GCA-TR-75-32-G(lll
ASSESSMENT OF MALEIC ANHYDRIDE
AS A POTENTIAL AIR POLLUTION PROBLEM
VOLUME XI
FINAL REPORT
Contract No. 68-02-1337
Task Order No. 8
Prepared For
U.S. ENVIRONMENTAL PROTECTION AGENCY
Research Triangle Park
Norrh Carolina 27711
January 1976
GCA TECHNOLOGY DIVISION
BEDFORD, MASSACHUSETTS 01730
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CCA-TR-75-32-G(ll)
ASSESSMENT OF MALEIC ANHYDRIDE
AS A POTENTIAL AIR POLLUTION PROBLEM
Volume XI
by
Robert M. Patterson
Mark I. Bornstein
Eric Garshick
GCA CORPORATION
GCA/TECHNOLOGY DIVISION
Bedford, Massachusetts
January 1976
Contract No. 68-02-1337
Task Order No. 8
EPA Project Officer
Michael Jones
EPA Task Officer
Justice Manning
U.S. ENVIRONMENTAL PROTECTION AGENCY
Research Triangle Park
North Carolina 27711
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This report was furnished to the U.S. Environmental Protection Agency by the
GCA Corporation, GCA/Technology Division, Bedford, Massachusetts 01730, in
fulfillment of Contract No. 68-02-1337, Task Order No. 8. The opinions,
findings, and conclusions expressed are those of the authors and not neces-
sarily those of the U.S. Environmental Protection Agency or of the cooperating
agencies. Mention of company or product names is not to be considered as an
endorsement by the U.S. Environmental Protection Agency.
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ABSTRACT
This report is one of a series which assesses the potential air pollution
impacts of 14 industrial chemicals outside the work environment. Topics
covered in each assessment include physical and chemical properties,
health and welfare effects, ambient concentrations and measurement meth-
ods, emission sources, and emission controls. The chemicals investigated
in this report series are:
Volume I
Volume II
Volume III
Volume IV
Volume V
Volume VI
Volume VII
Volume VIII
Volume IX
Volume X
Volume XI
Volume XII
Volume XIII
Volume XIV
Acetylene
Methyl Alcohol
Ethylene Bichloride
Benzene
Acetone
Acrylonitrile
Cyclohexanone
Formaldehyde
Methyl Methacrylate
Ortho-Xylene
Maleic Anhydride
Dimethyl Terephthalate
Adipic Acid
Phthalic Anhydride.
iii
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CONTENTS
Page
Abstract iii
List of Tables v
Sections
I Summary and Conclusions 1
II Air Pollution Assessment Report 3
Physical and Chemical Properties 3
Health and Welfare Effects 4
Ambient Concentrations and Measurement 7
Sources of Maleic Anhydride Emissions 9
Maleic Anhydride Emission Control Methods 12
III References 13
Appendix
A Maleic Anhydride Manufacturers 15
iv
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TABLES
No. Page
1 Significant Properties of Maleic Anhydride 3
2 Human Sensory Response to Maleic Anhydride 4
3 Estimated Maleic Anhydride Consumption 10
4 Sources and Emission Estimates of Maleic Anhydride - 1974 10
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SECTION I
SUMMARY AND CONCLUSIONS
Maleic anhydride is a white, crystalline solid with a sharp, irritating
odor. The primary method of manufacture is based on the reaction between
benzene vapor and air in the presence of a vanadium catalyst; and it is
used to manufacture phthalic anhydride, esters, polyester resins, dye
intermediates, Pharmaceuticals, agricultural chemicals, and fumaric acid.
Maleic anhydride dust or vapor is an acute skin, eye, and respiratory
tract irritant at concentrations of about 2 ppm. Sensitization is pos-
sible, so that much lower concentrations will be irritating to sensitized
persons. The U.S. occupational standard for exposure to maleic anhydride
3
is 1 mg/m (0.25 ppm) for an 8-hour time weighted average, based on skin,
eye, and upper respiratory tract irritation data.
Simple, worst case diffusion modeling estimates place the likely maximum
3
1-hour average ambient concentration at about 0.79 mg/m (0.20 ppra).
The maximum 24-hour average ambient concentration might be expected to
3
be about 0.44 mg/m (0.10 ppm).
About 283 million pounds of maleic anhydride were produced at seven
plants in 1974, with 50 percent of this being used in the manufacture
of polyester resins. Total production is expected to increase at 10 per-
cent per year for the next several years. The primary emission sources
in descending order are phthalic anhydride production, maleic anhydride
production, end product manufacture, and packaging losses. Total emis-
sions are estimated to have been 4.72 million pounds in 1974.
-------
Control of maleic anhydride emissions can be effected by scrubbing the
uncondensed portion of the reactor effluent after it passes through a
partial condenser. This is done principally to recover maleic anhydride.
Scrubbing is also used to control particulate emissions from flaking,
tableting, and packaging operations with efficiencies of at least 98 per-
cent. A number of other techniques are under development for controlling
maleic anhydride emissions.
Based on the results of the health effects research presented in this
report, and the ambient concentration estimates, it is possible that
maleic anhydride as an air pollutant might pose a. threat to the health
of the general population. However, the concentration estimates are
extremely conservative and the individual sources and ambient concen-
trations should be investigated further before any regulatory action is
contemplated.
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SECTION II
AIR POLLUTION ASSESSMENT REPORT
PHYSICAL AND CHEMICAL PROPERTIES
Maleic anhydride is a white crystalline solid with a sharp irritating
odor. The main method of manufacture is the reaction between benzene
vapor and air in the presence of a vanadium catalyst. It is used in the
production of esters, polyester resins, dye intermediates, Pharmaceuticals,
agricultural chemicals, and fumaric acid. Significant properties are given
in Table 1.
Table 1. SIGNIFICANT PROPERTIES OF MALEIC ANHYDRIDE
Synonyms: cis-buternedioic anhydride, 2,5-furandione, tnaleic acid anhydride,
toxilic anhydride
Chemical formula
Molecular weight
Boiling point
Melting point
Specific gravity
Vapor density
Vapor pressure
Solubility
At 25°C and 760 mm Hg
98.06
200-202°C at 760 mm Hg
52-53°C
0.934 (20°/4°C)
3.4 (air 1)
1.9 nan Hg at 50°C
0.10 nun Hg at 25°C
Soluble in water, but hydrolyzes slowly. Also soluble
in acetone, ethyl acetate, chloroform, and benzene.
1 ppm vapor 4.01 mg/m
1 ing/in-* vapor 0.25 ppm
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HEALTH AND WELFARE EFFECTS
Effects on Man
Acute Poisoning - Maleic anhydride dust or vapor is an acute skin, eye,
and respiratory tract irritant. Human sensory response data are pre-
12 1
sented in Table 2. ' The Russian literature gives the threshold of
3
irritative action as 1 mg/m (0.25 ppm vapor), and the odor threshold
3
as 1.3 mg/m (0.33 ppm vapor). Persons not accustomed to handling
maleic anhydride showed nasal and upper respiratory tract irritation
within 1 minute at 6.0 - 8.0 mg/m (1.5 2.Q ppm.) Eye irritation
followed within 15 to 20 minutes. However, maleic anhydride is a
respiratory tract sensitizer and any concentration may initiate a
reaction in highly sensitized persons. Concentrations above 10.0 mg/m
(2.5 ppm) vapor are immediately irritating to man. Chronic ulceration
and congestion of the nasal mucous membranes may occur from severe
exposures. No deaths have been reported in the literature.
Table 2. HUMAN SENSORY RESPONSE TO MALEIC ANHYDRIDE
1,2
Exposure
Q
mg/nr
6.
6.
1.0
1.0
1.3
2.0
0 - 8.0
0 - 8.0
10.0
ppm vapor
0.25
0.25
0.33
0.50
1.5 - 2.0
1.5 - 2.0
2.5
Time
2-3 hours
1 minute
15-20 minutes
Immediate
Response
Threshold or irritative action1
May cause eye discomfort
Smell threshold for sensitive
people1
Faint odor; no nose, throat,
*\
eye, or skin irritation^
Upper respiratory irritation;
nasal irritation
*\
Eye irritation^
Extreme, acute irritation^
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Contact of maleic anhydride and its dust with moist skin will cause an
immediate burning sensation. If the skin is dry there may be no burning.
Continued skin contact will cause reddening, burning, and blistering.
Maleic anhydride is a skin sensitizer, and contact dermatitis may result
from repeated and prolonged contact. It is readily absorbed through skin
despite the burning.
3 1
Eye irritation at 1 mg/m (0.25 ppm) has been observed. Marked irrita-
tion of the conjunctiva and corneal swelling can be caused by exposure
3
to vapor above 6.0 8.0 mg/m (1.5 - 2.0 ppm.) Double vision and in-
tolerance to light may result, but the effects, are usually temporary.
3
Severe exposure will cause corneal burns.
3
The U.S. occupational standard for exposure to maleic anhydride is 1 mg/m
4
(0.25 ppm) for an 8-hour time weighted average. This standard is based
on human skin, eye, and upper respiratory tract irritation data.
Chronic Poisoning Maleic anhydride vapors or dust mainly act as acute
3
irritants. However, repeated exposure to concentrations above 5 mg/m
(1.25 ppm) has caused an asthmatic response in workers, which can
persist after the removal of the vapor. An allergy can develop such
that lower concentrations can no longer be tolerated. There is an in-
creased incidence of chronic bronchitis. Repeated exposures may cause
dermatitis.
Effects on Animals
Acute Poisoning Maleic anhydride dust or vapor acts as an acute irritant
on the eyes, skin, and upper respiratory tract of animals. As in man, any
concentration of dust or vapor in air may initiate a reaction in sensitized
animals.
Direct contact with the powder or solution can produce severe eye burns.
The conjunctival sac of rabbits was filled with 1 percent and 5 percent
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maleic anhydride solutions and drained after 2 minutes. Membrane irri-
tation and cloudiness of the cornea lasted 1 day after administration of
the 5 percent solution. A minute amount of powder placed in the eyes of
rabbits was allowed to be washed away by tears. The cornea immediately
clouded, with the animal in obvious pain. After 24 hours severe inflam-
mation persisted, and edema and corneal ulcers had developed. Seven
weeks after treatment the rabbit corneas were white, opaque, and well
vascularized with obvious impairment of vision.
Maleic anhydride is a skin sensitizing agent in animals, and direct
contact with the powder or liquid can cause severe burns. The skin LD^
' 8
in guinea pigs x^as greater than 20 mg/kg body weight.
The oral LD,.n in rats for a single administration is in the range of
8
400-800 mg/kg. The single dose oral LDS_ for the guinea pig is 390 mg/kg,
465 mg/kg for the white mouse, 850 mg/kg for the white rat, and 875 mg/kg
9
for the rabbit.
Chronic Poisoning Maleic anhydride acts primarily as an acute irritant.
However, as in man, chronic vapor exposure at any level will cause respi-
ratory discomfort to sensitized animals.
9
Oral administration of 85 mg/kg (0.1 l-I>sn) in the white rat for 20 days
caused no cumulative toxic effects. One mg of maleic anhydride dissolved
in oil was subcutaneously injected twice weekly for 61 weeks into 100-gram
rats. The total dose corresponded to I'.
developing 80 weeks after the first dose.
Effects on Vegetation
rats. The total dose corresponded to 122 mg/kg body weight, with tumors
The effects of maleic anhydride on vegetation have not been documented
in the literature.
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Effects on Materials
Above 150 C maleic anhydride decomposes in the presence of alkali metals
and amines. Its vapors and dust are flammable.
AMBIENT CONCENTRATIONS AND MEASUREMENTS
Ambient Concentration Estimates
The largest emission source of maleic anhydride is a. production facility
for phthalic anhydride with a capacity of 130 million pounds per year.
This facility is located near Chicago, which has a population of over
3 million. The emission factor for phthalic anhydride is 0.0015, and
emissions of maleic anhydride are estimated to be 1.9 times those of
phthalic anhydride.
Hence, the emission rate is
(1.9) (0.0015 emission factor) (130 x 1Q6 Ib/yr) (453.6 g/lb)
3.1536 x 107 sec/yr
= 5.3 g/sec of maleic anhydride.
Some assumptions must be made regarding this chemical release to the
atmosphere. First of all, the emissions do not all come from one source
location, but rather from a number of locations within the plant where
maleic anhydride leaks to the atmosphere. Thus, the emissions can be
characterized as coming from an area source which will be taken to be
100 meters on a side. Secondly, the emissions occur at different heights,
and an average emission height of 10 meters is assumed.
Ground level concentrations can then be estimated at locations downwind
of the facility. To do this a virtual point source of emission is
-------
assumed upwind of the facility at a distance where the initial horizontal
dispersion coefficient equals the length of a side of the area divided
by 4.3. In this case:
a = 100m/4.3 = 23.3m
yo
Assuming neutral stability conditions (Pasquill-Gifford Stability Class D)
with overcast skies and light winds, the upwind distance of the virtual
point source is approximately 310 meters. With consideration of the plant
boundary, it is reasonable to assume that the nearest receptor location
is thus about 500 meters from the virtual point source. Finally, taking
2 m/sec as an average wind speed, the ground level concentration may be
calculated from:
,2
u-a a
y 2
5.3
or >
(2) TT (36) (18.5)
= 1.09 x 10~3 g/m3
for a 10-minute average concentration. Over a period of an hour this
-3 3
becomes 1.09 x 10 (0.72) = 0.79 mg/m (or 0.20 ppm vapor) 1-hour average
concentration. Over a 24-hour period, the average concentration might
3
roughly be expected to be about 0.44 mg/m (0.11 ppm vapor).
Malelc Anhydride Measurement Techniques
Very limited data exist in the literature for the determination of maleic
12
anhydride in air. A polarographic method has been modified for analysis
of airborne maleic anhydride by utilizing a midget impinger containing
10 ml of 1.0 N potassium hydroxide. However, no information is available
concerning its lower detection limit or its accuracy.
8
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Other methods for the determination of maleic anhydride are infrared
12 13
and mass spectrometry and gas chromatography. ' All of these methods
are capable of detecting maleic anhydride in the parts per million range,
and if a flame ionization detector is used with the gas chromatograph,
concentrations as low as 1 ppb can be detected.
SOURCES OF MALEIC ANHYDRIDE EMISSIONS
Maleic Anhydride Production and Consumption
14
The production of maleic anhydride in 1974 was, 283 million pounds and
is expected to increase at 10 percent per year for the next several years.
Its major use, accounting for about 50 percent of total production, is
in the formulation of polyester resins. An additional 25 percent is used
as an intermediate in the production of fumaric acid and agricultural
pesticides. Alkyd resins and other miscellaneous uses account for the
remaining 25 percent of production. Presently six companies at seven
locations are manufacturing maleic anhydride, as listed in Appendix A.
Consumption for final products and the expected growth rates for each
sector of the market are presented in Table 3.
Maleic AnhydrideSources and Emission Estimates
Primary sources of emissions of maleic anhydride result from the produc-
tion of phthai£c anhydride, the production of maleic anhydride, material
handling and packaging losses, and from the manufacturing of end products.
Total emissions from all categories are estimated to be 4.72 million
pounds, representing 1.7 percent of total production. See Table 4.
The major source of maleic anhydride emissions results from the manufac-
turing of phthalic anhydride. Maleic anhydride is formed as a side
reaction during the manufacturing process and is primarily emitted from
the main process vent gas stream. It is estimated, based upon recently
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Table 3. ESTIMATED MALEIC ANHYDRIDE CONSUMPTION 1974
15
Product
Unsaturated polyester resins
Fumaric acid
Lubricating additives
Reactive plasticizers
Copolymers
Maleic acid
Malathion
Chlorendic anhydride
Alkyd resins
Maleic hydrazide
Cap tan
Surface-active agents
Other
Total
Million pounds
141
25
22
15
16
13
12
10
5
4
4
2
14
283
% annual
growth
13
0
10
10
10
10
6
20
2
5
1
5
5
10
Table 4. SOURCES AND EMISSION ESTIMATES OF
MALEIC ANHYDRIDE - 1974
Source
Emissions,
million pounds
Phthalic anhydride production
Maleic anhydride production
Packaging losses
End product manufacturing
Total
2.96
0.85
0.06
0.85
4.72
10
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published data, that emissions of malcic anhydride are approximately
1.9 times greater than the emissions of phthalic anhydride. Since emis-
sions of phthalic anhydride from the manufacturing process have been
estimated at 1.56 million pounds, it is estimated that maleic anhydride
emissions from the manufacturing of phthalic anhydride are approximately
2.96 million pounds.
The second major source of emissions results from the manufacturing of
maleic anhydride. Maleic anhydride is manufactured primarily from
benzene, xj-hich is converted to maleic anhydride by catalytically oxidiz-
ing it in the vapor-phase. The reaction is presented below.
0 + 4 H20 + 4 C02
CHCO
18
Losses from this manufacturing process are reported to be approxi-
mately 0.3 percent with the scrubber exhaust from the product recovery
vent being the prime contributor (90 percent). Using this emission
factor and the total production (283 million pounds) results in approxi-
mately 0.85 million pounds being emitted. Since there are no data avail-
able concerning emission rates for end product manufacturing it is
assumed that the 0.3 percent factor will also apply to the manufacturing
of all end products. Therefore, this will also result in 0.85 million
pounds of maleic anhydride emissions.
The last major source of emissions results from product handling and
packaging. It has been reported that 0.0002 pounds of maleic anhydride
is emitted from product flaking, pelleting, packaging and storage per
18
pound of maleic anhydride produced. This factor applied to the most
recent production figure results in approximately 0.06 million pounds
of material lost.
II
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MALEIC ANHYDRIDE EMISSION CONTROL METHODS
Most plants currently scrub the uncondcnsed portion of the reactor
effluent after it passes through a partial condenser. This is done
principally to recover tnaleic anhydride. Many plants do utilize this
same control device to scrub vent gases from various other areas of
the plant. However, CO and hydrocarbon emissions (benzene, maleic
anhydride and formic acid) are quite high. Appreciably better control
could be achieved by combining the product scrubber with a combustion
type device. One plant is currently planning such an installation
18
with a reported total cost of $1,000,000.
Several plants utilize separate scrubbers to control emissions of maleic
anhydride particulates from their flaking, tablet ing, and packaging
operations. Expected scrubbing efficiencies are 98 percent and higher.
Developmental work in reducing emissions has been suggested for the
following areas. It is not currently known if any or all of these
practices have or will be studied.
1. Substitution of oxygen for air.
2. Fluidized bed development for reduction of air/benzene.
3. Development of a more selective catalyst.
4. Better utilization and design of current control equipment.
5. Use of recycled air to improve yield and reduce emissions.
12
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SECTION III
REFERENCES
1. Grigor'eva, K. U. Pollution of Atmospheric Air by Maleic Anhydride
and its Hygienical Assessment. Biol Deistvie L Gigien Znachenie
Atm Zagryaznni. 42-57, 1965. Cited in: Chemical Abstracts.
65:14319b, 1966.
2. American Industrial Hygiene Association. Hygienic Guide Series:
Maleic Anhydride. Amer Ind Hyg Assoc J. 31:391-94, 1970.
3. McLaughlin, R. S. Chemical Burns of the Human Cornea. Amer J
Ophthalmol. 29:1355-62, 1946.
4. The NIOSH Toxic Substances List 1974 Edition. U.S. Department of
Health, Education and Welfare, National Institute of Occupational
Safety and Health. Publication No. (NIOSH) 74-134. p. 46.
5. Gervais, P. Asthma in the Plastics Industry. Connais Plast.
7:20-22, 1966. Cited in: Chemical Abstracts. 66:4904t, 1967.
6. Winter, C. A. and E. J. Tullius. The Irritating Effects of Maleic
Acid and of Maleic Anhydride Upon the Eyes of Rabbits. Am J
Ophthalmol. 33:387-88, 1950.
7. Tsyrkunov, L. P. Toxic Effect of Epoxy Resins and Their Hardeners
in Vivo. Gig Tr Prof Zabol. 10:52-54, 1966. Cited in: Chemical
Abstracts. 66:27422p, 1967.
8. Fassett, D. W. Organic Acids and Related Compounds. In: Indus-
trial Hygiene and Toxicology, Patty, F. A. (ed.). New York, Inter-
science Publishers, Vol. 2, 1963. p. 1820-21.
9. Berzins, V. Toxicology of Maleic Anhydride. Mater Dokl Mauch Sees
Rizh Med Inst. 15:11-13, 1967. Cited in: Chemical Abstracts.
72:4ll31y, 1970.
10. Dickens, F. and H. E. H. Jones. Further Studies on the Carcinogenic
and Growth Inhibitory Activity of Lactones and Related Substances.
Brit J Cancer. 17:100-108, 1963.
13
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11. Turner, D. B. Workbook of Atmospheric Dispersion Estimates.
U.S. Environmental Protection Agency. Publication No. AP-26.
January 1973.
12. American Industrial Hygiene Association Journal. May-June 1973.
13. Leithe, W. The Analysis of Air Pollutants. Ann Arbor-Humphrey
Science Publishers, 1970.
14. Preliminary Report on U.S. Production of Selected Synthetic Organic
Chemicals. U.S. International Trade Commission. February 1975.
15 Chemical Economics Handbook. Stanford Research Institute. July
1972.
16. In-Depth Study of Phthalic Anhydride Manufacturers from Ortho-
Xylene. U.S. Environmental Protection Agency. Publication No.
EPA-450/3-73-006-g.
17. Patterson, R. M., M. I. Bornstein, and E. Garshick. Assessment of
Phthalic Anhydride as a Potential Air Pollution Problem, Volume XIV.
GCA/Technology Division, Bedford, Massachusetts. Prepared for U.S.
Environmental Protection Agency, Research Triangle Park, North
Carolina. January 1976.
18. Survey: Reports on Atmospheric Emissions from the Petrochemical
Industry. Volume III. U.S. Environmental Protection Agency.
Publication No. EPA-450/3-73-005-C. April 1974.
19. Maleic Anhydride. Chemical Profile. March 17, 1975.
14
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APPENDIX A
MALE1C ANHYDRIDE MANUFACTURERS
19
As of March 1975.
Annual capacity,'
million pounds
Koppers Co.
Monsanto
Petro-Tex Chemical
Reichold Chemicals
Reichold Chemicals
Tenneco Chemicals
U.S. Steel Corp.
Bridgeville, Pennsylvania
St. Louis, Missouri
Houston, Texas
Elizabeth, New Jersey
Morris, Illinois
Fords, New Jersey
Neville Island, Pennsylvania
Total
34
105
50
30
60
26
40
345
15
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