United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Cincinnati OH 45268
EPA 600 2 79 210a
Decer-ib«r 1979
Research and Development
Status
Assessment of
Toxic Chemicals
Acrylonitrile
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8, "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-79-210a
December 1979
STATUS ASSESSMENT OF TOXIC CHEMICALS:
ACRYLONITRILE
by
D. R. Tierney
T. R. Blackwood
Monsanto Research Corporation
Dayton, Ohio 45407
and
G. E. Wilkins
Radian Corporation
Austin, Texas 78766
Contract No. 68-03-2550
Project Officer
David L. Becker
Industrial Pollution Control Division
Industrial Environmental Research Laboratory
Cincinnati, Ohio 45268
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
-------
DISCLAIMER
This report has been reviewed by the Industrial Environmental
Research Laboratory - Cincinnati, U.S. Environmental Protection
Agency, and approved for publication. Approval does not signify
that the contents necessarily reflect the views and policies of
the U.S. Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or
recommendation for use.
11
-------
FOREWORD
When energy and material resources are extracted, processed,
converted, and used, the related pollutional impacts on our
environment and even on our health often require that new and
increasingly more efficient pollution control methods be used.
The Industrial Environmental Research Laboratory - Cincinnati
(lERL-Ci) assists in developing and demonstrating new and im-
proved methodologies that will meet these needs both efficiently
and economically.
This report contains a status assessment of the air emis-
sions, water pollution, health effects, and environmental signi-
ficance of benzidine. This study was conducted to provide a
better understanding of the distribution and characteristics of
this pollutant. Further information on this subject may be
obtained from the Organic Chemicals and Products Branch,
Industrial Pollution Control Division.
Status assessment reports are used by lERL-Ci to communicate
the readily available information on selected substances to
government, industry, and persons having specific needs and
interests. These reports are based primarily on data from open
literature sources, including government reports. They are indi-
cative rather than exhaustive.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
M-i
-------
ABSTRACT
An overview is given describing acrylonitrile sources, environ-
mental contamination, health effects, control technology and
regulatory action. Areas where information is needed include
the amount of acrylonitrile emissions caused by its use as a
raw material and the environmental levels of acrylonitrile
resulting from its production and consumption.
Approximately 860,000 metric tons of acrylonitrile are produced
and consumed in the U.S. annually. Of this amount, 42% is used
in making acrylic fibers; 19% is used for the production of ABS
and SAN resins and 4% for nitrile elastomer production. The
remaining acrylonitrile produced is either exported or used in
manufacturing miscellaneous products.
Acrylonitrile emissions resulting from its production and
transportation have been estimated at 696 metric tons/yr. An
additional 37 metric tons/yr are discharged to waterways during
transport. Information is needed concerning the release of
acrylonitrile from products composed of acrylonitrile copolymers.
Estimates indicate that no persons are exposed to concentrations
of nitriles above 0.07 ppm from a representative acrylonitrile
production facility. However, possible health effects from low-
level chronic exposure of acrylonitrile to a population have not
been documented.
Technology is available to control acrylonitrile emissions from
various sources. Incineration is used to control emissions from
process vent streams during acrylonitrile production. Methods
used to control emissions of acrylonitrile during storage and
transfer include vapor recovery systems, submerged filling and
floating roof tanks with double seals.
Government regulations involving acrylonitrile-based products
have been proposed or initiated, soft-drink bottles made from
acrylonitrile copolymers have been banned from the consumer
market by the FDA. A Threshold Limit Value of 45 mg/m3 has
been established as a workplace exposure standard. It is
expected that this standard will be revised downward. Present
use of acrylonitrile as a grain fumigant is being considered
for cancellation by EPA.
IV
-------
This report was submitted in partial fulfillment of Contract
68-03-2550 by Monsanto Research Corporation under the sponsorship
of the U.S. Environmental Protection Agency. This report covers
the period November 1, 1977 to December 31, 1977. The work was
completed as of January 20, 1978.
v
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CONTENTS
Foreword iii
Abstract iv
Figures viii
Tables .viii
Symbols and Abbreviations ix
Conversion Factors and Metric Prefixes x
Acknowledgement xi
1. Introduction 1
2. Summary 2
3. Source Description 6
Physical and chemical properties 6
Production /• , 7
Process description 7
Uses 10
Transportation and storage 13
4. Environmental Significance and Health Effects .... 14
Environmental significance 14
Health effects 17
5. Control Technology 22
Control methods 22
Control method efficiencies 24
Economics 25
6. Regulatory Action in Progress 26
References 27
VII
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FIGURES
Number Page
1 Potential sources of acrylonitrile pollution 3
2 Flow diagram for a representative acrylonitrile plant. 8
3 Acrylonitrile end uses 11
TABLES
1 Acrylonitrile Sources, Their Magnitude and Control . . 5
2 Physical and Chemical Properties of Acrylonitrile. . . 6
3 Acrylonitrile Plants 7
4 Stream Codes for Figure 2 9
5 Acrylonitrile Consumption (1976) 10
6 Acrylonitrile Used in Synthetic Fiber
Production (1976) 11
7 Producers of ABS Resins (1976) 12
8 Producers of Nitrile Rubber (1976) 12
9 Emission Factors for Acrylonitrile During Production . 14
10 Emission Factors for Acrylonitrile Manufacture
by Emission Point (Uncontrolled Emissions) 18
11 Emissions from Organic Chemical Industry 19
12 Acrylonitrile Plant Wastewater 20
13 Physiological Response to Various Concentrations
of Acrylonitrile in Air for Animals 21
14 Hydrocarbon Emission Factors for Acrylonitrile
Deep Well Ponds 23
viii
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SYMBOLS AND ABBREVIATIONS
ABS — acrylonitrile-butadiene-styrene resins
SAN — styrene acrylonitrile resins
TLV® — Threshold Limit Value
IX
-------
CONVERSION FACTORS AND METRIC PREFIXES
To convert from
Degree Celsius (°C)
Kilogram (kg)
Kilometer2 (km2)
Meter3 (m3)
Meter3 (m3)
Metric ton
Pascal (Pa)
Joule (J)
Joule (J)
CONVERSION FACTORS
to
Degree Fahrenheit
Pound-mass (pound-mass
avoirdupois)
Mile2
Foot3
Gallon (U.S. liquid)
Pound-mass
Pound-force/inch2 (psi)
Calorie (kg)
Newton-meter
Multiply by
t° = 1.8 t° + 32
J- \*
2.204
3.860 x 10-1
3.531 x 101
2.642 x 102
2.205 x 103
1.450 x 10-1*
2.386 x IQ~k
1.000
Prefix Symbol
Kilo
Milli
k
m
METRIC PREFIXES
Multiplication factor
103
10-3
Example
1 kg = 1 x 103 grams
1 mm = 1 x 10"3 meter
Standard for Metric Practice. ANSI/ASTM Designation:
E 380-76e, IEEE Std 268-1976, American Society for Testing and
Materials, Philadelphia, Pennsylvania, February 1976. 37 pp.
-------
ACKNOWLEDGEMENT
This report was assembled for EPA by Radian Corporation, Austin,
TX, and Monsanto Research Corporation, Dayton, OH. Mr. D. L.
Becker served as EPA Project Officer, and Dr. C. E. Frank, EPA
Consultant, was principal advisor and reviewer.
XI
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SECTION 1
INTRODUCTION
Acrylonitrile, an important synthetic organic chemical, is used
in a wide variety of products with broad consumer distribution.
It is a primary feedstock (or chemical intermediate) in the manu-
facture of acrylic fibers, nitrile rubber and plastic resins.
There is, however, concern of adverse health effects to the gen-
eral population from acrylonitrile exposure due to its toxicity.
There is a need to define the various sources from which acrylo-
nitrile may enter the environment, to establish the consequent
health and environmental effects, and to examine possible control
strategies and present regulatory actions. This report provides
a brief overview describing these items with emphasis on acrylo-
nitrile sources and the resulting environmental significance.
-------
SECTION 2
SUMMARY
Acrylonitrile is a commercially significant synthetic organic
chemical with 862,000 metric tons9 produced nationally in 1976.
It is manufactured in the United States solely by the SOHIO pro-
cess.
Physiological studies indicated that acrylonitrile in air is tox-
ic to animals in the range of 0.1 g/m3 to 1.0 g/m3. It is con-
sidered toxic to man having an established Threshold Limit Value
(TLV®) of 45 mg/m3.
For a representative acrylonitrile plant, acrylonitrile emissions
total 0.807 g/kg of acrylonitrile produced. Acrylonitrile emis-
sions due to its use as a raw material in manufacturing other
products or product use have not been documented. Acrylonitrile
has been qualitatively identified in effluents from chemical
acrylamide fiber and latex plants.
Figure 1 indicates potential sources of acrylonitrile pollution.
Hydrocarbon emissions from process vents during acrylonitrile
production are controlled by incineration and flaring. Emissions
from storage of acrylonitrile can be controlled by floating roof
tanks, internal floating covers, variable vapor space tanks,
flaring, and conservation vents. Plant wastewaters are currently
deep-well injected.
Possible emergency controls over worker exposure to acrylonitrile
may be the outcome of recent epidemiological studies that show an
increase in the cancer death-rate for workers exposed to acrylo-
nitrile. The Food and Drug Administration (FDA) has regulated
the acrylonitrile contents of nitrile rubber that comes into con-
tact with food at 11 ppm (parts per million). The FDA has also
withdrawn a permit for Monsanto to produce beverage containers
from nitrile barrier resins.
Table 1 briefly describes acrylonitrile emission sources, their
magnitude and control. Based on the information presented in
this report, the following items need to be considered in future
studies:
1 metric ton = 106 grams; conversion factors and metric system
prefixes are presented in the prefatory pages of this report.
2
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PRODUCTION
u>
PROPYLENE
AMMONIA
-ACRYLONITRILE
TRANSPORTATION
INDUSTRIAL USE
ACRYLIC FIBERS (42%)
ABS& SAN RESINS (19%)
-*•- NITRILE ELASTOMERS (4%) •
MISCELLANEOUS, INCLUDING
EXPORT
FABRICATION
-(35%)
CONSUMER USE
PLASTIC PRODUCTS,
TEXTILES, RUBBER
PRODUCTS
PESTICIDES, WIGS,
FOOTWEAR
ETC.
Figure 1. Potential sources of acrylonitrile pollution.
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Emission rates of acrylonitrile from industrial processes
using it as a raw material.
Rates of release of acrylonitrile from acrylonitrile-based
products.
Environmental levels of acrylonitrile.
Chronic effects of low-level exposure to acrylonitrile.
Atmospheric chemistry of acrylonitrile.
-------
TABLE 1. ACRYLONITRILE SOURCES, THEIR MAGNITUDE AND CONTROL
Emission source
Emission quantity
Extentof problem
Population exposed
Control method
Regulatory agency
or action
Production:
Process vent streams
Leaks, spills, and
fugitive emissions
Storage and transfer
operations
696 metric tons/yr
(emitted to air from
production and trans-
portation) .
EPA studies show no
population at risk
from levels in rep-
resentative produc-
tion facility.
Combustion or incineration
devices.
Improved maintenance and
good housekeeping prac-
tices.
Methods used for petroleum
product storage and
transfer including vapor
recovery, submerged fil-
ling, and floating roof
tanks with double seals.
OSHA has set threshold
limit of 45 mg/m3 as
workplace exposure
standard; to be re-
vised downward.
Acrylonitrile is listed
as a priority pollu-
tant under the Fed-
eral Water Pollution
Control Act.
Transportation:
Spills, ballasting
and other transit
losses
Industrial use:
Acrylic fibers (42%)
ABS and SAN resins
Nitrile elastomers
(5%)a
Miscellaneous, includ-
ing export (35%) a
Emissions produced
from polymerization,
fiber spinning and
resin and elastomer
fabrication formu-
lation
37 metric tons/yr
(1970) emitted to
ocean.
Literature indicates
that the total quan-
tity of emissions is
not large.
Unknown.
No data available.
Industrial workers are
exposed to unknown
levels of acryloni-
trile in combination
with other volatile
organic substances.
Unknown.
Vapor recovery during load- Unknown.
ing and unloading opera-
tions , proper containment
and cleanup procedures
for spills.
Vapor recovery and combus- Acrylonitrile as grain
tion; improved monomer
recovery and recycle;
improved hood, vent, and
exhaust systems.
Unknown.
fumigant being con-
sidered for cancel-
lation by FIFRA
(EPA).
Unknown.
Consumer use of end
products
Unknown low levels.
Unknown, poss ib1e
widespread chronic
exposure to low level
of acrylonitrile.
Better monomer recovery
during industrial use;
product substitution.
Ban on bottles
from acrylonitrile
copolymers (FDA).
Present monomer limit
on copolymer in con-
tact with food set
at 11 ppm.
Propose to lower
acrylonitrile migra-
tion limit (from
copolymer) from
0.3 ppm to 0.05 ppm.
Numbers in parentheses indicate consumption in 1976.
-------
SECTION 3
SOURCE DESCRIPTION
PHYSICAL AND CHEMICAL PROPERTIES
Table 2 lists the physical and chemical properties of acrylo-
nitrile (1).
TABLE 2. PHYSICAL AND CHEMICAL PROPERTIES OF ACRYLONITRILE (1)
Parameter
Property
Molecular weight
Boiling point
Freezing point
Specific gravity
Vapor density
Viscosity (liquid)
Surface tension
Flash point
Latent heat of vaporization
Refractive index
Vapor pressure
Dipole moment
Solubility
53.06
77.3°C
-83.5°C
0.8060 at 20°C
1.83
0.34 x 10~3 Pa-s at 24°C
27.3 x 10~7 N-m at 24°C
0°C (open cup)
33 x 106 J/mole, vapor, 25°C
1.3888 at 25°C
6.7 kPa at 8.7°C
13 kPa at 23.6°C
33 kPa at 45.5°C
67 kPa at 64.7°C
101 kPa at 77.3°C
3.3 x 10~18 esu-cm (in carbon tetrachloride)
5.35% at 20°C in water (solubility of water is
3.1% in acrylonitrile). Soluble in acetone,
benzene, carbon tetrachloride, ether, ethyl
acetate, ethylene cyanohydrin, methanol,
petroleum ether, toluene, xylene, kerosene,
and most other common organic solvents.
a
Electrostatic unit-centimeter is nonmetric unit, unknown equivalent.
(1) Handbook of Chemistry and Physics, 55th Edition. R. C.
Weast, ed., CRC Press, Cleveland, Ohio, 1974. 1-151-pp.
-------
PRODUCTION
Four companies manufacture acrylonitrile at six locations in the
United States. Table 3 list manufacturers, plant locations and
capacities. Most plants operate at or near capacity.
TABLE 3. ACRYLONITRILE PLANTS (2-4)
Company
American Cyanamid Co.
Du Pont Co.
Du Pont Co.
Monsanto Co.
Monsanto Co.
Vistron Corp.
Location
New Orleans, LA
Beaumont , TX
Memphis , TN
Alvin, TX
Texas City, TX
Lima , OH
Capacity,
metric
tons/yr
91,000
160,000
130,000
200,000
190,000
91,000
TOTALS
862,000
PROCESS DESCRIPTION
Acrylonitrile is manufactured in the United States exclusively from
propylene and ammonia by the SOHIO process (2) . The reaction may
be represented by the following chemical equation:
2CH2=CH-CH3
Propylene
2NH3 + 302 + 2CH2=CH-CN + 6H20
Ammonia Oxygen Acrylonitrile Water
Figure 2 is a flow sheet of a representative acrylonitrile plant
(2, 5). The numbered streams are identified in Table 4.
(2) Hughes, T. W. and D. A. Horn. Source Assessment: Acryloni-
trile Manufacture (Air Emissions), EPA-600/2-77-107J, U.S.
Environmental Protection Agency, Research Triangle Park,
North Carolina, September 1977. 120 pp-
(3) Chemical Profile: Acrylonitrile. Chemical Marketing
Reporter, 211(2):9, January 10, 1977.
(4) Statistical Abstract of the United States, 1974, 95th
Edition. U.S. Department of Commerce, Bureau of the Census,
Washington, D.C., 1974. pp. 445-461.
(5) Schwartz, W. A., F. B. Higgins, Jr., J. A. Lee, R. Newirth,
and J. W. Pervier. Engineering and Cost Study of Air Pollu-
tion Control for the Petrochemical Industry. Volume 2:
Acrylonitrile Manufacture. EPA-450/3-73-006-b, U.S. Environ-
mental Protection Agency, Research Triangle Park, North
Carolina. February 1975. 103 pp.
-------
COOLING COILS
CD
ABSORBER VENT GAS
*- RARE
FUGITIVE EMISSIONS
*- INCINERATOR STACK GAS
DEEP WELL POND EMISSIONS
•- STORAGE TANK EMISSIONS
PROOUCT TRANSPORT
LOADING
FACILITY
DENOTES MAIN PRODUCT ROW
DENOTES ALL OTHER STREAM FLOW
PRODUCT TRANSPORT LOADING
FACILITY VENT
TANK TRUCK
RAILROAD CAR
TO DEEP WELL
Figure 2. Flow diagram for a representative acrylonitrile plant (1, 2).
-------
TABLE 4. STREAM CODES FOR FIGURE 2
Stream number Description
1 Propylene feed
2 Ammonia feed
3 Process air
4 Reactor feed
5 Reactor product
6 Cooled reactor product
7 Quenched reactor product
8 Sulfuric acid
9 Stripping steam
10 Wastewater column volatiles
11 Wastewater column bottoms
12 Absorber vent gas
13 Acrylonitrile plant wastewater
14 Absorber bottoms
15 Water recycle
16 Crude acetonitrile
17 Crude acrylonitrile
18 Recovery column purge vent
19 Acetonitrile column bottoms
20 Acetonitrile
21 Hydrogen cyanide
22 Light ends column purge vent
23 Light ends column bottoms
24 Product acrylonitrile
25 Heavy ends
26 Product column purge vent
27 Flare
28 Fugitive emissions
29 Incinerator stack gas
30 Deep well pond emissions
31 Storage tank emissions
32 Product transport loading facility vent
Air, agricultural grade ammonia, and propylene (greater than 90%
purity) in approximately stoichiometric proporations are intro-
duced into a fluidized bed reactor at 125 kPa to 310 kPa and
400°C to 510°C (2, 5) . Conversion of propylene is virtually com-
plete, so that no recycle is required. The heat of reaction is
used to generate process steam. The reactor effluent is sent to
a water quench tower where unreacted ammonia is removed with sul-
fur ic acid. The stream is then charged to an absorber to recover
the reaction products. The resulting mixture of acetonitrile,
acrylonitrile, and hydrogen cyanide is separated in a series of
distillations. The final acrylonitrile product is 99+% pure.
By product acetonitrile and hydrogen cyanide are produced at
99+% purity for sales. Currently, only Vistron and DuPont market
-------
acetonitrile products. In all plants, a portion (50%) of the
hydrogen cyanide and most of the acetonitrile are incinerated.
Wastes generated during acrylonitrile production are a collection
of gaseous, liquid and solid types. Emissions originate from the
absorber vent (stream 12), incinerator (stream 29), flare (stream
29), deep well pond (stream 30), storage tanks (stream 31), prod-
uct transport loading facility (stream 32), and fugitive emission
points (stream 28) (2). Effluent streams are generated in the
wastewater and acetonitrile columns (streams 11 and 19 in Figure
2). Catalyst fines from the reactor and organic polymers from
the product columns (stream 25) make up the solid portion of
acrylonitrile-produced wastes (2). The composition of air emis-
sions and effluent streams are given in Section 4.
USES
Acrylonitrile is an important raw material in the production of
acrylic fibers, acrylonitrile-butadiene-styrene (ABS) and sty-
rene-acrylonitrile (SAN) resins, and liitrile elastomers. Table 5
shows acrylonitrile consumption by various industries in 1976
(6). Figure 3 is a product flow diagram for acrylonitrile (7).
TABLE 5. ACRYLONITRILE CONSUMPTION (1976) (6)
Consumption,Acrylonitrile
Use 10 3 metric tons/yr consumed / %
Acrylic fibers
ABS and SAN resins
Nitrile elastomers
Exports
Miscellaneous
362
164
34
150
150
42
19
4
17.5
17.5
TOTAL 860 100
The acrylic fiber industry is an important consumer of acryloni-
trile utilizing 42% of the acrylonitrile produced annually.
Acrylic fibers contain at least 85% acrylonitrile by weight with
modacrylic fibers containing 35% to 85% acrylonitrile. The
amount of acrylonitrile consumed by this industry in 1976 was
(6) Chemical Origins and Markets, Fifth Edition. G. M. Lawler,
ed., Chemical Information Services, Menlo Park, California,
1977. 118 pp.
(7) Kirk-Othmer Encyclopedia of Chemical Technology, Second Edi-
tion, Vol. 1. John Wiley & Sons, Inc., New York, New York,
1969. pp. 338-351.
10
-------
ACRYLONITRILE
rinrr>c
NITRILE RUBBER
SAN RESINS
ABS RESINS
BARRIER RESINS
AnfYi AMinr *.
CYANOETHYLATED COTTON
FATTY AMINES
PI IITAMIP APin
ACRYLIC
MOD ACRYLIC
ADHESIVES
DYES
PHOTOGRAPHIC EMULSIONS
INTERNAL PLASTICIZER
NYLON
~"* __ 1 HAs\Kis\^ssrsiiiii« /\< i t-i- * n »TI- 1
uLUIAFVUlf H^IU -"j muraujULMUIVI ULU IrtlVlrtIL ^j
FLOCCULANT
SIZING PAPER
PLASTICS
THICKENING AGENT
FLAVOR ENHANCER
Figure 3. Acrylonitrile end uses (7).
362 x 103 metric tons. Table 6 lists manufacturers of acrylic
fibers and fiber production.
TABLE 6. ACRYLONITRILE USED IN SYNTHETIC FIBER
PRODUCTION (1976) (2)
Fiber
production,
103 metric
Producer
American Cyanamid
Dow Badische Co.
E . I . DuPont de Nemours
E. I. DuPont de Nemours
Tennessee Eastman Co.
Monsanto Corp.
Location
Milton, FL
Williamsburg, VA
Camden , SC
Wanesboro, VA
Kingsport, TN
Decatur , AL
Fiber
A,Ma
A,M
A,M
A
A,M
A,M
tons/yr
57
33
138
_b
18
120
A-acrylic, M-modacrylic.
b
Plant consumption not known.
Manufacturers of ABS plastic and nitrile rubber consume approxi-
mately 23% of the acrylonitrile produced annually. This amounted
to 164 x 103 metric tons of acrylonitrile consumed in the pro-
duction of ABS plastic for 1976. Production of nitrile rubber
also consumed 34 x 103 metric tons of acrylonitrile.
Miscellaneous uses of acrylonitrile are as a chemical intermedi-
ate in the synthesis of antioxidants, Pharmaceuticals, dyes, and
surface active agents. In organic synthesis it is used 1) to
introduce a cyanoethyl group, 2) as a feedstock for producing
adiponitrile and acrylamide, 3) as a modifier for natural
polymers, 4) as a cyanoethylating agent for cotton, and 5) in
synthetic soil blocks (acrylonitrile polymerized in wood pulp).
It is also used as a pesticide fumigant for stored grain, dried
fruit, walnut, and tobacco. Acrylonitrile is a spot fumigant
in flour mills and bakeries and is used as a gasoline additive
(10, 11). The amount of acrylonitrile consumed in each of these
various uses has not been found in the literature.
11
-------
TABLE 7. PRODUCERS OF ABS RESINS (1976) (8)
Producer
Location
ABS production,
103 metric tons/yr
Borg-Warner Corp.
Borg-Warner Corp.
Rexene Polymers Co.
Dow Chemical, USA
Dow Chemical
Dow Chemical
Dow Chemical
Foster Grant Co., Inc.
B. F. Goodrich Co.
Carl Gorden Indust., Inc.
Hammond Plastics Div.
Monsanto Co.
Monsanto
Union Carbide
Uniroyal, Inc.
Uniroyal
Ottawa, IL
Washington, VA
Joliet, IL
Gales Feray, CT
Midland, MI
Pevely, MO
Torrance, CA
Leomister, MO
Louisville, KY
Workchester, MO
Oxford, MA
Addyston, OH
Muscatine, IA
Bound Brook, NJ
Baton Rouge, LA
Scotts Bluff, LA
91
120
25
29
32
45
9
_a
14
_a
_a
145
57
14
91
_a
Blanks indicate data not available.
TABLE 8. PRODUCERS OF NITRILE RUBBER (1976) (9)
Producer
Location
Rubber type
Production,
103 metric tons/yr
Copolymer Rubber Co.
Firestone Tire & Rubber Co.
B. F. Goodrich Co.
B. F. Goodrich Co.
B. F. Goodrich Co.
B. F. Goodrich Co.
Goodyear Tire & Rubber Co.
Goodyear Tire & Rubber Co.
Standard Brands , Inc .
Uniroyal, Inc.
Baton Rouge, LA
Akron , OH
Akron , OH
Louisville, KY
Louisville, KY
Akron, OH
Akron , OH
Beaumont , TX
Cheswold, DE
Baton Rouge , LA
NBR9
NBR
NBR
NBR
NBR latex
coxb
COX
NBR
NBR
NBR
5
5
14
28,.
_c
_c
5
Hc
\*
14
Buma N6 Nitrile.
NBR modified with carboxylic groups.
"Production unknown.
(8) Chemical Profile: ABS Resins. Chemical Marketing Reporter,
205(16):9, April 29, 1974.
(9) Chemical Profile: Nitrile Rubber. Chemical Marketing
Reporter, 210(17):9, October 25, 1976.
12
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TRANSPORATION AND STORAGE
Fixed-roof storage tanks are used to store acrylonitrile product,
crude acrylonitrile and acetonitrile prior to incineration (2).
Acrylonitrile is transported to the customer by one of four
methods: railroad tank car, tanker truck, barge, or in 0.21-m3
(55-gal) drums. Railroad tank car and tanker truck loading is
accomplished by either top or bottom loading. Transportation
of acrylonitrile to other industrial facilities is an important
large-scale operation since it is a vital raw material in secon-
dary industries such as acrylic fiber manufacturing.
(10) Assessing Potential Ocean Pollutants. PB 240 917, U.S. En-
vironmental Protection Agency, Washington, B.C., 1975. pp.
217-227.
(11) The Merck Index, Ninth Edition. M. Windholz, S. Budavari,
L. Y. Stromtsos and M. N. Fertig, eds., Merck and Company,
Inc., Rahway, New Jersey, 1976. pp. 127-128.
13
-------
SECTION 4
ENVIRONMENTAL SIGNIFICANCE AND HEALTH EFFECTS
ENVIRONMENTAL SIGNIFICANCE
Acrylonitrile can be introduced into the environment from
production, transportation, production of other products from
acrylonitrile, or the use of products containing acrylonitrile.
Emissions from Acrylonitrile Production
Emissions from acrylonitrile production have been studied by EPA
(2, 5). Table 9 contains emission factors for various emission
points in production plants. Emission factors express the mass
of emissions in grams per kilogram of acrylonitrile produced.
The absorber vent gas consists of the reactor effluent after neu-
tralization and recovery of nitriles and HCN.
TABLE 9. EMISSION FACTORS FOR ACRYLONITRILE
DURING PRODUCTION (2)
(g/kg)
Absorber
vent3
0.039 ± 41%
Incinerator
stack
0.0015
Flare
0.039
Fugitive
emissions
0.00042 ± 20%
Product transport
and loading
0.0065 ± 20%
Storage
(all tanks)
0.722
Total
0.807
Emissions for process employing catalyst 41.
The byproduct streams which are usually incinerated are aceto- -
nitrile and hydrogen cyanide. Polymers, heavy ends, and waste-
water are usually disposed of by deep well injection. During
deep well injection pump failure (about once a year), these
wastes are also incinerated. A flare is used to dispose of
various hydrocarbon plant streams. Feed streams to the flare
may be product fractionation vents, relief valves in propylene
storage tanks and preheaters, and streams resulting from plant
shutdown for equipment purging.
Fugitive emissions result from valves, flanges, pumps, compres-
sors, and leaks in equipment. Product transport and loading
emissions result from product transfer into containers, transport,
and unloading of product at its destination. Storage loss emis-
sions result from fixed roof tanks which are vented directly to
the atmosphere.
14
-------
Applying the total emission factor of 0.807 g/kg product to the
capacity data presented in a previous section, results in an es-
timate of 612 metric tons/yr of acrylonitrile emitted to the air
from production and transportation.
Unknown quantities of acrylonitrile have been found in plant
wastewater from acrylonitrile production (2). It has been esti-
mated that acrylonitrile discharged to the ocean from transport
and handling amounted to 37 metric tons in 1970 (10) .
Contamination from Industrial Applications of Acrylonitrile
Approximately 65% of acrylonitrile production is used in the U.S.
to manufacture polymer materials including fibers, resins, and
elastomers. Polymer production processes result in emissions of
monomers and other chemicals. Emissions may occur from the re-
actor vents, runaway reactions in which a batch is dumped, pro-
duct recovery, and extrusion. It has been estimated that only a
small amount of acrylonitrile is lost in acrylic fiber manufac-
ture (10). Twelve percent of acrylonitrile production is used
in nine miscellaneous applications. The mass of emissions from
these uses is unknown. Its use as a pesticide on agricultural
products involves the potential hazard of its being ingested by
man or entering the food chain.
Acrylonitrile Contamination from Product Use
Plastic and rubber products made from acrylonitrile polymers in-
clude clothing, carpeting, blankets, draperies, upholstery, wigs,
imitation fur, sand bags, automobile parts, appliances, piping,
tumblers, filaments, seals, gaskets, hoses, belts, adhesives,
footwear, and brake linings. No studies have determined whether
exposure of a population to chronic levels of acrylonitrile is
occuring due to its release during product use. It has been
suggested that acrylonitrile may be leached from fabrics in
laundering processes. Polyacrylamide, containing trace amounts
of acrylonitrile may also be a source of water contamination
since it is used in water treatment operations.
Environmental Levels
Persons may be exposed to acrylonitrile as a result of production
and storage, downstream chemical processing, transportation, and
use of products containing acrylonitrile.
The use of a model in an EPA study of air emissions from acrylo-
nitrile production predicted that no persons are exposed to
concentrations of nitriles above 0.07 ppm from a representative
acrylonitrile production facility (2).
15
-------
While acrylonitrile is produced in only six locations, the number
of downstream industrial processing facilities that use acryloni-
trile is much larger. Acrylonitrile emission levels from these
plants is not known. A study listing various organic compounds
found in water show that acrylonitrile is present in wastewaters
from acrylonitrile, acrylamide fiber, and latex plants (12).
Reactions and Pathways in the Environment
Reactions of acrylonitrile may involve the cyano group (CN), the
activated double bond (C=C), or both groups. It reacts readily
with olefins, alcohols, and aldehydes. The nitrile group can be
converted to an amide or an organic acid in the presence of acids
and bases, respectively. The double bond undergoes Diels-Alder
and related reactions, halogenation and hydrogenation. Purified
acrylonitrile will polymerize spontaneously. It polymerizes ex-
plosively in the presence of concentrated alkali.
Acrylonitrile can be removed from water by biological oxidation
and organisms that are capable of adapting to nitrile oxidation
are common in surface water (10, 13). Other studies show that
nitrile oxidation results in the formation of organic acids and
ammonia instead of HCN (14). The chemical reactivity and rela-
tive biodegradability of this molecule indicate that upon release
to aquatic environments it would degrade and have a short resi-
dence time as acrylonitrile (10) .
A description of the atmospheric chemistry of acrylonitrile is
unknown. Half-life in the atmosphere and degradation products
formed should be researched further. Because of its high reac-
tivity, it is probable that acrylonitrile has a short residence
time in atmospheric environments.
(12) Shackelford, W. M. and L. H. Keith. Frequency of Organic
Compounds Identified in Water. EPA-600/4-76-062, U.S. Envi-
ronmental Protection Agency, Athens, Georgia, December 1976.
629 pp.
(13) Ludzaek, F. J., R. B. Schaffer, R. N. Bloomhuff and M. B.
Ettinger. Biochemical Oxidation of Some Commercially Im-
portant Organic Cyanides, River Water Oxidations I. In:
Proceedings of the Thirteenth Industrial Waste Conference,
Purdue University, Lafayette, Indiana, 1958. pp. 292-312.
(14) Buzzell, J. C., Jr., R. H. F. Young and D. W. Ryckman.
Behavior of Organic Chemicals in the Aquatic Environment,
Behavior in Dilute Systems. Manufacturing Chemicals Associ-
ation, Washington, D.C., 1968.
16
-------
Secondary Emissions and Effluents
Emissions—
Table 10 contains emission factors for a number of pollutants
resulting from acrylonitrile production. The table shows that
a large amount of uncontrolled hydrocarbons is emitted to the
atmosphere from the production process. Ninety-six percent (96%)
of the hydrocarbons emitted are propylene and propane. The
number of persons possibly exposed to concentrations above the
Primary Ambient Air Quality standard for hydrocarbon emissions
from a representative acrylonitrile plant is estimated at
13,300 (2).
Some quantities of hydrogen cyanide are also emitted. Although
the byproduct stream is incinerated, small amounts of HCN can be
emitted from the process. The same is true for acetonitrile.
Table 11 puts emissions from acrylonitrile into perspective with
those from other organic chemical industries. Hydrocarbon emis-
sions from acrylonitrile production are high when compared to
emissions from other chemical manufacturing processes (5).
Wastewater—
Wastewater generated within an acrylonitrile plant contains ammo-
nium sulfate, catalyst fines, organic polymers, and miscellaneous
organic materials (2). This waste is sent to a deep-well pond
where suspended solids are removed. The aqueous portion is deep-
well injected. Table 12 shows the composition of acrylonitrile
plant wastewater (2, 15).
HEALTH EFFECTS
To evaluate the potential health effects of acrylonitrile contam-
ination in the environment, toxicity of acrylonitrile to animals
and man is described.
Effects on Animals
Numerous animal studies are described in the literature.
Table 13 contains some of the toxicity data generated in animal
studies (16) .
(15) Train, R. E. Development Document for Interim Final Efflu-
ent Limitations and New Source Performance Standards for the
Significant Organic Products Segment of the Organic Chemi-
cals Manufacturing Point Source Category. EPA-400/1-75/045,
U.S. Environmental Protection Agency, Washington, D.C.,
November 1975. 391 pp.
17
-------
00
TABLE 10. EMISSION FACTORS FOR ACRYLONITRILE MANUFACTURE BY
EMISSION POINT (UNCONTROLLED EMISSIONS) (2)
(g/kg of acrylonitrile produced)
Material emitted
Criteria pollutants :
Carbon monoxide
a
Hydrocarbons (as CHiJ
Nitrogen oxides
Sulfur oxides
Particulates
Chemical substances :
Methane
Ethane
Ethylene
Propane and propylene
Butene
Benzene
Toluene
Acrylonitrile
Acetonitrile
Hydrogen cyanide
Fumaronitrile
Pyridine
Propionaldehyde
Fur an
Ammonia
Allyl alcohol
Emission point
Product
transport
Absorber Incinerator Flare Deep well Fugitive loading storage
vent stack stack pond emissions facility tanks
79.3 ± 6% 0.0040 ± 10%
57.1 ± 7% 0.0203 + 428% 0.268 13 ± 61% 0.00038 ± 20% 0.0055 ± 20% 0.661 ± 20%
- 100%
0.542 -1- 107% 0.01
- 100%
0.176 ± 59%
0.67 ± 6% 0.0023 ± 10%
1.93 ± 92%
2.57 ± 81%
55.0 ± 60% 0.022 0.000006 ± 20%
0.400 ± 50%
0.146 ± 50%
0.065 ± 50%
0.039 ± 41% <0.0015 0.039 0.00042 ± 20% 0.0065 ± 20% 0.802 ± 20%
0.625 ± 49% <0.0015 0.000024 ± 20%
0.275 ± 22% 0.0343 + 428% 0.35
- 100%
0.036
5.2 ± 74%
0.0061 ± 50%
0.467 ± 50%
0.000006 ± 20%
0.024 ± 50%
Emission factors for total hydrocarbons do not equal the sum of, emission factors for all organic materials except methane.
To determine the hydrocarbon emission, the methane equivalent-emission factors (based on carbon) for each nonmethane
organic material are calculated and then summed. (Statement applies to all emission points except deep well pond where
7.8 g/kg of material [two species] were unidentifiable.)
Note: Blanks indicate no emissions present.
-------
TABLE 11. EMISSIONS FROM ORGANIC CHEMICAL INDUSTRY (5)
Estimated current air emissions.
Chemical Hydrocarbons
Acetaldehyde via ethylene
via ethanol
Acetic acid via methanol
via butane
via acetaldehyde
Acetic anhydride via acetic acid
Acrylonitrile6
Adipic acid
Adiponitrile via butadiene
via adipic acid
Carbon black
Carbon disulfide
Cyc lohexanone
Dimethyl terephthalate (+TPA)
Ethylene
Ethylene dichloride via oxychlorination
via direct chlorination
Ethylene oxide
Formaldehyde via silver catalyst
via iron oxide catalyst
Glycerol via epichlorohydrin
Hydrogen cyanide (direct process)
Isocyanates
Maleic anhydride
Nylon 6
Nylon 6,6
Oxo process
Phenol
Phthalic anhydride via O-xylene
via naphthalene
High density polyethylene
4pw density polyethylene
Polypropylene
Polystyrene
Polyvinyl chloride
Styrene
Styrene-butadiene rubber
Vinyl acetate via acetylene
via ethylene
Vinyl chloride
TOTALS
0.5
0
0
18
2.7
1.4
83
0
5.1
0
60
0.07
32
41
6.8
43
13
39
11
11.6
7.2
0.2
0.6
15
0
0
2.4
11
0.04
0
36
34
17
9.1
28
1.9
4.2
2.4
0
8
556
Oxides of
Particulates nitrogen
0
0
0
0
0
0
0
0.09
2.1
0.2
3.7
0.1
0
0.6
0.09
0.2
0
0
0
0
0
0
0.4
0
0.7
2.5
0.004
0
2.3
0.9
1.0
0.6
0.05
0.2
5.4
0.03
0.7
0
0
0.3
10
0
0
0.004
0.02
0
0
2.5
13
23
0.02
3.1
0.05
0
0.004
0.09
0
0
0.1
0
0
0
0.2
0
0
0
0
0.03
0
0.1
0
0
0
0
0
0
0.06
0
0 f
TR
0
19
Sulfur
oxides
0
0
0
0
0
0
0
0
0
0
9.8
2
0
0.45
0.9
0
0
0.05
0
0
0
0
0.009
0
0
0
0
0
1.2
0
0
0
0
0.5
0
0
0.4
0
0
0
7
metric tons/yra
' Carbon
monoxide
0
12
0
6.3
0.6
2.5
88
0.06
0
0
1,755
0
35
24
0.09
9.9
0
0
49
11
0
0
39
118
0
0
8.8
0
20
20
0
0
0
0
0
0
0
0
0
0
997
Total
0.5
12
0.004
24
3.3
3.9
174
14
30
0.2
1,841
2.3
67
66
8
53
13
39
59
23
7.2
0.4
40
133
0.7
2.5
11
11
23
21
37
35
17
9.8
33
2
5.4
2.4
TR
8.2
1,285
Total j
weighted
86
27
1
3,215
490
253
15,000
1,190
3,200
30
17,544
120
5,700
7,460
1,240
7,650
2,300
6,880
1,955
2,070
1,280
56
231
2,950
90
330
440'
1,940
422
160
6,400
6,100
2,950
1,650
5,700
355
870
425
TR
1,460
110, 2209
In most instances, numbers are based on less than 100% survey. All based on engineering judgement of best current control.
Probably has up to 10% low bias.
Excludes methane, includes hydrogen sulfide and all volatile organics.
Includes nonvolatile organics and inorganics.
Weighting factors used are: hydrocarbons - 80, particulates - 60, nitrogen oxides - 40, sulfur oxides - 20, and carbon
monoxide 1.
Emissions base
Trace amount.
^Totals are not equal across and down due to rounding.
19
-------
TABLE 12. ACRYLONITRILE PLANT WASTEWATER (2, 15)
Material discharged
Concentration,
mg/1
Effluent factor,
g/kg
Raw wastewater
Biological oxygen demand
Chemical oxygen demand
Total organic carbon
Total solids
Total suspended solids
Total dissolved solids
Oil and grease
Total nitrogen (as N2)
Ammonia nitrogen (as N2)
Nitrile nitrogen (as N2)
Phosphate
Phenol
Sulfate
Zinc
Chloride
Iron
Copper
Chromium
Cadmium
_a
8,620
32,800
14,400
36,700 to 57,800
184 to 630
36,500 to 57,200
135 to 168
4,040 to 22,000
2,600 to 13,600
197 to 270
0.152 to 6.15
0.165 to 2.28
2,700 to 5,309
0-052 to 2.1
125 to 858
3.13 to 4.24
<0.5
<0.05
£0.05
4,470
38.7
133
57.5
163 to 182
0.915 to 1.78
161 to 181
0.475 to 0.657
16.9 to 62.1
10.3 to 38.3
0.755 to 0.97
0.0004 to 0.0298
0.0007 to 0.0064
64.1 to 74.3
0.00002 to 0.0092
0.616 to 2.42
0.0088 to 0.0182
<0. 00024
SO. 00014
<0. 00024
Other compounds which have been qualitatively identified include:
Acetaldehyde
Acrolein
Hydrogen cyanide
Acetic acid
Fumaronitrile
Acrylic acid
Acrylamide
Acrylonitrile
Acetonitrile
Maleonitrile
Organic polymers
Propionitrile
Ammonium formate
Methacrylonitrile
trans-Crotonitrile
cis-Crotonitrile
Allyl cyanide
Benzonitrile
Nicotinonitrile
Malononitrile
Furonitrile
Ticoline
Lutidine compounds
Benzene
Toluene
Ammonium acetate
Ammonium methacrylate
Ammonium acrylate
Succinonitrile
Acetone
Acetaldehyde cyanohydrin
Acetone cyanohydrin
Acrolein cyanohydrin
Pyrazole
Methyl pyrazine
Cyanopyra z ine
Pyrazine
Not applicable.
20
-------
TABLE 13. PHYSIOLOGICAL RESPONSE TO VARIOUS CONCENTRATIONS
OF ACRYLONITRILE IN AIR FOR ANIMALS (16)
Concentration
Animal
Rat
Rat
Rat
Rabbit
Rabbit
Rabbit
Cat
Cat
Guinea pig
Guinea pig
Dog
Dog
Dog
Dog
1.38
0.28
0.21
0.56
0.29
0.21
0.60
0.33
1.25
0.58
0.24
0.213
0.12
0.063
636
129
97
258
133
97
276
152
576
267
110
98
55
29
Fatal after 4-hr exposure.
Slight transitory effect.
Slight transitory effects.
Fatal during or after exposure.
Marked transitory effects.
Slight transitory effects.
Markedly toxic.
Markedly toxic, sometimes fatal.
Fatal during or after exposure.
Slight transitory effect.
Fatal to three fourths of the dogs.
Convulsions and coma; no death.
Transitory paralysis; 1 dog died.
Very slight effects.
Effects on Humans
Acrylonitrile can be toxic when ingested, inhaled, or absorbed
through the skin. It exhibits many of the effects of cyanide
poisoning and is a severe skin and eye irritant (16).
The threshold limit value is 45 mg/m3 (17). Vapor poisoning may
result in nausea, vomiting, diarrhea, flushing, headache, sali-
vation, sneezing, altered respiration, weakness, asphyxia, and
loss of consciousness (16).
Chronic effects cited are inhibition of respiratory enzyme sys-
tems, irritation of eyes and nose, anemia, leucocytosis, and
alteration of liver and kidney function (16).
Carcinogenicity is suspected, but studies are not yet complete.
Preliminary indications are that workers exposed to acrylonitrile
in acrylic fiber plants have a higher incidence of cancer of the
lung and large intestine than the general population.
(16) Fassett, D. W. Cyanides and Nitriles. In: Industrial
Hygiene and Toxicology, Chapter 44, F. A. Patty, ed. Inter-
science Publishers, New York, New York, 1962. pp. 2010-2011.
(17) TLV's® Threshold Limit Values for Chemical Substances and
Physical Agents in the workroom Environment with Intended
Changes for 1976. American Conference of Governmental
Industrial Hygienists, Cincinnati, Ohio, 1976. 94 -pp.
21
-------
SECTION 5
CONTROL TECHNOLOGY
Control methods, efficiencies, and economics are presented here
for controlling emissions from production facilities. Technology
for controls in production facilities is available for industrial
use. This area of technology has been the subject of two EPA
studies (2, 5).
Control methods for transportation losses are similar to those
used in the petroleum industry and are defined in the litera-
ture (18). Control methods for downstream processing and use of
products containing acrylonitrile need to be assessed.
CONTROL METHODS
Control of hydrocarbon emission from acrylonitrile production is
described in the following subsection by noting applicable con-
trol technology for specific emission points in the process.
Absorber Vent Gas Control
The absorber vent gas emissions from acrylonitrile manufacture
may be controlled with a combustion device such as a carbon
monoxide boiler, thermal incinerator, catalytic incinerator, or
flare (5). Presently, existing plants utilize only thermal or
catalytic incineration for control of absorber vent gases (2).
Since hydrocarbon emissions result from incomplete conversion in
the reactor, the acrylonitrile industry has thus far concentrated
its efforts for reducing emissions on the development of more se-
lective catalysts. Such catalysts would increase acrylonitrile
production while lowering the amount of byproducts which are
vented (2).
For new plants, the best control system may be a combination of
thermal incineration with a waste heat boiler (5).
(18) Control Techniques for Volatile Organic Emission from
Stationary Sources, Draft Report. AP-68, by Radian Corpora-
tion, for U.S. Environmental Protection Agency, 19,77.
22
-------
Fractionating Column Vent Gas Control
Organic emissions in fractionation column vent gases may be con-
trolled by combustion. Flaring is the generally accepted proce-
dure in this case because the volume is small. Indications are
that this control method is practiced widely in the industry (2).
Settling Pond Emission Control
Emissions from the settling pond are reduced by covering the
surface with a high molecular weight oil (2). Emission factors
for controlled and uncontrolled pond emissions are listed in
Table 14.
TABLE 14. HYDROCARBON EMISSION FACTORS FOR ACRYLONITRILE
DEEP WELL PONDSa'b(2)
(gAg)
Component
Uncontrolled
Controlled
Percent
reduction
from use
of control
Pyridine
Fumaronitrile
Methanol
Acetaldehyde
Ethanol
Butanes
Pentane
Hexanes
Benzene
Toluene
Others, unidentified
5.2 ± 74%
0.036
0
0
0
0
0
0
0
0
7.8
0.
0.
0.
0.
0.
0.
0.
0.
2
06
1
06
04
04
1
2
0
0
+
+
+
+
+
+
+
+
0
138%
423%
315%
182%
172%
145%
150%
222%
^100
*100
0
0
0
0
0
0
0
0
-------
Control of Storage Tank Emissions
EPA reports on emissions from acrylonitrile production indicate
that storage is one of the largest sources of emissions. This
is also one of the easiest sources to control. There are two
ways generally used to control emissions from storage of low
volatility liquids. The first approach, applicable primarily
to new construction, is to install storage tanks with lower loss
rates than fixed cone roof tanks. Tanks with lower loss rates
include floating roof tanks, internal floating covers, and
variable vapor space tanks.
The second approach to controlling evaporation losses from fixed
roof storage tanks includes retrofitable control technology such
as internal floating roofs and vapor recovery systems. Internal
floating roofs are large pans or decks which float freely on the
surface of the stored liquid. The roof rises and falls according
to the depth of the stored liquid. To insure that the liquid
surface is completely covered, the roof is equipped with a slid-
ing seal around its periphery which fits against the tank wall.
Internal floating roofs reduce evaporative storage losses by
minimizing the quantity of exposed liquid surface area available
for evaporation. Emissions from internal floating roofs are
similar to those from exposed floating roof tanks.
Vapor recovery systems can also be installed on existing fixed
cone roof tanks. Vapors generated in the fixed roof tank are
displaced through a piping system to a storage tank called a
vapor saver. The vapor saver evens out surge flows and saves a
reserve of vapors to return to the storage tank during inbreath-
ing modes. Inbreathing saturated hydrocarbon vapors instead of
air prevents the evaporation of additional hydrocarbons. Several
storage tanks can be manifolded into a single vapor saver and
vapor recovery system.
CONTROL METHOD EFFICIENCIES
Incineration of the absorber vent gas can remove more than 95%
of combustible materials. Flaring is slightly less efficient,
but more than 90% of the combustibles can be removed (5).
Ninety to ninety-eight percent control efficiencies can be
achieved on storage tanks by substituting lower loss tanks or
retrofitting existing tanks with controls (20-22).
(20) Evaporation Loss from Fixed Roof Tanks. Bulletin 2518,
American Petroleum Institute, New York, New York, 1962.
38 pp.
(21) Use of Internal Floating Covers for Fixed Roof Tanks to
Reduce Evaporation Loss. Bulletin 2519, American Petroleum
Institute, New York, New York, 1962.
(continued)
24
-------
ECONOMICS
An EPA report addresses the economic impact of installing incin-
erators on absorber vents of acrylonitrile plants and waste heat
boilers on plant incinerators (5). The cost to industry was
judged insignificant.
Costs for storage tank controls are available in the literature.
Product recovery effectively decreases the cost of these con-
trols.
(22) Evaporation Loss from Floating Roof Tanks. Bulletin 2517,
American Petroleum Institute, New York, New York, 1962.
14 pp.
25
-------
SECTION 6
REGULATORY ACTION IN PROGRESS
The Occupational Safety and Health Administration (OSHA) has
established the threshold limit-value of 45 mg/m3 as a work
place exposure standard, A downward revision of the standard
has been promulgated at 4.5 mg/m3 as an emergency temporary stand-
ard (23) and is presently being legally contested by DuPont and
other chemical companies. This action follows an announcement
by Du Pont that its workers, exposed to acrylonitrile, have
experienced high cancer incidence rates (24).
Acrylonitrile use as a grain fumigant is being considered for
cancellation under the Federal Insecticide, Fungicide, and
Rodenticide Act (FIFRA). The substance is also registered under
the gasoline additive provisions of the Clean Air Act.
The Food and Drug Administration has regulated the unreacted
monomer content of nitrile rubber that comes into contact with
food at 11 ppm, and has banned plastic soft drink bottles made
of acrylonitrile. Also, acrylonitrile is a priority pollutant
for regulation under the Federal Water Pollution Control Act.
(23) Federal Register, Part IV 43(11):2586, January 17, 1978.
(24) DuPont Reports Problems with Acrylonitrile. Toxic Materials
News, 4(17):108, May 25, 1977.
26
-------
REFERENCES
1. Handbook of Chemistry and Physics, 55th Edition. R. C.
Weast, ed., CRC Press, Cleveland, Ohio, 1974. 1-151 pp.
2. Hughes, T. W., and D. A. Horn. Source Assessment: Acrylo-
nitrile Manufacture (Air Emissions), EPA-600/2-77-107j,
U.S. Environmental Protection Agency, Research Triangle
Park, North Carolina, September 1977. 120 pp.
3. Chemical Profile: Acrylonitrile. Chemical Marketing
Reporter, 211(2):9, January 10, 1977.
4. Statistical Abstract of the United States, 1974, 95th Edi-
tion. U.S. Department of Commerce, Bureau of the Census,
Washington, D.C., 1974. pp. 445-461.
5. Schwartz, W. A., F. B. Higgins, Jr., J. A. Lee, R. Newirth,
and J. W. Pervier. Engineering and Cost Study of Air Pol-
lution Control for the Petrochemical Industry. Volume 2:
Acrylonitrile Manufacture. EPA-450/3-73-006-b, U.S. Envi-
ronmental Protection Agency, Research Triangle Park,
North Carolina. February 1975. 103 pp.
6. Chemical Origins and Markets, Fifth Edition. G. M. Lawler,
ed., Chemical Information Services, Menlo Park, California,
1977. 118 pp.
7. Kirk-Othmer Encyclopedia of Chemical Technology, Second
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Inc., Rahway, New Jersey, 1976. pp. 127-128.
27
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12. Shackelford, W. M. and L. H. Keith. Frequency of Organic
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28
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23. Federal Register, Part IV 43(11):2586, January 17, 1978.
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29
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-79-210a
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Status Assessment of Toxic Chemicals:
Acrylonitrile
5. REPORT DATE
December 1979
issuing date
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
T.R. Blackwood, D.R. Tierney
G.E. Wilkins
8. PERFORMING ORGANIZATION REPORT NO,
. PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research Corp Radian Corp
1515 Nichols Road 8500 Shoal Creek Blvd
Dayton, Ohio 45^07 P.O. Box 99^8
Austin, Texas 78766
10. PROGRAM ELEMENT NO.
1AB604
11. CONTRACT/GRANT NO.
68-03-2550
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Lab - Cin., OH
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati. Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
Task Final 11/77 - 12/77
14. SPONSORING AGENCY CODE
EPA/600/12
15. SUPPLEMENTARY NOTES
IERL-Ci project leader for this report is Dr. Charles Frank, 513-684-4481
16. ABSTRACT
This report identifies the services and effects of environmental contaminators
by acrylonitrile, as well as the health hazards resulting from such contamination.
The present manufacturing processes, uses, control technologies, and regulatory
actions are described, and areas requiring further study are indicated.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. cos AT I Field/Group
Acrylonitriles, Nitriles, Methacryloni-
triles, Acrylonitrile Copolymers, EFitriL
Rubber, Acrylic Copolymers, Acrylic
resins, Addition Resins, ABS Resins,
Modacrylic fibers, Polyacrylonitrile
SAN Resins, nitrile
elastomers, Fumigants
68A
68D
68G
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)
Unclassified
21- NO. OF PAGES
42
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE
30
ir U.S. GOVERNMENT PRINTING OFFICE: 1980 -657-146/55ZO
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