey City, N.J.
Hercules, Inc.. Portland, Ore.
Eugene, Ore.
Tacoma, Wash.
Chicopee, Mass.
Milwaukee, Wise.
Savannah. Ga.
E. F. Houghton & Co., Philadelphia. Pa.
Inter-Pacific Resins, Inc., Sweet Home, Ore.
Ironsides Resins Inc., Columbus, O.
KoppersCo., Inc., Bridgeville, Pa.
Lancaster Chem. Corp., Wilmington, Del.
Millmaster Onyx Corp., Lyndhurst, N.J.
Minnesota Mining & Mfg. Co., Decatur, Ala.
Mobil Oil Corp., Kankakee, 111.
Monsanto Co., Addyston, O.
Alvin, Tex.
Everett, Mass.
Eugene, Ore.
Santa Clara, Calif.
Seattle, Wash.
National Casein Co., Chicago, HI.
Tyler, Tex.
Riverton, N.J.
National Starch & Chem. Corp., Salisbury, N.C.
A. P. Nonweiler Co., Oshkosh, Wise.
Onyx Oils & Resins, Inc., Newark, N.J.
Brooker, Fla.
Owens-Coming Fiberglas Corp., Newark. O.
PPG Industries, Inc.. Circleville, O.
Pacific Holding Corp., Chicago, Dl.
Pioneer Plastics Corp., Auburn, Me.
V-32
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EXHIBIT V - G (continued)
Environmental Protection Agency
PRODUCERS : AMINO RESINS <8)
Plastics Engineering Co., Sheboygan. Wise.
Plastics Mfg. Co., Dallas, Tex.
Quaker Chem. Corp., Conshohocken, Pa.
Reichhold Chems.. Inc., Azusa, Calif.
S. San Francisco, Calif.
Tacoma, Wash.
White City, Ore.
Andover. Mass.
Elizabeth, N.I.
Niagara Falls, N. Y.
Detroit, Mich.
Charlotte, N.C.
Houston, Tex.
Jacksonville, Fla.
Tuscaloosa, Ala.
Reliance Universal. Inc., Houston, Tex.
Louisville, Ky.
Renroh Resins, New Bern, N. C.
Rugel Textile Corp., Ware Shoals, S. C.
Rock Hill Printing & Finishing Co., Rock Hill, S. C.
Rohm and Haas Co., Philadelphia, Pa.
SCM Corp., Reading, Pa.
Chicago, HI.
Cleveland, O.
Huron, O.
San Francisco, Calif.
Sandoz-Wander, Inc., Hanover, N.J.
Scher Brothers Inc., Clifton, N. J.
Scott Paper Co., Everett, Wash.
Chester, Pa.
Fort Edward, N. Y.
Marinene. Wise.
Mobile. Ala.
Seydel-Woolley & Co., Atlanta, Ga.
Skelly Oil Co., Springfield, Ore.
The Sherwin-Williams Co., Chicago, 111.
Cleveland, O.
Newark, N.J.
Sauhegan Wood Products, Inc., Wilton, N. H.
Sow-Tix Chem. Co., Inc., Mount Holly, N.C.
Southeastern Adhesives Co., Lenoir, N. C.
Standard Oil Co. (N.J.), Odenton, Md.
Sun Chem. Corp., Chester, N. C.
Wood River Junction, R. I.
Sybron Corp., Haledon, N. J.
Synthron, Inc., Morganton, N. C.
Ashton, R.I.
Synvar Corp.. Wilmington, Del.
Taylor Corp., La Verne, Calif.
Betzwood, Pa.
Textilana Corp., Hawthorne, N. J.
USM Corp., Spartanbury, S. C.
Centredale, R.I.
Providence, R.I.
United-Erie, Inc., Erie, Pa.
United Merchants & Mfgs., Inc., Langley, S.C.
U. S. Oil Co., E. Providence, R. I.
Lumberton, N.C.
U.S. Ply wood-Champion Papers, Inc..
Redding. Calif.
VWR United Corp., Newark, O.
Portland, Ore.
Richmond, Ore.
Virginia Chems. Inc., Portsmouth, Va.
West Coast Adhesives Co., Portland, Ore.
Westinghouse Electric Corp., W. Mifflin, Pa.
Weyerhaeuser Co., Longview, Wash.
Marshfield. Wise.
Whittaker Corp., Colton, Calif.
Woonsocket Color & Chem. Co., Woonsocket, R. I.
Wright Chem. Corp., Acme, N. C.
V-33
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V-H ALKYDS
Alkyd resins are basically polyester resins (resinous reaction products
of polybasic acids and polyhydric alcohols) but differ from other polyesters by
containing drying oils or fatty monobasic acids and diluted with a nonreactive
solvent.
1. ALKYD RESIN PRODUCTION HAS INCREASED VERY LITTLE OVER
THE PAST 5 YEARS
Domestic production of alkyds in 1972 increased almost 20% over 1971,
keeping pace with increased construction activity. For the period 1967-1972
growth has averaged only 1.7% annually; in fact, there was a steady decrease
in production during the period 1968-1971 from 692 million pounds in 1968 to
580 million pounds in 1971. Production for the period 1967-1972 is shown in
Exhibit V-l.
Alkyd Consumption Will Probably Not Maintain The 1972
Growth Rate
Alkyds are used almost exclusively in the manufacture of
surface coatings (some is used in molding compounds). They are
competing with latex and other water-based coatings which are gain-
ing a larger share of the coating market. We expect alkyd production
will increase 1-2% per year over the next five years.
2. OVER 100 COMPANES PRODUCE ALKYD COATING RESINS
These 100 companies operate more than 180 plants throughout the
United States, with the heaviest geographical concentration in the Middle
Atlantic States, Great Lakes Region, Ohio River Valley and the state of
California. These four regions probably contain 75% of the plants. Producers
are listed in Exhibit V-H.
Plant Sizes Vary Over A Wide Range
Plant sizes will vary from small "garage type" operations to
large integrated operations. An average small size plant might con-
sist of a 500 gal. reactor capable of manufacturing less than 1 million
pounds per year to a multi-reactor plant with several large 300.0 to
5000 gal. reactors capable of producing 20-30 million pounds per year.
V-34
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EXHIBIT V-H
Companies and Resin Plant Locations
Adco Chemical Co., Newark, N. J.
Ball Chemical Co., Glenshaw, Pa.
Barrett Varnish Co., Cicero, HI.
Celanese Corp,. Los Angeles, Calif.
Louisville, Ky.
Newark, N. J.
Chemetron Corp., St. Louis, Mo.
Cook Paint & Varnish Co., Detroit, Mich.
Houston, Tex.
Milpitas, Calif.
N. Kansas City, Mo.
Defiance Industries, Inc., Baltimore, Md.
The Dexter Corp., Waukegan, Dl.
Dock Resins Corp., Linden, N. J.
Ford Motor Co., Mt. Clemens, Mich.
Foy-Johnston, Inc., Cincinnati, Ohio
P. D. George Co., St. Louis. Mo.
Grow Chemical Corp., St. Louis, Mo.
Hugh J. ~ Resins Co., Long Beach, Calif.
Kelly-Moore Paint Co., San Carlos, Calif.
McCloskey Varnish Co.. Los Angeles, Calif.
Philadelphia, Pa.
Portland, Ore.
Napko Corp., Houston, Tex.
National Lead Co., Philadelphia, Pa.
San Francisco, Calif.
Reliance Universal, Inc., Houston, Tex.
Louisville, Ky.
Schenectady Chemicals, Inc., Schenectady, N. Y.
The Sherwin-Williams Co., Chicago, Ql.
Cleveland, Ohio
Emeryville, Calif.
Garland, Tex.
Los Angeles, Calif.
Newark. N.J.
Detroit, Mich.
Dayton, Ohio
Gibbsboro, N.J.
The Valspar Corp., Rockford, DH.
Westinghouse Electric Corp., Manor, Pa.
Yenkin-Majestic Paint Corp., Columbus, Ohio
Environmental Protection
PRODUCERS : ALKYDS1
Companies and Resin Plant Locations
sncy
Haynie Products, Inc.. Baltimore, Md.
Hercules Inc., Burlington, N.J.
Industrial Oil & Varnish Co., Chicago Heights, HI.
International Minerals & Chemical Corp., Bensenville, 111.
Kelly-Pickering Chemical Corp., San Carlos, Calif.
Koppers Co., Inc., Bridgeville, Pa.
Richmond, Calif.
Lanson Chemical Corp., East St. Louis, ni.
Midwest Manufacturing Corp.. Burlington, Iowa
Onyx Oils & Resins, Inc., Brooker, Fla.
Newark, N.J.
C. J. Osbom Company, Linden, N.J.
Polychrome Corp., Newark, N. J.
Purex Corp.. Ltd., Chicago, 111.
Reichhold Chemicals Inc., Azusa, Calif.
Detroit (Ferndale). Mich.
Elizabeth, N.J.
Houston, Tex.
Jacksonville, Fla.
S. San Francisco, Calif.
Tuscaloosa, Ala.
Cicero, Ql.
Resinous Chemicals Corp., Linden, N.J.
Resyn Corp., Linden, N. J.
H. H. Robertson Co., Saukville, Wise.
Roblen Research & Development Corp., Colton, Calif.
Rohm and Haas Co., Philadelphia, Pa.
Shanco Plastics & Chemicals Inc., Tonawanda, N. Y.
Standard Oil Co. of Calif., Anaheim, Calif.
American Alkyd Industries, Carlstadt, N. J.
Ashland Oil & Refining Co., Los Angeles, Calif.
Newark. N.J.
Pensacola, Fla.
Valley Park, Mo.
Cambridge Industries Co., Cambridge, Mass.
Watertown, Mass.
Catgill, Inc., Carpentersville. 111.
Lynwood, Calif.
Philadelphia, Pa.
Commercial Solvents Corp., Chicago, 111.
Degen Oil & Chemical Co., Jersey City, N.J.
V-35
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EXHIBIT V-H (continued)
Environmental Protection Agency
PRODUCERS : ALKYDS*4'*5
Companies and Resin Plant Locations
Companies and Resin Plant Locations
Farac Oil & Chemical Co., Chicago, ni.
Farnow, Inc., South Kearny, N. J.
France, Campbell & Darling Inc., Ke nil worth, N. J.
Superior Varnish & Drier Co., Pennsauken, N. J.
Synthetic Resins & Chemicals, Inc., Carpentersville, ni.
Synvar Corp., Wilmington, Del.
Tenneco Inc., San Francisco, Calif.
Union Camp Corp., Valdosta, Ga.
U. S. Coatings Co., Bronx, N. Y.
Armstrong Paint & Varnish Works, Inc., Chicago, ni.
Beatrice Foods Co., Baltimore. Md.
Bennett's, Salt Lake City, Utah
Brooklyn Paint & Varnish Co., Inc., Brooklyn, M. Y.
M. A. Bruder & Sons, Inc., Philadelphia, Pa.
Carpenter Morton Co., Everett, Mass.
ConChemCo Inc., Baltimore, Md.
Kansas City, Mo.
Houston, Tex.
DeSoto. Inc.. Berkeley. Calif.
Chicago Heights, ni.
Garland, Tex.
Frank W. Dunne Co.. Oakland, Calif.
E. I. du Pont de Nemours & Co., Inc., Fort Madison, Iowa
Parlin, N.J.
Philadelphia. Pa.
S. San Francisco,
Calif.
Toledo, Ohio
Tucker, Ga.
Enterprise Paint Manufacturing Co., Chicago, HI.
Fibreboard Corp., Oakland, Calif.
Frisch & Co., Inc., Paterson, N. J.
General Electric Co.. Chelsea. Mass.
Schenectady, N.Y.
Georgia-Pacific Corp., Sumter, S.C.
Oilman Paint & Varnish Co.. Chattanooga, Term.
Grow Chemical Corp., Oakland, Calif.
Tampa, Fla.
Guardsman Chemical Coatings, Inc., Grand Rapids.
Mich.
Louisville, Ky.
The Hanna Paint Manufacturing Co., Inc., Columbus, Ohio
Pittsburgh. Pa.
Interchemical Corp., Anaheim, Calif.
Cincinnati, Ohio
Detroit, Mich.
Los Angeles, Calif.
Newark, N.I.
Jewel Paint & Varnish Co., Chicago, ni.
Jones- Blair Paint Co., Inc., Dallas, Tex.
Kohler-McLister Paint Co., Denver, Colo.
Kyanize Paints, Inc., Everett, Mass.
Lilly Industrial Coatings, Inc., Indianapolis, Ind.
Maas & Waldstein Co., Newark, N. J.
McDougall-Butler Co., Inc., Buffalo, N.Y.
Minnesota Paints, Inc., Fort Wayne, Ind.
Minneapolis, Minn.
Mobil Chemical Co., Cleveland, Ohio (2 plants)
Kankakee, 111.
Louisville, Ky.
Metuchen.N.J.
Pittsburgh, Pa.
Montgomery Ward & Co., Inc., Chicago, HI.
Staten Island, N.Y.
Benjamin Moore & Co., Cleveland, Ohio
Denver. Colo.
Los Angeles, Calif.
Newark, N.J.
Morwear Paint Co., Oakland, Calif.
A. P. Nonweiler Co., Oshkosh, Wise.
Norris Paint & Varnish Co., Salem, Ore.
The O'Brien Corp., Baltimore, Md.
South Bend, Ind.
South San Francisco, Calif.
Perry & Derrick Co., Dayton, Ky.
Pervo Paint Co.. Los Angeles, Calif.
PPG Industries, Inc., Atlanta, Ga.
Circleville. Ohio
Cleveland, Ohio
Houston. Tex.
Milwaukee, Wise.
Newark, N.J.
Spdngdale. Pa.
Tonance, Calif.
V-36
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EXHIBIT V-H (continued)
Environmental Protection Agency
PRODUCERS : ALKYDS(4'°)
Companies and Resin Plant Locations
Pratt & Lambert, Inc., Buffalo, N. Y.
Red Spot Paint & Varnish Co., Inc., Evansville. Ind.
Rust- Oleum Corp., Evanston. Dl.
Sapolin Paints, Inc., Brooklyn, N. Y.
SCM Corp., Chicago, 111.
Cleveland, Ohio
Reading, Pa.
San Francisco, Calif.
Standard Oil Co. (New Jersey), Houston, Tex.
Steelcote Manufacturing Co., St. Louis. Mo.
Sullivan Varnish Co., Chicago. HI.
Sun Chemical Corp., Northlake, HI.
Textron Inc., North Brunswick, N. J.
Whittaker Corp., Minneapolis, Minn.
V-37
-------
Producers of alkyds can produce polyesters in the same equip-
ment . In many instances the economics of production of either or both
products may depend upon the ability to produce both products.
V-38
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V-I ACRYLICS
Acrylic resins are polymers derived from acrylate monomers. A variety
of monomers are commercially available. Since they can be polymerized with
each other or a wide range of nonacrylic comonomers, they offer a versatile
span of products and properties. Among the more popular monomers used are
ethyl acrylate, methyl methacrylate. 2-ethylhexyl acrylate, butyl acrylate and
acrylic acid.
1. A MODEST VOLUME OF ACRYLICS IS BEING PRODUCED
Acrylic resin production in 1972 increased about 12% over 1971. Prior
to 1970, the U.S. Tariff Commission did not report acrylic resin production.
However, based on reported demand for acrylates, production for the period
of 1967-1972 has increased from about 220 million pounds in 1967 to 590 million
pounds in 1972. a compounded annual growth rate of about 22% per year. Pro-
duction rates are shown in Exhibit V-l. Acrylate producers are shown in
Exhibit V-I.
Acrylic Resin Demand Will Be Above Average
It is expected that acrylic resin demand will be above average
over the next 5 years and probably average 15% per year through
1977.
2. A MAJOR PORTION OF THE ACRYLATES PRODUCED IS USED
CAPTIVELY
There are 5 producers of acrylates (including acrylic acid) with
production at 7 locations as shown in Exhibit V-I.
Probably 60-65% Of The Acrylic Resins Produced Is
Produced By 4 Companies
The Rohm and Haas Co. probably uses over 50% of its own
acrylate production to produce acrylic emulsions for sale. Dow
Chemical Co., Celanese Corp. and Union Carbide Corp. uses prob-
ably account for an additional 10%. The remainder is used by numer-
ous producers of emulsion polymers used for surface 'coatings,
textiles, paper, polishes, leather and other uses as listed in Appendix
1.
V-39
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EXHIBIT V-I
Environmental Protection Agency
(15)
PRODUCERS: ACRYLICS
Estimated Capacity (1974)
(million pounds)
Celanese Corp. 300
Pampa, Tex. (180)
Clear Lake, Tex. (220)
Dow Badische Co. 40
Freeport, Tex.
The B.F. Goodrich Co. 5
Calvert City, Ky.
Rohm 6 Haas Co. 400
Houston, Tex.
Union Carbide Corp.
Institute, W.Va. 70*
Taft, La. 200
Total 1,015
*Will probably shut down when Taft
reaches capacity.
V-40
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V-J COUMARONE-INDENE AND PETROLEUM RESINS
Coumarone-indene and petroleum resins are thermoplastic hydrocarbon
resins prepared from by-products of large scale coking and petroleum opera-
tions . The raw material for coumarone-indene resins is coal tar distillation;
for petroleum resins, petroleum distillates resulting from cracking operations.
1. COUMARONE-INDENE AND PETROLEUM RESIN PRODUCTION IS
RELATIVELY SMALL
Production in 1972, for these resins, amounted to 325 million pounds.
This was a 22% increase over 1971. Production over the years has been highly
irregular. -For the 1967-1972 period, volume has increased from 284 million
pounds to 325 million pounds as shown in Exhibit V-l. Growth is expected to
be static over the near future.
Consumption Has Been Erratic
Its main use (asphalt tile) is being challenged by vinyl tile.
Increased use in rubber compounding will probably maintain its present
volume.
2. FIFTEEN COMPANIES PRODUCE COUMARONE-INDENE AND PETROLEUM
RESINS
These 15 companies produce at 20 locations as listed in Exhibit
V-J.
(1) We Have Not Been Able To Ascertain Plant Capacities
By-product production is difficult to determine since production
depends upon demand of the main product, economics of raw materials,
and composition of the raw material. Of course, demand for the resin
itself is also a determining factor.
(2) Plants Are Located At Raw Material Sources
These plants are concentrated near coking operations in Penn-
sylvania and petroleum cracking operations on the Gulf Coast.
V-41
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EXHIBIT V - J
Environmental Protection Agency
PRODUCERS : COUMARONE-INDENE
AND PETROLEUM RESINS (8)
DeSoto Inc.,
Chicago, 111.
Berkeley, Calif.
Garland, Tex.
Monsanto Co.,
Sauget (E.St.Louis), 111.
Northwest Industries, Inc.
Marshall, HI.
PPG Industries, Inc.,
Milwaukee, Wise.
Neville Chemical Co.,
Anaheim, Calif.
Neville Island, Pa.
Alabama Binder 6 Chemical Corp.
Tuscaloosa, Ala.
Chemfax, Inc.
Gulf port, Mi s s.
Masonite Corp.,
Gulfport, Miss.
Reichhold Chemical Inc.
Gulfport, Miss.
Standard Oil Co. of N.J.,
Baton Rouge, La.
Standard Oil Co. of Ind.,
Texas City, Tex.
Valentine Sugars, Inc.,
Lockport, La.
Carpenter Morton Co.,
Everett, Mass.
Kenrich Petrochemical, Inc.
Bayonne, N.J.
Pennsylvania Industrial Chemical Corp,
Chester, Pa.
Clairton, Pa.
West Elizabeth, Pa.
V-42
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V-K POLYURETHANES
The major uses of polyurethanes include flexible and rigid foams,
elastomers, adhesives, coatings and sealants. The manufacture of foams and
elastomers is not classified as "chemical/plastics" industry, SIC 2821. Plastic
foam manufacture is associated with SIC 3079, "Miscellaneous Plastics Products"
Further, the U.S. Tariff Commission does not note foams among "Plastic and
Resin Materials" in its reports entitled, U.S. Production And Sales Of
Synthetic Organic Chemicals. Hence, this study does not deal with polyure-
thane foams.
Polyurethane elastomers are similarly not classified in SIC 2821 as plas-
tic materials.
1. URETHANE RESIN PRODUCTION PERTAINING TO ADHESIVES.
COATINGS AND SEALANTS IS THE AREA OF INTEREST
The U.S. Tariff Commission data on "Polyurethane and Diisocyanate
Resins" deals with the manufacture of adhesives, coatings and sealants under
the broad category of "Plastic and Resin Materials" .
Exhibit V-K1 indicates the production trends. In our judgment, the
data is highly inaccurate.
(1) Growth Is Expected To Be At Least 10% Annually Through
1977
We believe this growth rate may be conservative. Many new
uses are being investigated, and any one of these could change total
demand drastically.
(2) In The Urethane Resin Categories Studied. Coating Resins
Are Most Important
These account for roughly two-thirds or more of urethane
resins in the adhesives, coatings, sealants and miscellaneous resins
category.
V-43
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EXHIBIT V-K1
Environmental Protection Agency
PRODUCTION OF POLYURETHANES FOR
ADHESIVES, COATINGS AND SEALANTS
MANUFACTURE (Resin; Compounded Basis)
Total Data
Production Source
(Million
Pounds)
1967 89 1
1968 76; (71) 1; (16)
1969 81; (84) 1; (16)
1970 95 16
1971 79; (106) 1; (4)
1972 116 4
1975 143 16
1977 177 4
V-44
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2. THERE ARE OVER 100 COMPANIES PRODUCING COATING, SEALANT
AND ADHESIVES RESINS
Exhibit V-K2 defines the producers of these resins and plant locations.
According to the Chemical Economics Handbook^)
There are 22 companies producing urethane coating
resins for sale only. They accounted for over 50% of
total urethane coating resin sales on a pound basis in
1969.
There are 43 companies that produce urethane coating
resins for sale as well as for their own captive use.
Collectively, they accounted for about 30% of total ure-
thane coating resin sales in 1969 on a pound basis.
The largest producers in this list are believed to be
Hughson Chemical, Poly vinyl Chemicals. K.J. Quinn,
Trancoa (largest), and Wilmington Chemical.
Many coating companies have the capability of producing
the urethane coating resins that go into their coatings.
Companies producing urethane resins primarily for
captive use include, E.I. Du Pont de Nemours 5 Co., Inc.;
Mobil Oil Corp.; Montgomery Ward Co.; Olin Corp.;
PPG Industries, Inc.; SCM Corp.; The Sherwin-Williams
Co.
Over 80 Producers Of Urethane Coating Resins Represent An
Average Plant Capacity Of Roughly One Million Pounds Of
Resin Per Year
In the manufacture of polyurethane coating and miscellaneous
resins, actual plant capacities are believed to be generally close to
the industry average.
V-45
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EXHIBIT V - K2
Environmental Protection Agency
PRODUCERS: POLYURETHANES14'8-14*
1. 22 Companies Produce Urethane Coating Resins For Sale Only And
Account For Over 50% Of Total Urethane Coating Resin Sales On A
Pound Basis In 1969
Companies and Plant Locations
Ashland Oil, Inc., Los Angeles, Calif.
Newark, N.J.
The Baker Castor Oil Co., Bayonne, N. I.
The Biggs Co.. Santa Monica, Calif.
Cargill, Inc., Carpentersville, HI.
Lynwood, Calif.
Philadelphia, Pa.
Commercial Solvents Corp., Carpentersville, HI.
Chicago, m.
Diamond Shamrock Corp., Harrison, N.J.
France, Campbell & Darling, Inc., Kenilworth, N.J.
General Latex and Chemical Corp., Ashland, Ohio
Cambridge, Mass.
General Mills, Inc., Kankakee, ni.
The B. F. Goodrich Co., Avon Lake, Ohio
Hugh J. — Resins Co., Long Beach, Calif.
Interplastic Corp., Minneapolis, Minn.
Mobay Chemical Co. /Naftone. Inc.. New Martinsville,
Companies and Plant Locations
Northeastern Laboratories Co., Inc., Melville, N. Y.
Purex Corp., Ltd., Chicago, 111.
Reichhold Chemicals, Inc., Azusa, Calif.
Detroit, Mich.
Elizabeth, N.J.
Houston, Tex.
S. San Francisco, Calif.
Tacoma, Wash.
H. H. Robertson Co., Am bridge, Pa.
Saukville, Wise.
Textron Inc.. Bellevue, Ohio
Thiokol Chemical Corp., Trenton, H J.
Union Carbide Corp., Institute, W. Va.
Witco Chemical Corp., Chicago, m.
Lynwood, Calif.
New Castle, DeL
WyandotteChemicals Corp., Wyandctte, Mich.
W.Va.
Of the companies just listed, the largest producers Con a total pounds
basis) are believed to be (in decreasing order of production volume)
Spencer Kellogg Division of Textron, Reichhold, Cargill, Ashland, and
Mobay. Spencer Kellogg is the largest producer of urethane alkyds;
Reichhold is the largest producer of moisture-curing prepolymers; and
Mobay is the largest producer of phenol-blocked prepolymers and two-
package prepolymer-polyol systems. B. F. Goodrich and Spencer Kellogg
are the leading suppliers of urethane thermoplastic lacquer resins. Nopco
Chemical Division of Diamond Shamrock and Wyandotte Chemicals are the
major producers of urethane latices.
V-46
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EXHIBIT V-K2 (continued)
Environmental Protection Agency
PRODUCERS: POLYURETHANES (4 •8 •
2. 43 Companies Produce Urethane Coatings Resins For Sale And Captive
Use And Account For About 30% (by weight) Of Total Urethane Coating
Resin Sales In 1969
Companies and Plant Locations Companies and Plant Locations
Allied Products Corp., Long Island City. N. Y. The P. D. George Co., St. Louis, Mo.
John L. Armitage & Co., Newark. N. J. The Goodyear Tire & Rubber Co., Akron, Ohio
Elk Grove, 111. Grow Chemical Corp., St. Louis, Mo.
Richmond, Calif. Hoover Ball and Bearing Co., Ann Arbor, Mich.
Ball Chemical Co., Glenshaw. Pa. Inrilco Corp., Chicago, 111.
Bay State Chemical Co., Leominster, Mass. Isochem Resins Co., Lincoln, R. I.
Beatrice Foods Co., Wilmington, Mass. Jewel Paint & Varnish Co.. Chicago, m.
Celanese Corp., Los Angeles, Calif. Kohler- Me Lister Paint Co., Denver, Colo.
Louisville, Ky. Lord Corp., Saegertown. Pa.
Newark, N.J. Lu-Sol Corp., El Monte, Calif.
Chem Seal Corp. of America, Los Angeles. Calif. Mr Plastics and Coatings, Inc., Maryland Heights, Md.
Conchemco Inc., Baltimore, Md. McCloskey Varnish Co.. Los Angeles, Calif.
Kansas City, Mo. Philadelphia, Pa.
Continental Poly mere Corp., Santa Ana, Calif. Portland. Ore.
Cook Paint & Varnish Co., Detroit, Mich. Midwest Mfg. Corp., Burlington, Iowa
Houston, Tex. Minnesota Mining and Mfg. Co., Decatur, Ala.
North Kansas City, Mo. National Lead Co., Philadelphia, Pa.
De Soto. Inc., Berkeley, Calif. San Francisco, Calif.
Chicago Heights, 111. Occidental Petroleum Corp.. HicksviUe, N. Y.
Garland, Tex. C. J. Osborn Chemicals, Inc., Pennsauken, N.J.
The Dexter Corp., El Monte. Calif. Poly Resins, Inc., Sun Valley, Calif.
Olean, N. Y. Prime Leather Finishes Co., Milwaukee, Wise.
Cleveland, Ohio Products Research & Chemical Corp., Maiden, Mass.
Hayward, Calif. Seabrook, N. H.
Los Angeles. Calif. Schenectady Chemicals, Inc., Schenectady, N.Y.
Rocky Hill, Conn. Sta-Crete, Inc., San Francisco, Calif.
Waukegan, m. A. E. Staley Mfg. Co., Marlboro, Mass.
Emerson & Cuming. Inc., Canton, Mass. Trancoa Chemical Corp., Reading, Mass.
The Epoxylite Corp., El Monte, Calif. Westinghouse Electric Corp., Manor, Pa.
Farnow. Inc., South Kearny. N.J. Wilmington Chemical Corp.. Wilmington, Del.
Furane Plastics. Inc., Los Angeles, Calif. Woburn Chemical Corp., Harrison, N. J.
The largest producers of urethane coating resins in the preceding list are
believed to be Hughson Chemical, Polyvinyl Chemicals, K. J. Quinn,
Trancoa (largest), and Wilmington Chemical.
V-47
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EXHIBIT V-K2 (continued)
Environmental Protection Agency
PRODUCERS: POLYURETHANES (4,8,14)
3. Companies Producing Urethane Coating Resins Primarily For
Captive Use
Many coating companies have the capacity to produce the urethane
coating resins that go into their coatings. The extent of their
coating-resin production depends both on the volume of their ure-
thane coatings sales and on the price situation in the urethane
coating resin market. Currently, the following 18 companies
are known to be producing some or all of their urethane coating
resin requirements.
Companies and Plant Locations Companies and Plant Locations
American Herberts Corp.. Woodside, N.Y. Olin Corp., Rochester, N. Y.
American Pipe & Construction Co., Brea. Calif. PPG Industries, Inc., Circleville. Ohio
Armstrong Chemcon. Inc., Chicago, m. Houston, Tex.
Beatrice Foods Co., Peabody, Mass. Milwaukee, Wise.
Chemical Coatings & Engineering Co., Media, Pa. Springdale, Pa.
Defiance Industries. Inc., Baltimore, Md. Torrance, Calif.
E. I. Du Pont De Nemours & Co., Inc., Chicago, Ql. Cleveland, Ohio
Fort Madison, Iowa Preservative Paint Co., Seattle, Wash.
Parian, N.J. Raffi and Swanson, Inc., Wilmington, Mass.
Philadelphia, Pa. SCM Corp., Chicago, fll.
S.San Francisco, Calif. Cleveland, Ohio
Toledo. Ohio Reading, Pa.
Tucker, Ga. San Francisco, Calif.
Marcor, Inc., Chicago, HI. The Sherwin-Williams Co. .Chicago, HI.
The Master Mechanics Co., Cleveland, Ohio Cleveland, O.
Minnesota Paints, Inc., Fort Wayne, Ind. Emeryville, Calif.
Minneapolis, Minn. Garland, Tex.
Mobil Oil Corp., Cleveland, Ohio Los Angeles, Calif.
Norris Paint & Varnish Co.. Inc., Salem, Ore. Newark, N.J.
V-4B
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V-L CELLULOSICS
The cellulosic plastics of interest are the acetates and mixed esters
of cellulose and cellulose nitrate.
1. CELLULOSICS ARE A RELATIVELY LOW VOLUME PLASTIC
Cellulosics are considered low volume plastics as compared to others,
and production amounted to only 190 million pounds in 1972. Production has
been somewhat irregular for the period 1967-1972 showing an average annual
growth of 2.2% per year as shown in Exhibit V-l.
Cellulosics Will Grow At A Modest 2-3% Annually
The almost 10% growth in cellulosic resin uses in 1972 will probably
not be maintained. This growth was principally in molding and ex-
trusion uses where the immediate advantage was in the biodegradability
aspects of the resin. In the long run, ABS resins will probably continue
to replace Cellulosics.
2. THERE ARE 6 PRODUCERS OF CELLULOSICS
The U.S. Tariff Commission (1970) reports nine producers. However,
we have been able to locate only 6 producers operating at 8 locations as
shown in Exhibit V-L.
(1) The Majority Of Operating Locations Are Concentrated On
The Atlantic Coast
Most of the plants are located in New Jersey, Maryland,
and Massachusetss. The largest plant, probably accounting for more
than 50% of total production, is operated by Eastman Chemical Products,
Inc. atKingsport, Tennessee.
(2) Plant Capacities Are Confidential
Because of the large share of production accounted for by a single
producer, plant capacities are not available. It is believed that Eastman
Kodak may account for over 50% of production.
V-49
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EXHIBIT V - L
Environmental Protection Agency
PRODUCERS: CELLULOSICS{8)
Celanese Corp.
Belvidere, N.J.
Cumberland, Md.
Newark, N.J.
Marcor Inc.
Linden, N.J.
The Richardson Co.
Kearny, N.J.
Standard Pyroxoloid Corp.
Leominster, Mass.
Tenneco Inc.
Nixon, N.J.
Eastman Kodak Co.
Kingsport, Tenn.
Other companies reported producing
cellulosics are:
Dow Chemical Company
Hercules Inc.
Monsanto Company
Rosenberg Bros. 6 Company
Textron Inc.
V-50
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V-M EPOXY RESINS
Epoxy resins are thermosetting resins which, in the uncured form,
contain one or more reactive epoxide or oxirane groups. These groups
serve as cross-linking points in the subsequent curing step, in which the
uncured epoxy resin is reacted with a curing agent or hardener, generally
an amine or anhydride, although other hardeners containing active or reac-
tive hydrogens are also used.
Epoxy resins are usually based on the reaction of epichlorohydrin and
Bisphenol A. About 90% of all unmodified epoxy resins produced are of this
type. Other types include glycidyl compounds, epoxidized olefins, linear
aliphatic epoxides and others.
In addition to the unmodified resins discussed briefly above, modified
epoxy resins are also produced. Modified resins are, in general, produced
by reacting unmodified epoxy resins with unsaturated fatty acids, rosin acids,
tall oil and similar materials. In many cases these modified epoxies are fur-
ther modified with melamine or urea resins.
1. THE VOLUME OF EPOXIES PRODUCED IS SMALL
Domestic production of epoxy resins for the 1967-1972 period increased
from 135 million pounds in 1967 to 174 million pounds in 1972, a compounded
growth rate of 5.2%. Growth in 1972 was only slightly better — 4.2%. Pro-
duction for the period 1967-1972 is shown in Exhibit V-l.
Epoxy Resin Consumption Will Continue At About The Same
Rate As In 1972
These resins should be considered as specialty resins because
of their high price, and special end uses such as encapsulating elec-
tronic components, high performance adhesives, filament winding of
vessels and pipes and reinforced plastic circuit boards. As long as
raw material prices remain at their high levels, epoxy prices will
remain high resulting in low volume uses. Growth over the near term
should be 5% per year or less.
2. ONLY 7 COMPANIES PRODUCE UNMODIFIED EPOXIES
These 7 producers operate plants .at 8 locations. Exhibit V-M
lists locations and plant capacities of producers.
V-51
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EXHIBIT V - M
Environmental Protection Agency
PRODUCERS : EPOXY RESINS (14)
Company and Location
Celanese Corporation
Louisville, Ky.
Ciba Corporation
Toms River, N.J.
The Dow Chemical Company
Freeport, Texas
Reichhold Chemicals, Inc.
Ballard Vale, Mass.
Resyn Corporation
'Linden, New Jersey
Shell Oil Company
Houston, Tex.
Union Carbide Corporation
Marietta, Ohio
Bound Brook, N.J.
TOTAL
Estimated Capacity,
April 1970
(Millions of Founds
Per Year)
35
60
50
12
25
88
26
296
V-52
-------
(1) About 85% Of The Production Capacity Is Located In Two
States
The major share of production capacity is located in Texas and
New Jersey. The remaining capacity is located in Kentucky, Massa-
chusetts , and Ohio.
(2) Production Capacity Has Generally Been Appreciably
Larger Than Actual Production
Most of the extra capacity is required to permit production
changeovers for the manufacture of different types of epoxy resins.
We estimate overall utilization to be at 70-75% of installed capacity.
Based on plant utilization then, the largest plant would be
producing about 64 million pounds, while the smallest would be
producing less than 10 million pounds per year.
3. MODIFIED EPOXIES ARE PRODUCED IN OVER 100 LOCATIONS
The total volume of modified epoxies produced is very small — probably
less than 5% of the volume of unmodified epoxies. The principle use for these
products is as adhesives which are packaged for retail consumer use.
V-53
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V-N POLYAMIDES
Folyamide resins are polymers in which recurring amide groups form
an integral part of the main polymer chain. They are of two main types:
(1) nylon resins which are used to make the well-known nylon fibers and
plastics, and (2) those which are made by the condensation of polycarboxylic
acids with polyamines, and which are called non-nylon resins.
1. THE OUTPUT OF POLYAMIDE RESINS FOR NON-FIBER USE IS LOW
Only 115 million pounds of polyamide resins were produced in 1972
(nylon resins used to make fibers are not included). This, however, was an
increase of 15% over 1971 and somewhat better than the average annual growth
rate of 12.8% for the period 1967-1972. Production for the period 1967-1972 is
shown in Exhibit V-l.
Polyamide Consumption Will Increase At A Slower Rate
Nylon resins must compete with other plastics, notably acetal
and polycarbonate resins, and their use depends on cost/benefit
performance. Nylon resins are also relatively high priced, and
therefore it is doubtful that large volume uses will be uncovered.
Non-nylon resins are very seldom used alone, and can be
used in combination with less expensive resins such as phenolics,
urea-formaldehydes, etc. They therefore find a greater variety of
uses, yet must still be considered specialty resins.
It is believed that polyamide resins, as a whole, will probably
grow at the rate of 8-10% per year in the foreseeable future.
2. THERE ARE 8 PRIME PRODUCERS OF POLYAMIDE RESINS
The prime producers of polyamide resins are those companies producing
Nylon 6 and/or 66 for fiber use. These companies producing for plastic appli-
cations have a total capacity of over 136 million pounds per year and produce
at 10 locations as listed in Exhibit V-N.
There are considerably more producers of non-nylon polyamide resins.
Total production capacity, we believe, is less than 40 million pounds and
producers and plant locations are listed in Appendix 1.
V-54
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EXHIBIT V - N
Environmental Protection Agency
PRODUCERS: POLYAMIDE RESINS (8)
Estimated Capacity
Nylon 66 Type (million pounds)
El Paso Natural Gas., Etowah, Tenn. 2
Celanese Corp. Deer Park, Tex. n.a.
Louisville, Ky. 12
Du Pont, Parkersburg, W. Va. 70
Monsanto Co., Pensacola, Fla. 25+
Nylon 6 Type
Allied Chemical Corp., Chesterfield, Va. 15
Firestone Tire 6 Rubber Co., Pottstown, Pa. 2
Foster Grant Co., Leominster, Mass. n.a.
Manchester, N.H. 5+
Custom Resins, Henderson, Ky. 5
Total 136+
Reported producers of non-nylon polyamide resins^ are
listed in Appendix 1.
V-55
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Production Capacities Vary Widely
Company nylon polyamide resin capacity varies from 2 million
pounds to 70 million pounds per year. These capacities are probably
quite flexible.
Company non-nylon polyamide capacity also varies widely.
Companies such as General Mills, Emery Industries, Stepan Chemical,
Epoxy lite'and Celanese probably have the bulk of the capacity. Aver-
age individual capacities for these five companies is probably in the
order of 5 million pounds each. The remaining companies share the
rest and probably average less than 0.5 million pounds each.
V-56
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V-O ROSIN MODIFICATIONS
Rosin modifications are thermoplastic resins and are usually
prepared by esterification of rosin acids with glycerol or other alcohols.
The process not only esterifies but polymerizes the rosin acids.
1. ROSIN ESTER PRODUCTION HAS BEEN DECLINING
Rosin ester production has been erratic since its high of 152 million
pounds in 1962, but is declining. In 1972 production was only 95 million pounds,
slightly higher than the 89 million pounds the previous year. For the period
1967-1972 production declined at an average compounded annual rate of 6.5%
per year. Exhibit V-l shows yearly production rates for this period.
Consumption Will Continue To Decline
Rosin esters have few uses, and are used in relatively small
amounts in various formulations, particularly varnishes, lacquers
and other coatings, to impart special properties. Many of these coat-
ings are being replaced, and rosin esters will find fewer markets.
We expect rosin production to decline at the rate of about 1% per year
through 1977.
2. THERE IS AN EXTRAORDINARILY LARGE NUMBER OF PRODUCERS
FOR THE SMALL VOLUME OF ROSIN ESTERS AND ADDUCTS
PRODUCED
There are 36 companies producing 97 million pounds of rosin esters
and adducts at 71 locations as shown in Exhibit V-O. Most of the producers
are alkyd producers and/or suppliers to the coatings industry.
Plants Are Widely Scattered
Rosin ester producers are usually alkyd or coatings producers.
The latter are located near their customers.
V-57
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EXHIBIT V - O
Environmental Protection Agency
PRODUCERS : ROSIN ESTERS
AND ADDUCTS
(8)
Carpenter Morton Co., Everett, Mass.
Celanese Corp., Newark, N. J.
Conchemco Inc., Baltimore, Md.
The Dexter Corp., Rocky Hill, Conn.
Eastern Color & Chem. Co., Providence, R. I.
Farnow, Inc., South Kearny, 'N.J.
Lawter Chems. Inc., South Kearny, N.J.
McCloskey Varnish Co., Philadelphia, Pa.
Benjamin Moore & Co., Newark, N. J.
The O'Brien Corp., Baltimore, Md.
Onyx Oils & Resins, Inc., Newark, N. J.
C. J. Osborn Chems. Inc., Linden, N. J.
PPG Indust., Inc., Springdale, Pa.
Reichhold Chems., Inc., Elizabeth, N. J.
Rohm and Haas Co., Philadelphia, Pa.
Schenectady Chems., Inc., Rotterdam Junction. N. Y.
Schenectady, N. Y.
Shanco Plastics & Chems., Inc., Tonawanda, N.Y.
Union Carbide Corp., Bound Brook, N. J.
Ashland Oil, Inc., Pensacola, Fla.
Celanese Corp., Louisville, Ky.
Crosby Chems., Inc. ,• De Ridder, La.
Picayune, Miss.
De Soto, Inc., Garland, Tex.
Dixie Pine Products Co., Inc., Hattiesburg, Miss.
Gilman Paint & Varnish Co., Chattanooga, Tenn.
Hercules, Inc., Hattiesburg) Miss.
Monsanto Co., Baxley, Ga.
PPG Indust., Inc., Atlanta (East Point), Ga.
Houston, Tex.
Reichhold Chems., Inc., Houston, Tex.
Union Camp Corp., Savannah, Ga.
Valdosta, Ga.
Valentine Sugars, Inc., Lockport, La.
Westvaco Corp., Charleston Heights, S. C.
Conchemco Inc., Detroit, Mich.
Kansas City, Mo.
Cook Paint & Varnish Co., North Kansas City, Mo.
De Soto, Inc., Chicago Heights, m.
The Dexter Corp., Cleveland, Ohio
Waukegan, HI.
Guardsman Chem. Coatings, Inc.,
Grand Rapids, Mich.
Internat'l Miherals&Chem. Corp., Bensenville, 111.
Midwest Mfg. Corp., Burlington, Iowa
Benjamin Moore & Co., Cleveland, Ohio
St. Louis, Mo.
The O'Brien Corp., South Bend, Ind.
PPG Indust. Inc.. Cleveland, Ohio
Milwaukee, Wise.
Pacific Holding Corp., Chicago, 111.
Purex Corp., Ltd., Chicago, 111.
Reichhold Chems., Inc., Cicero, 111.
Benjamin Moore & Co., Denver, Colo.
Los Angeles, Calif.
Napko Corp., Emeryville, Calif.
The O'Brien Corp., South San Francisco, Calif.
PPG Indust., Inc., Torrance, Calif.
Preservative Paint Co., Seattle, Wash.
Re'ichhold Chems., Inc., Azusa, Calif.
S. San Francisco, Calif.
De Soto, Inc., Berkeley, Calif.
The Dexter Corp., Hayward, Calif.
McCloskey Varnish Co., Los Angeles, Calif.
Portland, Ore.
V-58
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SECTION VI
GENERAL PROFILE OF THE CHEMICAL/PLASTICS INDUSTRY REGARDING
PROCESS TECHNOLOGY AND AIR POLLUTANT EMMISSIONS
-------
SECTION VI
GENERAL PROFILE OF THE CHEMICAL/PLASTICS INDUSTRY
REGARDING PROCESS TECHNOLOGY AND AIR POLLUTANT EMISSIONS'
This section presents our findings concerning the processing aspects of
each of the major plastics and resins manufactured in the United States.
The information regarding the process technology associated with the
manufacture of each plastic was compiled from published information. We
believe the state-of-the-art is generally described, but particularly newer
installations may feature appreciably different design and operating conditions
that are proprietary and are, therefore, not described in the literature.
General process descriptions for the following plastic/resin groups are
described.
A - Polyethylene and Copolymers
B - Vinyl Resins
C - Styrene Resins
D - Polypropylene
E - Phenolic and Other Tar Acid Resins
F - Polyesters
G - Amino Resins
H - Alkyds
I - Acrylics
j - Coumarone-Indene and Petroleum Resins
K - Polyurethanes
L - Cellulosics
M - Epoxy Resins
N Polyamides
VI-i
-------
VI-A POLYETHYLENE AND COPOLYMERS
There are two basic types of polyethylene (PE) resins available - high
density (HOPE) and low density (LDPE), the latter accounting for about 69%
of total PE capacity.
1. LDPE PRODUCTION IS A HIGH TEMPERATURE, HIGH PRESSURE
CONTINUOUS PROCESS
All high-pressure PE plants have similar complexities.
All high-pressure polyethylene plants have roughly similar
complexities in terms of gas compression and recycling systems as
well as handling of the product. There are, however, two major
differences in the types of reaction vessels used which may be either
the stirred autoclave or tubular design. A generalized flow sheet is
shown in Exhibit VI-A 1. (lfl) The process starts with the compression
of purified ethylene to between 1,000 and 3,500 atm. Initiators ,
are introduced into the compressed gas stream or into the reaction
vessel, before which the gas may be optionally heated to 100-200°C.
Water and solvents may also be introduced at this stage. Following
polymerization at conversions of between 6 and 25% and the optional
removal of water and solvents, the principal separation of ethylene
from polyethylene takes place at between 100 and 500 atm, followed
by the final separation at much lower pressures. Unreacted ethylene
is recycled to the secondary compressor after cooling to provide
correct conditions at the intake of the compressor. At the cooling
stage a small quantity of low-molecular-weight material may also be
removed although this is not the purpose of return gas cooling.
The polymer is then extruded into strands or ribbons. chilled
and pelletized. PE is sold as a natural product or reprocessed with
various pigments, stabilizers, slip agents, etc.
2. HDPE PRODUCTION IS A RELATIVELY LOW TEMPERATURE. LOW
PRESSURE PROCESS WHICH CAN BE EITHER CONTINUOUS OR
BATCH
HDPE is manufactured either by solution or slurry type of polymeriza-
tion (vapor phase plants are being used in some foreign operations) using
either a Phillips or Ziegler type catalyst. Based on various information sources,
the producers and plant locations by type of catalyst are listed below.
VI-2
-------
EXHIBIT VI-A1
Environmental Protection Agency
FLOW SHEET:
LD POLYETHYLENE PRODUCTION
(High Pressure Process)
Pine clh|lcne
so-looo in/in'
Lo» pressure
500-3400 a tm
T
i
t
Prchealer
I Initiator -—'
Stirred
autoclave
Solvent
and water
Tube
Sewialor
50-1000 atm
fielurti
jas
cooler
I
T
COOlel
Lo«-pressuie
separator
T
Water
Reactor
|~] Decanter
-*• Molten product Icr granulation and blending
llii;h-)ii<.—iinu jKilMjilivk-iu1 -v
-------
Manufacturer Plant Location Type of Catalyst System
Phillips Petroleum Pasadena, Texas Phillips
Celanese Corporation Deer Park, Texas Phillips
Union Carbide Corp. Seadrift, Texas Phillips
Allied Chemical Baton Rouge, La. Phillips
National Petro-Chem Deer Park, Texas Phillips
Chemplex Company Clinton, Iowa Phillips
Dow Chemical Company Freeport, Texas Ziegler
duPont Orange, Texas Ziegler
Victoria, Texas
Monsanto Texas City, Texas Ziegler
Sinclair-Koppers Co. Port Arthur, Texas Ziegler
(1) The Polymerization Of PE Using The Phillips Catalyst Can
Be By A Solution Or Slurry Process
In a typical solution process as shown in Exhibit VI-A2(19)
the catalyst, hydrocarbon solvent boiling in the range of 60 - 90°C.
and ethylene or comonomer are fed together into the reactor. Poly-
merization takes place in the reactor held at 125 - 175°C and pressures
of 20-30 atm at a residence time of 1 - 3 hours. The effluent stream
from the reactor is passed through flash or fractionation steps to
remove dissolved ethylene which is recycled to the reactor. The
polymer-solvent solution is diluted and the catalyst removed by fil-
tration or centrifugation operating at 150°C and 20-30 atm pressure.
The polymer is precipitated from solution by contacting the polymer
solution with water, or by cooling the solution by partial evaporation
of the solvent at low pressure; the solvent being recycled to the reaction
area following removal of water and polymer impurities. The polymer
is dried, extruded and palletized in conventional equipment; anti-
oxidants, heat stabilizers and other additives may be added during
the extrusion step.
The particle form (PF) or slurry process is shown schematically
in Exhibit VI-A2 and consists of the following steps: the catalyst,
ethylene and hydrocarbon diluent are fed continuously to a liquid-full
reactor at temperatures of 100-110°C , pressure and residence time of
20-30 atm and 1 .- 4 hours respectively. The effluent from the reactor
is removed through a quiescent zone and the low-boiling diluent and
dissolved ethylene flash, and are separated and recycled. The
remaining hydrocarbon is removed from the polymer in auger-dryers
which convey the polymer to storage.
VI-4
-------
EXHIBIT VI-A2
Environmental Protection Agency
FLOW SHEET:
HD POLYETHYLENE PRODUCTION
(Phillips Solution and Slurry Processes)
Solvent
Catalyst
storage
Catalyst
I- feeder
Elhylene and
comonomer
Etlv/lcne and
comonomer
recycle
Solvent
recycle
Catalyst
discard
Finished
resin
Bagging
Phillips Mllllllllll (Illll O-
Diluent-
Catalyst
storage
Catalyst feeder
Stirred
reactor
o
Ethylene and _
comonomer"
Slimy imlynicfu.il ion
Diluent, elhylene
and comonomer
recycle
Flash
V V V V
Drier
Resin
(I'lnlliji-).
VI-5
-------
(2) PE Polymerization Using The Ziegler Catalyst Is A Slurry
Process
The flow diagram for this process is very similar to the
Phillips process and is shown in Exhibit VI-A3. (2°) The greatest
variations plant to plant are the washing and purification sections
and are largely dependent upon solvent and alcohol supplies.
Reaction temperatures vary from 50 - 90°C with pressure of less
than 5 atm and residence time from 1/4 - 2 hours. Continuous
reaction at 30% solids is considered very good.
3. INITIATORS AND/OR CATALYST ARE USED FOR PE POLYMERIZATION
(1) LDPE Is Produced By High Pressure Free Radical
Polymerization
The initiators used are usually "oxygen supplying" products
including small amounts of oxygen, oxides of nitrogen, organic
peroxides, and others. Numerous initiators are available, and each
company has its own product(s) and this information is confidential.
Chain modifiers are also used and include solvents, diluents, co-
monomers , inhibitors, and others.
(2) HOPE la A Catalytic Polymerization
The Phillips process is usually based on a chromium oxide
and silica-alumina gel, silica gel or other substrate.
Generally, Ziegler catalysts result from the reaction between
compounds of transition elements in groups IV-VIII and compounds
chosen from the hydrides and alky Is of elements in groups I-III
which are capable of producing carbanions or hydrides. Typical
catalysts include aluminum isopropyl or isobutyl with combinations
of TiCl4 andV C15.
4. THERE ARE SEVERAL POTENTIAL EMISSION SOURCES
Emissions are present both inside and outside the plant.
(1) In-Plant Emissions Can Occur As A Result Of Manufacture
Vapors escape from valves, line and pumps.
VI-6
-------
EXHIBIT VI-A3
Environmental Protection Agency
FLOW SHEET:
HD POLYETHYLENE PRODUCTION
(Ziegler Slurry Process)
HYDROCARBON 1
SOLVENT t
TRANSITION 1
METAL MAUDE J
ALUfcMNUM
ALKYL
CATA~YST
MODIFIER
(OPTIONAL)
DRY HYDROCARBON SOLVENT
SEQUESTERING AGENT
PRODUCT FINISHING
(COMPOUNDING 8 BAGGING)
SOLVENT
A 1} pieal Mow (hngrnin—//n-filcr puljotlijlcnc plant.
VI-7
-------
The drying equipment may be a major source.
Reactor and separator venting contributes sub-
stantially •
(2) Emissions Are Noticeable Outside The Plant
Odorous products produced by decomposition are
vented to the air.
Because of the flammability and explosiveness of
ethylene, the air in the plant is ventilated by large
volumes of air and vented to the outside.
5. THERE ARE THREE PRINCIPAL EMISSIONS
Polymerization Recipes Are Varied And Secret, But In
General, The Following Emissions Are Noticeable
Solvents in the drier area.
Catalyst odors.
Hydrocarbon decomposition odors due to
strenuous operating conditions.
6. PLANT SAFETY IS DILIGENTLY PRACTICED
Safety is practiced mainly from an explosive and fire viewpoint.
However, the instrumentation for detecting leaks of raw materials, process
stream instrumentation, explosion proof equipment, use of non-sparking
tools, contribute to keeping odors and emissions to a minimum.
The exhaust systems installed in plants contribute to outside odor
problems.
VI-8
-------
VI-B VINYL RESINS
The most important resin of this group is that produced by polymeriz-
ing vinyl chloride alone or with another comonomer such as vinyl acetate,
vinylidene chloride, etc. These resins are considered as poly vinyl chloride
(PVC) resins if the vinyl chloride content is over 50%.
Two other vinyl resins are important — poly vinyl acetate (PVAc) and
polyvinyl alcohol (PVA) and will be discussed here.
1. ALL VINYL CHLORIDE POLYMERIZATION IS CONDUCTED AT LOW
TEMPERATURE AND PRESSURE AS BATCH OPERATIONS
The two most important methods of preparing PVC in the United States
are the suspension and bulk polymerization methods although some emulsion
polymerization capacity is still in operation.
(1) Probably 80% Or More Of The PVC Produced Is By
Suspension Polymerization
A schematic diagram of a typical suspension polymerization
process is shown in Exhibit VI-B1. (21) Most reactors in use are water-
jacketed and glass-lined ranging from 2,000 - 6,000 gallon capacity.
The desired quantity of monomers (s) is measured in the weigh tank
and transferred to the reactor containing the proper amount of water.
Ratios of water to vinyl chloride range from 1.5:1 to 4:1. Initiators
such as lauroyl peroxide or azobisisobutyronitrile, suspending agents
such as polyvinyl alcohol, gelatin or methylcellulose and buffers are
charged into the reactor. Agitation is started and the mixture brought
up to 45-55°C until polymerization is carried to 90% conversion. Cooling
water is used to remove the heat of polymerization. The mixture is then
transferred to the dump tank, where it is stripped of unreacted monomer
by the application of vacuum. This monomer is recovered and recycled.
The bulk of the water is separated in a centrifuge and the resin dried
in a stream of hot air in a rotary drier. The product is separated from
the wet air stream in a cyclone separator, from which it is screened and
sent to storage. The wet air stream containing the fines is passed
through a filter.
VI-9
-------
EXHIBIT VI-B1
Environmental Protection Agency
FLOW SHEET:
POLYVINYLCHLORIDE PRODUCTION
(Suspension Polymerization Process)
Hixovcivd vinyl clilmiclc
Crude vinyl chloride -f
Storage unk r -fS
rvT
Rcboilcr
JIUl
dcacralcd
water
PVC 10 storage
buuiililicd flow diugmm uf a Initcli-t.ypo Bi^pcnsioii-pulyiuciuuliDit plant.
VI-10
-------
(2) The Next Most Important Polymerization Is Bulk
Polymerization
A simplified flow diagram of a two-step bulk polymerization
plant is shown in Exhibit VI-B2. ^2) Monomer is pumped into a
prepolymerizer (a vertical stainless steel-clad vessel equipped with
a flat-blade turbine stirrer and baffles), and converted to polymer
at a conversion of only 7-10% at temperatures of 40-70°C. The
mixture from the prepolymerizer, together with an equal amount of
fresh monomer, are transferred to the autoclave. a horizontal reactor
equipped with slowly rotating agitator blades. Reaction time is
5-9 hours. Unreacted monomer is removed by vacuum and recovered
by vapor compression and condensation in the recycle condenser.
The resin is transferred to the resin receiver by means of an air
eductor.
(3) Emulsion Polymerization Is Also Used
Vinyl chloride is emulsified in water using surface active
agents. Initiator is added and the contents stirred gently at 40-55°C
for 12-18 hours. The resultant latex is stripped of monomer. The
latex is usually spray dried.
2. POLYVINYL ACETATE (PVAc) IS GENERALLY PRODUCED BY LOW
TEMPERATURE BATCH POLYMERIZATION OF VINYL ACETATE
While vinyl acetate can be produced by bulk, solution, suspension and
emulsion polymerization techniques, we believe over 90% is produced by emul-
sion techniques as shown in the schematic in Exhibit VI-B3. <23) Exhibit VI-B4(24)
and VI-B5C25) are schematics for a solution and bulk polymerization process.
The latter two processes will not be discussed here.
FVAc is prepared and sold as a 55% water emulsion. The average
batch size will range from 500 - 2,000 gallons. Polymerization is conducted
at vinyl acetate/water reflux temperature of 67 - 80°C. Copolymers can be
produced in the same equipment and fashion. Reaction time is about 5 hours.
The emulsion is then cooled to room temperature in the reactor and trans-
ferred to drums or storage vessels.
VI-li
-------
EXHIBIT VI-B2
Environmental Protection Agency
FLOW SHEET:
POLYVINYLCHLORIDE PRODUCTION
(Bulk Polymerization Process)
(22)
\
V
D|
•==
u<
Pn-|iUlv
T
dim
fl
Cf
Ccmd
unsci
1
«H*r
1
V*uu...
<•> VJI..K
^~\ r— -, C'jiwwi
^^ "T" Older
/— . ^^ IIIC5-.
/A Dusl
SCIIH
r>ilur
Aiiluclju1
To rcsiri
rccPiwsr
Edjclor
ill ;i tuti—
Vent
FIUIII vinyl
clilundc
slorjyo
Uink
HIH:VI lu vinyl
Ojy Uill
j
Vinyl chlonilo
lecd pump
caitiun /VoccBsinj.
, Hydro-
VI-12
-------
EXHIBIT VI-B3
Environmental Protection Agency
FLOW SHEET:
POLYVINYL ACETATE PRODUCTION
(23)
(Emulsion Polymerization Process)
REACTOR
950 GAL WORK CAP
73OOAL TOTAL CAP
-OR-
ANT SIZE
REQUIRED
Polyvinyl acetate emulsion unit (Courtesy Star Tank and Filler Corp )
VI-13
-------
EXHIBIT VI-B4
Environmental Protection Agency
FLOW SHEET:
POLYVINYL ACETATE PRODUCTION
(Solution Polymerization Process)
i MEASURING T«N«
PRODUCT ~_'
3 ADJUSTING TANKS
rss for vinyl acctal.c solution polymers .
VI-14
-------
EXHIBIT VI-B5
Environmental Protection Agency
FLOW SHEET:
POLYVINYL ACETATE PRODUCTION S)
(Bulk Polymerization Process)
SCREEN FILTEflS
ENDLESS SreEL BELT WITH
*iR COQUliO ft>*D CUIItR
ftTTACHEO
Continuous process for bulk pol3*nicrization of vinyl acetate*
VI-15
-------
3. POLYVINYL ALCOHOL (PVA) IS PRODUCED BY ALCOHOLYSIS OF
PVAc AND CAN BE CONTINUOUS OR BATCH PROCESS CONDUCTED
AT LOW TEMPERATURE
The PVAc used must be beads and contain less than 1% water. The
PVAc is probably made by suspension techniques. A schematic of PVA plant
is shown in Exhibit VI-B6. <26)
PVA is prepared in different grades and is a function of degree of
alcoholysis. PVAc beads are dissolved in hot methanol (50-60°C). Sodium
hydroxide in methanol is added to convert the acetate to alcohol, at which
point it begins gelling. After the gel is aged, it is ground and mixed with
additional methanol to drive the hydrolysis to the desired degree. Excess
alcohol is removed and fed to a dryer with an inlet temperature of 140-160°C
and an exit temperature of 70-80°C. The PVA is then pulverized and bagged.
4. EMISSION SOURCES WILL VARY DEPENDING UPON THE RESIN
PRODUCED AND DEGREE OF PRODUCT INTEGRATION
When several vinyl resins are produced within a single plant, emission
sources would be additive.
(1) There Are Several Sources Of Emissions In A PVC Plant
Vapors escape from reactors through vents and
packing on stirrers.
Solvent odors are prevalent in the compounding
and shipping area.
(2) Emissions From PVAc Plants Originate Mainly In The
Manufacturing Section
Vapors escape from vents in the reactor, feed
tank and condenser.
The drumming section could be a minor source
of monomer vapor.
VI-16
-------
EXHIBIT ,VI-B 6
Environmental Protection Agency
FLOW SHEET:
POLYVBMYL ALCOHOL PRODUCTION (26)
WATER
LIQUID
Flow tliugram for the alcoholjsii of polyvinyl acetate.
VI-l?
-------
(3) Potential Emissions Are Present Both In-Plant And Outside
Prime sources of emissions would be losses from
pumps, valves and solvent recovery systems.
Odors/emissions may originate in the effluent
from the plant.
5. MONOMERS AND COMPOUNDING SOLVENTS ARE THE PRINCIPAL
EMISSIONS
(1) Vinyl Chloride And Ketones Are Major Emissions Of
PVC Plants
PVC polymerization employs only vinyl chloride
and/or copolymer and water.
Ketones, principally Methyl Ethyl Ketone (MEK)
is the principal volatile solvent used - plasticizers
are not volatile.
(2) Vinyl Acetate Is The Major Emission In PVAc Production
(3] Methanol And Methyl Acetate Are The Principal Emissions In
PVA Preparation
Methanol acts as both solvent and alcoholysis agent
and is present in excess of required amounts.
Methyl acetate is formed during the polymerization.
VI-18
-------
VI-C STYRENE RESINS
Polystyrene, impact polystyrene and styrene-butadiene-acrylonitrile
(ABS and styrene-acrylonitrile (SAN) copolymers make up the bulk of this
group of resins. Polystyrene is manufactured by polymerizing styrene;
impact styrene is a blend of polystyrene with rubber; and ABS and SAN are
high tensile strength copolymers. Polystyrene and impact styrene each
account for about 30% of the styrene polymers; ABS , SAN and styrene-butadiene
copolymers accounting for the remainder with ABS representing about 20% of
total styrene resins. Discussion will concentrate on polystyrene, impact
polystyrene and ABS.
1. THE BULK CONTINUOUS AND SUSPENSION PROCESSES ARE THE
MOST IMPORTANT METHODS FOR PRODUCING POLYSTYRENE (27)
(CRYSTAL OR GENERAL-PURPOSE POLYSTYRENE)
Over half of the current United States production of general-purpose
polystyrene is made by suspension polymerization, the remainder by some
variation of bulk polymerization to high conversion. (2&)
(1) In The Suspension Process Fpr The Manufacture Of
General-Purpose Polystyrene, Water Is The Prevalent
Suspending Medium And Production Is Batch-Wise
Exhibit VI-C 1 depicts a flow scheme for manufacture of general-
purpose polystyrene by the suspension process. Styrene monomer is
pumped directly into hot water containing tricalcium phosphate (TCP) ,
suspending agents and dyes. Typical water to monomer ratios are
1:1 to 3:1. Plasticizers and catalysts or initiators (e.g. benzoyl peroxide
and/or tert-butyl hydroperoxide) are added directly to the monomer.
A series of temperature rises - from 90°C to 115°C to 130°C - over
8 to 10 hours to complete polymerization. The material is then flushed
from the reactor into a mechanical separator which separates the TCP
from the polymer beads. The beads are dried, extruded, cooled,
chopped and packaged. The driers may be rotary, co-current air
driers, counter-current steam-tube driers or rotary vacuum driers.
VI-19
-------
EXHIBIT VI-C1
Environmental Protection Agency
FLOW SHEET:
CRYSTAL POLYSTYRENE PRODUCTION^)
(Suspension Polymerization Process)
STYRENE
STORAGE
S-l
METER
PUMP S-3
WEIGHED CATALYST
ADDITION SYSTEM
-6
SUSPENSION
POLYMERIZATION
VESSEL S-7
SCALE
S-4
AIR OR MECH
LIFT S-12
LUBRICATOR
CENTRIFUGE DRYER
S-9
CRYSTAL BEAD
STORAGE .
S-13
r
S-IO f-1 >
m^^^
TO TRANSPORTATION
OR EXTRUSION
Flow scheme (or crystal polystyrene by suspension process.
VI-20
-------
(2) Bulk Continuous Processes With Or Without Solvent Are
Also Used
Exhibits VI-C2 and VI-C3 depict bulk continuous process with
and without solvent respectively. In the continuous tower solvent
process, 5-25% ethylbenzene is mixed with the monomer prior to enter-
ing the first stage polymerizer. Typically, the solution will pass through
with each stage being at higher reaction temperatures - the first is at
110-130°C and the last stage being at 150-170°C. The polymerization
mass is pumped into a low-pressure, high-temperature devolatilization
tank (225-250°C at 5-30 torr pressure) where the unreacted monomer
and solvent is flashed off, condensed and recycled. The hot polymer
is fed into an extruder and the polymer strands are cooled, cut and
bagged.
2. THE BULK CONTINUOUS AND SUSPENSION PROCESSES ARE OF
APPROXIMATE EQUAL IMPORTANCE IN THE MANUFACTURE OF
IMPACT POLYSTYRENE
(1) In The Bulk Continuous Process For Impact Polystyrene,
Rubber Is Dissolved In Styrene, Prepolymerized, Run
Into A Continuous Tower, Then Devolatilized And Often
Extruded
Exhibit VI-C4 depicts an idealized continuous process for the
manufacture of impact polystyrene. Rubber is cut, ground, weighed
and transported to a dissolving vessel to which styrene monomer is
metered separately; 3-10% by weight rubber is used. The solution is
filtered to remove gels and emulsion acids. Polymerization is started
in a stirred autoclave either thermally or using catalysts such as
benzoyl nitrile or azobisisobutylnitrile. When 35 - 40% polymer
content is reached, the polymerization is completed in a continuous
tower having temperature gradients of 90°C, 130 C, 150°C and per-
haps as high as 200°C. The product is devolatilized in a thin-film
evaporator or a Herringbone gear devolatilizer with recycling of the
volatiles. The product is then extruded or forced through a spinnerette
by a gear pump and the final pellet is made and packaged.
(2) In The Suspension Process For Impact Polystyrene, Rubber
Is Dissolved in Styrene, Prepolymerized, Suspended And
Polymerized, Washed and Dried
Exhibit VI-C5 depicts the flow scheme for impact polystyrene
using the suspension process. The initial rubber is dissolved and
prepolymerized in a manner similar to the bulk continuous process
described above. When 10-20%polymer is reached, the material is
suspended in a prepared kettle of water:TCP in about 50: 50 proportions.
VI-21
-------
EXHIBIT VI-C2
Environmental Protection Agency
FLOW SHEET:
CRYSTAL POLYSTYRENE PRODUCTION
(28)
(Continuous Solvent Polymerization Process)
Hocoviift) iivrene and solvent
Slyrene
Reader
TJ
Rc-ocior
Reactor
TJ
Duvola-
tili/er
f
Poly-
*• siyrene
uulluis
Cxiiudur Cooler Cutler
Diagram of the oontimmub solvent proci-is for slyrene polyincrizat.ioii.
VI-22
-------
EXHIBIT VI-C3
Environmental Protection Agency
FLOW SHEET:
CRYSTAL POLYSTYRENE PRODUCTION
(Continuous Bulk Polymerization Process)
rai POMP
fILlEP ftOW WE«R
e-3
^lltlllllllll|—n—I
ZONE I
Continuous polystyrene process uses this polymeriza-
tion system.
VI-23
-------
EXHIBIT VI-C4
Environmental Protection Agency
FLOW SHEET:
IMPACT POLYSTYRENE PRODUCTION (29>
(Idealized Continuous Process)
o
v=
o
=y
TOE-PCLV
VESSEL
AIR FEED
CONVEYOR
FINAL
POLYMERIZATION
VESSEL
OEVOLALIZING
INTERNAL
STORAGE
WEIGH i
SYSTEM
VI-24
-------
DISSOLVING W.VK
MEIER 1-7
I-Z IJ
EXHIBIT VI-C5
Environmental Protection Agency
FLOW SHEET:
IMPACT POLYSTYRENE PRODUCTION <29)
(Suspension Polymerization Process)
EXTRUDERS
Flow scheme for impact polystyrene using the suspension process.
VI-25
-------
Catalysts used include benzoyl peroxide or butyl perbenzoate. Poly-
merization takes between 8-10 hours with a series of temperature rises
from 90°C to 115°C to 130°C. The material is then flushed into a
mechanical separator which separates the 400 mesh TCP from the
approximately 80 mesh impact polystyrene beads. The beads are
washed, centrifuged and dried to reduce volatiles to 0.5-0.7% and
then extruded with further reduction of volatiles to about 0.2-0.25%.
The uncontrolled emission factor in extrusion is about 0.3-0.5% as
volatiles.
3. ABS RESINS ARE GENERALLY MANUFACTURED BY EMULSION
PROCESSES
ABS resins represent approximately one sixth of the production of
styrene based plastics.
Exhibit VI-C 6 depicts the flow diagram of ABS polymerization by
batch emulsion processes. Reaction temperatures may range from 5 to
80°C • or higher in making the various ABS components. Pressures may vary
from 0.1 - 10 atm or more. Reaction time may be from several hours to
several days. In a typical emulsion plant, polymerization takes place in a
standard jacketed 3,750 gallon reactor. Catalysts are usually peroxides.
Carbon tetrachloride is a typical modifier.
ABS is generally sold in a pigmented, compounded and pelletized form.
4. IN THE MANUFACTURE OF STYRENE PLASTICS. STYRENE MONOMER
IS POTENTIALLY THE PRINCIPAL EMISSION
Some odor is generally perceptible both inside and outside the plant.
5. THERE ARE MANY POTENTIAL EMISSION SOURCES
(1) In Continuous Processing, Polymerization And Devolatilization
Are Potential Emission Sources
In polymerization, emissions are likely to occur
during production interruptions
VI-26
-------
EXHIBIT VI-C6
Environmental Protection Agency
FLOW SHEET:
ABS PRODUCTION (30)
RUBBER
POLYMERIZATION
Emulsiiter Sol'n
Co'qlYSl Sol'n
Modifiers
MONOMER
STORAGE
AREA
BUTADIENE
ACftYLONITRILE
Shortstop
Monomer Recovery
r
STrRENE
SteomTT
REACTOR STRIPPER
RESIN POLYMERIZATION
RUBBER LATEX
STORAGE
REACTOR
GRAFT POLYMERIZATION
Cmulsiltcr
" ID.
Catalyst
Sol-n
MONOMER
MIX
TANK
LATEX STORAGE
RESIN LATEX
STORAGE
/>nl.o..dor.l
;—~| Anlio«iJonl
LATEX
BLEND
TANK Flocculonl
S W°'*I-
~~-v'ii f FLOCCULATION
" " TANK
I (Resin-Rubber]
1 V °'6""' I
REACTOR
L
GRAFT ABS
LATEX STORAGE
*___
BLEND
TANK
DRY STORAGE
Flow diagram—ABS manufacture.
BAGGER
WAREHOU^r
VI-27
-------
Leaks in storage and reaction equipment are
maintenance related sources
Solvent and monomer recovery and extrusion
equipment are potential continuous emission
sources
(2) In Suspension Processing, Drying Is The Principal Potential
Emission Source
Leaks in storage and reaction equipment are
maintenance related sources
The filling/dumping cycle in the suspension
polymerization vessel is a potential intermittent
source
Washing and centrifugation are a potential source
of monomer emissions
Driers can release monomer in relatively low
concentrations but in large volumes of air
Vented extruders are another emission source
6. IN THE MANUFACTURE OF STYRENE PLASTICS. STYRENE AND
TO A LESSER EXTENT, ACRYLONITRILE, ARE THE PRINCIPAL
EMISSIONS
(1) Some Odor Is Generally Perceptible Both Inside And Outside
The Plant
Styrene monomer odor can be sensed at very low
concentrations. The odor is rubbery and sweet.
Acrylonitrile odors potentially emanate from the
manufacture of ABS and SAN. The odor threshold
of acrylonitrile is 400-500 times greater than that
of styrene monomer. Acrylonitrile monomer smells
pungent, onion-like and is 5 times more toxic than
styrene.
VI-28
-------
Other potential emissions to the atmosphere include
ethylbenzene (from continuous solution
processing of impact polystyrene)
vinyl alcohol (suspending agent)
rubber dust (impact polystyrene ingredient)
carbon tetrachloride (ABS modifier)
(2) Both For Economic Reasons And Because Of The Odorousness
Of Styrene, Modern Plants Manufacturing Styrene Plastics
Feature Closed Systems
Older manufacturing processes, such as filter
press processes, have a more significant emission
potential per unit of product than large, modern
continuous plants.
Besides utilization of closed systems and pollution
abatement equipment, consciencious plant maintenance
is the most important emission control means.
VI-29
-------
VI-D POLYPROPYLENE
1. MANUFACTURE IS CONDUCTED AT RELATIVELY LOW TEMPERATURE
AND PRESSURE AND CAN BE EITHER A CONTINUOUS QR
BATCH OPERATION
Every process for producing polypropylene (PP) involves three key
steps: (1) polymerization, (2) purification, and (3) finishing. A schematic
diagram for a typical PP plant is shown in Exhibit VI-D.
(1) Basic Equipment And Operational Steps For PP Polymerization
Are Similar
All streams entering the reactor (fresh and recycle diluent,
fresh or recycle propylene, catalyst, modifiers) are individually
metered and introduced separately into the reactor. (If premixing
is practiced, diluent and propylene may be added together, while
catalyst components are introduced into lines not containing propy-
lene) . Catalyst and propylene concentrations, reaction temperatures
and pressure, and residence time are dictated by economics and
polymer property requirements , i.e.: reactor temperature and
pressure range from 40 - 95°C and below 14 atm respectively;
the catalyst is a Ziegler type and a yield of 300-600 pounds of PP
per pound of catalyst is considered acceptable. Propylene conver-
sion to PP per pass is 50-70%. The resultant PP slurry contains a
maximum of 25% solids.
(2) Purification Consists Of Removing Catalyst, Diluent And
Amorphous Polymer
When polymerization is complete, the slurry is passed into
the flash tank which is maintained at relatively low pressure. Un-
reacted propylene along with diluent vapor (e.g. n-heptane, cyclo-
hexane) and other volatiles are flashed off and sent either to the
recovery section or condensers and recycled directly to the reactor.
The catalyst is deactivated by intimate intermixing of the slurry with
a polar compound, i.e., alcohol or water. Inert diluents are removed
from the solid PP by filtration or centrifugation. The filter cake con-
taining some volatiles and diluent is conveyed to the drying zone for
drying using either a rotary vacuum drier or spray drier.
VI-30
-------
EXHIBIT VI-D
Environmental Protection Agency
FLOW SHEET:
POLYPROPVLENE PRODUCTION
(Continuous Process)
Pllt*ftfp
NOPTCCM
1
^*_^
si
i«EUr» **-r*~~
IW 1
DIIICMT J
T
.. OHJIXl SICrtll
"
^ •o1
/ Be
BCCTCLC ' jfUT
/uwctNsn
LiMinr
J< ("Hyt J I MNlPIFUCt
^~—' i SXHSf ^~i*-^
V^_^J L J t (HLUfNT
VOJtXCtilltll t\ ASH SLWCC
T
r~M—\
stoadOM I
o"
ftffift
OHCAMC AND
VAT [A WASH
i r
E>IPUOfR »«e> COOI.INC »rn DKfO
Diagram of a continuous process Tor polypropylene in.iniifncturc
VI-31
-------
(3) PP Is Usually Compounded And Consolidated Into Pellets
The pellets or beads from the drier section are mixed with
various additives, melted, extruded and cut into pellets. The num-
ber of additives used is large and includes antioxidants, metal
deactivators, U.V. screeners, slip agents, antistats, fillers, plas-
ticizers, others. The pellets are removed by mechanical or pneumatic
conveyor to surge bins from which bagging is carried out.
2. THERE ARE SEVERAL POTENTIAL EMISSION SOURCES
Potential emissions are possible both inside and outside the plant.
Vapors escape from compressors, pumps and vents.
Solvent vapors are present in the drying area.
The distinctive odor of catalysts is prevalent
outside the plant.
3. THERE ARE THREE PRINCIPAL EMISSIONS
(1) The Metallic Compounds Formed During Polymerization
Are Odorous And Toxic
The odor is prevalent in the catalyst storage and
preparative areas.
Outside plant odors are noticeable.
(2) Solvent Or Diluent Odors Can Be Detected
Methanol and ethanol are detectable at 2,000 ppm
and 350-1,000 ppm respectively.
Threshold limits should be well below 500 ppm.
(3) Monomers Are Emitted In Greatest Volume
VI-32
-------
VI-E PHENOLIC AND OTHER TAR ACID RESINS
Phenols react with formaldehyde to form resinous products and although
these two products are the most widely used, other phenolic compounds and
aldehydes are used.
1. PHENOLICS ARE ORDINARILY MANUFACTURED BY A LOW TO MEDIUM
TEMPERATURE BATCH OPERATION
(1) Regardless Of The Final Form Or The Re act ants Used In The
Process, Equipment And Plant Layouts Are Similar
The schematic diagram for a typical phenolic resin production
unit is shown in Exhibit VI-E1 and equipment consists of the following:
Warehousing facilities and materials handling
equipment for resin production.
Jacketed acid-resistant stainless-steel kettles,
heated with either steam or Dowtherm, ranging
in size from 500 - 6,000 gallon capacity, equipped
with shell and tube condensers and heavy-duty
anchor or turbine blade agitator.
Weigh tanks
Vacuum pump
Compounding equipment including ribbon blender,
heated rolls and low speed cutters.
(2) Polymerization Of Novolak And "One-Step" Phenolic Resins
Are Similar
If a catalyzed mixture of phenol and formaldehyde contains one
or more moles of formaldehyde per mole of phenol it is called a "one-step
resin". When the catalyst is alkaline and there is less than one mole of
formaldehyde per mole of phenol, the initial product consists of a solution
of a "one-step resin" in phenol. Upon heating without the loss of phenol
it can be converted into a Novolak. A Novolak is also formed if the
original mixture is catalyzed with an acid.
VI-33
-------
EXHIBIT VI-E1
Environmental Protection Agency
FLOW SHEET:
PHENOLIC RESIN PRODUCTION(32J
Weigh tanks
Formaldehyde. ^Phenol
.Safety
blow-off
Temperature
recorder
Resin coolers for solid one-step resins
j, — Resin pans or (laker for novolacs
fjiu of Ijjtlr.il plicnolit. rcaiu pitjilucliiMi tpiiil.
VI-34
-------
Molten phenol or alternate raw materials such as resorcinol,
meta cresol or xylenols at 60-65°C and warm 37-40% formaldehyde
at about 40°C are charged to the kettle from the weigh tanks and
agitation started. Catalyst is added and steam applied to raise the
temperature until the exothermic reaction becomes strong enough to
cause the batch to heat without further steam. In Novolak prepara-
tion using an acid catalyst (usually sulfuric acid) mild reactions
may be allowed to heat up to atmospheric reflux (60-85°C) while
strongly exothermic reactions will be held to 85-90<>C by vacuum
reflux for 3-6 hours. In "one-step resin" preparation, steam pro-
vides the initial heat to 60-70°C while the exotherm heat will increase
temperature to 80-100°C at low vacuum and reflux for 1-3 hours.
Water is then removed from the reaction mass. In Novolak
preparation, the water is removed by slowly bringing the pot
temperature up to 120-150°C, then applying vacuum to remove final
traces at which time the temperature is 140-150°C and final vacuum
up to 100 torr. The "one-step resins" are dehydrated under
vacuum and the temperature is not allowed to go over 100°C .
When the desired characteristics are attained, the resins are
discharged through a quick-opening bottom cock. If the resin is to
be used in solution, solvent is added while the batch is still molten
in the kettle and while the condenser is still set for atmospheric
reflux. If the finished resin is solid, it is cooled in shallow pans
or on specially cleared floor areas, or it may be fed to a flaker.
Liquid resins are usually made-to-order for immediate shipment and
are protected from aging by refrigeration.
Most solid-resins are further processed and a flow diagram of
the processing is shown in Exhibit VI-E2. Resin for molding materials
is compounded with fillers such as wood flour. Novolak resin for
adhesive or bonding uses is pulverized with hexamethylenetetramine.
A small volume of special "one-step" liquid resin is manufactured for
casting whereby the resin is transferred directly from the kettle to
molds which are oven-cured for several days at 70-90°C .
2. SOURCES OF EMISSIONS OCCUR PRINCIPALLY DURING
POLYMERIZATION AND POLYMER PROCESSING
(1) The Prime Source Of Emission Is The Production Unit
During polymerization odors/emissions escape through the
condenser, vacuum line, sample ports and vents. Reactions that
become too exothermic are vented through safety blow-offs. When
solid resins are made, odors are prevalent after discharge from the
reactor since the resins are cooled either in pans, plant floor space
or flaker.
VI-35
-------
EXHIBIT VI-E2
Environmental Protection Agency
FLOW SHEET:
PHENOLIC RESIN PRODUCTION133)
Manufacture of phcnol-[orm:dilcli)dc muldmg and laminating ]in»lucts.
KEY TO FLOW SHEETS
/liuvj indicate operations or apparatus used during a particular stage of the process.
Cirilrs indicate basic mad-rials wed
nutlet! cir.li-s indicate materials \vliich nin> be used at the discretion of the manufacturer, or
to product: .special effects
.•/rnit.'j indicate the dii 1x111111 of fluii.
Dotted rtniiH'cliny lines imlicatc optional paths to be followed, or supplementary processes.
Solid lines ha>c been Uicd \\hcrc processes of equal merit may be used.
VI-36
-------
(2) Emissions Are Also Noted During Compounding
Odors are noticeable during blending, crushing and mixing
of lubricants and activators.
(3) Many Manufacturers Of Phenolics Produce Products Made
From These Resins And Odors Are Common In The Molding
And Laminating Plant
During phenolic resin use, heat is usually applied to cure
the phenolic resins.
3. THERE ARE FOUR PRINCIPAL EMISSIONS
(1) The Reactants Are Main Sources Of Air Pollution
Phenol and formaldehyde are very noticeable.
Phenol is considered toxic and may be absorbed
through the skin or inhaled.
Formaldehyde is an eye, skin and respiratory
irritant
(2) The Solvents Used In Making Solutions Of These Resins
Contribute To Total Emissions
Important solvents include:
Cellosolve Acetate
Butanol
Ethanol
Methyl Ethyl Ketone (MEK)
C y clohexanone
(3) The Formaldehyde Used Is Normally Stabilized With Methanol
About 1% methanol is used to stabilize the formaldehyde and
this would be emitted through the condenser during polymerization.
(4) The Activator Used Is A Source Of Odor
Activators normally used include ammonia and/or hexamethyl-
enetetramine which have sharp ammoniacal odor.
VI-37
-------
4. PHENOLIC RESIN PLANTS REPRESENT AN EMISSION PROBLEM
While the phenolic resin industry has an excellent record of serious-
injury rates, it does have a reputation as an industry with a high odor
factor. Phenols, for example, are detectable as low as 5 ppm and formalde-
hyde can be detected well below 1 ppm.
Good ventilation and other safety standards are normally practiced
within the plant so that odor/emission effects would be most pronounced
outside operating plants.
VI-38
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VI-F POLYESTERS
Polyester resins are unsaturated prepolymers made by esterifying
dihydric alcohols with unsaturated dibasic acids or anhydrides. These
unsaturated prepolymers are dissolved in an unsaturated monomer with
which it cross-links to form the ultimate polymer.
1. MANUFACTURE IS A HIGH TEMPERATURE BATCH OPERATION
(1) Manufacturing Equipment And Plant Layout Are Similar To
That Used In Alkyd Manufacture
The equipment layout of a typical polyester plant is shown
in Exhibit VI-F and consists of stainless-steel reactors from
500 - 5,000 gallons. (Glass-lined vessels are used only
where exceptionally light colored resins are required or when
halogenated starting materials are used) . The steam condensers
which operate at 100-110°C separate the water of reaction from the
process. The thinning tank has a capacity double that of the reactor.
(2) The Reaction Is An EsterificatLon Reaction
The dibasic acids or anhydride, usually phthalic anhydride or
isophthalic acid and maleic anhydride, fumaric acid, succinic acid
are reacted at 190-220°C with polyhydric alcohols such as propylene
glycol, ethylene glycol, diethylene glycol, for 8-20 hours. Sparging,
during esterification, with an inert gas shortens reaction time by
assisting in removing the water formed during condensation.
When the esterification has progressed to the desired stage,
the reaction mixture is cooled to 100-150°C and dropped into the
thinning tank containing the monomer, e.g. styrene or methyl styrene
and inhibitors .e.g. hydroquinone or para-tertiary butyl catechol.
The solution is filtered and sent to storage or shipping.
2. THERE ARE SEVERAL POTENTIAL EMISSION SOURCES
(1) In-Plant Emissions Occur As A Result Of Manufacture, Handling
And Storage
Vapors escape through packing on reactor and
thinning tank stirring equipment.
VI-39
-------
EXHIBIT VI-F
Environmental Protection Agency
FLOW SHEET:
POLYESTER RESIN PRODUCTION
Weigh
Tank
if From Row Material
Inventory Partial
Condenser
Total
Dowtherm
Liquid
To
Storage
Vent
Scrubber
.Decanter
.Water Receiver
Baffle Plates
Condenser ^ |
Motor
\
^-^.
Inert Gos "Blanket" Line _
Steam or
Filler
^
V
1
Srliniiiit.ic
-------
Vapors escape through vents on reactor and
thinning tank.
Monomer odors/emissions are prevalent in
raw material storage areas, and in drumming
areas.
Solvents are usually not used.
3. THERE ARE TWO PRINCIPAL EMISSIONS
Unchanged reactants are the prime offenders.
Anhydrides sublime or vaporize during the
reaction.
Monomers have relatively high vapor pressures, and
are particularly odorous even at room temperature.
4. MOST PLANTS FOLLOW GOOD HEALTH AND SAFETY PRACTICES
Reasonable precautions, such as the use of rubber or leather gloves,
protective clothing, eye protection and respiratory devices are employed in
handling the various ingredients. Cleanliness and careful handling of poly-
ester ingredients are available from raw material suppliers.
VI-41
-------
VI-G AMINO (U-F and M-F) RESINS
A large class of thermosetting resins are made by the reaction of an amine
with an aldehyde. The only aldehyde in commercial use is formaldehyde (F),
and the most important amines are urea (u) and melamine (M).. Most important uses
include molding, adhesives, laminating, textile finishes and paper manufacture.
Butylated melamine resins are also available and these resins are solu-
ble in paint and enamel solvents and lead to uses in surface coatings, often in
combination with alkyds.
1. AMINO RESIN PRODUCTION IS A LOW TEMPERATURE BATCH
OPERATION
(1) U-F And M-F Resins May Vary Considerably As To
Amine: Formaldehyde Ratio And Are Available As
Liquids Or Solids
U-F and M-F resins can be produced in the same equip-
ment consisting of a nickel-clad steel reactor which is jacketed
and equipped with fume ducts, agitator and condenser. The batch
size can vary from 100 - 6,000 gallons.
The reaction between amine and formaldehyde (Formalin, 37%)
is carried part way to completion: U-F resins are reacted at tempera-
tures between 20-70°C for molding resins, and at reflux for laminating
resins; M-F resins are usually reacted at reflux because of the low
solubility of melamine in water. When the required degree of conden-
sation is reached, the resin syrup is circulated through a steel plate-
and-frame filter press until the filtrate is water-white and clear.
While many applications utilize liquid resins. there is a large
market for solid resins - filled or unfilled resins. Schematics of a
typical molding and spray-dried resin plant are shown in Exhibit
VI-Gl. The procedure for preparing M-F resins follows. U-F resins
are handled similarly.
VI-42
-------
EXHIBIT VI-G1
Environmental Protection Agency
FLOW SHEET:
SOLID AMINO RESIN PRODUCTION
C-CLONt Pfti't."
! . "«^ <•="/'» ^' •' \:' ' -",.'
,-' . "UL.I" »U
; i .U'"' !<• •..
r • ' ''i ti..,' r ' : v, .-f.
-i j || I-]. ' 1 i ' '••5>a-J' »C'GM
p.'.' """ SHIP
ICONTIS ;0lll BELT 'nn-^a.-j^ LJ
L-,. ..-:.••.,.!
powder jilant, iVtucriciin ('y:\i\iiinid O>.
- , .
j MOIOIN'; tANKS L
.
PUMP FILTER PRESS
Sjiray-dritxl resin plant, American Cyaiuimid Co.
VI-43
-------
In the preparation of molding powders, the resin syrup and
filler are fed to a mixing tank and held at 50°C then discharged.into
the dryer hopper then into a continuous tunnel dryer heated and/or
cooled by circulating air so that the dried product contains about 6%
volatiles. On emerging, the dryer cake is broken up by means of a
revolving blade cutter; the pieces falling directly into the hammer
mill where the resulting fine powder is caught up in a stream of con-
veying air and charged to the ball mill along with lubricants, pig-
ments , catalyst and inhibitor. When the ingredients are blended to
specification, the powder is densified by feeding it onto the preheating
rolls operating at about 120°C where the powder is formed into a sheet
which is fed to the cutter. The cut granules pass through the screener
and are packed.
Spray-dried resins are prepared by introducing the resin syrup
into a spray tower approximately 25 ft. in diameter and 24 ft. high.
Hot air is directed downward in the form of a converging cone at the
atomizing wheel. A main fan provides the necessary suction to draw
approximately 40,000 cfm of air into the drying chamber and through
the dry resin collectors. The air stream leaving the drying chamber
conveys the dried resin particles to a collection of cyclones arranged
in parallel. Each cyclone discharges at the bottom through a venturi-
type air lock into a positive pressure, secondary air conveying system.
This secondary system discharges the resin beads into conventional
ribbon blenders by way of another cyclone collector, and it is then
packaged. The effluent air from the secondary system is returned to
the main air stream.
(2) Amino Resins Used In Surface Coatings Are Basically
Different
These resins are usually water-insoluble, but are soluble or
dispersible in hydrocarbons and higher alcohols. Since they are pre-
dominantly used in enamels containing alkyd resins, their solubility
and compatibility with various solvents such as naphtha, toluene and
butanol is a prime requisite. A manufacturing schematic is shown in
Exhibit VI-G 2.
Condensation of urea or melamine with formaldehyde is carried
out in the same manner as described above, but not much beyond the
monomeric methylol urea or melamine stage. A large excess of the
alcohol, the most common being butanol, is added and the reaction mix-
ture brought to reflux until the water initially present in the formalin
and split out by condensation is partly removed and the solution clears.
VI-44
-------
EXHIBIT VI-G2
Environmental Protection Agency
FLOW SHEET:
BUTYLATED MELAMINE RESIN PRODUCTION
(36)
VACUUM
EJECTOR
ICquipnient for manufacturing mclamine coating resins.
VI-45
-------
A separator trap or weir in the reflux line allows the water to be
drawn off while the butanol is returned to the reactor. When the
desired degree of esterification is reached the butanol-water is
diverted to a separate collecting tank for subsequent recovery of
the butanol. Solvents such as xylene are now added to the reaction
kettle to yield products containing 50-60% resin in a mixture of
butanol and xylene.
Melamine-urea resins are available in various solvent combi-
nations of butanol, xylene, butyl "Cellosolve" and mineral spirits.
2. POTENTIAL EMISSION SOURCES OCCUR IN MATERIALS HANDLING,
POLYMERIZATION AND COMPOUNDING OPERATIONS
(1) Emissions Occur During Storage And Materials Transport
Vents in storage tanks
Leakage in liquid transport piping and valves
Drum filling
(2) There Are Three Major Sources Of Emissions In Manufacturing
Leakage through agitator packing
Spills and leakage through the filter press
during operation and clean up
Condenser venting
(3) The Compounding Operation Probably Presents The Prime
Source
Molding powder plant
mixing tank
dryer
preheating and densifying rolls.
Spray dried resin
cyclone collectors and exhausts
spray tower
VI-46
-------
3. THERE ARE THREE PRINCIPAL EMISSIONS
(1) In Preparation Of The Basic Polymer, Formaldehyde Is
The Prime Source Of Emissions
The amino (amido) compounds normally used as raw
materials have boiling points far above the reaction tempera-
tures as shown by the following.
Materials For Amino Resins
Raw Material Melting Point °C Boiling Point °C
Aniline -6.2 184.4
Benzenesulfonamide 156
Dicyandiamide 207.8 d
Melamine 354 sublimes
Thiourea 180-182 d
p-Toluenesulfonamide 137
Urea 132.7 (d) d
d = decomposes
(2) Alcohols Used In Alkylating U-F And M-F Resins Are
Noticeable
The common alcohols used in alkylation are either low
boiling or odorous and include
methanol
butanol
octanoJ
(3) The Solvents Ordinarily Used In The Preparation Of Coating
Or Alkylated Resins Are Evident
The solvents used provide compatibility of the amino resins
with alkyds and include combinations of
xylene
butanol
'butyl "Cellosolve"
mineral spirits
VI-47
-------
VI-H ALKYDS
Alkyds are usually made by reacting dibasic acids or anhydrides,
usually phthalic anhydride, with apolyhydric alcohol such as glycerol.
The alkyd resins can be varied and modified by the use of other anhydrides
(maleic), dibasic acids, glycols, polyols or other substances. Regardless
of the composition of the finished resins, they are prepared by either a
solvent or fusion process described in detail in Section VIII. Quantification
of the emissions from these processes is also detailed in Section VIII.
1. MANUFACTURE IS GENERALLY A HIGH TEMPERATURE BATCH
OPERATION
Processing temperatures will range between 210- 250°C, although in
a few instances temperatures slightly above or below this range may be used.
Reactor size can range from 500 gal. to 5,000 gal. Agitation is supplied by
motor driven propellers, paddles or turbines and gas sparging. Sparging not
only agitates the reaction mass but blankets the mass to minimize oxidative
degradation of the alkyd. When the reaction has progressed to the desired
point, the mass is cooled somewhat and dropped into a thinning tank where it
is diluted with organic solvents usually xylene and/or naphtha.
2. THERE ARE SEVERAL POTENTIAL EMISSION SOURCES
Emissions are present both inside and outside the plant.
(1) In-Plant Emissions Occur As A Result Of Manufacture And
Handling
Vapors escape through packing on the stirring
equipment of reactors and thinning tanks
Solvent vapors are prevalent in the drumming area
(2) Vapors Escape Through Stacks And Vents
Solvents and raw materials are intrained with
the sparging gases
Vapors are released to the atmosphere when
scrubbers are vented
VI-48
-------
3. THERE ARE THREE PRINCIPAL POTENTIAL EMISSIONS
(1) Reactants Escape Because Of High Temperatures Used In
Preparation
Many of the ingredients used have boiling points in
the neighborhood of the reaction temperature. This
includes the anhydrides, and alcohols
Phthalic anhydride sublimes just below its melting
point and it is not uncommon to see crystals of this
product adhering to plant walls and ceilings
The characteristic odor of maleic anhydride is also
detectable
(2) Solvent Odors Are Particularly Strong In Filling Areas
Aromatic solvents are common, the most common being xylene.
4. MOST PLANTS FOLLOW GOOD HEALTH AND SAFETY PRACTICES
Reasonable precautions, such as the use of rubber or leather gloves,
protective clothing, eye protection and respiratory devices are employed in
handling the various ingredients. Cleanliness and careful handling by the
employees are essential. Information needed for the safe handling of alkyd
ingredients is available from alkyd raw material suppliers.
VI-49
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VI-I ACRYLICS
Acrylic resins are thermoplastic or thermosetting polymers or copoly-
mers of acrylic acid, methacrylic acid or esters of these acids. These monomer
liquid esters polymerize readily in the presence of light, heat, or catalysts.
Because of the high emission potential and odorous/toxic nature of the
emissions, this group of resins will be discussed in detail in Section
1. BULK, SOLUTION, EMULSION OR SUSPENSION METHODS ARE USED
IN THE POLYMERIZATION OR CO-POLYMERIZATION OF ACRYLIC
MONOMERS
(1) Emulsion Polymerization Is Widely Accepted And Is A Low
Temperature Batch Operation
Typically, monomers, emulsiflers and water are charged to
a reactor. The air is displaced by an inert gas, and the initiators,
reducing agents and activators are added and the charge heated to
30-50°C at which time a vigorous reaction occurs and the exotherm
will raise the temperature to 90-95°C. Conversion to polymer is
almost quantitative. The unconverted monomers are removed by
•stripping and evaporation and the finished resin emulsion sent to
storage.
(2) Suspension Polymerization Produces Dry Beads
Polymerization of the monomer or comonomer mixture is carried
out by charging the water, suspending agent, monomer mixture and
initiator to a reactor similar to that used in emulsion polymerization.
Heat the well-agitated mixture under an atmosphere of nitrogen to just
below the reflux temperature and polymerization is complete in about
1 hour. The slurry is filtered or centrifuged to separate the resin
beads from the water and the beads washed with water and then dried
in a circulating air oven at 80-120°C.
VI-50
-------
(3) Solution Polymerization Is Especially Suited To Preparation
Of Polymers When They Are To Be Used In A Solvent
Polymerization is carried out by slowly adding monomer and
initiator to a solvent held at near-reflux temperature. After all the
monomer (s) is added, mixing is continued for an additional 4-20
hours when polymerization is complete. Additional solvent is then
added and the solution sent to storage.
(4) In Bulk Polymerization, The Monomer Acts As The Solvent
Commercial bulk processes for acrylic polymers are used
primarily in the production of sheets, rods and tubes. Bulk processes
are also used on a much smaller scale in the preparation of dentures
and novelty items. The process is used primarily with methyl methac-
rylate polymerization.
Polymerization is a two-step operation in which the monomer is
first partially polymerized to a syrup consistency by heating the mono-
mer at 80-85°C for about 5 minutes. The syrup is then poured into
molds, cured at 40-90°C for some time, then post-cured at 140-150°C.
2. THERE ARE MANY POTENTIAL SOURCES OF EMISSIONS AND
WILL VARY DEPENDING UPON THE POLYMERIZATION PROCESS
Emissions can occur during storage, materials handling and poly-
merization operations.
Vents on both monomer and polymer emulsion
and solution storage tanks are a source of air
pollution.
Monomers and solvents used are all liquid, but
odorous/hazardous emissions occur as a result
of the line leaks and spills.
Polymerization equipment is vented to the atmosphere.
Sparging gases form aerosols with the monomers.
The rapid rate of polymerization and subsequent
heat of reaction makes it difficult to prevent vapor
escape from the reactors or, for that matter, the
entire polymerization system.
Spills from molds and during curing of the molded
products in bulk polymerization is a major source
of emissions.
VI-51,
-------
VI-J COUMARONE-INDENE AND PETROLEUM RESINS
Coumarone-indene resins were first prepared as by-products in the
refining of coal-tar solvents. More recently, resin formers containing
indene were obtained from cracked crude oils. These latter resin formers
do not, however, contain coumarone or its homologs.
While coumarone-indene and petroleum (hydrocarbon) resins are
reported together by the U.S. Tariff Commission, probably no more than
15% of the total are coumarone-indene resins.
1. PRODUCTION OF BOTH RESIN TYPES IS A LOW TEMPERATURE
BATCH OPERATION
The operations in the manufacture of these resins include: blending
and purification of raw materials (feed stock); polymerization; recovery of
solvent, and finally packaging of the finished resin. A schematic of a typical
plant is shown in Exhibit VI-J.
(1) Crudes May Be Blended To Average Out Variations Or They
May Be Fractionated
The presence of cyclopentadiene dimer is often undesirable
and may be converted to the monomer; however, small amounts
may be removed by treatment of the crudes with clay.
The crudes are fractionated into specific boiling ranges to
produce resin formers which, on polymerization, will produce
specific softening prints.
(2) Polymerization Is Conducted At Low Temperature In A Solvent
While batch polymerization is traditional because temperature
control is easier, polymerization can be made continuous. The raw
material is diluted to 50%, and more often 30% with an aromatic solvent.
Catalyst is added at no higher than 35°C, usually close to 0°C , and
the exotherm raises the temperature to 95-105°C. Reaction is completed
in 15-30 minutes. Sludges formed during polymerization are removed
by treatment with clay and filtration and acids are removed by succes-
sive washes with alkali and then water.
VI-52
-------
EXHIBIT VI-J
Environmental Protection Agency
FLOW SHEET:
COUMARONE-INDENE AND HYDROCARBON
RESIN PRODUCTION
catalyst
solvent
still
reactor
vent
wash
tank
I
flaker
or
package
Source: Snell
VI-53
-------
(3) While The Resin Is Often Finished In Batch Stills, Continuous
Finishing Can Be Employed
The resin is heated to about 2QO°C and flashed under vacuum.
Steam is often injected to complete the removal of heavy oils.
(4) The Finished Resin Can Be Shipped Molten Or Drummed
The softer resins (below 100 C softening point) are dropped
into lightweight steel drums. The harder resins may also be drummed,
but are usually flaked and bagged. Molten handling has been adopted
by large users.
Solutions at about 60% solids in an aromatic hydrocarbon
thinner are also sold.
2. EMISSIONS ARE WIDESPREAD AND OCCUR AT ALMOST ALL
POINTS OF HANDLING AND PROCESSING
(1) The Aromatic Nature Of The Raw Materials And Finished
Products Makes Emissions Detectable At Very Low Levels
Vents in raw material storage tanks, distillation
columns, reactor and flash evaporators are potential
sources of emissions.
Odors are prevalent in flaking areas.
Solvent odors are detectable in finishing and
shipping areas.
3. THE VARIATION OF THE COMPOSITION OF FEED STOCK AND
FINISHED RESIN (S) MAKES IT DIFFICULT TO IDENTIFY
SPECIFIC EMISSIONS
(1) The Coal- And Gas-Tar Fractions Used Have Wide
Boiling Ranges
The resin formers found in gas-derived oils
contain all the resin formers found in coal-tar
oils with the exception of coumarone and its
homologs.
VI-54
-------
The composition of the remainder of the resin
formers, most of which are odorous at concen-
trations in the range of 1 - 10 ppm, include:
Indene
Cyclopentadiene (monomer and dimer)
Styrene
Methyl homologs of cyclopentadiene
Vinyltoluenes
Methylindenes
Methylstyrenes
(2) Other Odor Contributing Solvents Used During Polymerization
And Thinning Include The Following
Xylene
Hi-flash naphtha
Other aromatics
VI-55
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VI-K POLYUHETHANES
There are over 100 producers of urethane resins used in the formulation
of coatings, adhesives and- sealants. Annual production volume is relatively
low, from 80 to over 100 million pounds of resin, with coating resins accounting
for the bulk of this. Plant capacities are also relatively low, about one million
pounds per year, on the average.
The manufacture of some typical urethane resins is discussed in detail
in Section vm.
1. MANUFACTURING PROCESSES ARE LOW TEMPERATURE BATCH
OPERATIONS
Urethane coating resins are prepared by reacting di- or polyisocyanates
with an intermediate containing at least two active hydrogen atoms per molecule.
Formulations are numerous and most are proprietary. ExhibitVI-Kl lists a
few formulations that are commercially available.
Resins are usually prepared in closed kettle reactors, blanketed with
nitrogen to keep out atmospheric moisture. In general, the polyisocyanate is
reacted with the polyhydroxy compounds or polyamines at temperatures
ranging from ambient to about 95°C. The isocyanate content of the resulting
resin will vary from no free isocyanate to as much as 25% or more.
2. THE MANY URETHANE RESINS PRODUCED CAN BE CATEGORIZED
AS NONREACTIVE OR REACTIVE
A simplified classification of the various types of urethane coatings is
shown in Exhibit VI-K2. (14) The ASTM designation refers to a classification
set up in 1960 by the American Society for Testing Materials, Committee D-l,
Paint. Varnish, Lacquer and Related Products. which does not include some
of the more recent resin developments.
(1) Nonreactive Urethane Coating Resins Contain No Free
Isocyanate Groups
Nonreactive urethane surface coatings include urethane alkyds.
lacquers, and latices. These coatings are nonreactive only in the sense
that they contain no free isocyanate groups. They are all one-package
systems. The urethane alkyd cures by air oxidation and the urethane
lacquer and latex cure by solvent evaporation (water in the case of latex)
VI-56
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EXHIBIT VI-Kl
Environmental Protection Agency
SOME URETHANE COATING RESINS
AS SUPPLIED BY THE PRODUCERS
Ur ethane alkyds:
60% NVR (nonvolatile resins) in mineral spirits
50% NVR in mineral spirits
Moisture-curing prepolymers:
60% NVR in Cellosolve acetate/xylene blend
50% NVR in Cellosolve acetate /xylene blend
42% NVR in Cellosolve acetate /xylene blend
42% NVR in Cellosolve acetate/xylene blend (non-yellowing)
Prepolymers for two-package systems:
60% NVR in Cellosolve acetate/xylene blend
60% NVR in Cellosolve acetate/xylene blend (non-yellowing)
Urethane polyols (100% NVR)
Thermoplastic lacquer (20% NVR)
Note: Cellosolve is a Union Carbide Corporation trade name
for ethylene glycol monoethyl ether.
These are shipped as drums, can or lot or truck-load quantities.
VI-57
-------
EXHIBIT VI-K2
Environmental Protection Agency
CLASSIFICATION OF URETHANE
SURFACE COATINGS (14)
Pescription
Nonreactive
Urethane alkyd
Urethane lacquer
Urethane latex
ASTM
Designation
Type 1
System
One package; air oxidation
One package; solvent evapor-
ation
One package; water evapora-
tion
Reactive
Moisture-curing prepolymer Type 2
Blocked prepolymer and polyol Type 3
Catalyzed prepolymer
Prepolymer and polyol
Type 4
Type 5
One package; isocyanate-
water reaction
One package; heat (to unblock) ,
isocyanate-hydroxyl reaction
Two packages; catalyzed
isocyanate-water or
hydroxyl reaction
Two packages; isocyanate-
hydroxyl reaction
VI-58
-------
(2) Reactive Urethane Coatings Contain Unreacted Or Blocked
Isocyanate Groups
Reactive urethane surface coatings are systems that contain
unreacted (or blocked) isocyanate groups. These coatings may be
one-package or two-package systems. One-package systems include
(1) urethane prepolymers that cure by reaction of the isocyanate
group with atmospheric moisture and (2) combinations of polyol and
urethane prepolymer in which the isocyanate group is blocked (usu-
ally with phenol) . When the system is heated, the phenol is released
and the isocyanate groups in the prepolymer react with the hydroxyl
groups in the polyol. Two-package systems include (1] combinations
of urethane prepolymer and polyol and (2) combinations of moisture-
curing urethane prepolymers and a small quantity of catalyst to
accelerate curing.
3. THERE ARE SEVERAL EMISSION SOURCES
Emission Sources Are Present In Raw Material Handling,
Prepolymer Manufacture And Finished Product Handling
Prepolymer manufacturers that are basic in
isocyanate manufacture will have less problem
in raw materials handling than small, non-basic
producers.
Basic producers will pump product directly
from bulk storage while small producers must
hand-handle drums and spillage by the latter
is more prevalent.
This same situation is true of solvent handling.
Displacement of moist air in reactors would cause
some vapors to vent.
Shipments of finished product are usually in small
lots, and the filling and shipping area would be a
source of vapors from
Solvents
Isocyanates
VI-59
-------
4. MOST PLANTS FOLLOW REASONABLE SAFETY PRECAUTIONS
Isocyanates can be handled, stored and used safely if their properties
are understood and the precautions are observed. The irritating character
of isocyanate vapors are the most objectionable feature of these compounds.
Some of the low molecular weight isocyanates have relatively high
vapor pressures. TDI, for example, can be detected, by smell, in concen-
trations as low as 0.1 - 1 ppm. The maximum allowable concentration in the
air fpr extended exposure is said to be 0.1 ppm.
The main precaution taken, in plant, is proper ventilation or the use
of respirators or gas masks.
VI-60
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VI-L CELLULOSICS
Cellulosic plastics are those products obtained by the esterification
of cellulose. Cellulose itself is a stable polymer of glucose and is the pre-
ponderant and essential constituent of all vegetable tissues and fibers,
including especially cotton and wood. Pure cellulose is now generally
obtained from treatment of wood. In terms of production volume, cellulose
acetate and cellulose nitrate are of about equal importance.
1. THE PRINCIPAL PROCESSING STEPS IN THE MANUFACTURE OF
CELLULOSE ACETATE ARE PRETREATMENT OF CELLULOSE,
ACETYLATION, HYDROLYSIS . PRECIPITATION , STABILIZATION
AND ACETIC ACID RECOVERY
(1) Pretreatment Is Essentially Drying Cellulose To A Fixed
Moisture Content In The Presence Of A Pretreating Reagent
The cellulose is first dried to a fixed optimum moisture
content by pretreating with acetic acid to swell the cellulose. This
permits the acetylation reagent to diffuse into the fiber more readily.
The time of treatment varies from 15 minutes to several hours, de-
pending upon the pretreating liquid and the amount used.
(2) The Acetylation Mixture Consists Of Acetic Anhydride, Acetic
Acid Or Methylene Chloride And Sulfuric Acid
The acetylation of cellulose is highly exothermic and tempera-
ture control is very important. In the process in which acetic
anhydride, acetic acid and sulfuric acid are used, two types of
acetylators have been employed - the brine cooled, sigma-bladed
mixer, and the cylinder mixer which rotates on a horizontal axis.
These reactors are large enough to acetylate 200-600 Ib of cellu-
lose per charge. The temperature is controlled between 5 - 45°C.
In the methylene chloride process, much of the reaction heat
can be dissipated in refluxing the methylene chloride, so that large
batches can be acetylated. Batches of up to 7,000 Ib have been
handled by this process, although most reactors are smaller. The
reactors are horizontal bronze alloy or stainless-steel cylinders
equipped with stirring blades on a horizontal axis.
VI-61
-------
(3) The Acetylated Dope Is Hydrolyzed
The water content of the dope is adjusted to 5-10%. The
rate of hydrolysis is controlled by the sulfuric acid/water ratio
and by the hydrolysis temperature, which is generally slightly
above room temperature. The catalyst/water ratio must be kept
below a certain level to avoid degradation. This can be accom-
plished by increasing the water content or decreasing the amount
of catalyst (by neutralization), depending upon how rapid a
hydrolysis is desired. The hydrolysis is then arrested by
neutralizing the sulfuric acid catalyst, usually with sodium
acetate.
The hydrolyzers are vessels large enough to handle one
or more acetylation batches. Some are equipped with agitators,
generally rotating blades on a vertical shaft. When the hydrolysis
is carried out without agitation. the product is precipitated in
another vessel in which the reaction mixture may be agitated.
Hydrolyzers are generally of stainless-steel, copper, bronze alloy
or glass-lined steel.
(4) Precipitation And Purification Involves Generation Of
Significant Volumes Of Dilute Acetic Acid
Cellulose acetate is precipitated by diluting the dope with
water to a point somewhat short of precipitation and then mixing
with an excess of aqueous acetic acid solution with vigorous
agitation. It is then purified by washing with water, 10% sodium
bicarbonate or magnesium ion to neutralize the sulfuric acid
catalyst, centrifuged and dried at 95°C.
Acetic acid is a major by-product in the manufacture of
cellulose acetate and must be recovered to make the process econom-
ical. All wash liquors containing an appreciable amount of acetic
acid are combined to give an aqueous solution containing 18-20%
acetic acid. Glacial acetic acid is obtained by concentrating this
liquor and is returned to the process.
VI-62
-------
2. THE USUAL TECHNIQUE FOR THE MANUFACTURE OF CELLULOSE
NITRATE IS THE MECHANICAL-DIPPER PROCESS
This is a batch process as shown in Exhibit VI-L. A continuous
nitration process with countercurrent washing of the crude, acid wet nitrate
has been developed but details of the process are not available.
(1) Nitration Is Accomplished With Mixed Acid
About 30 Ib of cellulose (containing less than 1% moisture)
is added to the dipper containing about 1,600 Ib of mixed acid
(sulfuric acid and nitric acid). The reaction temperature is con-
trolled by adjusting the temperature of the acid before it is added
to the reactor. When nitration is complete (20-30 minutes), the
reaction mixture is dropped into a centrifuge which removes most
of the acid which is pumped to a tank where it is brought back to
strength for reuse by adding concentrated acid. The centrifuged
cellulose nitrate is dropped through the bottom of the centrifuge and
drowned in water. It is then pumped as a water slurry to the puri-
fication area.
(2) Purification Is Accomplished By Boiling In Dilute Mixed
Acid Or Water
Purification and stabilization are carried out in batches as
large as 12,000 Ib in tubs lined with stainless-steel. The cellulose
nitrate is first washed to a low level of acidity, then boiling one or
more times in very dilute mixed acid or pure water, water-washing
between boils. Finally, the product is steeped or boiled in dilute
sodium carbonate and washed free of alkali.
(3) Cellulose Nitrate Is Dehydrated Before Shipment Or Storage
It is hazardous to ship or store cellulose nitrate in the dry state
and it is shipped either water-wet or, more commonly, alcohol-wet.
Alcohol-wet cellulose nitrate is often used without drying, since
alcohol is generally part of the formulation in which cellulose nitrate
will be used. It is prepared by compressing the water-wet material
into blocks at pressures of 17 atm, and pumping alcohol through the
blocks at this pressure. The compressed blocks are then broken
mechanically, and the alcohol-wet (about 35% alcohol) material is
shipped in galvanized steel drums.
VI-63
-------
EXHIBIT VI-L
Environmental Protection Agency
FLOW SHEET:
THE MECHANICAL DIPPER PROCESS
FOR NITRATING CELLULOSE (37)
Measuring
tank —I,
'I
Air connection
for blowing oul
fume ouliels
Dipping tanks —ri!-
Air conneclicn for
blowing chokes
^ '.^i'v^.
Cellulose niirate header
nx-wsfnr iiitr:»tinn
VI-64
-------
3. ACETIC ACID AND NOX FUMES CHARACTERIZE THE PREPARATION
OF CELLULOSE ACETATE AND NITRATE RESPECTIVELY"
Methylene chloride vapors may also be associated with cellulose
acetate manufacture. Sulfuric acid fumes may emanate from both acetate
and nitrate production. Acetic acid vapors can occur in both the manu-
facture and acid recovery cycle.
NO fumes evolve during nitration of cellulose. Alcohol vapors are
vented in the dehydration cycle.
VI-65
-------
VI-M EPOXY RESINS
1. MANUFACTURE IS A LOW TEMPERATURE BATCH OPERATION
(1) Each Producer Has Developed His Own Technique, But The
Following General Procedure Is Applicable
Bisphenol A, epichlorohydrin and caustic are added together
to the reactor and heated to 50-60°C. The exothermic heat of reac-
tion raises the temperature and must be controlled to 90-95°C.
Excess epichlorohydrin is removed after condensation is complete,
by vacuum distillation. (Toluene may be added to facilitate removal
of the salt formed.) The resin is washed with warm water, filtered
and dried at 150°C under vacuum. A thin film evaporator may be
used to remove last traces of solvent/water.
(2) Most Epoxy Resin Plants Have Similar Layouts And Equipment
Equipment layout for a typical resin plant is shown in
Exhibit VI-M. This exhibit is for the manufacture of solid resins.
A liquid resin plant would be essentially the same except there would
be no flaking equipment. Equipment requirements include a jacketed
steel or stainless steel reactor equipped with a reflux column, agita-
tor and condenser, a separator tank for washing the resin, a filter,
a finishing kettle for removing the last traces of solvent/water, a
Rodney-Hunt thin film evaporator may be alternate equipment, and a
flaker for solid resins.
(3) There Are Three Major flaw Materials Used
Between 80-90% of the epoxy resins produced are made from
Bisphenol A and epichlorohydrin. Sodium hydroxide is the other
major raw material used as a catalyst for the condensation and reacts
to dehydrohalogenate the resultant bisphenol glycidyl chlorhydrin
and is thereby removed from the reaction as salt.
-VI-66
-------
EXHIBIT VI-M
Environmental Protection Agency
FLOW SHEET:
EPOXY RESIN PRODUCTION (38)
^•- .. Ifc I -,1 ... - ... f— . .j
/S»iC«lO« »»*•'« \ Y I *CT *1*1'* \ I [ ItQOlO "till
I ilOn*OC 1 I STORAGE 1 iMr.Ti^c I S'O»*OE
V ' J \ /] =«n-\>
o—J ^-o^^..
VI-67
-------
2. THERE ARE SEVERAL POTENTIAL EMISSION SOURCES
In-plant emissions occur as a result of the manufacturing process.
Vapors can escape through reactor packings and pumps.
Vapors escape by way of the vacuum pumps on
distillation columns.
There is some entrainment of epichlorohydrin in
wash liquors.
Liquid from pumps.
Hot resin odor on flakers.
3. THERE ARE THREE PRINCIPAL EMISSIONS
Bisphenol A has a mild phenolic odor, b .p. = 220°C
(4mm) minimal odor /hazard.
Epichlorohydrin has a boiling point of 115°C and is
highly volatile, unstable and narcotic with a chloroform-
like odor. It is absorbed and accumulated by the body
and can lead to serious physiological, particularly nerve,
disorders.
Methanol has a boiling point of 64.5°C and is poisonous.
VI-68
-------
VI-N POLYAMIDES
Polyamide resins can be divided into two principal types; (1) Nylon
type, and (2) Non-nylon type. The former are primarily those based on
Nylon 6 and Nylon 66 and account for over 80% of polyamide resins produced.
The non-nylon resins are based primarily on dimerized polycarboxylic acids
and polyamines.
1. POLYAMIDE RESIN PROCESSES ARE HIGH TEMPERATURE, LOW
PRESSURE BATCH OR CONTINUOUS OPERATIONS
(1) Nylon 6 Involves Heating Caprolactam With A Catalyst And
Chain Terminator
Schematics for batch and continuous polymerizations are
shown in Exhibit VI-N1.
Molten caprolactam is mixed with water, catalysts, stabilizer
and delusterant (if fibers are to be made) and is fed into a reactor
which is operated at about 500°F. The mass slowly proceeds down
the reactor which is usually divided into several zones. The over-
all reaction is slightly exothermic and heat exchange is provided by
Dowtherm. The reactor effluent consists of molten polymer, monomer,
oligomers and water. Monomer and oligomer constitute 10-15% of the
reactor effluent.
There are two methods being used to purify the crude polymer
and recover unreacted polymer. In the first, the polymer is cast into
ribbon form, quenched and cut into chips. Unreacted monomer and
some oligomer are removed from the chips by extraction with hot water.
The water is sent to monomer recovery where the oligomers are de-
polymerized and the monomer is dehydrated and returned to the system,
The chips are dried and are then ready for melting and spinning or
bagging.
In the second method, the molten polymer exiting from the
reactor is sent to a vacuum distillation column where monomer, water
and oligomers are removed overhead. The molten polymer can then
be spun directly into fibers or cut into chips for bagging.
VI-69
-------
EXHIBIT VI-N1
Environmental Protection Agency
FLOW SHEET:
NYLON 6 PRODUCTION 139)
L1CMM
KILTER
Hated polymerization uf N \loix G.
Conlinnoiia polympnziilion of Nylon 6.
VI-70
-------
(2) Nylon 66 Is Made By Polymerization Of Nylon Salt
[hexamethylenediammonium adipate)
The polymerization can be either batch or continuous. A
typical plant and schematic is shown in Exhibit VI-N2.
Nylon monomer (nylon salt) is usually fed as a water suspen-
sion or homogeneous mixture to an evaporator where it is concentrated
to a 50-60% aqueous slurry by removal of water. This aqueous slurry
together with additives such as 0.5% by weight acetic acid as a chain
terminator (viscosity, m. wt. control), TiO? as a delusterant, are
pumped to an autoclave reactor. Here temperature is increased to
260°C - 2BO°C and pressure is allowed to build to 17 atm by
controlled venting of the steam produced from the condensation poly-
merization . Any water remaining after this point is reached is then
removed by lowering the pressure to atmospheric while maintaining a
constant temperature. The polymer (12,000 - 20,000 m.wt.) is a clear
melt which is removed from the reactor under nitrogen, cooled and
cast (palletized) quickly as it is not stable at high temperatures. The
solid nylon 6,6 resin is flaked or chipped and can then go to product
storage. These flakes can be remelted and spun into filaments or
molded to various shapes.
Continuous Process
A more recent development in nylon 6,6 manufacture is the
continuous process. The chemistry of this reaction is identical to the
batch process. However, where it may take 2-4 hours to convert nylon
salt to finished polymer in the batch process, monomer goes to polymer
in the continuous process in about 5 minutes.
Nylon salt solution is fed to a thin film evaporator at about
110°C. where the bulk of the water of solution is removed. Any addi-
tives needed are generally added after the evaporation stage and
these plus the dewatered monomer are fed to another thin film evapor-
ator held at 230°C and elevated pressure where the condensation
polymerization takes place and the water is removed as steam. Molten
polymer goes to a "flasher" at atmospheric pressure to remove more
water of condensation. The polymer may be put through a finishing
step at 280°C to be sure polymerization is complete or it may by-pass
this step. In any event the hot molten polymer goes directly to spin-
ning, drawing and beaming operations rather than cooling and casting
into resin as in the batch process.
VI-71
-------
EXHIBIT VI-N2
Environmental Protection Agency
FLOW SHEET:
NYLON 66 PRODUCTION <4t))
VENT (HjO!
Polymerization of Nylon 66.
VI-72
-------
(3) The Non-Nylon Polyamides Are Prepared By Condensing
Dimerized Polycarboxylic Acids With Polyamines
The process is a batch operation. Initial condensation is
conducted at 100°C until all water of reaction is distilled off. In-
crease the temperature to 150 ~ 250°C to advance the polymerization
to desired viscosity or molecular weight. The molten product is
packaged in metal containers directly.
(4) Soluble Polyamides Which Are Copolymers Of Nylon 6,
Nylon 66, And Nylon 610 Are Available.
These copolymers are usually available as solutions con-
taining water, alcohol (methanol, ethanol or isopropanol) or other
solvents. Solutions of 30-55% polyamides can be prepared.
2. THERE ARE SEVERAL POTENTIAL EMISSION SOURCES
The driers and surge tanks are principal sources of
emissions.
The vacuum lines are also potential sources of emissions.
3. EMISSIONS ARE MINIMAL
(1) Acetic Acid Is The Main Offender In Nylon 6 Production
This modifier could vaporize in the evaporator stage as well
as from reactor venting.
(2) Hexamethylene Diamine And Acetic Acid Could Be Emitted
In Nylon 66 Preparation
Hexamethylene diamine (ammoniacal odor) could come from
handling and on venting the blend tank.
VI-73
-------
SECTION VH
PRIORITY DECISION MODEL
-------
SECTION VII
PRIORITY DECISION MODEL
A decision model is a useful tool in establishing priorities among
the various sectors of the chemical/plastics industry with appropriate
weight given to each of the principal factors considered in formulating
and implementing air pollution control policy and defining the direction
of related research and development.
The model defined in this section assimilates the systems analysis
criteria of the study in a standardized fashion to enable the determination
of priorities and the selection of candidates for detailed study.
Exhibit VII-1 presents a summary of the required systems analysis
factors featured in the priority decision model. The detailed characteriza-
tion of each broad factor appears in subsections 2,3,4 and 5.
1. THE DECISION MODEL IDENTIFIES POLYURETHANES AND
ACRYLICS IN THE CHEMICAL/PLASTICS INDUSTRY AS
THE LEADING CANDIDATES FOR DETAILED STUDY
Exhibit VII-2 presents a summary of the priority decision model.
The overall selection index number ranges from a low of 23.3 to a high of
160.2. Within this range, the 14 chemical/plastics industry sectors
studied are well differentiated.
Polyurethanes with an overall selection index number of 160.2 and
acrylics with 137.3 are identified as candidates for detailed study.
Subsection 2 discusses the detailed derivation of the production and
population exposure related index in the model.
Subsection 3 discusses the detailed derivation of the total potential
emission index in the model.
Subsection 4 describes the derivation of the hazard index, while
subsection 5 describes the odor index.
VII-1
-------
EXHIBIT VII-1
Environmental Protection Agency
SUMMARY OF FACTORS IN THE
PRIORITY DECISION MODEL
Broad Systems Analysis Factors For
Each Chemical/Plastics Industry Sector
A:
Market and Production from
data in Section V
B:
Emission Potential from
information in Section VI
Hazard Potential from
information in Section VI
Odor Potential from
information in Section VI
Sub-Factor
Sub-Factors Weight
A^Total Potential 0.4
Population Exposed
A2=Population Exposure 0.2
Potential of the
Average Plant
A3=Plastic Production 0.2
Volume
A4=Production Growth 0.2
Trend
Process Technology 1.0
Assessment
Toxicity (TLV) 1.0
of Principal Likely
Emissions
Odor Threshold of 1.0
Principal Likely
Emissions
Priority Decision Formula
AC + BC + AD = R, where R is the overall rating
The formula has the following features:
The hazard factor, C, appears twice as a multiplicant and
is given significant emphasis, as required by EPA
The product of A x C emphasizes situations where the hazard
potential is high and the potential population exposure is great
The product of B x C emphasizes situations where hazard
potential and emission potential are high and, therefore, the
relative magnitude of potential concentrations of hazardous
substances at receptor locations are factored in qualitatively
The product of A x D emphasizes the relative magnitude of the
potential nuisance to the population from odorous substances
Source: Snell (and EPA and Snell in development of priority decision formula)
VII-2
-------
EXHIBIT VH-2
Environmental Protection Agency
SELECTION OF PLASTICS SECTORS
FOR DETAILED STUDY
Selection formula:
G
i
co
Plastic
Production 8
Population
Exposure
Related Index
Number
AC + BC + AD = R
B
Emission
Potential
Index
Number
Vinyl Resins 10.0
Styrene Resins 8.5
Acrylics 8.5
Alkyds 8.0
Polyurethanes 8.0
Phenolic and Other Tar
Acid Resins 7.5
Polyethylene and
Copolymers 6.5
Polyesters 6.5
Amino Resins 6.5
Cellulosics 6.0
Polyamides 5.5
Polypropylene 5.0
Coumarone-Indene and
Petroleum Resins 5.0
Epoxy Resins 3.5
7.0
7.4
5.0
4.8
2.6
4.0
8.0
4.8
5.3
6.7
7.0
8.8
7.1
4.2
Hazard
Index
Number
2.8
4.5
6.6
9.3
5.2
1.3
6.6
4.8
3.5
1.2
1.7
4.2
5.4
D
Odor
Index
Number
2.3
7.4
9.0
5.0
7.7
6.9
2.5
5.3
6.8
4.3
1.5
1.9
7.7
4.1
Overall
Selection
Index
Number
91.0
107.4
137.3
124.5
160.2
111.6
35.2
109.1
100.8
70.3
23.3
33.0
89.3
56.0
Priority
Order
8
6
2
3
1
4
12
5
7
10
14
13
9
11
I1) Based on 50 ppm TLV for vinyl chloride
Source: Snell
-------
2. THE PRODUCTION AND POPULATION EXPOSURE RELATED
INDEX WAS DEVELOPED CONSIDERING TOTAL POTENTIAL
POPULATION EXPOSED. POPULATION EXPOSURE POTENTIAL
OF THE AVERAGE PLANT. PLASTIC PRODUCTION VOLUME
AND GROWTH TREND
To develop the production and population exposure related index,
Column A in Exhibit VII-2, a decision matrix approach was used.
A decision matrix can be depicted as a rectangular grid containing
values for a specific set of co-ordinates. In this case, the vertical co-
ordinate contains the plastics under consideration, and the horizontal co-
ordinate lists the variables under consideration. This matrix is shown
in Exhibit VII-3.
(1) The Population Exposed To Potential Emissions From
The Manufacture Of Each Plastic Was Estimated Using
SMS A And State Population Densities
In developing a population exposure index, we considered
the average population per square mile for the major Standard
Metropolitan Statistical Areas (SMSA's) with which each plant
location could be identified or the average population per square
mile for the state with which each plant could be identified, if no
SMSA correlation was apparent. The U.S. Department of Commerce's
Statistical Abstract of the United States, 1972, was the source of
these data.
Production locations for each resin, regardless if there were
more than one resin manufactured at this site, were located by SMSA
and/or state using the information from Section V. The number of
plant locations, or establishments listed is, therefore, significantly
more than that given by the Bureau of Census.
The total potential population exposed for each resin was
estimated by the following procedure:
assume that the area of influence of each plant is
one square mile
correlate each plant location with an SMSA
VII-4
-------
EXHIBIT VH-3
Environmental Protection Agency
DEVELOPMENT OF THE PRODUCTION
AND POPULATION EXPOSURE RELATED
INDEX
1-4
a
Ol
Plastic
Total
Potential
Population
Exposed
Polyethylene and
Copolymers 2
Vinyl Resins 8
Styrene Resins 6
Polypropylene 2
Phenolic and Other
Tar Acid Resins 8
Polyesters 6
Amino Resins 8
Alkyds 10
Acrylics 8
Coumarone-Indene and
Petroleum Resins 4
Polyurethanes 8
Cellulosics 4
Epoxy Resins 2
Polyamides 4
Rosin Modifications 6
Population
Exposure
Potential of
the Average
Plant
1
3
3
1
2
2
1
4
3
4
3
5
2
2
3
Plastic
Production
Volume
5
4
3
2
1
1
1
1
1
1
1
1
1
1
1
Growth
Trend
5
5
5
5
4
4
3
1
5
1
4
2
2
4
1
Total
Score
Index
13
20
17
10
15
13
13
16
17
10
16
12
7
11
11
6.5
10.0
8.5
5.0
7.5
E.5
6.5
B.O
8.5
5.0
8.0
6.0
3.5
5.5
5.5
1 - Total Score normalized on a scale of 10. See Exhibit VE-2 for use of index
Source: Snell
-------
sum the average population per square mile for each
plant associated with an SMSA or if a plant is not
associated with an SMSA use the average population
per square mile for the state in which each plant is
located.
Values for the total potential population exposed for each resin
are tabulated in decreasing order in Exhibit V-4, and scoring values
of 2 to 10 are based on total population exposed as follows:
Score 2 = less than 15,000
Score 4 = 15,000to50.000
Score 6 = 50,001toiOO,000
Score 8 = 100,001to200,000
Score 10 = over 200,000
(2) The Population Exposure Potential Of The Average Plant
Indicates To What Extent Each Plastic Producing Industry
Is Located In Densely Populated Areas
The population exposure potential of the average plant in each
plastic manufacturing category is estimated by dividing the total
potential population exposed by the number of plants. Values for
the population exposure potential of the average plant in each plastic
manufacturing category are tabulated in decreasing order in Exhibit
VII-5, and are scored from 1 to 5 as follows:
Score 1 = less than 500
Score 2 = 500 to 1,000
Score 3 = 1,001 to 1,500
Score 4 = 1,501 to 2,000
Score 5 = over 2,000
Plastic categories appearing at the top of the list represent
relatively urban industries in terms of plant sites while those to-
ward the bottom of the list represent relatively rural siting.
(3) The Total Volume Of Plastic Production Is A Factor
Broadly, the greater the volume of resin produced, the
greater the odor or hazard potential, particularly if differences in
production volumes are large. The percent volume production is
shown in Exhibit V-4. These values are scored from 1 to 5 and are
entered under Column A3, Plastic Production Volume, in Exhibit VH-3.
VII-6
-------
EXHIBIT VII-4
Environmental Protection Agency
TOTAL POPULATION EXPOSURE
MEASURE
Number of
Resin System Plants
Alkyds 173
Vinyl Resins 153
Amino Resins 166
Phenolic and Other Tar
Acid Resins 168
Acrylics 127
Pplyurethanes 86
Rosin Modifications 64
Polyesters 81
Styrene Resins 65
Coumarone-Indene and
Petroleum Resins 20
Cellulosics 8
Polyamides 24
Polyethylene and Copolymers 25
Epoxy Resins 8
Polypropylene 11
Total Potential
Population Exposed
264,500
171,800
164,800
164,600
150,100
122,200
90.800
78,200
74,200
30,200
20,900
18,700
11,500
7,800
3,200
1,2
Score*
10
8
8
8
8
8
6
6
6
4
4
4
2
2
2
Assuming the area of potential exposure per plant is one square mile
Weighted Average Population Exposed for a given Resin System =
/ Plant \
| Location/
PlantN
Location/
/Average Population per Square Mile\ +
\ associated with location i in SMSA /
/Average Population per Square Mile in State associated \
\ with j _if correlation with SMSA is not possible /
See Exhibit VII-3, Colume Aj for use of scores to indicate total potential
population exposed.
Source: Information in Section V and Snell estimates
VH-7
-------
EXHIBIT VII-5
Environmental Protection Agency
THE POPULATION EXPOSURE POTENTIAL
OF THE AVERAGE PLANT
Weighted Average
Population Exposure
Resin System Index Per Plant Per Square Mile Score
Cellulosics 2,620 5
Alkyds 1,530 4
Coumarone-Indene and
Petroleum Resins 1,510 4
Polyurethanes 1,420 3
Rosin Modifications 1,420 3
Acrylics 1,180 3
Styrene Resins 1,140 3
Vinyl Resins 1,120 3
Phenolic and Other Tar Acid Resins 980 2
Epoxy Resins 970 2
Polyesters 965 2
Polyamides 980 2
Polyethylene and Copolymers 460 1
Polypropylene 290 1
Amino Resins 100 1
Total Potential Population Exposed -j- Number of Plants,
shown in Exhibit VII-4
o
See Exhibit VII-3, Column A2, for use of scores to indicate
the population exposure potential of the average plant
Source: Snell
VIl-8
-------
Score 1 = less than 6.2% of total production
Score 2 = 6.2% to less than 12.4% of total production
Score 3 = 12.4% to less than 18.6% of total production
Score 4 = 18.6% to less than 24.8% of total production
Score 5 = 24.8% of total production or greater
(4) Growth Rate And Need For Additional Capacity Is A
Factor Related To Future Production
The average rate of consumption over the near future will
determine if new capacity will be required. Exhibit V-l summarizes
the outlook for the resins studied through 1977, assuming normal
trends, that is, there will be no impact upon growth from the current
shortages of raw materials.
Scores from 1 to 5 were assigned as shown below and entered
under Column A4, Growth Trend, of Exhibit VII-3.
Score 1 = negative growth rate or no growth
Score 2 = less than 5% growth rate and capacity adequate
Score 3 = less than 5% growth rate and new capacity
will be needed or 5-10% growth rate and
capacity adequate
Score 4 = 5-10% growth rate and new capacity will be
needed or greater than 10% growth rate and
capacity adequate
Score 5 = greater than 10% growth rate and new capacity
will be needed
3. THE EMISSION POTENTIAL INDEX WAS DEVELOPED FROM
STANDARDIZED EVALUATION AND COMPARISON OF THE
MAJOR POLYMERIZATION PROCESSES
To develop the emission potential index a decision matrix approach was
used, and is described below.
Polymer plants operate under widely differing conditions. It is still
possible, however, to consider certain operating functions common to all
plastic processes. These are:
Receiving and storage of process chemicals
Purification of monomers and solvents
VII-9
-------
Prepolymerization
Polymerization
Polymer separation
Compounding.
Each of the above functions will, to some degree, contribute to the
total emissions of a process. Individually, each can be rated on the basis
of a very high (10) to a very low (2) emission potential related to the variable
factors of process design, operating conditions and the chemistry involved.
It is also understood, that the emission contribution of each factor may be
different and must be weighed to reflect its relative importance to the total
emission potential of the process. The sum of the values obtained (intensity
rating times percent of total contribution) will represent the best relative
estimate of the emission potential for that plastic process. Repetition of this
analysis for all the plastic processes will produce a series of index numbers
which can be compared on the basis of seriousness of potential emissions.
For example, the emission potential, during storage of a liquified gas
may be very high (rating of 10); during polymerization, the emission potential
may be low (rating of 4). But, the relative emission contribution from storage
may only be 10% as compared to polymerization of 90%, so that the total emission
potential is the sum of (10 x 0.1) plus (4 x 0.9) or 1 plus 3.2 or a total of 4.2.
Exhibit vn-6 shows the decision matrix used for process screening.
The vertical co-ordinate lists the factors under consideration, and the hori-
zontal co-ordinate indicates the emission ratings assigned, based on the oper-
ations within each phase.
Manufacturing processes range from very complex to rather simple
procedures, and from single large operating units to small multi-batch units.
For the purpose of this evaluation, all processes were considered in their
simplest unit operations.
Appendix 2 presents the technical evaluation grids for each plastic
class. A summary listing of the results ranked according to total emission
potential is shown in Exhibit VII-7.
VII-10
-------
EXHIBIT VII-6
Environmental Protection Agency
DECISION MATRIX FOR EMISSION
POTENTIAL
^^v^^ EMISSION/ODOR
^POTENTIA L
OPERATING FUNCTION^^^^
RECEIVING, STORAGE AND
HANDLING OF PROCESS
CHEMICALS
PURIFICATION OF MONOMER
AND
SOLVENTS
PREPOLYMERIZATION
POLYMERIZATION
POLYMER SEPARATION
COMPOUNDING
VERY
HIGH
(10)
gases or
liquified gases
Venting of monomer
and solvent
purification systems
Pressure over 70
atm and above the
b.p. of ingredients
Polymer injected
into solvent or water,
filtered, dried and
extruded
Direct casting or
molded
HIGH
(8)
Liquids with high
vapor pressure
(over 25 mm Hg)
Venting of monome
purification
system
Pressure between
10-70 atm and
above the b.p. of
ingredients
Reaction mass
dried and
extruded
Partial polymer-
ization or " B"
staging
MEDIUM
(6)
Liquids with low
vapor pressure
: Venting of solvent
purification
system
Premixing of gaseou
monomers with
catalyst and pre-
>olymerization
Pressure below 10
atm and above the
b.p. of ingredients
Reaction mass
dissolved in
solvent
Mixing with
volatile solvents
and plasticizer
LOW
(4)
Solids with high
vapor pressure
(over 25 mm Hg)
Mixing of monomer
with solvent
compressing gases
Atmospheric pressure
and reflux temp.
Reaction mass
dispersed in
water
Mixing with solids
and making molding
compounds
VERY
LOW
(2)
Solids with low
vapor pressure
Mixing of monomer!
with water
melting solids
Atmospheric pressure
and below the b.p
of ingredients
Reaction mass
stored directly
Source- Snell
-------
EXHIBIT VII-7
Environmental Protection Agency
TOTAL POTENTIAL EMISSION
INDEX
6
Plastic Index Number
Polypropylene 8.8
Polyethylene1 and Copolymers 8.0
Styrene Resins 7.4
Coumarone-Indene and Petroleum Resins 7.1
Vinyl3 Resins 7.0
Poly amides^ 7.0
Cellulosics 6.7
Amino Resins 5.3
Acrylics5 5.0
Alkyds 4.8
Polyesters 4.8
Epoxy Resins 4.2
Phenolic and Other Tar Acid Resins 4.0
Polyurethanes 2.6
1. 70% LD and 30% HD Polyethylene
2. 76% Polystyrene and 24% ABS
3. 94% PVC, 5% PVAc and 1% PVAlc
4. 80% Nylon 66 and 20% Nylon 6
5. 50% Emulsion and 50% Solution
6. See Exhibit VII-2 for use of the index
Source: Snell, details in Appendix 2
VII-12
-------
(1) Receiving And Storage Of Process Chemicals (Monomers,
Solvents, Catalysts) Is A Source Of Emissions
Emissions originating from storage facilities are dictated, to
a large extent, by the physical and chemical characteristics of the
raw materials used in the process. Most of the emissions are due
to venting of storage tanks, line and valve leaks and spillage during
handling. Ratings in terms of potential emissions can range from
very high (10) to very low (2) as follows:
10 - gases or liquified gases
8 - liquids with high vapor pressure (greater than
25 mmHg (25°C))
6 - Liquids with low vapor pressure
4 - solids with high vapor pressure (greater than
25 mm Hg (25°O)
2 - solids with low vapor pressure
(2) Purification Of Monomers And Solvents Can Be A Potential
Source Of Emissions
While most monomers and solvents are available commercially
in relatively pure states they may contain trace impurities which must
be removed to avoid adverse effects on the polymerization reaction, or
they may contain inhibitors which are added to prevent polymerization
in transit or storage. Whatever the source of impurity, monomers and
solvents must be properly purified when necessary.
In many processes, monomer and solvents are removed from
the polymerization and are purified and recycled. Purification usually
takes the route of condensation and redistillation. In most instances
emissions originate from condenser vents and line leakage. Ratings
in terms of potential emissions can range from very high (10) to medium
(6) as follows:
10 - Venting of solvent and monomer purification systems
8 - Venting from monomer purification system
6 - Venting from solvent purification system
VII-13
-------
(3) Another Emission Source Is In The Preparation Or
Prepolymerization Phase
Chemicals and catalysts may be diluted, premixed, aged,
ground or otherwise treated before polymerization. While some of
these processes can be carried out in separate vessels, reactors or
tanks, they may also be carried out directly in the reactor before
polymerization. The emission potential may range from medium (6)
to low (2) as follows:
6 - premixing of gaseous monomers with catalyst and
prepolymerizing
4 - mixing of monomers with solvent
- compressing gases
2 - mixing of monomers with water
- melting solids
- preheating liquids
Emissions can occur as a result of leaks and purging and
venting of prepolymerization equipment.
(4) The Polymerization Section Is A Prime Source Of Emissions
There are many conditions and combinations of conditions in
which polymerization takes place. Polymerization methods include
bulk, solution, suspension and emulsion. Operating conditions can
range from very high temperatures and/or pressures to low pressure
and ambient or cooler temperatures. The polymerization can be con-
tinuous or batch or may even start as one type and end as another, i.e.,
nylon 66 polymerization starts as a solution and at the end is essentially
a bulk polymerization.
Nevertheless, certain generalities must be assumed in order to
evaluate the emission potentials of this phase of the process. As would
be expected, the emission potential can range from very high (10) to
very low (2). Emissions occur through reactor venting agitator packing,
piping and valve leaks, condenser venting and/or reactor leaks. Ratings
are as follows:
10 - Pressure and temperature above 70 atm and the boiling
point (at 760 mm) of the ingredients respectively
8 - Pressure and temperatures of 10-70 atm and the boiling
point (at 760 mm) of the ingredients respectively
6 - Pressure and temperature below 10 atm and above the
boiling point (at 760 mm) of the ingredients respectively
4 - Atmospheric pressure and reflux temperature
2 - Atmospheric pressure and temperature below the boiling
point (at 760 mm) of the ingredients respectively.
VII-14
-------
(5) Many Operations Can Be Involved In The Separation Of
Polymers From The Reaction Mass
This section of the total polymerization process can range from
a single operation to a combination of operations culminating in pro-
duction of a solid or liquid product, the former being essentially a
"pure polymer" and the latter being a polymer in a solution or emulsion
form.
Emissions can occur in any single or combination
of several operations. Operations most commonly
used include:
Precipitation
Dilution with solvent or water
Extrusion
Flaking
Drum drying
Spray drying
Various materials handling operations.
All operations contribute to total emissions and the
intensity range can vary from very high (10) to very
low (2).
10 - Polymerization mass injected into water or
solvent, filtered, washed, dried and extruded
8 - Polymerization mass dried and extruded
6 - Polymerization mass is dissolved in solvent
4 - Polymerization mass is dispersed in water or
solvent
2 - Polymerization mass packaged directly.
(6) In Some Cases Further Compounding Within The Chemical/
Plastics Industry Should Be Considered
While the primary function of the Chemical/Plastics Industry is
the manufacture of plastics, the market is such that many of the major
plastics must be compounded further. This operation can contribute
to emissions, and can include any one or a combination of operations
including remelting, extruding, grinding, milling, spray drying and
other drying operations.
VII-15
-------
Emissions result from drier exhaust gases, extruder
exhausts. monomer or low molecular weight polymer evapor-
ation , decomposition of the plastic during the operation, solvent
addition or removal of residual solvent from previous operations,
and others. Emission potential can range from very high (10)
to low (4).
10 - Direct casting or molded
8 - Partial polymerization or "B" staging
6 - Mixing with volatile solvents and plasticizers
4 - Mixing with solids and making molding compounds
(7) Assignment Of Intensity Ratings Must Be Flexible
The intensity ratings assigned to the various process
factors, discussed in the previous section are based on the
observation that there are many operations and operating con-
ditions common to several processes. There are, of course, many
others that do not fall into any of these classifications, and arbit-
rary ratings, based on expert opinion, must be assigned to them.
Secondly, detailed data on emission factors may shift the ratings.
4. THE HAZARD POTENTIAL INDEX EXPRESSES THE SEVERITY
OF THE HUMAN EXPOSURE HAZARD ASSOCIATED WITH THE
PRINCIPAL POTENTIAL PLANT EMISSIONS
Toxic hazard is determined from the concentration, measured in
parts of volume of a gas or vapor per million parts by volume of air, below
which ill effects are unlikely to occur to an exposed worker (during an eight-
hour working day). This concentration is the threshold limit value (TLV)
for each chemical. The population in the vicinity of a producing plant is
potentially exposed to the emissions from this plant. The TLV concentrations
are a useful index of the relative hazardousness of the chemicals to which
the surrounding populations could be exposed. TLV values provide a
standardized comparison base, and this data is generally available.
The hazard index rating is based on the approach expressed in
Table G-12 (Determination of Hazard Potential) published in the Federal
Register, 36, No. 105, page 10515, May 29, 1971. This table rates the
hazard potential on a scale from A to D, as follows:
A - TLV at a level of 0 - 10 ppm
B - TLV at a level of 10.1 - 100 ppm
C - TLV at a level of 101 - 500 ppm
D - TLV over 500 ppm
VD-16
-------
We have refined this scale to enable sensitive differentiation between
the hazard potential of each plastic sector, and to account for the fact that
ambient concentrations are likely to be significantly lower than the work
place concentrations addressed by TLV's. The hazard scoring used in this
study follow:
Score 10 - TLV is 0.02 ppm or less
Score 9 - TLV is 0.1 ppm or less but greater than 0 .02 ppm
Score 8 - TLV is 1.0 ppm or less but greater than 0.1 ppm
Score 7 - TLV is 2.0 ppm or less but greater than 1.0 ppm
Score 6 - TLV is 5.0 ppm or less but greater than 2 .0 ppm
Score 5 - TLV is 25 ppm or less but greater than 5.0 ppm
Score 4 - TLV is 75 ppm or less but greater than 25 ppm
Score 3 - TLV is 150 ppm or less but greater than 75 ppm
Score 2 - TLV is 400 ppm or less but greater than 150 ppm
Score 1 - TLV is greater than 400 ppm
Appendix 3 identifies the most likely emittants from each process
with safety data when available.
Determination of the hazard potential index for most probable emissions
in each plastic group is shown in Appendix 4 . For the manufacture of each
resin the chemical species most likely to be emitted are identified. A "factor
weight" is assigned to each species reflecting its potential importance as an
emittant. For each species identified with a given process, its factor weight
is multiplied by its hazard rating. The products are summed to provide a
hazard index number for the process.
Exhibit VII-8 summarizes hazard index number by resin category.
5. THE ODOR POTENTIAL INDEX IS BASED ON DETECTABILITY
There have been several attempts to describe odor sensations. The
best known classification is that whereby odors are classified as spicy,
flowery, fruity, resinous, foul and scorched. This classification is depen-
dent upon memory and association and few odors can be associated directly
with any of these specific adjectives.
We, therefore, elected to use the Odor Threshold (OT). This is the
concentration at which a trained person can first detect an odor. We are
not considering the intensity nor the classification of odors. Ratings for
odor threshold range from 10 for products which can be detected at very low
concentrations to 1 for products which are noticeable only at very high con—
centrations. The odor ratings are based on the same scale as used for ex-
pressing hazard potential.
VII-17
-------
Rating 10 - OT is 0.02 ppm or less
Rating 9 - OT is 0.1 ppm or less but greater than 0.02 ppm
Rating 8 - OT is 1.0 ppm or less but greater than 0.1 ppm
Rating 7 - OT is 2.0 ppm or less but greater than 1.0 ppm
Rating 6 - OT is 5.0 ppm or less but greater than 2.0 ppm
Rating 5 - OT is 25 ppm or less but greater than 5.0 ppm
Rating 4 - OT is 75 ppm or less but greater than 25 ppm
Rating 3 - OT is 150 ppm or less but greater than 75 ppm
Rating 2 - OT is 400 ppm or less but greater than 150 ppm
Rating 1 - OT is greater than 400 ppm
Appendix 3 identifies the most likely emittants from each process
with their respective odor threshold values when available.
Determination of the potential odor index for each plastic appears in
Appendix 4. The same methodology was used as for developing the hazard
indices, described under subsection 4 above.
Exhibit VII-9 summarizes odor index number by resin category.
The section that follows presents more detailed information regarding
polyurethanes, acrylics, alkyds, high volume resins and emission control
technology.
VH-18
-------
EXHIBIT VII-8
Environmental Protection Agency
HAZARD POTENTIAL INDEX
6
Plastic Hazard Index Number
Polyurethanes 9.3
Alkyds 6.6
Polyesters 6.6
Epoxy Resins 5.4
Phenolic and Other Tar Acid Resins 5.2
Amino Resins 4.8
Acrylics1 4.5
Coumarone-Indene and Petroleum Resins 4.2
Vinyl Resins 4.0
Cellulosics 3.5
Styrene Resins3 2.8
Polypropylene 1.7
Polyethylene and Copolymers 1.3
Polyamides5 1.2
1. 50% Emulsion and 50% Solution
2. 94% PVC, 5% PVAc and 1% PVAlc
3. 76% Polystyrene and 24% ABS
4. 70% LD and 30% HD Polyethylene
5. 80% Nylon 66 and 20% Nylon 6
6. See Exhibit VII-2 for use of the index
Source: Snell, details in Appendices 3 and 4
VII-19
-------
EXHIBIT VII-9
Environmental Protection Agency
ODOR POTENTIAL INDEX
Plastic Odor Index Number
Acrylics 9.0
Polyurethanes 7.7
Coumarone-Indene and Petroleum Resins 7.7
Styrene Resins2 7.4
Phenolic and Other Tar Acid Resins 6.9
Amino Resins 6.8
Polyesters 5.3
Alkyds 5.0
Cellule sic s 4.3
Epoxy Resins 4.1
Polyethylenejtnd Copolymers 2.5
Vinyl Resins 2.3
Polypropylene 1.9
Polyamides 1.5
1. 50% Emulsion and 50% Solution
2. 76% Polystyrene and 24% ABS
3. 80% Nylon 66 and 20% Nylon 6
4. 70% LD and 30% HD Polyethylene
5. 94% PVC, 5% PVAc and 1% PVAlc
6. See Exhibit VII-2 for use of the index
Source: Snell, details in Appendices 3 and 4
VII-20
-------
SECTION VIH
IN-DEPTH STUDIES
-------
SECTION VIII
IN-DEPTH STUDIES
This section discusses in detail
The three chemical/plastics industry processes
identified by the priority decision model with the
highest priority ranking
polyurethanes
acrylics
alkyds
Emission quantification and control techniques for
some high volume resins
General control technology and costs.
These five topics constitute the subject matter for respective chapters
in this section.
VIII-1
-------
VHI-A POLYURETHANES
Polyurethanes are produced by reacting a polyisocyanate with di- or
polyfunctional hydroxyl compounds. Of interest to this study are those poly-
urethane products falling within the category of the chemical/plastics industry,
SIC 2821. Polyurethane foams, both rigid and flexible, are outside the scope
of this study, although the manufacture of some of the intermediates used to
make foam falls within this category.
1. POLYURETHANE RESINS FALLING IN THE CATEGORY OF
CHEMICAL/PLASTICS INDUSTRY ARE PRINCIPALLY
PREPOLYMERS
Polyurethane polymers are used in a large number of applications
including surface coatings (see Exhibit VI-K2), and intermediates in the
manufacture of foams, adhesives, sealants and elastomers. These polymers
are classified as either non-reactive (contain no free isocyanate groups) or
reactive (contain unreacted or "blocked" isocyanate groups) which will react
further with active hydrogens. This latter category included the prepolymers
which are the most important products falling within the scope of this study.
2. THE PRODUCTION PROCESSES FOR MAKING THE VARIOUS
PREPOLYMERS ARE SIMILAR AND ARE LOW TEMPERATURE.
BATCH PROCESSES
Three types of bonding encountered in polyurethane prepolymer manu-
facture are (1) biuret branching, (2) allophanate branching, and (3) urethane
branching. However, from the processing standpoint, these chemical classi-
fications do not represent significantly different processes, since during
manufacture all three can (and do) occur simultaneously.
Production is carried out as batch operations involving reactors
ranging in size from a few hundred to a few thousand gallons. Reactions are
carried out at or near atmospheric pressures under a nitrogen blanket at
temperatures ranging from 70°C - 120°C. Cycle time may vary from a few
hours to about 24 hours. Exhibit VIII-A 1 presents a process flow sheet
characteristic of a biuret branching operation. Exhibit VIII-A2 shows a
slightly different method of preparation.
VIH-2
-------
Biuret Type Branching
EXHIBIT VIII-A 1
Environmental Protection Agency
POLYURETHANE PREPOLYMER
PROCESS FLOW SHEET
Glycol 100 parts
Water 0.4 part
WATER ADDITION
30 rain. 35-40°C.
TDI
(NCO/OH ratio
1.25/1.0)
(NCO/H O ratio
1.0/1/0)
I
EXOTHERMIC REACTION
fzSQmin. 40-100°C.
HEATED REACTION
90 min . 120°C .
COOLING
min . 80°C .
TDI
(to 9.5%NCO)
PREPOLYMERIZATION
60min. 80-100°C.
I
COOLING AND DRUMMING
£r 120 min. to ambient
Note: N_ blanketing in each step
Source: Snell and confidential industry sources
VIII-3
-------
EXHIBIT VHI-A2
Environmental Protection Agency
POLYURETHANE PREPOLYMER
PROCESS FLOW SHEET
Isocyanate
(TDI - MDI)
Polyhydroxy
Compound
ISOCYANATE
HEATING
1 Hr.
50-70°C
REACTION
2-5 Hr.
70-90°C
COOLING
IHr.
20-25°C
DRUMMING
Vacuum
.N,
Cool to Maintain
Temperature
Vent to TDI
^Scrubber
Source: Snell and confidential industry sources
VIH-4
-------
An equipment diagram is presented in Exhibit VIII-A3. This equip-
ment would not change radically from plant to plant, except that nitrogen
sparging throughout the reaction may be used, particularly in older plants.
Normal operating procedure is to purge the reactor with nitrogen to
remove air and moisture. The TDI or other isocyanate is added to the reactor
and the mass heated to 50-70°C and the polyhydroxy compound added with the
temperature maintained between 70-90°C until reaction is complete. The pre-
polymer is then cooled and drummed.
The bulk (90%) of the prepolymers produced is based on three iso-
cyanates: (1) toluene diisocyanate (TDI); (2) methylene diphenylisocyanate
(MDI) , and; (3) polymethylene polyphenylisocyanate (PMPPI) . TDI probably
accounts for 70% and MDI accounts for about 25%, but its use is growing. PMPPI
is reserved for special applications.
3. EMISSIONS FROM POLYURETHANE PREPOLYMER MANUFACTURING
AMOUNTS TO ABOUT 3 x 10~7 POUNDS PER POUND OF PREPOLYMER
PRODUCED
A theoretical emission of TDI or MDI from a prepolymer manufacturing
plant having no emission control equipment can be estimated. The prime
source of emission would be associated with displacement of the nitrogen in
the reactor by TDI or MDI during reactor charging. Under the worst condi-
tion the isocyanate would be charged to the empty reactor at about 25°C. At
this temperature TDI has a vapor pressure of 0.02 mm Hg. The equilibrium
concentration of TDI in the nitrogen atmosphere would be 200 ppm. Then,
for a 5,000 gal reactor, filled with 4,000 gal of TDI the vented TDI would
amount to 0.01 Ib or 3 x 10 Ibs per Ib of prepolymer produced.
(1) Emission Control Equipment Is Built In The Reactor Design
As shown in Exhibit VIII-A 3, the reactor vent line is connected
to a vacuum system equipped with a reflux condenser and a cold trap.
The temperature of this cold trap is maintained at about -18°C by an
ethylene glycol brine which reduces the vapor pressure of the TDI to
about 0.006 mm Hg. Under this condition, no measurable emission to
the atmosphere takes place. In fact, the system is designed to prevent
contamination of the vacuum pump oil with TDI.
VHI-5
-------
EXHIBIT VIII-A3
Conservation
Valve
N2
8
r*
I Wei
I *•'
Isocyanate
Weigh Tank
000 gal
Water
Drain
Vent
Catalysts
Accelerators
Modifiers
Alcohol
i Tank
.DOO gal
5,000 gals
Environmental Protection Agency
EQUIPMENT FLOW SHEET FOR
POLYURETHANE PREPOLYMER
MANUFACTURE
Iter
\rv
t
RE A
^
,, r~"
\
C TOR
*s
x Ste
Scrub
Tow
Cold
Trap
-18°C
Condenser
Water
Scrubbed Vent
Vent
Drum
Spent
Caustic
Vac
Pump
Pressure
Regulating
Valve
Operating Conditions
Pressure = Atmospheric to 50 mm Hg.
Temperature = Room to 90°C
Cycle Time = 4-24 Hours
Source: Snell and confidential industry sources
Vln-6
-------
(2) Isocyanate Storage Tanks Are Equipped With Conservation
Valves And Vented Through Scrubbers
TDI can be stored in tanks of up to 80,000 gal capacity. These
tanks are equipped to "breathe" through the conservation valves
which in turn are vented to antipDilution devices.
Conservation valves are devices which minimize the "breathing"
of tanks due to temperature variations. They are loaded port valves
operating at positive pressures of a few torr and negative pressures
of few centimeters of water.
During bulk transfers and shipment, the atmosphere of the
receiving vessel is connected to that of the delivery vessel, thus
avoiding discharge to the atmosphere.
Vent streams containing isocyanates are routed through caustic
scrubbers having removal efficiencies of over 99.9%. The scrubbers
are either packed with suitable material (generally polypropylene
intalox saddles or pall rings) or venturi-type scrubbers. Both of
these systems are usually operated with recycle of a weak caustic
solution (5-10%). Emissions are monitored.
(3) More Elaborate Emission Control Systems Are Used Where
Prepolymers Are Produced At Monomer Manufacturing Plants
Where prepolymers are made at monomer production plants,
vent streams are tied into the emission control systems required for
isocyanate control.
In addition, compliance with OSHA requirements and aware-
ness of internal hazards involved insure a minimization of the occur-
rence and the effects of accidental (episodal) emissions. Availability
of maintenance crews is also a factor in reducing the occurrence and
effects of fugative emissions, from valves, pumps, seals, etc.
4. THE USE OF PREPOLYMERS OUTSIDE THE CHEMICAL/PLASTICS
INDUSTRY PROPER MAY BE A MORE SIGNIFICANT SOURCE OF '
AIR POLLUTION
The major share of the prepolymers produced is confined to a few
plants operated by large sophisticated producers of monomers. These
plants are well equipped with antip Dilution devices.
VIII-7
-------
Industry sources are unanimous at expressing concern over the poten-
tial pollution hazard in value added operations downstream. The final
production of consumer goods or end-use products from polyurethanes are
often carried out in comparatively small unsophisticated installations. Of
particular significance is the area of "foamed-in-place" heat insulation.
Direct monomer handling from drums is often involved and in spite of manu-
facturer's warnings and instructions, less than ideal usage conditions often
prevail.
However, these industries fall outside the scope of this study but we
feel that specific investigation of this area seems warranted. Polyurethane
foam fabricators are listed under SIC 3079. Their number is orders of mag-
nitude larger than those of TDI or SIC 2821 polyurethane producers.
Vin-8
-------
SECTION VIII-B
ACRYLICS
1. EMULSION, SUSPENSION. SOLUTION AND BULK POLYMERIZATION
SYSTEMS ARE USED COMMERCIALLY TO PREPARE ACRYLIC RESINS
(1) Emulsion Polymerization Is Widely Accepted And Is A
Low Temperature Batch Operation
This is the most useful industrial method for the preparation of
polymers of acrylic esters. The principal reasons are the economy
and safety of water as a polymerization medium, the ease of tempera-
ture control, the speed and completeness of reaction and the conven-
ience of application of the polymer as an aqueous dispersion. At
concentrations of 30-50% the aqueous dispersions obtained by emulsion
polymerization have relatively low viscosities, whereas solutions of
polymers of equivalent molecular weight are often too viscous to handle.
There are two ways in which the polymerization can be conducted.
Using the first method (redox) , all the reactants are stirred together
in the reactor and heated until polymerization is complete. This is
practical as long as the heat of polymerization can be removed adequately
during the reaction. In extremely exothermic polymerizations, as with
the lower acrylates, adequate control of the temperature by this batch
polymerization is extremely difficult and the operation is hazardous.
This danger can be avoided by using the second method (reflux) in
which only a small portion of the monomer is present initially in the
reaction vessel, the remainder being held separately to be added grad-
ually after polymerization has been started with the initial charge.
The rate of addition is adjusted to permit the removal of the heat of
polymerization.
In redox polymerization the reactor is first flushed with an
inert gas such as nitrogen or carbon dioxide to remove any oxygen
present, and this blanket is maintained throughout the polymerization.
With the agitator rotating, the water, emulsifiers and monomer (s) are
added. Then initiators (persulfates), reducing agents (bisulfite,
thiosulfate, hydrosulfite, etc.) and activator (ferric ammonium sulfate)
are added. After a brief induction period, the temperature will rise
to 85-95°C and the reaction is 99-100% complete within 15-30 minutes.
VIH-9
-------
It is desirable to remove unconverted monomers, and stripping is
accomplished by post-heating at temperatures and pressures con-
sistent with the stability and foaming tendency of the emulsion. The
finished emulsion is filtered through a cheese-cloth filter bag or
basket screen.
In the reflux method, part of the water containing emulsifiers
and initiators (persulfates, organic hydroperoxides] is placed in the
reactor. heated to a temperature approaching that desired for the
reaction, and monomer emulsified in another portion of the water is
fed in. Work-up of the polymer is the same as in the redox method.
The same equipment can be used for both redox and reflux
polymerizations. Reactions are carried out in steam-jacketed, stain-
less steel or glass-lined kettles equipped with an agitator, such as
a three-pronged, curved impeller rotated at a peripheral speed of
150-600 ft. per min. The kettle has dished top and bottom heads
capable of withstanding 4 atm and is equipped with an emergency
stack, fitted with a rupture disc, piped to a safe location. The stack
leads to a stainless steel tube and shell condenser where condensate
may be returned to the reactor or discharged to a small receiver.
The monomer emulsion is made up in an overhead stainless steel tank
equipped with a turbine-type agitator and a tankometer. The emulsion
is added to the reaction kettle by gravity through a control valve.
(2) Suspension Polymerization Produces Dry Beads
In suspension polymerization, the monomer or monomer mixture
is suspended in water in droplets by means of agitation. To keep the
droplets from coagulating, a protective colloid such as bentonite,
starch, poly vinyl alcohol, etc. is added.
The polymerization is carried out at a temperature just below
the point at which refluxing would occur. For example, a suspension
of acrylate monomer, buffer and benzoyl peroxide catalyst is heated
at about 80°C, with vigorous agitation, until polymerization is complete.
Cool the slurry and filter through a stainless steel screen or centrifuge,
wash the beads with water and dry in a circulating air oven at 80-12 0°C
or in a rotary vacuum drier.
VIH-10
-------
(3) Solution Polymerization Is Especially Suited To The
Preparation Of Polymers Which Are To Be Used In
A Solvent
Although solutions could be made from bulk polymers, these
do not dissolve easily. Direct production of this type of product by
a solution polymerization process is the most convenient method.
The equipment for solution polymerization is generally similar
to an emulsion plant.
Polymerization is usually carried out at or near the solvent re-
flux temperature. Most of the solvent is placed in the kettle and
heated to the desired temperature or to reflux. Separate streams
of the monomer (s) and the initiator dissolved in the reaction solvent
are then added over a period of 1- 4 hours, the duration of the
polymerization is usually 8 ~ 24 hours. Additional solvent is added,
if necessary , and the product sent to storage or is drummed.
(4) In Bulk Polymerization Processes, No Solvents Are Employed
And The Monomer Acts As The Solvent
Commercial bulk processes for acrylic polymers are used
primarily in the production of sheets. rods and tubes. Bulk pro-
cesses are also used in a small scale in the preparation of dentures
and novelty items. The process is used primarily with methyl raeth-
acrylate polymerization.
Methyl methacrylate monomer catalyzed with a peroxide
catalyst — ordinarily benzoyl peroxide — is difficult to control,
particularly where large masses are concerned. The difficulties
involve removal of dissolved gases, adjustment for volume shrinkage,
and adequate control of the highly exothermic polymerization reaction
in the early stages especially after the material has reached the gel
stage. These difficulties can be alleviated by using a casting syrup
or partially polymerized product rather than the monomer.
The casting syrup is usually prepared by heating the monomer
with 0.02-0.1% benzoyl peroxide at 70-80°C with constant agitation
until the consistency while still hot approximates that of glycerine,
but when cooled to room temperature approximates that of molasses.
The solids (polymer) content of this syrup is about 10%. It may be
stored at 5°C or below.
Vin-11
-------
2.
The syrup is poured into the mold and cured at either
atmospheric pressure or up to 10 atm and temperature cycles of
40-110°C or 70-135°C respectively for 45 minutes for each 1/2 inch
of casting thickness.
MONOMERS ARE THE PRINCIPLE SPECIES EMITTED
All commercially available monomers have significant vapor pressures.
Since the main polymerization processes are water /monomer or monomer
only systems, their concentrations in venting gases would be significant.
An indication of the magnitude of the potential emissions due to
handling of monomers alone, i.e., displacement of inert gas blankets in
storage and reactor charging can be calculated as is summarized in
the following table. The gas phase is assumed to be air and equivalent
concentrations would be encountered with nitrogen at atmospheric pressure.
Monomer
Ethyl Acrylate
Acrylic Acid
Butyl Acrylate
Cellosolve
Acrylate
2-Ethylhexyl
Acrylate
Methyl Acrylate
Methyl
Methacrylate
Molecular
Weight
100
72
128
144
185
86
100
Vapor
Pressure
Equilibrium
Concentration
in Air
(mmHg@ 25UC) (% by wt)
40
4.0
4.5
0.8
0.2
70
40
16.2
1.3
2.6
0.52
0.17
20.8
16.2
Lb. Monomer
Emitted perLb.
Monomer Handled
2.1 x 10
-4
-4
0.17 x 10
0.34 x 10 ~4
0.07 x 10
-4
0.02 x 10
2.7 x 10 ~4
-4
2.1 x 10
-4
Source: Snell estimates based on physical data provided in a confidential
industry submission.
VIII-12
-------
(1) Except For Storage Venting. Emission Sources Are
Generally In-Plant
The table below summarizes significant emission sources
as a function of the polymerization processes.
Emission Sources In Acrylic Polymerization
Polymerization Process
Emission
Sources Bulk Solution Suspension Emulsion
Monomer Handling X XXX
Solvent Handling X
Reactor X XXX
Filtration X
Drying X
Product Handling X XXX
Fugitive and Accidental X XXX
With comparatively high vapor pressures of the monomers,
there is considerable opportunity for escape to the atmosphere.
One industry source"' indicates that in a typical methyl meth-
acrylate plant, concentrations as high as 2.4 ppm have been en-
countered. The concentration decreased as the distance from the
plant increased, but could still be as high as 0.1 ppm 70 ft.
outside the building.
Three companies have submitted confidential data quantifying
emissions from some of their processes. Their data were obtained
principally by estimation (with an occasional measurement being
made] on a typical yearly production with a typical product mix and
process. The information is not sufficient to accurately define the
total emission, but does define the order of magnitude.
The manufacturing processes and emissions described below
are from well operated and maintained plants. It is expected that
smaller plants would have emissions at least as high, if not higher
than these.
VIII-13
-------
(2] Emission From Solution Polymerization Processes Include
Both Monomer And Solvents, According To A Case Study
This solution process is used in the manufacture of a
acrylic oil additive. The plant is about 15 years old and has
a capacity of about 30 million Ibs per year. It is a batch
polymerization process in which monomers are polymerized
in a hydrocarbon solvent using a peroxide catalyst and mer-
captan type chain transfer agents. At completion of polymeriza-
tion, the solvent is removed, and recycled, the resin is blended,
sent to storage and, when ready for shipment, is filtered.
Emissions are expressed in pounds of raw material per
pound of product produced based on a typical yearly production
with a typical product mix. The products are solutions of acrylic
polymer in mineral oil. Emissions have been estimated at each
point source. The estimates are not sufficient to accurately
define the total emissions but do define the order of magnitude.
Manufacturing unit emissions under normal operating conditions
summed are:
Source
Total non-fugitive emissions
acrylic esters
solvent
Chemicals receiving and storage
heavy acrylic esters
light acrylic esters
solvent
Polymerization
heavy acrylic esters
light acrylic esters
solvent
Polymer separation
solvent
Fugitive emissions
Emission Factor
(lbs/lb product)
2.2 x 10
9 x 10
.-4
-4
4 x 10
2 x 10
1.4 x 10"
f5
r4
1.3xlO"5
not available
-6
8 x 10
7.5 x 10"4
not available
Source: Confidential industry submission
Vm-14
-------
Primary odor and emission control techniques involve good
housekeeping practices, standard operating procedures and
maintenance practices. All process chemical storage tanks are
diked and dikes contain locked valves for spill protection and
control. Spills average about one every five years.
(3) According To A Case Study. Emissions From An Emulsion
Process Are Primarily Monomer, Of The Order Of 1 x 10~a
Lbs Acrylates/Lb Product And The Same Factor For Vinyl
Acetate
This emulsion process is a batch process. The plant is
about 3 years old with a capacity of about 50 million Ibs/yr.
The process consists of emulsifying a vinyl acetate/acrylate ester
mix in water and polymerizing with persulfate and peroxide
catalysts. Other ingredients include emulsifying agents, pro-
tective colloids and buffer salts.
The emissions have been estimated based on raw material
balances across the entire system. Estimated emissions are:
_Q
Acrylate type monomers: 1 x 10 Ibs/lb.of product
Vinyl acetate: 1 x 10~ Ibs/lb of product
The estimates include fugitive emissions but their magnitude
is not known. Spills do occur and are not included in these estimates.
Primary odor and emission control techniques involve good
housekeeping practices, standard operating procedures and main-
tenance practices. Devices planned for installation include
collection systems for emissions from storage and processing areas
connected to a scrubbing system based on mixtures of triethylene-
tetramine in ethylene glycol/water solvent. Also planned are
collection systems for transfer areas where spills have occurred
in the past.
Another manufacturer using the emulsion process indicates
emissions of acrylate esters from storage areas are controlled by
closed circuit loading and conservation vents. Reactor area
emissions are controlled by a proprietary scrubbing system designed
to treat 20 SCFM gas flow rate containing 20 Ibs/hr monomer to a
level of 0.02 Ibs/hr monomer. The scrubbed gas is discharged
high enough to prevent ground level odor.
VHI-15
-------
(4) According To A Case Study, Emissions From A Suspension
Process Are Principally Monomer, Of The Order Of 5 x 10~4
Lbs/Lb Product
This process in a 25 year old plant consists mainly of suspend-
ing various methacrylate and acrylate monomers in water and poly-
merizing by the aid of azo and peroxide initiators. The complete process
is not -well defined but probably consists of filtering the suspended
polymer, and later compounding.
Emissions for the point sources have been obtained by calcu-
lation of storage tank losses based on vapor pressures. by calculations
based on a few atmospheric samples throughout the process, and on
estimates and observations in the cases of intermittent leaks of spills.
The estimated emissions are:
Source Emission Factor
(Lbs/lb of product)
Storage:
Monomers: 1.46x10
Other: 9.30xlO~7
Polymerization:
Monomer: 1.73xlO~4
Other: 6.09 x 10~6
Compounding:
Monomer: 9.22 x 10~
Other: 4.98 x 10
Waste disposal:
Monomer: 1.63 x 10~jj
Other: 5.60x 10
Source: Confidential industry submission
Emission control methods include: closed liquid systems
and spill control; condensation of vents, and; preventative main-
tenance .
VHI-16
-------
3. EFFICIENT EMISSION CONTROL METHODS ARE AVAILABLE BUT
ODORS WILL PROBABLY STILL BE NOTICEABLE BECAUSE OF THE
ODOROUS NATURE OF THE MONOMERS EVEN AT EXTREMELY LOW
CONCENTRATIONS
The emission control methods used by the larger, more sophisticated
producers of acrylic resins, appear to be relatively efficient. The use of
closed liquid systems, conservation vents and nonregenerative water scrubbers
removes over 99% of the vapors from these processes.
The ultimate goal of most producers is to eliminate odors. This
may not be possible because of the extremely low odor threshold value
of these monomers. For example, ethyl acrylate is noticeable at a concen-
tration of 0.00024 ppm. ' At this low concentration, combustive materials
in an air stream does not provide enough BTU's to maintain the temperature
necessary for catalytic oxidation.
One producer dilutes its plant air exhaust stream and discharges it
high enough to prevent ground odor.
VIIl-17
-------
SECTION VIII-C
ALKYDS
Alkyds are polymers derived by condensing fatty acids or oils,
glycols and polybasic acids. The recipes for these resins vary
tremendously, but can be very broadly classified as Short Oil (contain-
ing 33 - 45% oil and 35% phthalic anhydride), Medium Oil (containing
46 - 55% oil and 30 - 35% phthalic anhydride) and Long Oil (containing
56 - 70% oil and 20 - 30% phthalic anhydride).
Alkyds are produced by either the fusion or solvent process.
In the fusion process the water formed during condensation is removed
by a continuous purge of mist gas, while the solvent process uses-a
solvent, such as xylene, to remove the water. The latter usually results
in an alkyd having a lighter color.
There are numerous literature references regarding alkyd formu-
lations and manufacturing procedures, but no data on emissions from
the process(s) have been found. Recently, however, emissions from
a model paint plant have been described* 3^ and we have quantified the
emissions from a typical alkyd plant which would be part of this paint
plant.
1. MANUFACTURE IS GENERALLY A HIGH TEMPERATURE BATCH
OPERATION
(1) Most Modern Alkyd Resin Plants Have Similar Layouts
And Equipment
Alkyd processing plants consist of four major operating areas:
(1) raw material and solvent storage; (2) polymerization; (3) alkyd
work-up including thinning and final product polishing, and
(4) finished product storage and/or packaging.
Raw materials can be stored either inside or outside the
plant. Liquids, such as oils, alcohols, solvents, etc. are usually
stored in tanks. Solids such as phthalic anhydride, pentaerythritol,
etc. are stored in bags usually weighing 50 Ibs each. Large alkyd
plants may receive molten phthalic anhydride in bulk shipments in
which case the product is stored in heated tanks.
Vin-18
-------
Polymerization is carried out in jacketed resin kettles
(reactors) ranging in size from 500 gallons to 6,000 gallons
capacity. These are generally constructed from stainless steel
alloy types 304,316, or 347 and equipped with an agitator
capable of rotating at peripheral speeds of 600-600 ft. per min.
Additional agitation is provided by means of an inert gas sparge
at rates of 0.005-0.04 CFM per gallon of charge. The reactors
can be used as either a fusion or solvent reactor. If used as
a solvent reactor, it is usually equipped with condensers and
a decanter-receiver. If used as a fusion reactor, the condenser
and decanter-receiver are omitted or shut off. Reaction temper-
atures may vary from 210 - 250°C. An equipment flow sheet
for a typical alkyd manufacturing process is presented in
Exhibit VIII-C1.
All alkyds (with the exception of those used in making molding
compounds) are diluted or thinned with solvents usually xylene or
mineral spirits. When the desired degree of polymerization has been
reached, the alkyds from the reactor are dropped into a thinning
tank containing the desired solvent. The tank is usually twice the
capacity of the reactor and is equipped with a condenser and stirrer.
Cooling is accomplished by circulating cold Dowtherm or water through
the jacket.
The diluted alkyd is filtered hot, usually through a plate and
frame filter and sent to storage or directly to drumming facilities.
2. THE MODEL PLANT DESCRIBED HAS A CAPACITY OF 2.2 TO 2.4
MILLION POUNDS PER YEAR AND EMPLOYS BOTH SOLVENT AND
FUSION PROCESS EQUIPMENT
The model plant operates 250 days per year on a two-shift basis.
This quantity of alkyd resin solids produces about 722,000 gallons of alkyd
base paints.
About 50,000 gallons of tankage will be required for solvents and
other raw material storage. A minimum of one month's supply is necessary
and it is assumed that the average alkyd prepared contains 53% oil and the
plant operates on a two-shift operation (the efficiency of the second shift
being 90%). All alkyds are to be diluted to 50% non-volatile solids (NVS)
with xylene. Separate storage tanks are available for xylene, oils,
glycerine and waste solvent and have the following capacities:
VIII-19
-------
EXHIBIT Vin-Cl
Environmental Protection Agency
ALKYD PROCESSING (34)
ln«tl Cei "Hori
Tmnrinq TonL
Sftoni or
V/ottr JocV.i
F,h.r
"•• L""» — ,1
1 >
SJ
L^ ^^i
Hi I >•••> ,'ii •Ine-im aH|ni-il ilLnl iwoine HUH
vm-20
-------
Volume (gal ) Contents
25,000 Xylene
25,000 Oil
7,500 Glycerine
2,000 Waste Solvent
Phthalic anhydride is stored in 50 Ib bags, although larger
alkyd producers receive molten phthalic anhydride and this would
require additional tankage.
The plant is equipped with two reactors. A small reactor of
500 gallon capacity will be used as a fusion reactor and can produce
about 2,375 Ibs of resin solids per batch. A larger reactor having a
capacity of 1,500 gallons can be used as both a fusion and solvent
reactor and can produce about 7,125 Ibs of resin solids per batch.
Production consists of an average of one batch in each reactor per
24 hour day.
Two thinning tanks are required, one for each reactor. They
should have double the capacity of the respective reactors with which
they are associated. Therefore, tanks should have capacities of 1,000
gallons and 3,000 gallons.
It is expected that 35,000-40,000 gallons of finished alkyd product
storage is adequate. Many different alkyd formulations are made de-
pending upon end uses and specifications and separate storage tanks
are therefore required. Individual tanks ranging from 1,000 gallons
to 10,000 gallons should suffice.
(1) Production Is Almost Equally Divided Between Long Oil
And Short Oil Alkyds
Probably more than 95% of alkyd production is used for
making trade or industrial coatings and averages about 53% oil.
Two formulations were used in calculating emissions from an
alkyd plant. A short oil alkyd and long oil alkyd typify alkyd
production in fusion and solvent processes respectively. Typical
formulations are shown below.
Short Oil (40% oil) Long Oil (60% oil)
1,000 Ibs oil 4,500 Ibs oil
600 Ibs glycerine 1,000 Ibs glycerine
900 Ibs phthalic 2,000 Ibs phthalic
anhydride anhydride
VIH-21
-------
(2) The Fusion Process Is Usually Carried Out At Temperatures
Of 400-450°F
The reactor (500 gallons) is charged with the oil and
glycerine and blanketed with inert gas. Agitation is started and
heat is applied (435-450°F) until alcoholysis is complete. This
takes about 3 hrs. Phthalic anhydride is added through the
manhole and heating is continued for about five more hours or
until the desired viscosity and acid number is reached. Gas
sparging exhaust rates are about 2 CFM during alcoholysis,
then at a decreasing rate of 0.04 CFM per gallon of charge
during the first two hours of esterification, 0.02 CFM during the
third hour, and 0.01 CFM for the remainder of the cook.
(3) The Solvent Process Is Carried Out Under Xylene Reflux
Conditions
Total reaction time is approximately 12 hrs. for a long oil
alkyd charge in the 1,500 gallon reactor. The normal procedure
is to charge the reactor with the oil, blanket with an inert gas,
heat to 450-500°F, add glycerine and continue heating at this
temperature for 4.5-5 hrs. Cool to 390>OF. add phthalic anhydride,
hold at 450 °F until esterification is complete and the desired
viscosity and acid number is reached. The condenser vent
temperature is assumed to be about 100°F.
3. TOTAL EMISSIONS FROM THE MODEL PLANT AMOUNT TO 0.008
POUNDS PER POUND OF ALKYD SOLIDS PRODUCED
Total emissions for the model plant are summarized in Exhibit
VIII-C2. Over 98% of the emissions arise from reactor venting and
fugitive sources such as filter press, agitator seals and spillage.
The emissions estimated for this model plant are in agreement
with actual emissions measured (based on 15 resin cooks) of 0.0001
to 0.007 Ibs/lb of alkyd produced. *4^ The major component of the
emissions was xylene.
On a pound for pound basis, there appears to be little difference
in emissions from the fusion or solvent process.
VIH-22
-------
EXHIBIT VIII-C2
Environmental Protection Agency
SUMMARY OF EMISSIONS FROM AN
ALKYD PLANT PRODUCING 2.2 -
2.4 MILLION POUNDS OF ALKYD
SOLIDS U4)
Pounds Emitted Per Year
Contribution
0.4
9.4
1.2
0.2
88.8
100.0
Source of
Emission
Raw material
storage
Reactor
Thinning
Finished Resin
Storage
Fugitive
Principle
Emission
Xylene
Mixed
organics
Xylene
Xylene
Fusion
Cook
20
288
53
Solvent
Cook
60
1,400
160
Total
80
288
1,400
213
Total
Xylene
Xylene
12
4,000
4,373
33
12.000
13,653
45
16,000
18,026
Pounds Emissions/Pound
Alkyd
.0074
.0077
.0076
VIII-23
-------
4. MINIMAL EMISSION CONTROL IS PRACTICED IN THIS INDUSTRY
Solvent tanks are normally vented to the atmosphere.
When phthalic anhydride is received and stored in the molten
state, it is usually kept under a blanket of inert gas. Conservation
vents set at about 2-3 torr of pressure are usually used.
Many small producing plants heat reactors with gas burners.
This leads to local hot spots which produces acrolein, a very odorous
product. When tall oil is used, mercaptans and other odorous sulfur
compounds are often formed.
In addition, plants using solid phthalic anhydride usually add
this product to the reactor through a manhole. During this addition,
gas sparging is continued resulting in particulate emissions through
the manhole and vents, as well as aerosol emissions containing water,
phthalic anhydride, phthalic acid, and esters. The high sparging rate
corresponds to a stream of about 60 SCFM for a typical 1,500 gallon
kettle.
In the solvent process, a partial reflux condenser is used to
return most of the vapors to reactor. This is followed by the so-called
total condenser which condenses the azeotrope and the continuous
decanter separates the water from the solvent. Finally, there is a
circulating scrubber on the vent line. There is no concensus as to the
efficiency of this scrubber, but it is known that it has little or no effect
on gaseous products.
5. FURTHER TREATMENT OF ALKYD PRODUCTION VENT STREAMS
MAY BE REQUIRED
In view of the poor performance of scrubbing in the control of
emissions from alkyd manufacture, some other method may be required
to control, in particular, the odors emitted.
Two methods present themselves - carbon adsorption and com-
bustion .
VIII-24
-------
(1) Carbon Adsorption Would Probably Not Be Beneficial
For Control Of Alkyd Emissions
A problem associated with the emissions from sparged
reactors used in alkyd production is that highly turbulent
conditions in the reactor cause the formation of all sorts of
aerosols. Deposition on adsorbent carbon would then very
severly limit the usefulness and life cycle of the adsorbent.
If used downstream from an efficient filter or precipitator, an
activated carbon unit could control solvents and odors efficiently.
The economy of this combined system is, however, questionable
compared to that of combustion in terms of both the original
cost and the operating cost.
(2) Combustion Of The Vent Gases Would Be Beneficial But
Additional Fuel Costs Would Be Encountered
Combustion at 1200°F with a residence time of 2 - 3
seconds in the fire zone destroys practically all organic species.
Where a stream containing organic materials is too dilute to
sustain its own combustion, as would be the case for vent gases
from alkyd production, a gross approximation of heating costs is
possible. The energy necessary to raise a pound of air to 1200°F
is about 250-270 BTUs per Ib. Thus a stream of 60 CFM of inert
gas would require a gas air mixture with a net BTU content of
about 1250 BTUs per minute. Due to variations in the sparging
rates, a total of about 500,000 BTUs per day would be required.
This would represent about $3 - $5 per day which is quite
acceptable. A more complete analysis of the incineration is given
in the review of general control methods.
VIII-25
-------
SECTION Vm-D
EMISSION QUANTIFICATION AND CONTROL TECHNIQUES FOR SOME HIGH
VOLUME PLASTICS
Literature sources™' •' have provided data related to quantitative
emission factors and emission control methods for several large volume resin
materials. The emission factors, however, are based on material balances
rather than quantitative analysis of vent or exhaust streams. A discussion
of some emission control devices used and emission factors calculated for
some major chemical/plastic processes follows.
Exhibit Vin-Dl summarizes the emission control devices reportedly
used by polymer manufacturers. Exhibit Vin-D2 summarizes the emissions
from some resin plants.
1. EMISSION CONTROL DEVICES USED IN PVC PRODUCTION INCLUDE
VENT CONDENSERS. CYCLONES AND BAG FILTERS
Vent condensers condense and retain most of the vinyl monomer which
would otherwise reach the atmosphere. With these devices, hydrocarbon
emissions from the reactor area and monomer recovery units would amount
to 0.01 to 0.02 pounds per pound of polymer produced.
Participate control is most important during the manufacture of PVC .
Processes which generate dusts include the dryer and materials handling
(including pneumatic conveyors and loading equipment). Cyclones are
usually used and have efficiencies of 99.9%. Bag filters will collect 100%
of the fines above approximately 50 micron particle size and can be used
alone or as backup for cyclones. Particulate emissions are in the order of
0.003 pounds per pound of polymer produced.
Cost of cyclones and bag filters is mainly dependent upon the air flow
volume. Installed costs can vary from about $20,000 to over $120,000 rated
at 1,000 - 67,000 SCFM respectively. Operating costs also range from
0.0026 - 0.0157 cents per pound of PVC production. In some instances
there is a net credit for recycling PVC recovered amounting to almost 0.05
cents per pound of PVC production.
Vent condensers recovering 9-12 pounds of monomer per hour cost
about $4,000 - $6,000, respectively. These show operating costs of 0.023
cents per pound credit to 0.003 cents per pound cost, respectively.
VIH-26
-------
EXHIBIT VIII-D1
Environmental Protection Agency
EMISSION CONTROLS REPORTEDLY USED BY POLYMER MANUFACTURERS(3>45|47)
I I I ? L ?!
„. a g s i. t "> a MRI
S 2 fl) W) Q> 0} 3 *9 ^
5 E a s P" I 1 f «-3 8 1 §
" oo 3 -^ I o H 2 a g 2 2 So
>s M .2 X OOrl utiOf)U(Lk
Polymer O no u, s U U
-------
Fugitive emissions from pumps, compressors, storage and normal
operations amount to about 0.002 pounds of hydrocarbons per pound of
PVC produced.
2. POLYPROPYLENE PLANT EMISSION CONTROL DEVICES WHICH MAY BE
USED INCLUDE CYCLONES AND/OR BAG FILTERS . WATER SCRUBBERS,
FLARES. INCINERATORS AND VENT CONDENSERS
We judge that particulate removal costs would be of the same order of
magnitude as described above. However, reported emissions are considerably
lower and are about 0.001 pounds per pound of PP produced.
Installed costs for flare systems can range from $37,000 to over $300,000
with operating costs ranging from 0.014 to 0.039 cents per pound of PP produc-
tion. Hydrocarbon emissions (including fugitive emissions) would be in the
order of 0.016 pounds per pound of PP produced.
3. VENT CONDENSERS AND CYCLONES AND/OR BAG FILTERS ARE BEING
USED BY SOME POLYSTYRENE PRODUCERS
These devices are used primarily for product recovery rather than
control devices.
Hydrocarbon emissions have been estimated at 0.006 pounds per pound
of polystyrene produced with over 50% of this appearing at the reactor vent.
Particulate emissions amount to about 0.0001 pounds per pound of PS
produced.
VIII-28
-------
EXHIBIT VID-D2
Environmental Protection Agency
EMISSION FACTORS FOR SOME
LARGE VOLUME RESINS
(Lbs/Ib product)
Plastic
Poly vinyl Chloride
Nylons
Polypropylene
Polystyrene
HD Polyethylene
LD Polyethylene
Particulates/Aerosols
0.0002 - 0.004
(45)
0.00034
(3)
:(45)
0.0003 - 0.005
0.00001 - 0.0002(45^
0.00001 - 0.0002
(45)
0.0013t3)
Hydrocarbon
0.001 - 0.02
(3)
0.00021
0.001 - 0.02
(45)
(45)
0.0002 - 0.04(45)
0.0002 - 0.04(45)
0.00029(3)
0.085<3)
0.044(3)
Vin-29
-------
SECTION Vm-E
ECONOMICS OF TYPICAL EMISSION CONTROL METHODS
1. IN THE CHEMICAL/PLASTICS INDUSTRY. A GOOD DEAL OF CONTROL
EQUIPMENT IS CONTRIBUTING TO PROFITS
There are two fundamental types of control equipment
one type separates material (s) from a waste stream
one type destroys undesirable materials in a waste
stream
Dust collectors and condensers belong in the first category. Flares
and scrubbers belong in the second. However, the heat generated by the
flares can sometimes be usefully recovered.
Adsorbing devices, which are also useful can belong to either category
depending upon the disposition of the spent adsorbent.
The table below presents a cursory analysis of the equipment reported
as "Emission Control Equipment" in various monomer-polymer production
plants <45> .
Percent of "Profitable"
Industry Emission Control Equipment
Styrene-Butadiene Rubber 50%
Polypropylene 20
Polystyrene 100
Polyvinyl Chloride 50
Nylon 6 40
Vinyl Chloride Monomer 30
Isocyanates 10
Source: Snell estimates based on data in Reference 45.
VIII-30
-------
The figures refer to the gross number of pieces of equipment reported,
regardless of type, capital or operating costs.
It can be seen that a large proportion of such equipment falls into the
category of "profitable" equipment, showing a negative operating cost when
the value of the product recovered is taken into consideration. Examples are
cyclones and bag dust collectors.
A relatively low proportion of "profitable" equipment is encountered in
isocyanate manufacture. In this respect it should be noted that:
the monomers of the isocyanate family are highly
noxious
there is a considerable amount of phosgene in the
atmospheric waste streams and that a limit of 200
ppm has been in force for the emission of this
chemical for a number of years.
2. AN ECONOMIC OVERVIEW WAS DEVELOPED FOR FIVE EMISSION CONTROL
METHODS APPLICABLE TO THE CHEMICAL/PLASTICS INDUSTRY
Exhibit VIH-E1 shows some of the capital costs and other characteristics
of typical pieces of equipment actually in use in the polymer industry.
(1) The Installed Cost (C) Of A Bag Collector Is C =• 3.5 V -9,
Where V = Thousand CFMs
In a recent survey, unrelated to this project, we have found
that
there is a keen competition between manufacturers
of essentially similar equipment, leading to a more
or less uniform pricing policy.
most of the installations sold until recently, were
based on value of recovered material.
VIII-31
-------
EXHIBIT Vffl-El (1)
EPA
REVIEW OF SPECIFIC PIECES OF EQUIPMENT
IN ACTUAL USE
G
CO
to
Polyvinyl Chloride (Suspension)
Vent Condenser
Dryer Bag Filter
Silo Bag Filter
. Bagger Bag Filter
Bulk Loading Bag Filter
Dryer Bag Filter
"Day Storage" Bag Filter
Bulk Storage Bag Filter
Bagger Bag Filter
Vent Condenser
Various Bag Filters
Capacity
Plant (tons/yr)
i)
A 50,000
B 30,000
Flow Of
Pollutants
(Ibs/hr)
12
135
4
1
3
2
0.03
0.02
0.02
Capital
Cost
(1973 $)
7,000
125,000
65,000
31,000
12,500
57,000
9,000
6,000
5,000
Efficiency
(%)
83
99.8
99.9+
99.9+
99.9+
99+
99.9+
99.9+
99.9+
Rate
12 Ib/hr
45,000 SCFM
4,500 SCFM
1,500 SCFM
3,000 SCFM
25,000 CFM
3,750 CFM
1,600 CFM
1.100 CFM
45.000
Vent Condenser
Vent Condenser*
Dryer Cyclone
Dryer Bag Filter
Dryer Bag Filter*
70,000
4,500
96.3
9 Ib/hr
trace
trace
10
8
9
68.000
15,000
28.000
62,000
15.000
5.000
205.000
62.000
110,000
110,000
160,000
99.9+
99.9+
99.9+
99.9+
99.9
99.9+
99+
99+
99.9+
99.9+
99.6
27,000 CFM
5,000 CFM
9,800 CFM
38,350 CFM
5,000 CFM
1,400 CFM
trace
trace
27,000 CFM
20,000 CFM
67,000 CFM
Remarks
Mikro-Pulsaire
Flex-Kleen Corp.
Mikro-Pulsaire
Mikro-Pulsaire
U.O.P. Dust Collector
Flex-Kleen Corp.
Flex-Kleen Corp.
Flex-Kleen Corp.
Process Engineering
and Machine Co.
Flex-Kleen Corp.
Flex-Kleen Corp.
Fuller Co.
Pulverizing Machinery
Pulverizing Machinery
Fuller Co.
Dustex
* Emulsion Process
-------
EXHIBIT VIH-El (2)
Polyamides
Nylon 6
Reactor Vent Condenser
Recovery Vent Condenser
Capacity
Plant (tons/yr)
A 119,000
t
Pelletizer Vent Scrubber
Depolymerizer Vent Scrubber
Nylon 66
Finisher Off-Gas Scrubber A
Polypropylene
Reclaim Vent Condenser A
Recovery Vent Condenser B
Various Bag Filters
62,500
60,000
150,000
62,500
Flare Pit C
Bag Filter
Process Vapor Condenser 5
K.O. Drum
Process Vapor Condenser
Flare System D 75,000
Flow Of Capital
Pollutants Cost
(Ibs/hr) (1973$)
Efficiency
(%) Rate
-700 SCFM
n.a.
n.a.
40
344
729
n.a.
n.a.
variable
3,336
85,000
2,000
45,000
58,000
115.000
67,000
12,000
230,000
120,000
85,000
89,000
24,000
5,000
340,000
n.a.
near 100
n.a.
99.7
n.a. 120 SCFM
n.a.
near 100
143 Ib/hr
1,585 Ib/hr
8 Ib/hr
near 100
-------
EXHIBIT VIH-El (3)
00
Process Vapors Scrubber
Process Fluids Incinerator
Flare System
Flare System
Handling and Storage
Cyclone
Screens
Screens
Bag Filter
SBR Rubber (Emulsion Polymerization)
Carbon Black Water
Scrubber
Flare
Butadiene Oil Scrubber
Carbon Black Spray Water
Scrubber
Flare
Butadiene Oil Scrubber
Carbon Black Water Scrubber
Capacity
Plant (tons/yr)
E 50,000
F 140,000
rization)
A 219,000
B 112,000
C 175,000
D 342,000
r
Flow Of
Pollutants
(Ibs/hr)
25.3
23
401
5,996
4 total
variable
variable
variable
180
1
62
715
-10
-600
Capital
Cost
(1973 $)
7,000
58,000
52,000
96,000
9,000
7,000
33,000
140,000
19,000
18,000
70,000
17,000
19,000
34,000
3,600
Efficiency
(%)
98.5
99.5+
99.5+
99.5+
n.a.
n.a.
99.3
96.5
98
95
Rate
68 Ib/hr
variable
n.a.
10,000 SCFM
3,000 SCFM
22,000 SCFM
16,000 SCFM
75 SCFM
360 SCFM
500 SCFM
8 SCFM
90 SCFM
Design Rating 20,000 Ibs/hr
Source: Snell estimates based on data from Reference 45
-------
A plot of the capital cost versus equipment capacity in terms
of CFM handled is presented in Exhibit VIII-E2. The outlying points
can be sometimes attributed to the high temperature of the stream,
requiring highly sophisticated, and therefore expensive fabric (e.g.
Du Pont "Nomex"). The plot indicates that the 1973 installed cost of
a "normal" bag dust collector, with ancillary equipment, is given by
the formula
C = 3450V-92
where C is the cost in $ and V the volume handled in 1000 CFM.
(2) The Annual Continuous Operating Costs Of Bag Collectors
Can Be Estimated At $0.30 - $0.50 Per CFM
Assuming that on the average bag dust collectors operate at
a differential pressure of a few torr, the power requirements can
be estimated at 0.25 HP of air HP per 1000 eft. handled assuming a
60% efficiency.
Thus, the energy requirement for a 50,000 CFM dust collector
is of the order of 100,000 KWH per year for a continuous operation.
With electricity at $0.02/KWH the cost of energy alone can be about
$2,000.
Assuming an installed cost of $125,000, the annual operating
cost including 10 year depreciation can be between $15,000 - $17,000 .
Industry figures indicate: $23,000/year for a 45,000 CFM bag
collector and $27,000/year for a 67,000 CFM bag filter. But at the
same time, figures of $400/year have been reported for a 25,000
CFM unit and $12,000/year for a 1,500 CFM unit.
Thus, as a first approximation, the annual continuous operating
costs for bag dust collectors could be calculated at about $0.30 to
$0.50 per CFM.
(3) Where The Monomers Are Highly Volatile Compression
And/Or Refrigerated Condensation May Be Economical
There are two cases to be considered. In the first case, the
stream is essentially unreacted monomer .e.g. ethylene, propylene
or vinyl chloride.
VHI-35
-------
EXHIBIT VIII-E2
Environmental Protection Agency
CAPITAL COSTS OF BAG
DUST COLLECTORS
200
100 ;
100
Capacity(1000 CFM)
VIII-36
Source: Snell estimates based on data from Reference 45
-------
Release to the atmosphere is undesirable for economic reasons.
In that case, the fairly elaborate equipment required to recover the
unreacted monomer should not be considered as emission control
equipment.
In the second case, the stream is a mixture of monomer and
"uncondensable" gas, e.g. air, nitrogen, or methane. Then,
especially if the value of the product recovered is negligible compared
to the operating cost, the compression and/or refrigerated condensa-
tion may be truly considered an emission control.
It is difficult to give equipment and operating costs in a
general fashion. As an example the refrigeration to -40°F of a
stream of nitrogen leaving a reactor at 100°F would require about
35 BTU's per Ib. or 2,800 BTUs per 1,000 eft. Thus a stream of
10,000 CFM of N_ (or air) would require 140 tons of refrigeration.
This would necessitate a refrigeration system costing about $90,000
and an operating cost of the order of $140 per day or $46,000 per
year.(50J
(4) Scrubbing Of Gases Is Effective In Removing Particulates
And Some Very Soluble Vapors, Such As Acrylates - For
Jet Scrubbing Operating Costs Are In The Order Of $2
Per 100 CFM Per 24 Hour Day
Scrubbing is bringing a stream of gas in as intimate contact
as possible with a stream of liquid. The most common scrubbing
agent is water, then various water solutions (e.g. caustic or hypo-
chlorite). Low volatility oils can be sometimes used to dissolve
hydrocarbon vapors or gases. The scrubbing stream is usually
recycled with or without intermediate treatment.
There are two fundamental methods for scrubbing. The
spray methods use the infringement of finely divided water counter-
currently, crosswise or co-currently with the gas stream. A par-
ticular case is the venturi scrubber in which venturi effect is used
to provide the pressure differential necessary to move the gas stream.
Another method is the use of packed towers (sometimes even
plate towers). In these a stream of liquid flows by gravity counter-
currently to the gas stream over suitable packing, generally in towers
essentially similar in design to distillation towers. These devices
are particularly successful when dissolution of a gaseous substance
(e.g. ammonia, or HC1) is the objective. They may be adversely
affected by high concentrations of particulates.
VIU-37
-------
The capital cost of spray scrubbers varies in function of the
capacity and the materials of construction. Exhibit VIII-E3 shows
typical capacity cost relationships for jet scrubbers. (5) The power
requirements for the flow of water is said to vary from 2 - 5 HP per
1,000 CFM of gas handled. Thus, a daily operating cost can be about
$2.00 per 1,000 CFM per 24*hour day.
.(5) Flaring, Even With Added Fuel, May Be A Costwise
Attractive Method For Control Of Emissions, e.g.
Hydrocarbon Resins
Destruction of most organic species by combustion in air is
essentially complete atl.ZQOPF with residence time of 1 - 3 seconds.
Again, two alternatives can be considered. In the first alter-
native the waste stream contains enough organic material to sustain
its own combustion at the required temperature. In that case, the
costs are essentially the amortization cost of the equipment. Flares
and their auxiliaries are only nominal in costs (less than $10,000),
but the need to provide a stack of several hundred feet of height may
be quite significant. For example, a capital cost of $340,000 for a
flare system was claimed for a polypropylene installation producing
75,000 tons per year; the system disposed of 3,400 Ibs of pollutant
per hour; however, due to the value of products recovered in the
Knock Out Drums there was a negative operating cost of $100,000 per
year.<45)
In other installations a captial cost of about $20,000 is claimed
for flare systems handling 500 SCFM with a height of 150 feet. The
operating cost is said to be $10,600 per year.
For a similar system on a stream of negligible heating value,
the estimated heat requirements would be 15 x 106 BTU's per 24
hours or 15,000 CFM of natural gas. At a cost of $0.028 per 100 CFM
the cost of fuel would be about $5.00 per day or about $1,500 per
year.(52)
(6) Adsorption Devices Represent Another Form Of Emission
Control In Which Product Recovery May Be Possible, e.g.
Alkyds
Carbon adsorption may be used in some cases. It usually
is limited to streams containing a significant percentage of organic
vapors and is particularly successful in solvent vapor recoveries.
The method is not known to find appreciable application in the
industry studied.
Vin-38
-------
EXHIBIT VIII-E 3
Environmental Protection Agency
CAPITAL COSTS OF JET SCRUBBERS
1,000
10,000
Cubic Feet per Minute
loopoo
VIII-39
-------
Pressure drops through the system limits its applicability to
streams of moderate capacity, say less than 5,000 CFM.
Two factors limit their usefulness to this industry:
Thebeds are quite sensitive to solid particles
accumulation
Adsorbed monomers may have a tendency to
polymerize due to the possible catalytic effect
of the adsorption process itself.
Two possible methods of utilization can be contemplated:
Regeneration - It is often possible to regenerate
the adsorbent "on site" either by pyrolysis or by
steam stripping. In the latter case product values
can be recovered.
Spent adsorbent disposal - the spent adsorbent
could be disposed of by incineration or landfill.
Costs for the steam regeneration process can be
estimated as follows: 153)
Capital cost for a unit handling 3,000 cfm -
$12,000- $13,000
Operating cost - $0.25 per hour for
electricity, $0.50 for water and $0.90 for
steam - with $250 per year for maintenance
for a unit recovering about 24,000 gals per
year of solvent. (0.2% concentration by
weight)
Thus, a total operating cost of $13,500 per
year can be estimated. This would represent
$4.50 per CFM capacity per year.
It is to be noted that the utility costs would be
somewhat proportional to the amount of solvent
adsorbed. Thus, a range of $2 to $6 per CFM per
year appear reasonable.
VIII-40
-------
An adsorption capacity of about 8% by weight is indicated.
This as an alternative, the carbon could be disposed of. With a
carbon cost of about $0.30 per lb this represents a cost of $3.75
per lb of adsorbate. This, therefore, looks like a highly uneco-
nomical process and should be resorted to only for extremely
toxic substances in very diluted streams.
As a first approximation a range of values can be assigned for the
operation of various emission control devices, discussed above, based on
their nominal capacity.
These values are presented in Exhibit VIH-E4.
VIH-41
-------
EXHIBIT VID-E4
Environmental Protection Agency
EMISSION CONTROL COSTS
SUMMARY OF OPERATING COSTS OF VARIOUS METHODS
Bag Filters $0.30 to 0.50 per year per CFM of capacity (*)
Compression
Refrigeration $3.0 to 6.0 per year per CFM of capacity (*)
Scrubbers $0.40 to 0.60 per year per CFM of capacity (*)
Flare $0.10 to 0.20 per year per CFM of capacity (**)
Regenerative
Adsorption $2.0 to 6.0 per year per CFM of capacity (***)
(*) Neglecting the value of recovered product.
(**) This figure assumes no heating values for the stream itself, but
does not include supplying the necessary air in case of an essen-
tially inert gas stream.
(***) Excluding value of recovered material and assuming a 0.05 to 0.3%
by weight concentration of adsorbate. Excluding also the cost of
any pretreatment of the gas stream.
Source: Snell
VID-42
-------
SECTION IX
REFERENCES
-------
SECTION IX.
REFERENCES
1. United States Tariff Commission Reports: Synthetic Organic Chemicals,
Production and Sales, 1967, 1968, 1969, 1970, 1971. Washington,
Government Printing Office, (TC Publications, 295, 327, 412, 479, 614)
2. Anon: Journal of Commerce: December 27, 1972
3. Society of Plastics Industry: Confidential Communications, November 1973
4. Foster D. Snell, Inc.: Confidential Files, November 1973
5. Anon: Chemical Marketing Reporter 204: 9, December 24, 1973
6. Macbride, Roland R.: Will PVC's 1973 Crunch Become A Glut in 1975?
Modern Plastics 50, No. 1:66-69, January, 1973
7. Various Manufacturers: Private Communications, November, 1973
8. Chemical Information Services: Regional Directories of Chemical
Producers, Stanford Research Institute, MenloPark, California
9. Anon: Polyvinyl Alcohol Behemoth of Du Pont Comes On Stream Hungry
For Textile Size Mart. Chemical Marketing Reporter 203: 3,12, April 2,
1973
10. ibid: August, 1971
11. Macbride, Roland R.: Still Plenty of Capacity in Polystyrene, But The
Squeeze Is On. Modern Plastics 49, No. 8:14-15, August, 1972
12. Anon: Tight Despite Expansion. Chemical Week 112, No. 11: 9,
March 14, 1973
13. Anon: Plastics World 30: 42, August, 1972
14. Stanford Research Institute: Chemical Economic Handbook, Stanford
Research Institute, MenloPark, California
15. Anon: Chemical Marketing Reporter 201: October 26, 1970
K-l
-------
16. Anon: Booming Growth Seen For Polyurethanes. Chemical 6 Engineering
News 50, No. 8:10-11, February 21, 1972
17. Department of Commerce: Statistical Abstracts of the United States, 1971:
829-894, Department of Commerce, Washington, D.C.
18. Repka, Jr., B.C.: Olefin Polymers. Kirk-Othmer Encyclopedia Of
Chemical Technology, 2nd Edition 14: 231, 1967
19. ibid: 252-253
20. Smith, W.M.: Manufacture of Plastics, Part 1:119, 1964, Reinhold
Publishing Corp., New York
21. Cantaw, M.J.R.: Vinyl Polymers (Chloride) Kirk-Othmer Encyclopedia
Of Chemical Technology, 2nd Edition 21: 376, 1970
22.
23.
24.
25.
26,
27.
ibid: 372
Smith, W.M.: Manufacture of Plastics, Part I: 234,
Publishing Corp . , New York
ibid: 229
ibid: 286
ibid: 276
Bishop , R .B . : Practical Polymerization for Polystj
1964, Reinhold
rrene: 9, 1971,
Cohners, Boston
28. Mark, H.F. et al: Encyclopedia of Polymer Science and Technology
13:132, 1971. John Wiley 6 Sons, Inc., New York
29. Bishop, R.B.: Find Polystyrene Plant Costs, Hydrocarbon Processing
51, No. 11:137-140, November, 1972
30. Smith, W .M.: Manufacture of Plastics, Part I: 451, 1964, Reinhold
Publishing Corp., New York
31. ibid: 209
32. Mark, H .F. et al: Encyclopedia of Polymer Science and Technology.
10: 50, 1971. John Wiley 8 Sons, Inc., New York
33. Simonds, H.R. et al: Handbook of Plastics, 2nd Edition: 700, 1949.
D. Van Nostrand Co., Inc., New York
K-2
-------
34. Mraz, R.G. and Silver, R.P.: Alkyd Resins. Kirth-Othmer Encyclopedia
of Chemical Technology, 2nd Edition 1: 851-882, 1963
35. Smith, W.M.: Manufacture of Plastics, Parti: 504, 1964, Reinhold
Publishing Corp., New York
36. ibid: 399
37. Klug, E .D.: Cellulose Derivations. Kirk-Othmer Encyclopedia of
Chemical Technology, 2nd Edition 4: 629, 1964
38. Smith, W.M.: Manufacture of Plastics, Part I: 504, 1964, Reinhold
Publishing Corp., New York
39. ibid: 520
40. ibid:524
41. Niehaus, W .R.: Safe Handling Practice for Acrylate Monomers.
Paint and Varnish Production (PVP) 61, No. 5:41-44, 1971
42. Toshihide, O.: The Chemical Components of Odor From Plastic Plants
and Some Examples of Odor Control. Odor Research Journal, Japan 1
(1): 46-50, 1970
43. EPA: Private Communications, December, 1973
44. Anon: The Ideal Paint Plant, Manufacturing Committee, Toronto Paint
Society
45. EPA: Private Communications, November, 1973
46. Arthur D. Little: Research On Chemical Odors, Part I - Odor Thresholds
for 53 Commercial Chemicals: 21-24, Ocotber, 1968 for Manufacturing
Chemists Assn., Washington, D .C.
47. Pacific Environmental Services, Inc., 2932 Wilshire Blvd., Santa Monica,
Calif. 90403
48. Perry, J.H. et al: Chemical Engineers'Handbook: 20-74, 1963.
McGraw-Hill Book Company, New York
49. ibid: 20-71
50. ibid: 26-25, 26-29
51. Webb: Paint Industry Magazine: January, 1958
K-3
-------
52. Anon: Confidential Communications
53. Manzone, R .R. and Oakes, D .W.: Profitably Recycling Solvents From
Process Systems. Pollution Engineering 5, No. 10:23-24, October, 1973
54. Rolk, R.W. et al: Afterburner Systems Study: Environmental
Protection Agency Office of Air Programs. Contract EHS-D-71-3,
August, 1972, PB 212-560
55. Occupational Safety and Health Standards; National Concensus Standards
and Established Federal Standards. Federal Register 36, No. 105, Part II:
10504-10505, May 29, 1971. Department of Labor, OSHA, Washington, D.C,
56. Patty, F .A.: Industrial Hygiene and Toxicology, Toxicology, Part II:
Inter science Publishers, New York, 1966
57. Summers, W.: Odor Pollution of Air: 22-24, 1971. CRC Press, Cleveland
58. Anon: Putting the Nose To the Test, Chemical Week 112, No. 11: 35-36,
March 14. 1973
59. Manufacturing Chemists Assn.: Physiological Effects. Air Pollution
Abatement Manual: 22-26, 1951. Manufacturing Chemists Assn.,
Washington, D.C.
60. Anon: Detectors, Reagents, and Accessories for MSA Universal Testing
Kits; Summary Data Sheets: Mine Safety Appliance Co., Pittsburgh,
Pa., January, 1969
61. Compilation of Odor and Taste Threshold Values Data: ASTM Data
Series DS 48: American Society for Testing and Materials, 1973
62. Press Release: Public Relations, B. F. Goodrich, Akron, O.,
January 23, 1974
63. Occupational Safety and Health Standards; Emergency Temporary
Standard for Exposure to Vinyl Chloride; Federal Register 39,
No. 67: 12342-12344, Aprils, 1974. Department of Labor, OSHA,
Washington, D.C.
K-4
-------
APPENDICES
-------
APPENDIX 1
ADDITIONAL PRODUCERS' LOCATIONS
-------
APPENDIX 1
Producer and Location
CPC International, Inc., Charlotte, N. C.
Conchemco, Inc., Houston, Tex.
Dan Riber Mills, Inc., Baltimore, Md.
Kansas City, Mo.
Danville, Va.
De Soto, Inc., Berkeley, Calif.
Garland, Tex.
Chicago Heights, m.
H. B. Fuller Co., Atlanta, Ga.
St. Bernard (Cincinnati), O.
General Latex & Chem Corp., Charlotte, N. C.
Ashland, O.
Dalton, Ga.
Cambridge, Mass.
Jones- Blair Paint Co., Dallas, Tex.
Minnesota Mining & Mfg. Co., Decatur, Ala.
Napko Corp., Houston, Tex.
Onyx Oils & Resins, Inc., Brooker, Fla.
Newark, N.J.
Owens-Corning Fiberglas Corp., Anderson, S. C.
Philip Morris, Inc., Greenville, S. C.
Springdale, Conn.
Reliance Universla, Inc., Houston, Tex.
Louisville, Ky.
Seydel-Woolley & Co., Atlanta, Ga.
Standard Brands, Inc., Forest Park (Atlanta), Ga.
Clifton, N.J.
Cheswold, Del.
Chicago, HI.
Stein, Hall & Co.. Inc., Charlotte, N. C.
Bridge view, 111.
Newark. Calif.
Amalgamated Chem. Corp.. Philadelphia, Pa.
Colloids, Inc., Franklin, N.J.
Defiance Indust. Inc., Baltimore, Md.
Emkay Chem. Co., Elizabeth, N. J.
Farnow, Inc., S. Kearny, N.J.
Great Northern Paint & Chem. Corp., E. Paterson,
Gulf Oil Corp., Lansdale, Pa.
H & N Chemical Co., Totowa, N.J.
Environmental Protection Agency
PRODUCERS: POLYVINYL ACETATE
Producer and Location
Hart Products Corp., Jersey City, N.J.
McClosky Varnish Co., Philadelphia, Pa.
Los Angeles, Calif.
Portland, Ore.
Benjamin Moore & Co., Newark, N.J.
St. Louis, Mo.
Northeastern Labs. Co., Inc., Melville, N. Y.
The O'Brien Corp., Baltimore, Md.
South Bend, Ind.
Polymeric Resins Corp., Wilmington. Mass,
Quaker Chem. Corp., Conshohocken, Pa.
SCM Corp., Reading, Pa.
Chicago, ni.
Cleveland, O.
Huron, O.
San Francisco, Calif.
Scholler Bros., Inc., Elwood, N.J.
Squibb Beech-Nut, Inc., Canajoharie, N.Y.
Sun Chemical Corp., Wood Riber Junction, R, I.
Sybron Corp., Haledon, N. J.
Chas. S. Tanner Co., Providence. R. I.
U. S. Coatings Co., Inc., Kenilworth, N. J.
Franklin Chem. Co., Columbus, O.
The Hanna Paint Mfg. Co., Inc., Columbus, O.
The National Casein Co., Chicago, Ul.
PPG Indust., Inc., Circleville, O.
Pacific Holding Corp., Chicago, Dl.
Purex Corp., Ltd., Kansas City, Ka.
Morris, 111.
Carson, Calif.
The Sherwin-Williams Co., Chicago, 111.
Yenkin- Majestic Paint Corp., Columbus, O.
Bennett's. Salt Lake City. Utah
Diamond Shamrock Corp., Richmond, Calif.
Grow Chemical Corp., Oakland, Calif.
Kelly-~Moore Paint Co., San Carlos, Calif.
Kohler- Me Lister Paint Co., Denver, Colo.
N.J. Norris Paint & Varnish Co., Salem, Ore.
Preservative Paint Co., Seattle, Wash.
Sinclair Paint Co., Los Angeles, Calif.
Union Oil Co. of California, La Mirada, Calif.
-------
APPENDIX 1 (continued)
Environmental Protection A'gency
PRODUCERS: STYRENE RESINS
Producer and Location
Borden Inc.. Uliopolls. ni.
Bainbridge, N.Y.
Leominster, Mass.
Compton, Calif.
Demopolis, Ala.
S. C. Johnson & Sons, Inc., Racine, Wise.
Morton Chem Co., Ungwood, 111.
The O'Brien Corp,, South Bend, Ind.
South San Francisco, Calif.
PurexCorp.. Ltd., Chicago, ni.
Bristol, Pa.
Carson, Calif.
A. E. Staley Manufacturing Co., Lemont, HI.
Kearney, N.J.
Beatrice Foods Co., Wilmington, Mass.
Howard Industries, Inc., Hicksville, N. Y.
Pennsylvania Industrial Chem. Corp.. Clairton. Pa.
Phillip Morris, Inc., Springdale, Conn.
Polymeric Resins, Corp.. Wilmington, Mass.
Reichhold Chems., Inc., Elizabeth, N. J.
Scholler Bros. Inc., Elwood, N.J.
Sybron Corp., Haledon, N. J.
Alabama Binder and Chemical Corp., Tuscaloosa, Ala.
Southern Petrochemical Corp., Channelview, Tex.
-------
APPENDIX 1 (continued)
Producer and Location
Poly Resins, Inc.. Sun Valley. Calif.
Allied Chemical Coip., Los Angeles, Calif.
Capiagne. N.Y.
Whippany, N.J.
Des Plaines, 111.
Allied Products Coip., Los Angeles, Calif.
Seattle, Wash.
Memphis, Tenn.
Orlando, Fla.
Long Island City, N.Y.
Chicago, 111.
Detroit. Mich.
De Soto, Inc., Berkeley, Calif.
Garland, Tex.
Chicago Heights, 111.
The Dexter Corp., Hayward, Calif.
Rocky Hill, Conn.
Cleveland, O.
Waukegan. Ql.
Georgia Pacific Corp., Coos Bay, Ore.
Conway, N. C.
Columbus, O.
Crossett, Ark.
Savannah. Ga.
Louisville, Miss.
Lupkin, Tex.
Hercules Inc., Eugene, Ore.
Tacoma. Wash.
Wilmington, Del.
Inmont Corp., Anaheim, Calif.
Chicago, ni.
Cincinnati, O.
Grand Rapids, Mich.
Los Angeles, Calif.
Morganton, N.C.
Huntington, Ind.
Clifton, N.J.
Elizabeth. N.J.
Newark, N.J.
Environmental Protection Agency
PRODUCERS: PHENOLICS
Producer and Location
PPG Industries, Inc., Cleveland, O.
Milwaukee, Wise.
Torrance, Calif.
Atlanta (East Point), Ga.
Houston, Tex.
Springdale, Pa.
Preservative Paint Co., Seattle, Wash.
Rezolin, Inc., Chatsworth, Calif.
Taylor Corp., La Verne, Calif.
Betzwood, Pa.
Tenneco, Inc., San Francisco, Calif.
U. S. Plywood, Redding, Calif.
VWR United Corp., Portland, Ore.
Richmond, Calif.
Newark, O.
West Coast Adhesives, Co., Portland, Ore.
Weyerhaeuser Co., Longview. Wash.
Marsh.fi.eld, Wise.
Gulf Oil Corp., Alexandria, La.
Lansdale, Pa.
Masordte Corp.. Gulfport, Miss.
MMM, Decatur, Ala.
Napko Corp., Houston, Tex.
National Casein Co., Tyler, Tex.
Riverton, N.J.
Chicago, m.
Onyx Oils & Resins, Inc., Brooks, Fla.
Newark, N.J.
Owens-Coming Fiberglas Corp., WaxahacMe, Tex.
Barrington, N.J.
Kansas City, Kans.
Newark, O.
Sonoso Products Co., Hartsville. N.C.
Union Camp Corp., Valdosta, Ga.
Valentine Sugars, Inc., Lockport, U.
The Bendix Corp., Troy, N.Y.
The Budd Co., Bridgeport, Pa.
The Carbarundum Co., Niagara Falls, N. Y.
Clark Oil & Refining Corp., Tewksbury, Mass.
-------
APPENDIX 1 (continued)
Environmental Protection Agency
PRODUCERS: PHENOLICS
Producer and Location
Crowley Tar Prod. Co., Inc., Paulsboro, N. J.
Firestone Tire and Rubber Co., Fall River, Mass.
Kroedler, Alphonse & Co.. Lancaster, Pa.
Koppers Co., Inc., Petrolia, Pa.
Kyanize Paints, Inc., Everett, Mass.
Lawter Chems., Inc.. South Keamy. N.J.
Millmaster Onyx Corp., Lyndhurst, N. J.
Pennsylvania Indust. Chem. Corp., Clairton, Pa.
Pioneer Plastics Corp., Auburn, Me.
Polyrez Co., Inc., Woodbury, N.J.
Raybestos-Manhatten Inc., Stratford, Conn.
Resyn Corp., Linden, N. J.
Rogers Corp., Manchester, Conn.
Rohm & Haas Co., Philadelphia, Pa.
Schenectady Chems. Inc., Rotterdam Junction, N. Y.
Schenectady, N.Y.
Shanco Plastics & Chem. Inc., Tonawanda, N. Y.
Standard Oil of New Jersey, Odenton, Md.
Stepan Chem. Co., Wilmington, Mass.
Sybron Corp., Birmingham, N. J.
Synvar Corp., Wilmington, Mass.
TRW Inc., Downington, Pa.
Uniroyal Inc., Naugatuck, Conn.
United-Erie, Inc., Erie, Pa.
U. S. Coatings Co., Inc., Kenilworth, N. J.
Westinghouse Electric Corp., W. Mifflin (Pittsburgh), Pa.
American Cyanamid Co., Evendale (Cincinnati), O.
CPC International, Inc., Forest Park, 111.
Carboline Co., Xenia, O.
Clark Oil & Refining Corp., Blue Island, 111.
P. D. George Co., St. Louis, Mo.
Hereseti & Chem. Co., Manetowoc. Wise.
Illinois Central Indust., Inc., Troy, Mich.
Inland Steel Co., Alsip, HI.
Ironsides Resins, Inc., Columbus, O.
Midwest Mfg. Corp., Burlington, Iowa
Mobil Oil Corp., Kankakee, 111.
Plastics Engineering Co., Sheboygan, Wise.
The Richardson Co., De Kalb, 111.
-------
APPENDIX 1 (continued)
Environmental Protection Agency
PRODUCERS: ACRYLICS
Producers of Acrylic Coating Resins
The following companies supply acrylic coating resins to U. S. paint
companies. They do not produce paint. Companies that also produce
paint will be listed in a subsequent table.
Allied Chemical Corp., Lynwood, Calif. Rohm and Haas Co., Bristol, Pa.
Toledo, Ohio Knoxville. Tenn.
Whippany, N.J. Louisville, Ky.
American Cyanamid Co., Azusa, Calif. A. E. Staley Mfg. Co., Cambridge, Mass.
Wallingford, Conn. Lemont, 111.
Archer Daniels Midland Co., Valley Park, Mo. Marlboro, Mass.
Ashland Oil & Refining Co., Fords, N. J. Union Carbide Corp., Bound Brook, N. J.
Minnesota Mining & Manufacturing Co., St. Paul, Minn. South Charleston, W. Va.
Monsanto Co., Addyston, Ohio Union Oil Co. of Calif., Charlotte, N. C.
Santa Clara, Calif. Chicago, 111.
Springfield, Mass. Los Angeles, Calif.
National Starch and Chemical Corp., Meredosia, HI. The Borden Chemical Co., Bainbridge, N.Y.
Piainfield, N.J. Compton, Calif.
Onyx Oils & Resins, Inc., Brooker, Fla. Demopolis, Ala.
Newark, N.J. Dliopolis, ffl.
Polyvinyl Chemicals, Inc., Wilmington, Mass. Leominster, Mass.
Purex Corp., Ltd., Chicago, HI. The Dow Chemical Co., Freeport, Tex.
Los Angeles, Calif. Midland, Mich.
Philadelphia, Pa. Pittsburgh, Calif.
Reichhold Chemicals, Inc., Azusa, Calif. Freeman Chemical Corp., Ambridge, Pa.
Detroit, Mich. Saukville, Wise.
Elizabeth, N.J. H. B. Fuller Co., St. Bernard, Ohio
Jacksonville, Fla. The Goodyear Tire & Rubber Co., Akron, Ohio
S. San Francisco, Calif. Jersey State Chemical Co., Haledon, N.J.
S. C. Johnson & Son, Inc., Waxdale, Wise.
-------
APPENDIX 1 (continued)
Environmental Protection Agency
PRODUCERS : ACRYLICS
Producers of Polyacrylic Acid and Its Salts
Alco Standard Coip., Chattanooga, Tenn. The B. F. Goodrich Co., Calvert City, Ky.
Philadelphia, Pa. W. R. Grace & Co., Lake Zurich, HI.
American Aniline & Extract Co., Calvert City. Ky. Jordan Chemical Co., Folcrott, Pa.
Philadelphia, Pa. Rohm and Haas Co., Bristol, Pa.
Colloids, inc., Newark, N.J. Knoxville, Tenn.
Diamond Shamrock Corp., Cedartown. Ga. Philadelphia, Pa.
B. F. Goodrich and Rohm and Haas are the largest producers of poly-
acrylic acid and its salts.
Producers of Specialty Acrylates
Aceto Chemical Co., Inc., Carlstadt, N.J.
Alcolac Chemical Corp.. Baltimore, Md.
American Aniline & Extract Co., Calvert City, Ky.
Philadelphia, Pa.
Borden Inc., Philadelphia, Pa.
Sartomer Resins, Inc., Essington, Pa.
Producers of Polyacrylamide Flocculants
American Cyanamid Co., Princeton, N.J. Merck & Co., Inc., Ellwood City, Pa.
Warners, N. J. Nalco Chemical Co., Chicago, Ell.
Woodridge, N.J. National Starch and Chemical Corp., Meredosia, 01.
Betz Laboratories, Inc.. Trevose. Pa. Standard Brands. Inc.. Tylac Chemicals Div.,
The Dow Chemical Co., Midland, Mich. Sayreville. N.J.
Hercules Inc., Hopewell, Va. Stein, Hall & Co., Inc., Charlotte, N.C.
-------
APPENDIX 1 (continued)
Environmental Protection Agency
PRODUCERS : ACRYLICS
Producers of Acrylic Coatings and Resins
The following companies produce acrylic coatings and supply all or part
of their resin demand from captive resin production.
Armstong Paint & Varnish Works, Inc., Chicago, ni.
Baltimore Paint & Chemical Corp., Baltimore, Md.
Celanese Coatings Co., Detroit, Mich.
Newark, N.J.
Riverside, Calif.
Belvideie, N.J.
Louisville, Ky.
Cook Paint & Varnish Co., Detroit. Mich.
Houston, Tex.
De Soto Chemical Coatings, Inc., Berkeley, Calif.
Chicago Heights, HI.
Garland, Tex.
E. I. du Pont de Nemours & Co., Inc., Belle, W. Va.
Chicago, ni.
Everett, Mass.
Flint, Mich.
Fort Madison, Iowa
Parlin. N.J.
Philadelphia. Pa.
S. San Francisco, Calif.
Toledo, Ohio
Tucker, Ga.
The Glidden Co., Chicago, m.
Cleveland, Ohio
Huron, Ohio
Reading, Pa.
San Francisco, Calif.
Guardsman Chem. Coatings, Inc., Grand Rapids, Mich.
Hunt Foods & Industries, Inc., Los Angeles. Calif.
Seattle, Wash.
S. San Francisco, Calif.
Interchemical Corp., Anaheim, Calif.
Detroit, Mich.
Cincinnati, Ohio
Newark, N.J.
Jones-Blair Paint Co., Inc., Dallas, Tex.
Midland Industrial Finishes Co., Inc., Waukegan.ni.
Mobil Chemical Co., Cleveland, Ohio
National Lead Co., Philadelphia, Pa.
The O' Brien Corp., South Bend, Ind.
PPG Industries, Circleville, Ohio
Milwaukee, Wis.
Newark, N.J.
Springdale, Pa.
The Sherwin-Williams Co., Chicago, m.
Standard T. Chemical Co., Inc.. Chicago, HI.
Staten Island, N. Y.
-------
APPENDIX 1 (continued)
Environmental Protection Agency
PRODUCERS: POLYAMIDE RESINS *8)
Producer and Location
AZ Products. Inc.. Eaton Park, Fla.
Cooper Polymers, Inc., Wilmington. Mass.
Emery Industries, Inc., Cincinnati, O.
The Epoxylite Corp., South El Monte, Calif.
Buffalo. N.Y.
General Mills, Inc., Kankakee, 111.
LawterChemicals, Inc., South Kearny, N.J.
Mobil Oil Corp., Cicero, 111.
Reichhold Chemicals, Inc., Ballard Vale, Mass.
Stepan Chemical Co.. Millsdale, 01.
Sun Chemical Corp., Chester, S.C.
Wood River Junction. R. I.
Tenneco Chemicals, Inc., Garfield, N. J.
U. S. M. Corporation, Middleton, Mass.
-------
APPENDIX 2
DEVELOPMENT OF EMISSION POTENTIAL INDICES
roster 0 Snell. Inc
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Polypropylene
Work Sheet
A = Receiving and storage of process chemicals:
Propylene is stored as a liquid. Diluents are stored blanketed with an
inert gas. Tank vents and feed lines are emission sources. Catalysts
are shipped either as solids or diluted with a hydrocarbon solvent -
emissions may occur as a result of materials handling.
B = Purification of monomers and/or solvents:
Propylene and solvent are recovered from polymerization unit and are
condensed and recycled to reactor. The deactivation solvent is distilled
and recycled.
C = Prepolymerization:
Propylene, solvent and catalyst are premixed. An emission source is the
premix tank vent.
D = Polymerization:
Polymerization conducted at under 200 psig and between 100 and 200°F.
Solvent and propylene may be vented.
E = Polymer separation:
Propylene and other volatiles are flashed off. The catalyst is deactivated
by adding water or alcohol and polymer filtered off and dried in a rotary
or spray drier. Emissions occur during catalyst deactivation, transport
of polymer to and through driers.
F = Compounding:
Polymer is compounded with the necessary additives, melted and extruded.
Some residual solvent is emitted during melting and extrusion.
Factor Intensity Rating
(A)
A 10
B 10
C 6
D 8
E 10
F 6
Factor Weight
(B)
0.1
0.2
0.1
0.2
0.3
0.1
Index Number
AxB
1.0
2.0
0.6
1.6
3.0
0.6
8.8
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
HD Polyethylene
Work Sheet
A = Receiving and storage of process chemicals:
Ethylene is stored as a liquid. Tank vents and feed lines may be a source of
emissions. Cycloparaffins such as cyclohexane are liquids.
B = Purification of monomers and/or solvents:
Ethylene and diluent/solvent are recovered, purified and recycled. Venting
of compressors and condensers can be a source of emissions.
C = Prepolymerization:
Ethylene and diluent/solvent are premixed. Venting of this chamber is a
source of emission.
D = Polymerization:
Polymerization is conducted at 20-30 atm and 125-175°C .
E = Polymer separation:
Monomer is flashed off and recycled. Polymer/solvent solution contacted with
water or cooled and polymer precipitates and is filtered. Polymer is dried.
Conveyer systems and dryer vents are a major source of emission.
F = Compounding:
Polymer may be remelted, additives added and extruded. Vents on extruders
and volatilization of solvent during remelting may be a source of emission.
Factor Intensity Rating Factor Weight AxB
(A) (B)
A 10 0.05 0.5
B 10 0.2 2.0
C 4 0.05 0.2
D 8 0.2 1.6
E 10 0.3 3.0
F 6 0.2 1.2
Index Number 8.5
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
LD Polyethylene
Work Sheet
A = Receiving and storage of process chemicals:
Ethylene is stored as a liquid and tank vents may be a source of emissions.
Initiators such as organic peroxides are stored separately in relatively small
containers.
B = Purification of monomers and/or solvents:
Ethylene monomer is separated from the polymer mass, purified and recycled.
Emissions can occur from venting and leaks.
C = Prepolymerization:
Ethylene is compressed in stages. Emissions are possible at the compressor.
D = Polymerization:
Ethylene is polymerized at 15,000-50,000 psi and 100-200°C. Polymerization
is continuous and emissions can occur at vents, valves, and other leaks.
E = Polymer separation:
Polymer is usually extruded as strands directly from the devolatilizer and
a major source of emission is at extruder vents where the monomer still
dissolved in the polymer is emitted.
F = Compounding:
The polymer may be remelted, additives added and again extruded.
Extruder vents are a major source of emission, but not as great as the
previous stage.
Factor Intensity Rating Factor Weight AxB
(A)
A 10
B 8
C 4
D 10
E 8
F 6
(B)
0.1
0.1
0.1
0.2
0.3
0.2
Index Number
1.0
0.8
0.4
2.0
2.4
1.2
7.8
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Styrene Resins
(Bulk Continuous Solution
Work Sheet For Crystal Polystyrene)
A = Receiving and storage of process chemicals:
Styrene is the monomer used and ethyl benzene is the solvent. Some emissions
can occur as a result of styrene storage vents.
B = Purification of monomers and/or solvents:
Monomer and ethylbenzene are recovered and recycled.
C = Prepolymerization:
Monomer and solvent are premised.
D = Polymerization:
Polymerization conducted in stages starting at about 110°C and increasing
to 170°C.
E = Polymer separation:
Polymer is devolatilized at 225-250°C and polymer fed to an extruder,
cooled, cut and bagged.
F = Compounding:
Factor Intensity Rating Factor Weight AxB
(A) (B)
A 6
B 10 0.3 3.0
C 2 - -
2+6 = 4 0.1 0.4
D
E
F
E 28 0.6 4.8
Index Number 8.2
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Styrene Resins
(Suspension Process For
Work Sheet Crystal Polystyrene)
A = Receiving and storage of process chemicals:
Styrene is the only monomer used. Other ingredients include small amounts
of additives, suspending agents, buffering agents and initiators.
B = Purification of monomers and/or solvents:
None
C = Prepolymerization:
Monomer pumped into hot water containing the additives. Reactor venting
is a source of emission.
D = Polymerization:
Polymerization conducted in a stirred reactor at 190°F. Reactor vents are
a source of emissions.
E = Polymer separation:
Polymer mass is washed with water, the beads are centrifuged, dried,
extruded and packaged.
F = Compounding:
None
Factor Intensity Rating Factor Weight AxB
(A) (B)
A 6 0.05 0.3
B -
c 2 0.05 0.1
D 2 0.2 0.4
E 10 0.7 7.-
F ~
Index Number 7.8
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Styrene Resins
(Suspension Process For
Work Sheet Impact Polystyrene)
A = Receiving and storage of process chemicals:
Rubber and styrene are raw materials. Styrene storage tank vent is minor
emission source.
B = Purification of monomers and/or solvents:
None
C = Prepolymerization:
Rubber is dissolved in styrene monomer and converted to 10-20% polymer.
D = Polymerization:
The Rubber-styrene is suspended in water, peroxide added and polymeri-
zation conducted at 90°-130°C. Emissions result from reactor venting.
E = Polymer separation:
Polymer mass is flushed into a mechanical separator, the beads are washed,
centrifuged, dried and extruded. Emissions result from extruder and drier
vents.
F = Compounding:
Factor Intensity Rating Factor Weight AxB
(A) (B)
A 6 0.1 0.6
B -
C 6 0.1 0.6
D 8 0.4 3.2
E 8 0.4 3.2
F -
Index Number 7.6
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Styrene Resins
(Bulk Continuous Process
Work Sheet por Impact PoiyStyrene)
A = Receiving and storage of process chemicals:
Rubber and styrene are raw materials. Styrene storage tank is a minor
emission source.
B = Purification of monomers and/or solvents:
Styrene is recovered and recycled.
f. = Prepolymenzation:
Rubber IF. dissolved in styrene monomer.
D = Polymerization:
Polymerization conducted in a continuous tower operating in temperature
gradients from 90°C to 150-200°C .
P = Polymer separation:
Polymer mass is devolatilized in a thin-film evaporator or gear
evolatilizer, extruded and packaged.
F - Compounding:
Factor Intensity Rating Factor Weight AxB
(A) (B)
A 6 0.05 0.3
B 8 0.1 0.8
C 4 0.05 0.2
D 6 0.5 3.-
E 8 0.3 2.4
F - - -
Index Number 6.7
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Styrene Resins-
(ABS Process)
Work Sheet
A = Receiving and storage of process chemicals:
Raw materials include styrene, butadiene and acrylonitrile with peroxides
being used as catalysts. Emission sources are vents from storage tank.
B = Purification of monomers and/or solvents:
Monomers are recovered and recycled.
C = Prepolymerization:
D = Polymerization: Two separate polymerizations are conducted.
1) Acrylonitrile and Butadiene are emulsified in water and polymerized
at 105°F. Monomers are removed by stripping with steam under vacuum.
2) Styrene and acrylonitrile are emulsified in water and polymerized at 122°F.
E = Polymer separation:
Both (1) and (2) above are emulsions and are stored.
F = Compounding: (1) and (2) above are mixed and coagulated or floculated by
acidification, the crumb is washed with water and dried. It is further compounded
by feeding the dried crumb to an extruder or banbury type mixer where ABS is
fluxed, milled and extruded.
Factor Intensity Rating Factor Weight AxB
(A) (B)
A 8 0.05 0.4
B 10 0.05 0.5
C 2
D 6 0.7 4.2
E -
F 8 0.2 1.6
Index Number 6.7
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Coumarone-Indene And
Work Sheet Petroleum Resins
A = Receiving and storage of process chemicals:
Coal and petroleum tar oils are the basic raw materials. Aromatic solvents
are used extensively.
B = Purification of monomers and/or solvents:
Tar oils are fractionated and blended. Emissions occur at condenser vents.
C = Prepolymerization:
None
D = Polymerization:
Polymerization begins at low temperature and the exotherm raises temperature
to 95-lOSoC.
E = Polymer separation:
Polymer is washed and heated to 200°C and flashed under vacuum or injected
with steam and drummed or flaked.
F = Compounding:
Factor Intensity Rating Factor Weight AxB
(A)
A 6 0.1 0.6
B 8 0.2 i.a
C
D 2 0.2 0.4
E 8+10 = 9 0.5 4.5
F 2 4 _
Index Number 7.1
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Vinyl Resins
Work Sheet (Polyvinyl Chloride)
A = Receiving and storage of process chemicals:
Vinyl chloride and comonomers, i.e. vinylidene chloride, vinyl acetate are
principle monomers. Plasticizers and ketone solvents are also used in compounding,
Emissions can occur from storage tank vents.
B = Purification of monomers and/or solvents:
Vinyl chloride is recovered from reactor and distilled and recycled.
C = Prepolymerization:
Monomer and water are mixed with the initiator.
D = Polymerization:
Polymerization conducted at 45-55°C to 90% conversion.
E = Polymer separation:
Polymer transferred to a dump tank, monomer is removed under vacuum and
sent to distillation unit. Polymer separated by centrifugation and dried in a
rotary drier.
F = Compounding:
PVC may be dissolved in ketones or plastic!zed by mixing in heated blenders.
Factor Intensity Rating Factor Weight AxB
(A) (B)
A 10 0.05 0.5
B 8 0.2 1.6
C 2 0.05 0.1
D 6 0.3 1.8
E 8 0.3 2.4
F 8 0.1 0.8
Index Number 7.2
10
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APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Vinyl Resins
Work Sheet (Polyvinyl Alcohol)
A = Receiving and storage of process chemicals:
Polyvinyl acetate (beads) is the basic raw material. Methanol is used in
alcoholysis of the poly vinyl acetate. Sodium hydroxide is the catalyst.
B = Purification of monomers and/or solvents:
Methanol recovery. Impurities consist of methyl acetate.
C = Prepolymerization:
PVAc is dissolved in hot methanol (120-140°F)
D = Polymerization:
Sodium hydroxide in methanol is added to convert the acetate to alcohol and
gellation occurs. Additional methanol is added, after the gel is ground, and
alcoholysis is completed to desired degree.
E = Polymer separation:
The slurry is sent to an expressor where liquid and solid are separated.
The solid is dried in a rotary drier.
F = Compounding:
Factor Intensity Rating Factor Weight AxB
(A) (B)
A 8 - -
B 4 0.2 0.8
C 6 - -
D 2 0.1 0.2
E 8 0.7 5.6
F -
Index Number 6.6
11
-------
Work Sheet
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Vinyl Resins
(Polyvinyl Acetate)
A = Receiving and storage of process chemicals:
Vinyl Acetate is the main constituent. Many other ingredients, i.e. emulsifier,
catalyst, protective colloids, buffers are used in minor quantities. Emissions
are principally vinyl acetate venting.
B = Purification of monomers and/or solvents:
None
C = Prepolymerization:
Vinyl acetate is mixed with water and other ingredients
Venting of reactor is a source of emissions.
D = Polymerization:
Polymerization conducted at 67-80°C with reflux.
E = Polymer separation:
Emulsion is cooled and transferred to storage.
F = Compounding:
Factor
A
B
C
D
E
F
Intensity Rating
(A)
8
2
4
2
Factor Weight
(B)
.1
.1
0.7
.1
AxB
0.8
0.2
2.8
0.2
Index Number 4.0
12
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Polyamides
Work Sheet (Nylon 6)
A = Receiving and storage of process chemicals:
Caprolactam and acetic acid are raw materials.
B = Purification of monomers and/or solvents:
Monomer is recovered by steam distillation of polymer at 300-400°C.
C = Prepolymerization:
None.
D = Polymerization:
Polymerization conducted at 255-260°C in presence of acetic acid.
E = Polymer separation:
Polymer removed to surge tank, extruded, washed with water at 180-195°F,
dewatered by filtering or centrifugation and dried. Emissions through
extruder vents, drier.
F = Compounding:
Factor Intensity Rating Factor Weight AxB
(A) (B)
A 7 -
B 8 0.6 4.8
C
D 4 0.1 0.4
E 8 0.3 2.4
F
Index Number 7.6
13
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Polyamides
Work Shea.
-------
Work Sheet
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Cellulosics
(Cellulose Acetate)
A = Receiving and storage of process chemicals:
Cellulose is the "monomer" used. Major process chemicals include acetic
acid, acetic anhydride, methylene chloride, solvents (MEK, ethanol,
methanol, benzene)
B = Purification of monomers and/or solvents:
Distillation of acetic acid, methylene chloride.
C = Prepolymerization:
Cellulose is added slowly to a mixture of acetic anhydride and glacial acetic
acid with small amounts of sulfuric acid (7-10°C) in a mixing tank, then
pumped to the acetylator.
D = Polymerization:
The temperature is kept below 30°C until acetylation is complete; then pumped
to a hydrolyzer. (If methylene chloride is used, acetylation is conducted at
reflux , about 40-50°C) .
E = Polymer separation:
The mixture is dumped into a large volume of water, centrifuged (the acetic
acid is recovered and reused) , washed with water, centrifuged and dried.
Emissions occur as a result of drier vents.
F = Compounding:
Cellulose acetate is usually compounded by either dry compounding or solution
compounding. In dry compounding, emissions are very small. In solvent
compounding, however, solvent emissions are common and relatively high.
Factor Intensity Rating Factor Weight AxB
(A) (B)
A 8
B 6 0.1 0.6
C 2
D 2+4 = 3 0.1 0.3
E 26 0.3 1.8
F 8 0.5 4.-
Index Number 6.7
15
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Amino Resins
Work Sheet
A = Receiving and storage of process chemicals:
Urea and melamine are solids; formaldehyde in the form of 37% solids.
B = Purification of monomers and/or solvents:
None.
C = Prepolymerization:
None.
D = Polymerization:
Polymerization conducted at 75-150°F or at reflux temperature. Formaldehyde
is probably emitted.
E = Polymer separation:
Package directly after filtering or pass on to compounding. Formaldehyde odors
emitted during packaging.
F = Compounding:
Most U-F and M-F resins are compounded into molding powders. Others are
spray dried directly. Emissions occur in drying hoppers or in cyclone exhausts.
Factor Intensity Rating Factor Weight AxB
(A) (B)
A 2 + 4 = 3 0.1 0.3
B 2 -
C -
D 4 0.4 1.6
E 2 0.1 0.2
F 8 0.4 3.2
Index Number 5.3
16
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Acrylics
(Emulsion Polymerization)
Work Sheet *
A = Receiving and storage of process chemicals:
Acrylic monomers.
B = Purification of monomers and/or solvents:
None.
C = Prepolymerization:
Monomer is added to the water containing initiators and reactor purged with
an inert gas. Emissions and aerosols can occur as result of purging.
D = Polymerization:
There is a short induction period (30-50°C) and a vigorous reaction occurs
arid temperatures may approach 90-95°C. Polymerization essentially complete
in 15 minutes.
E = Polymer separation:
Monomers are removed by steam stripping to lower odor. Monomers are
usually not reused and are destroyed. Emissions are possible during
drumming operations or during storage.
F = Compounding:
None.
Factor Intensity Rating Factor Weight AxB
^ (A) (B)
A 8 .1 0.8
B
C 2
D 5 .8 4.0
E 6 .1 0.6
F - -
Index Number 5.4
17
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Acrylics
(Solution Polymerization)
Work Sheet '
A = Receiving and storage of process chemicals:
Acrylic monomers; aromatic solvents, i.e. xylene, toluene; ketones, i.e. MIBK,
MEK; others.
B = Purification of monomers and/or solvents:
None.
C = Prepolymerization:
None/
D = Polymerization:
Solvent is placed in the kettle and at reflux, separate streams of monomer
and initiator are added over a period of 8 to 24 hours. Emissions through
condenser venting and leakage.
E = Polymer separation:
Polymer mix is sent to storage or drummed directly. Emissions during
drumming.
F = Compounding:
None.
Factor Intensity Rating Factor Weight AxB
(A) (B)
A 8 0.1 0.8
B -
C -
D 4 0.8 3.2
E 6 0.1 0.6
F -
Index Number 4.6
18
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Alkyds
Work Sheet
A = Receiving and storage of process chemicals:
Anhydrides, fatty acids, oils, and polyhydric alcohols are either liquids
or solids with low vapor pressure. Solvents, mostly aromatic, are used
as thinners.
B = Purification of monomers and/or solvents:
None.
C = Prepolymerization:
None.
D = Polymerization:
Polymerization carried out at 210-250°C with solvent or azeotropic distillation.
Sparge gas used to supplement agitation. Emissions occur through solvent
losses in distillation, aerosol formation with sparge gas.
E = Polymer separation:
Polymer is dropped into a thinning tank containing solvent. Addition is made
at reflux. Solvent emissions occur during venting.
F = Compounding:
Solvent odors prevalant in shipping area because of filling open-head drums
and spillage.
Factor Intensity Rating Factor Weight AxB
(A) (B)
A 3 0.05 .2
B -
C -
D 4 Q.5 2.0
E 6 0.4 2.4
F 4 0.05 Q.2
Index Number 4.8
19
-------
APPENDIX '2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Polyesters
Work Sheet
A = Receiving and storage of process chemicals:
The anhydrides used are all solids. Glycols are liquids of low vapor pressure
and the reactive monomer or solvent is usually styrene, a liquid of high vapor
pressure.
B = Purification of monomers and/or solvents:
None.
C = Prepolymerization:
None.
D = Polymerization:
Polymerization conducted at 190-220°C with water of reaction removed through
a condenser. Reaction mass is sparged during cooking to remove water. Emissions
occur through condenser vents, reactor gaskets.
E = Polymer separation:
Polymer mass is cooled to 100-150°C and dropped into a thinning tank containing
monomer. Venting results in emissions.
F = Compounding:
Factor Intensity Rating Factor Weight AxB
(A) (B)
A 2 0.1 0.2
B
C
D 4 0.4 1.6
E 6 0.5 3.0
F
Index Number 4.8
20
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Epoxy Resins
Work Sheet
A = Receiving and storage of process chemicals:
Epichlorohydrin and Bisphenol A are the monomers. Small quantities of
xylene or methanol are used for salting out purposes.
B = Purification of monomers and/or solvents:
Recover epichlorohydrip.
C = Prepolymerization:
None.
D = Polymerization:
Polymerization conducted at epichlorohydrin b.p. 116°C .
E = Polymer separation:
Excess epichlorohydrin removed by vacuum distillation and recycled.
Filter, wash resin with warm water; heat resin to 100°C under vacuum
and drum.
F = Compounding:
Factor Intensity Rating Factor Weight AxB
(A) (B)
A
B 6 0.1 0.6
C
D 4 0.4 1.6
E 4 0.5 2.0
F
Index Number 4.2
21
-------
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNICAL EVALUATION GRID
Phenolic and Other Tar Acid Resins
Work Sheet
A = Receiving and storage of process chemicals:
Phenol and Formalin (37% formaldehyde) are the reactive ingredients.
Sometimes a solvent such as Butanol, Ethanol, MEK are used in making
solution resins.
B = Purification of monomers and/or solvents:
None.
C = Prepolymerization:
Venting of reactor during charging.
D = Polymerization:
Polymerization at atmospheric reflux temperature (60-85°C) , then temperature
raised to 85-90oC by refluxing under pressure. Emissions of phenol, formalde-
hyde and methanol occur during reflux through condenser vents.
E = Polymer separation:
Water is removed by vacuum distillation. Resin can be discharged directly into
drums, diluted with solvent, flaked or cured in molds.
F = Compounding:
Resins may be compounded with filler. Some may be pulverized with
hexamethylenetetramine.
Factor Intensity Rating Factor Weight AxB
(A) (B)
A 2 + 6 = 4
B 2 -
C 2 0.1 0.2
D 4 0.4 1.6
E 2+6 = 4 0.4 1.6
F 2 ' 6 0.1 0.6
Index Number 4.0
22
-------
Work Sheet
APPENDIX 2 (continued)
Environmental Protection Agency
TECHNiqAL EVALUATION GRID
Polyurethanes
A = Receiving and storage of process chemicals:
Diisocyanates, polyols and polyesters are major raw materials. Solvents,
when used, are Cellosolve esters, and aromatic solvents, i.e. xylene, or
toluene. Nitrogen is used to blanket reaction kettles.
B = Purification of monomers and/or solvents:
None.
C = Prepolymerization:
None.
D = Polymerization:
Diisocyanates are added rapidly to polyols or polyesters cold, then heated
at 110-115°C. The reaction mass is blanketed with nitrogen. Emissions
result from reactor vents during reaction, and when solvents are added.
E = Polymer separation:
Polymer mass is cooled, solvent added and stored.
F = Compounding:
Factor Intensity Rating Factor Weight AxB
(A) (B)
A 6 0.1 0.6
B -
C -
D 2 0.8 1.6
E 4 0.1 0.4
F -
Index Number 2.6
23
-------
APPENDIX 3
HAZARD , ODOR AND PHYSICAL DATA ON PRINCIPAL
POLYMER INDUSTRY CHEMICALS
Foster 0 Snell. Inc
-------
Product
OSHA
(55)
Other
Odor Threshold
APPENDIX 3
Environmental Protection Agency
POLYURETHANES
Physical Data
b.p. (°C) Vapor Pressure (mmHg(°C))
Toluene Diisocyanate .02 ppm = .14 mg/m3
4.4' - Diphenylmethane
Diisocyanate . 02 ppm = . 2 mg/m3
"Hexamethylene
Diisocyanate
n.a.
4,4',4" - Triphenylmethane
Triisocyanate n.a.
Xylene
100 ppm = 435 mg.m
Ethylene Glycol Monoethyl
Ether 200 ppm = 740 mg/m
Toluene
Mineral Spirits
200 ppm
n.a.
Ethyl Acetate 400 ppm = 1,400 mg/md
Butyl Acetate 150 ppm = 710 mg/m3
Methyl Ethyl Ketone 200 ppm = 590 mg/m3
Methyl Isobutyl
Ketone 100 ppm = 410 mg/m3
n.a.
n.a.
500 ppm
(56)
.4 ppm
(56)
n.a.
n.a.
n.a.
20 ppm = 100 mg/m
ethereal odor
3 (57)
40 ppm = 140 mg/m
3 (57)
n.a.
50 ppm = 180 mg/m
3 (57)
n.a.
3 (57)
25 ppm = 80 mg/m
8 ppm = 32 mg/m3 (57)
250.0
n.a.
n.a.
n.a.
139.0
134.7
110.6
150-210
77.0
125.0
79.6
115.8
n.a.
n.a.
n.a.
10 (29)
5.3 (25)
30 (26)
n.a.
100 (25)
15 (25)
100 (25)
7.5 (25)
-------
APPENDIX 3 (continued)
Environmental Protection Agency
ALKYDS
Product
OS HA
(55)
Safety
Phthalic Anhydride 2 ppm = 12 mg/mj
Isophthahc Anhydride n.a.
Maleic Anhydride .025 ppm = 1 mg/m
to
Fumanc Acid
Azelaic Acid
Succinic Acid
Adipic Acid
Sebacic Acid
Xylene
Toluene
n.a.
n.a.
n.a.
n.a.
n.a.
Other
n.a.
very low toxicity
very low toxiclty
(56)
(SB)
very low toxicity (56)
very low toxiaty
(56)
very low toxicity * '
100 ppm = 435 mg/nr
Odor Threshold
choking odor
(56)
choking odor (»)
n.a.
n.a.
(56)
n.a.
odorlese
(56)
n.a.
n.a.
20 ppm = 100 mg/m
3 (57)
n.a. 200 ppm olifactory fatigue
.17 ppm
(46)
Physical Data
b.p. (°C) Vapor Pressure (mmHg(°Cl)
284.0
n.a.
202.0
200.0 sublimes
286.5
235.0
265.0
294.5
139.0
110.6
n.a.
n.a.
n.a.
n.a.
*1
n.a.
10 (29)
30 (26)
-------
Product
OSHA t55*
Safety
Phthalic Anhydride 2 ppm = 12 mg/ra
M-aleic Anhydride .025 ppm = 1 mg/m3
Eumaric Acid
Succimc Acid
Adipic Acid
Propylene Glycol
Ethylene Glycol
Diethylene Glycol
Neopentyl Glycol
Dipropylene Glycol
Styrene
n.a.
Isophthalic Anhydride n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
Q
Methylstyrene 100 ppm = 480 mg/m°
Other
very low toxicity
n.a.
very low toxicity (56)
very low toxidty (56)
none necessary
(56)
100 ppm (56)
not established (56)
n.a.
none necessary
(56)
100 ppm (60)
Odor Threshold
choking odor<56)
n.a.
n.a.
choking odor (?)
odorless
(56)
n.a.
n.a.
odorless
(56)
n.a.
n.a.
n.a.
.148 ppm
(46)
APPENDIX 3 (continued)
Environmental Protection Agency
POLYESTERS
;•. Physical Data
b.p. (°C) Vapor Pressure CmmHg(°C))
n.a.
284.0
202.0
200.0 sublimes
n.a.
235.0
265.0
187.2
197.6
245.0
n.a.
231.9
145.2
n.a.
n.a.
n.a.
n.a.
n.a.
.13 (25)
n.a.
4.3 (15)
1 (17)
-------
Product
Safety
OSHA155) Other
Odor Threshold
APPENDIX 3 (continued)
Environmental Protection Agency
EPOXY RESINS
Physical Data
b.p. (°C) Vapor Pressure (mmHg( Q)
Bisphenol A
.Sppm = 2.8 mg/nr
odorless
(56)
n.a.
n.a.
Bpichlorohydrin 5 ppm = 19 mg/md
Phenol
Cresol
Butanol
Glycerol
5 ppm = 19 mg/m
5 ppm = 22 mg/m
100 ppm = 300 mg/m
n.a.
Phthalic Anhydride 2 ppm = 12 mg/m3
n.a.
10 ppm
(56)
3 ppm = 12 mg/m'
3 (57J
5 ppm
25 ppm
(56)
(56)
n.a.
choking odor
(56)
116.1
182.0
195.0
117.7
290.0
284/0 sublimes
5 (25)
.35-(25)
.15 (25)
6.5 (25)
n.a.
n.a.
Stearic Acid
n.a.
not toxic
(56)
slight odor
(56)
291.0
n.a.
Phenylene Diamine
.1 mg/mj
n.a.
287.0
n.a.
Methanol
200 ppm = 260 mg/m
5.900 ppm = 7.800 mg/m3 t57) 64.5
125 (25)
-------
APPENDIX 3 (continued)
Environmental Protection Agency
PHENOLIC AND OTHER TAR ACID RESINS
Product
Phenol
Formaldehyde
Meta Cresol
en Resorcinol
Xylenols
Sulfuric Acid
Ammonia
Butanol
Ethanol
OSHA
(55)
Physical Data
5 ppm = 19 mg/m3
n.a.
5 ppm = 22 mg/nr
n.a.
100 ppm = 435 mg/m3
1 mg/m3
50 ppm = 35 mg/m
100 ppm = 300 mg/m3
1.000 ppm = 1,900 mg/m
Other
5 ppm
(60)
Methyl Ethyl Ketone 200 ppm = 590 mg/m3
Odor Threshold
3 ppm = 12 mg/m3 ^ 7)
037
50
25
lPPm<46>
.19 ppm 159>
odorless (56)
200 ppm (56)
n.a.
ppm= .026 mg/m3 <57)
15 ppm ^56)
3 f*71
ppm = 9 mg/m ia/J
ppm = 80-mg/m3 (57)
b.p. (°C)
182.0
-19.5
202.7
276.0
139.0
330.0
-33.4
117.7
78.4
79.6
Vapor Pressure (mmHg(°C))
.35 (25)
10 (88J
.15 (25)
"
10 (29)
«
n.a.
6.5 (25)
50 (25)
100 (25)
n
Cyclohexanone 50 ppm = 200 mg/m0
.12 ppm
(46)
155.6
4.5 (25)
-------
Product OSHA(55)
-Formaldehyde n. a.
Aniline
5 ppm = 19 mg/m3
os
Benzene Sulfonamide n. a.
Dicy andiamide n. a.
Melamine n.a.
Thiourea n.a.
p-Toluene Sulfonamide n.a.
Urea
Methanol
Butanol
Octanol
n.a.
200 ppm = 260 mg/m3
100 ppm = 300 mg/m
n.a.
Other
5 ppm (60)
n.a.
-n.a.
nontoxic
n.a.
n.a.
n.a.
n.a.
Odor Threshold
l.Oppm'46'
.23 ppm (59)
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
APPENDIX 3 (continued)
Environmental Protection Agency
AMINO RESINS
0 Physical Data
b.p. ( C) Vapor Pressure (mmHg((
-19.5
184.4
n.a.
decomposes
sublimes
n/a.
n.a.
n.a.
5900 ppm = 7800 m g/m3 (57) 796.0
15 ppm
(56)
n.a.
Xylene 100 ppm = 435 mg/m3 20 ppm = 100 mg/m3
Butyl Cellosolve n.a. 100 ppm eye. nose irritation (56) mild odor (56)
10 (-88)
15 (77)
n.a.
n.a.
50 (315)
n.a.
n.a.
n.a.
796.0
117.7
178.0
139.0
170.6
125 (25)
6.5 (25)
1
10 (29)
.88 (25)
Mineral Spirits
n.a.
500 ppm (56)
n.a.
150-210
n.a.
-------
APPENDIX 3 (continued)
Environmental Protection Agency
ACRYLICS
Product
OSHA<55)
Safety
Other
Odor Threshold
Physical Data
b.p. (°C) Vapor Pressure (mmHg(°C))
Ethyl Acrylate 25 ppm = 100 mg/nr
2-Ethylhexyl Acrylate n. a.
o
Methyl Acrylate 10 ppm-= 35 mg/m"
Isobutyl Acrylate n. a.
2-Cyanoethyl Acrylate n. a.
n.a.
n.a.
n.a.
2- Ethoxyethyl Acrylate n.a.
LC = 500 ppm (rat)
50
(56)
Toluene
Xylene
n.a.
200 ppm olifactory fatigue
(56)
100 ppm = 435 mg/nr
Ethyl acetate 400 ppm = 1.400 mg/m3
Methyl Ethyl Ketone 200 ppm = 590 mg/m3
Methyl Isobutyl
Ketone
.00024 ppm (46)
n.a.
n.a.
n.a.
n.a.
n.a.
.17ppm<4«
20 ppm = 100 mg/m3 (57)
n.a.
25 ppm = 80 mg/m
3 (57)
100 ppm = 400 mg/nr
ketone-hke odor
(56)
99.5
130.0
80.0
n.a.
n.a.
n.a.
110.6
139.0
77.0
79.6
30 (20)
1 (20)
68 (20)
n.a.
n.a.
n.a.
30 (26)
10 (29)
100 (25)
100 (25)
115.8
7.5 (25)
-------
Product
OSHA
(55)
Safety
Other
APPENDIX 3 (continued)
Environmental Protection Agency
COUMARONE-INDENE AND PETROLEUM RESINS
Odor Threshold
Physical Data
b.p. (°C) Vapor Pressure (mmHe(°C)l
oo
Coumarone
Indene
n.a.
n.a.
Styrene
10 ppm = 200 mg/m
Cyclopentadiene 75 ppm = 200 mg/m
n.a.
Methy Icy clopentadiene n.a.
Vinyltoluene
Methylindene
Methylstyrene
Xylene
Naphtha
100 ppm = 480 mg/m
n.a.
3
100 ppm = 480 mg/m
100 ppm = 435 mg/m
3
100 ppm = 400 mg/m
100 ppm t80)
n.a.
n.a.
n.a.
n.a.
n.a.
.148
(46)
n.a.
n.a.
n.a.
n.a.
20 ppm = 100 mg/m
3 (57)
n.a.
173.0
181.0
41.. 0
145.2
n.a.
n.a.
n.a.
n.a.
139.0
65.1
n.a.
n.a.
n.a.
4.3 (15)
n.a.
n.a.
n.a.
n.a.
10 (29)
n.a.
-------
APPENDIX 3 (continued)
Environmental Protection Agency
VINYL RESINS
^^,.j Physical Data
Product OSHA Other Odor Threshold b.p. (°C) Vapor Pressure (mmHg( O)
i (56)
Vinyl Chloride 50 ppm = 1300 mg/m" slight at 4100 ppm -13.8 2580 (20)
Vinyl Acetate n.a. 1C = 400 ppm (rat) (5B) .12 ppm <46) 73.^) 115(25)
50
10 Vinylidene Chloride n.a. n.a. 5000 ppm some, 1000 ppm most"" 31.7 591(25)
Methyl Ethyl Ketone (57)
(PVC) 200 ppm = 590 mg/m3 25 ppm = BO mg/md 79.5 100(25)
Methanol (PVA) 200 ppm = 260 mg/m3 5900 ppm = 7800 mg/m3 ( 64.5 125(25)
Methyl Acetate , f57i
(PVA) 200 ppm = 610 mg/m 200 ppm = 550 mg/m3 57.0 235(25)
-------
APPENDIX 3 (continued)
Environmental Protection Agency
CELLULOSICS
Product
Acetic Add
OSHA
f55)
Other
Odor Threshold
10 ppm = 25 mg/m*
2.6 ppm
(59)
Acetone 1,000 ppm = 2.4000 mg/m3 320 ppm = 770 mg/m
« (601 (56)
Methylene Chloride n.a. 500 ppm = 1750 mg/m3 IOUJ
Methanol 200 ppm = 260 mg/m3
3 (57)
b.p. (°C)
18.1
56.1
40.1
3 (57)
Ethanol
1.000 ppm = 1.900 mg/m
Ethyl Acetate 400 ppm = 1.400 mg/m3
.3
300 ppm
5.-900 ppm = 7.800 mg/m" *"" 64.5
50 ppm = 93 mg/m3 (57) 78.4
77.0
Dimethyl Phthalate
Diethyl Phthalate
Nitric Acid
Sulfuric Acid
5 mg/m
n.a.
50 ppm = 180 mg/m
(56)
3 (57)
n.a.
2 ppm - 5 mg/m3
lmg/m3
aromatic
aromatic
n.a.
n.a.
(56)
Physical Data
Vapor Pressure (mmHg(°Cl)
15 (25)
226 (25)
440 (25)
125 (25)
50 (25)
100 (25)
282.0
296.1
86.0
330.0
«1
n.a.
-------
APPENDIX 3 (continued)
Environmental Protection Agency
STYRENE RESINS
Product
OSHA
(55)
Other
Odor Threshold
Physical Data
b.p. (°C1 Vapor Pressure (rnrnHgt O)
Styrene
n.a.
Acrylonitrile 200 ppm = 45 mg/m3
1.4-Butadlene 1.000 ppm = 2.200 mg/m3
3
Ethyl Benzene 100 ppm = 435 mg/m
Vinyl Alcohol n.a.
C arbon Tetrachloride n.a.
100 ppra
(60)
n.a.
10 ppm
(60)
.148 ppm
21.4 ppm
(46)
(60.)
n.a.
n.a.
n.a.
BO ppm
(56)
14S.2
77.3
-4.4
136.2
n.a.
76.8
4.3 (15)
112 (25)
n.a.
10 (26)
n.a.
113 (25)
-------
APPENDIX 3 (continued)
Environmental Protection Agency
POLYPROPYLENE
Product
Propylene
Ethylene
Butane-1
n-Heptane
Cyclohexane
OSHA
n.a.
n.a.
n.a.
(55)
Safety
Other
Odor Threshold
1000 ppm (56)
lO.OOOppm - drowsiness1
500 ppm = 2,000 mg/m
300 ppm = 1050 mg/m
Titanium Tetrachloride n.a.
not established(56J
Titanium Trichloride
n.a.
n.a.
Ethanol
Methanol
1.000 ppm = 1,900 mg/m
200 ppm = 260 mg/m
slightly sweet smell (56)
5000 ppm
(56) cnnn „„„, (56)
n.a
300 ppm
(56)
n.a.
n.a.
Physical Data
b.p. ( C) Vapor Pressure (mmHg(°O)
not established (56) slightly sweet smell (56) -103.7
-47.7
-0.5
98.4
BO.7
136.4
n.a.
50 ppm = 9 mg/m3 (5?) 70.4
5900 ppm = 7800 mg/m3 (57) 64.5
large
large
1823 (25)
47.7 (25)
103 (26)
n.a.
n.a.
50 (25)
6.5 (25)
-------
CO
Product
Ethylene
Vinyl Acetate
Ethyl Acrylate
Propylene
1-Butene
OSHA
n.a.
(55)
APPENDIX 3 (continued)
Environmental Protection Agency
POLYETHYLENE AND COPOLYMERS
Physical Data
Other
Odor Threshold
1000 ppm
(56)
slightly sweet smell
(56)
n.a. LC= 4,000 (rat) inhalation (56)
50
.12 ppm
(46)
25 ppm = 100 mg/m
.00024 ppm
(46)
n.a.
n.a.
Isobutylene n.a.
Titanium Tetrachloride n.a.
not established
not established
not established
not established
(56)
(56)
(56)
(56)
slightly sweet smell
(56)
slightly sweet smell
slightly sweet smell
(56)
(56)
n.a.
Cycloparaffins
Naphtha
Light Diesel Oil
300 ppm = 1050 mg/m
3 (60)
300 ppm
(60)
100 ppm = 400 mg/m
n.a.
n.a.
n.a.
800 ppm = 3300 mg/m
3(57)
b.p. (°C) Vapor .Pressure (mmHg( O)
103.7
73.0
99.5
-47.7
-6.3
-6.3
n.a.
80.7
65-120
n.a.
large
115 (25.3)
30 (20)
n.a.
n.a.
n.a.
n.a.
1(25)
5 (25)
n.a.
-------
APPENDIX 3 (continued)
Environmental Protection Agency
POLYAMIDES
Product
OSHA
(55)
Safety
Other
Odor Threshold
Physical Data •
b.p. (°C) Vapor Pressure (mmHg(°C))
Caprolactam
n.a.
n.a.
n.a.
n.a.
3 (100)
Acetic Acid
100 ppm = 25 mg/m
2.6ppm
118.1
15 (25)
Hexamethylene Diamine n.a.
n.a.
n.a.
190.0
n.a.
-------
APPENDIX 4
DEVELOPMENT OF HAZARD AND ODOR POTENTIAL INDICES
rosier 0 Snell. Inc
-------
APPENDIX 4
Environmental Protection Agency
HAZARD/ODOR POTENTIAL
WORK SHEET (By Plastic)
Probable Emission
Odor Potential Hazard Potential
Factor Index Factor Index
Weight Rating Number Weight Rating Number
(A) (B) (AxB) (C) (D) (CxD)
Polyethylene (LD)
Ethylene
Catalyst
Polyethylene (HP)
Ethylene
Cycloparaffin
Catalyst
Vinyl Resins (PVC)
Vinyl Chloride
Other
. Copolymer monomers
. Solvents
. Catalyst
Vinyl Resins (PVAc)
Vinyl Acetate
Vinyl Resins (PVAlc)
Methanol
Methyl Acetate
.9
.1
2
(7)
1.8
.7
2.5
.9
.1
1
(4)
.9
.4
1.3
.6
.3
.1
.8
.2
2
2
(7)
1
6
1.2
.6
.7
2.5
.8
1.2
2.0
.6
.3
.1
.8
.2
1
1
(4)
4
4
.6
.3
.4
1.3
3.2
.8
4.0
1.0
8
8
1.0
4.0
9
1
1
2
.9
.2
1.1
.9
.1
2
2
1.8
.2
2.0
Foster D Snell, Inc
-------
Odor Potential
APPENDIX 4 (continued)
Hazard Potential
Probable Emission
Polystyrene (Bulk-crystal)
Styrene
Ethyl Benzene
Polystyrene (Suspension-crystal)
Styrene 1.0
Polystyrene (Impact)
Styrene 1.0
Styrene Resins (ABS)
Factor Index Factor Index
Weight Rating Number Weight Rating Number
(A) (B) (AxB) (C) (D) (CxD)
6
4
8
(5)
4.B
2.0
6.8
.6
.4
3
3
1.8
1.2
3.0
Styrene
Butadiene
Aery Ion trile
Polypropylene
Propylene
Diluent
Methanol
Catalyst
Phenolic and Other Tar Acid Resins
8
8
8
8
1.0
1.0
5
3
1
1
(D
2
1
(7)
.5
.6
. .1
.7
1.9
.5
.3
.1
.1
(1)
2
2
3.0
3.0
6
3
1
8
(5)
5
4.8
1.5
.5
6.8
.6
.3
.1
3
1
2
1.8
.3
.2
2.3
.5
.6
.2
.4
1-7
Formaldehyde
Phenol
Ethanol
Butanol
.6
.2
.1
.1
8
6
4
5
4.8
1.2
.4
.5
6.9
.6
,2
.1
.1
6
6
1
3
3.6
1.2
.2
.3
5.2
Foster 0 Snail. Inc.
-------
APPENDIX 4 (continued)
Odor Potential
Probable Emission
Polyesters
Phthalic Anhydride
Styrene
Amino Resins
Formaldehyde
Butanol
Xylene
Alkyds
Phthalic Anhydride
Xylene
Acrylics
Acrylates
Xylene
MEK
Factor
Weight
(A)
.9
.1
.6
.3
.1
.9
.1
.8
.1
.1
Rating
(B)
(5)
8
8
5
5
(5)
5
10
5
5
Index
Number
(AxB)
4.5
.8
5.3
4.8
1.5
.5
6.8
4.5
.5
5.0
8.0
.5
.5
9.0
Hazard Potential
Factor
Weight
(C)
.9
.1
.6
.3
.1
.9
.1
.8
.1
.1
Rating
(D)
7
3
6
3
3
7
3
5
3
2
Index
Number
(CxD)
6.3
.3
6.6
3.6
.9
.3
4.8
6.3
.3-
6.6
4.0
.3
.2
4.5
Coumarone-Indene and Petroleum Resins
Indene
Styrene
Xylene
Polyurethanes
TDI
MDI
Xylene
.6
.3
.1
.7
.2
.1
(8)
8
5
8
8
5
4.8
2.4
.5
7.7
5.6
1.6
.5
7.7
.6
.3
.1
.7
.2
.1
5
3
3
10
10
3
3.0
.9
.3
4.2
7.0
2.0
.3
9.3
Foster D. Snell. Inc
-------
APPENDIX 4 (continued)
Odor Potential
Probable Emission
Factor
Weight
(A)
Rating
(B)
Index
Number
(AxB)
Hazard Potential
Factor Index
Weight Rating Number
(C) (D) (CxD)
Cellulosics
Acetic Acid
Methylene Chloride
Methanol
6
3
1
6
2
1
3.6
.6
.1
.6
.3
.1
5
1
2
3.0
.3
.2
4.3
3.5
Epoxy Resins
Bisphenol A
Epichlorohydrin
1
8
1
5
.1
4.0
4.1
.1
.8
6
6
.6
4.8
5.4
Polyamides
Caprolactam
Acetic Acid
Hexamethylenediamine
8
1
1
(1)
6
(D
.8
.6
.1
.8
.1
.1
(D
3
(D
.8
.3
.1
1.5
1.2
Foster 0. Snell. Inc.
-------
TECHNICAL REPORT DATA
(Plcoie read Inunctions on the reverse before Completing)
1. REPORT NO.
EPA-650/2-74-106
3. RECIPIENT'S ACCESSION>NO.
4. TITLE AND SUBTITLE
System Analysis of Air Pollutant Emissions from the
Chemical/Plastics Industry
5. REPORT DATE
October 1974
6. PERFORMING ORGANIZATION CODE
7. AUTHORIS) ' r~
Herbert Terry and {Stephen Nagy
I. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING OR6ANIZATION NAME AND ADDRESS
Foster D. Snell, Inc.
Hanover Road
Florham Park, NJ 07932
10. PROGRAM ELEMENT NO.
1AB015; ROAP 21AXM-060
11. CONTRACT/GRANT NO.
68-02-1068
12. SPONSORING AGENCY NAME ANp ADDRESS
EPA, Office of Research and Development
NERO-RTP, Control Systems Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final; 3/73-^74
14. SPONSORING AGENCY CODE
IS. SUPPLEMENTARY NOTES
16. ABSTRACT
The report defines chemical/plastics industry producers, production vol-
ume, forecasted growth rates, plant capacities and locations, and average population
densities at each plant site. It despribes major processes in terms of equipment,
reaction conditions, specific process chemicals, and general air pollution controls.
A decision model was used to relate the interactions of such factors as total popula-
tion exposed, production volume, growth trends, emission, odor, and hazard poten-
tial of the most likely pollutants. The report identifies polyurethanes, acrylics, and
alkyds as the most likely candidates for in-depth study, estimating emissions fac-
tors and discussing emission controls and their costs. It gives similar information
for some high-volume plastic materials: polyethylene, polystyrene, polypropylene,
nylon, and poly vinyl chloride. Most of the pollution control devices used in the
industry are associated with large volume resin manufacture and function primarily
to recover product or heat values: in most instances, economics dictate against
installing control devices solely for pollution control. The report gives calculated
costs for various controls.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Air Pollution
Plastics Industry
hemical Plants
Systems Analysis
Production Capacity
Populations
Polyurethane Resins
CosJ: Estimates
Acrylic Resins
Alkyd Resins
Equipment
Odors
Air Pollution Control
Stationary Sources
Chemical/Plastics Ind-
ustry
Process Chemicals
Resin Manufacture
Hazard Potential
13B, HA
111
07A
13 H
05E
11J
8. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OR PAGES
293
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
-------