EPA-450/3-88-014
SUMMARY OF EMISSIONS
ASSOCIATED WITH PROPYLENE OXIDE
Emission Standards Division
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Radiation
Office of Air Quality Planning and Standards
Research Triangle Park, North Caroling 27711
November 1988
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This report has been reviewed by the Emission Standards Division of the
Office of Air Quality Planning and Standards, EPA, and approved for
publication. Mention of trade names or commercial products is not intended
to constitue endorsement or recommendation for use. Copies of this report
are available through the Library Services Office (MD-35), U.S. Environmental
Protection Agency, Research Triangle Park NC 27711, or from National
Technical Information Services, 5285 Port Royal Road, Springfield YA 22161.
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TABLE OF CONTENTS
Page
LIST OF TABLES v
CONVERSION FACTORS vii
1. PROPYLENE OXIDE CHARACTERISTICS 1-1
1.1 Physical Properties 1-1
1.2 Reactions 1~3
i.3 References I-4
2. PROPYLENE OXIDE PRODUCTION 2-1
2.1 Indirect 2-1
2.2 Commercial 2-2
2.2.1 Chi orohydri nation 2-2
2.2.2 Peroxidation 2-3
2.3 References 2-5
3. PROPYLENE OXIDE USES 3-1
3.1 Polyether Polyols 3-2
3.1.1 Urethane Applications 3-2
3.1.2 Non-Urethane Applications 3-3
3.2 Propylene Glycol 3-4
3.3 Glycol Ethers 3-b
3.4 Miscellaneous 3-6
3.4.1 Isopropanol amines 3-6
3.4.2 Propylene Carbonate 3-6
3.4.3 Non-polyol based Surfactants . 3-b
3.4.4 Fumiyation 3-7
3.4.6 Other 3-9
3.5 References 3-10
4. INDUSTRIAL GROWTH 4-1
4.1 History 4-1
4.2 Outlook 4-2
4.3 References 4-3
5. PROPYLENE OXIDE EMISSIONS . . 6-1
5.1 Domestic Production, Consumption, Imports, and Exports. . . 5-2
5.2 Production Facilities 5-4
5.3 User Facilities 5-6
b.3.1 Polyether Polyols 5-7
5.3.1.1 Urethane Applications 5-7
6.3.1.2 Non-Urethane Applications 5-7
5.3.2 Propylene Glycols 5-15
5.3.3 Glycol Ethers 5-17
5.3.4 Miscellaneous 5-20
5.3.4.1 Site Specific Data 6-20
5.3.4.2 Short-Term Data b-2U
6.4 References 5-22
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TABLE OF CONTENTS (Continued)
6. OTHER INFORMATION 6-1
6.1 Aqueous Emissions 6-1
6.2! Ambient Ai r Concentrations 6-1
6.3 Environmental Fate 6-2
6.4 Occupational Exposure Data 6-4
6.5 Regulations 6-6
6.6 References 6-7
APPENDICES
A Production, Consumption, Imports, Exports A-l
B Production Facilities B-l
C Comments Regarding the HEM Input Tables C-l
D Approximations of Stream Compositions D-l
E Equipment Leaks or Fugitive Emissions E-l
F Storage and Transportation Emissions F-l
G Consumption Estimates for Use Categories G-l
H Process Vent Parameters . . H-l
I Short-Term Modeling 1-1
J Short Term Emission Estimates J-l
J.I Propylene Oxide Fumigation J-l
J.2 Annual Consumption Method .- J-5
J.3 Consumption per Cycle Method J-7
J.4 References J-8
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LIST UF TABLES
1-1 Chemical and Physical Properties of Propylene Oxide 1-2
2-1 Crude Product Stream Composition . . 2-3
2-2 Relative Quantities of Feed Product, and By-product 2-3
3-1 Names of Glycol Ethers 3-b
3-2 Non-Polyol based Surfactants 3-7
5.1-1 Propylene Oxide Supply and Demand 5-1
5.1-2 Number of Major Facilities 5-2
5.2-1 Production Estimates for Manufacturing Facilities ... 5-3
5.2-2 HEM Inputs - Propylene Oxide Producers 5-4
5.3-1 Propylene Oxide Consumption Estimates 5-b
5.3.1-1 HEM Inputs - Polyether Polyols for
Urethane Applications 5-8
5.3.1-2 HEM Inputs - Polyether Polyols for Non-Urethane
Applications 5-12
5.3.2-1 HEM Inputs - Propylene Glycol, Dipropylene
Glycol, Tripropylene Glycol 5-16
5.3.3-1 HEM Inputs - Glycol Ethers b-18
5.3.4-1 Sterilization Unit Emission Parameters. . . . . 5-21
6.3-1 Propylene Oxide Degradation in Water 6-2
6.3-2 Atmospheric Degradation Products of Propylene Oxide 6-3
6.4-1 Maximum Peak Propylene Oxide Concentrations b-4
6.4-2 Time Weighted Average Exposure 6-4
6.4-3 8-Hour Time Weighted Average Exposure 6-5
B-l Process Vent Parameters B-2
B-2 Chiorohydrination-Model Facility- Vent Emissions B-2
B-3 Chi orohydri nation - Emissions from Process Vents ....... B-3
B-4 Peroxidation - Model Facility-Vent Emissions B-3
B-5 Peroxidation - Emissions from Process Vents B-4
D-l Stream Compositions.. D-l
0-2 Possible Products from Streams D~2
E-l Baseline VUC Emissions , E-l
E-2 Emission Parameters E-l
F-l Storage Emission Parameters F-l
F-2 Storage Emissions at Production Facilities F-2
G-l Propylene Oxide Usage Patterns 1983, 1985. G-l
G-2 Propylene Oxide Usage Patterns 1978, 1983 G-l
G-3 Propylene Oxide Consumption Estimates 1986 G-2
H-l Process Vent Parameters H-l
J-l Propylene Oxide Fumigation J-4
J-2 Propylene Oxide Emissions J-7
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CONVERSION FACTORS AND ABBREVIATIONS
Symbol
G
M
mil
k
c
Prefix
or name
giga
mega
mi 1 1 i on
kilo
centi
Factor by
unit is mul
11)9
106
106
103
10-2
which
ti plied
Units of length, area, and volume
1 m * 3.28 ft. * 1.09 yd.
1 cm = 0.394 in.
1 m2 * 10.76 ft2
1 m3 = 35.31 ft3 ซ 264.2 U.S. gal
Units of mass
1 Ib = .4636 kg
1 mi 1 . 1 b * .4636 (ig
1 ton = 2,000 Ib
Units of pressure
1 atm = 760 mm Hg = 101,325 Pa
1 kPa = 9.87 x 10~3 atm * 0.146 psi
Units of temperature
xฐF ซ (y"C)(9/5) + 32
z K * 273.15 + yฐC
Abbreviation
atm
ft
9
gal
in
Ib
m
Pa
psi
yd
Symbol
Unit
atmosphere
foot
gram
gallon
inch
pound
meter
Pascal
pounds per
square inch
yard
Definition
Organic
Mercury
Weight
compound
Ambient Conditions
1 atm, 20-26ฐC
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1. PROPYLENE OXIDE CHARACTERISTICS
A
Propylene oxide, CH2-CHCH3, 1s a highly flammable, low boiling liquid
at ambient conditions. Because of its asymmetry, this chemical exists as
two optical isomers. It is produced and used commercially as a mixture of
these isomers.1,2
1.1. Physical Properties
Propylene oxide is soluble with most organic solvents.3 It is only
partially soluble in water and forms a two-layer aqueous system. At 25ฐC,
the upper layer is 90 weight (wt) percent propylene oxide; the lower
layer, 45 wt percent.2
Table 1-1 lists alternative names and various properties of this
chemical.
1-1
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Table 1-1 Chemical and Physical Properties of Propylene Oxide
0 H
Basic Structure: H-C-C-C-H
H H H
Alternative names: 1,2 epoxy propane; methyloxi rane; propene oxide
Chemical Abstract Service (CAS) Registry Number: 76-56-9
Property
Molecular weight
Weight
Density
Freezing Point
Boiling Point
Vapor Pressure
Explosive Limits
Solubility
Value
Conditions
Reference
68 .08
6.9 Ib/gal
.830 g/cm3
~112ฐC
34.2ฐC
446 mm Hg
638 mm Hg
2.3 to 37 volume %
partial
compl ete
compl ete
20 ฐC
20 ฐC
101.3 kPa
(760 mm Hg)
20 ฐC
26ฐC
in ai r
in water
in alcohol
in ether
4
6
3
3
3
6
1
3
6
5
6
1-2
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1.2 REACTIONS
Propylene Oxide is a very reactive chemical. Its reactivity is the
result of the highly strained three-member ring geometry. * The characteristic
epoxide ring (ฃฃ.,) can undergo cleavage catalyzed by acids or bases. Reactions
with water, ammonia, amines, carbon dioxide, alcohols, and phenols and
polymerization all have industrial applications.6
S
A chemical homologue of propylene oxide is ethyl ene oxide,
These two chemicals react in similar ways based upon the epoxide rings, and
have some similar uses.
1-3
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1.3 REFERENCES
1. Bogyo, D.A., S.S. Lande, W.M. Meylan, P.H. Howard, and J. Santodonato.
Investigation of Selected Potential Environmental Contaminants:
Epoxldes. Office of Toxic Substances, U.S. Environmental Protection
Agency. Washington, D.C. EPA~b60/ll-80-005. March 1980. p.2, 4, b.
2. Hancock, E.G., ed. Propylene and Its Industrial Derivatives. New York,
NY, John Wiley and Sons. 1973. p.273, 274.
3. Grayson, M., ed. Ki rk-Othmer Encyclopedia of Chemical Technology, 3rd
edition, Vol 19. New York, NY, John Wiley and Sons. 1982. p. 247, 248.
4. Weast, R.C., ed. The CRC Handbook of Chemistry and Physics, 60th
edition. Boca Raton, FL. CRC Press. 1979. p.C-448.
b. Hawley, G.G., ed. The Condensed Chemical Dictionary, loth edition.
New York, NY. Van Nostrand Reingold Company. 1981.
6. Morrison, R.T. and R.N. Boyd. Organi c Chemistry, 3rd edition. Boston,
MA. Allyn and Bacon, Inc. 1973, p.564-566.
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2. PROPYLENE OXIDE PRODUCTION
2.1 INDIRECT
While the direct production of propylene oxide is readily identified as
a source of propylene oxide emissions, it is also necessary to consider
other sources of emissions. Fuel combustion can be an indirect source of
propylene oxide.
Propylene oxide was found to be a product of the combustion of n-pentane,1
and the combustion of n-hexane.2 These studies did not measure the amount of
propylene oxide produced. One reference estimated that the total quantities
of ethylene oxide and propylene oxide emitted by these sources could approach
millions of pounds.3 The sources of hydrocarbon combustion include automobiles
and large stationary sources.
Other indirect sources of propylene oxide have been mentioned in the
literature. It is possible that epoxides are formed during the photochemical
smog cycle.3 In a study to assess the toxic hazard from thermally stressed
polymers, propylene oxide was among the eluted compound from a heated poly-
urethane coated wire.4
Because of the high reactivity of propylene oxide, it is unlikely that
propylene oxJde is an unintentional by-product in other industrial processes
or a contaminant in some other final product.3 That is, even if it were
produced in very small quantities it would probably undergo another reaction
quickly and form a different compound such as propylene glycol.
While it is necessary to keep in mind all possible sources of propylene
oxide, in the judgement of the author, the available literature and monitoring
data do not support the claim (in reference 3) that propylene oxide is indirectly
produced in significant amounts.
2-1
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2.2 COMMERCIAL
Propylene oxide is produced at four sites in the United States. All
of these sites are located along the Texas-Louisiana Gulf Coast near propyl-
ene supplies.5 Two of these facilities manufacture propylene oxide using
the chlorohydrin method. The other two facilities use the peroxidation
method of manufacture.^
Ethylene oxide can be manufactured through the direct oxidation of
ethyleneo Although patents have been issued for direct oxidation of
propylene, none of these processes have been found commercially feasible.
Low yields, low raw material conversion, numerous by-products from complex
catalyst systems and preferential attack of the methyl group, which results
in acrolien, CH2SCHCHO, are all problems arising in the direct oxidation
methods of propylene oxide.13^
Propylene, a colorless gas, is a raw material for the chlorohydrination
and peroxidation processes. The oxidation of propylene to propylene oxide
is an exothermic reaction and may produce significant quantities of heat.**
Brief descriptions of both of these processes follow. Detailed
descriptions of these processes are available elsewhere.7ป8,9,10
2.2-.1 Chlorohydri nation
The chlorohydri nation of propylene to propylene oxide is a two-step
process. In the first step, propylene, chlorine and an excess amount of
water are in aqueous solution at, or slightly above atmospheric pressure
and near 4bฐC. The chlorine and water form hydrochloric acid. This acid
reacts with the propylene to form propylene chlorohydrin. Maintaining a
dilute solution, i.e. 5 wt percent propylene chlorohydrin, helps to keep
formation of by-products to a minimum in this step.5ป7ป&,10
In the second step, the chlorohydrin reacts with a base, to form
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The crude product stream is distilled under vacuum to reduce the
hydrolysis of propylene oxide to propylene glycol. The composition of a
crude product stream Is given In Table 2-1.
Table 2-1 Crude Product Stream Composition*
Component Estimated Weight Percent
Water 7u
Propylene oxide 26
Propylene dichloride 3
Other compounds 1
*Grayson, M.ed, Ki rk-Othmer Encyclopedia of Chemical Technology, 3rd edition,
vol. 19, New York, John Wiley and Sons, 1982.p.256.
One of the major drawbacks of this process is the large amount of by-
products and waste materials that can be generated. Table 2-2 lists estimated
amounts of feed, product and by-product. Recycle and sale of the generated
salts is hindered by high energy costs. Research has been done in this
area^ but no evidence found during this study indicated that such processes
have been commercialized.
Table 2-2 Relative Quantities-of Feed. Product and By-productaปb
Feed:propylene90 kg
Product: propylene oxide 1UO kg
By-products: propylene di chloride 9 kg
dichloropropyl ethers 2 kg
calcium chloride brine 215 kg
a. Peterson, C.A. (IT Envi roscience) Propylene Oxide Product Report.
In: Organic Chemical Manufacturing, Volume 10: Selected Processes.
Office of Air Quality Planning and Standards, U.S. Environmental
Protection Agency. Research Triangle Park, NC. EPA-4bU/3-80-U28e.
December 1980..
b. Bogyo, D.A., S.S. Lande, W.A. Meylan, P.H. Howard, and J. Santodonato.
Investigation of Selected Environmental Contaminants: Epoxides. Office
of Toxic Substances, U.S. Environmental Protection Agency. Washington,
D.C. EPA-b60/l1-80-005. March 1980. p.26-28.
2.2.2 Peroxidation
In 1986, two facilities were using the peroxidation method to produce propylene
oxide. In these facilities, an organic hydroperoxide is used to epoxidize
propylene.5 Propylene oxide is a co-product with tertiary alcohol or styrene.
The reactions for this process are:
2-3
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RH + 02 > ROOH
a. peroxidation of organic
ROOH + CH3CH=CH2 > CH3CHCH2 + ROH
b. oxidation of propylene
Peroxidation, t-butyl alcohol coproduct
In this process, the first step is the air oxidation of isobutane in
the liquid phase to tertiary-butyl hydroperoxide.3 Some tertiary-butyl
alcohol is already formed at this step. In the next step, the propylene is
introduced and metal, e.g. molybdenum, catalyzes the production of propylene
oxide and t-butyl alcohol. This reaction usually occurs at 80-130ฐC and
1.8-7 MPa(250-1000 psiy).5 Finally, the products are separated and purified.
The stoichiometric minimum ratio of coproducts is 1.28 Ib of t-butyl
alcohol per Ib of propylene oxide. The actual weight ratio is 3 Ib t-butyl
alcohol per Ib propylene oxide.11
Peroxidation, styrene coproduct
Ethyl benzene is the organic chemical that is peroxidized in this
process. The products of this first step are ethyl benzene hydroperoxide,
methyl benzyl alcohol, and acetophenone. A metal such as molybdenum or
titanium is used in a soluble metal catalyst system to catalyze the ethyl
benzene hydroperoxide and propylene. This produces propylene oxide and alpha-
methyl benzyl alcohol. The propylene oxide is separated and distilled.
The alpha-methyl benzyl alcohol is dehydrated to styrene.^
The stoichiometric minimum ratio of coproducts is 1.79 Ib styrene to 1
Ib propylene oxide. The actual ratio is 2.b Ib styrene to 1 Ib propylene
oxide.11
2-4
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2.3 REFERENCES
1. Barnard, J.A. and RKY Lee. Combustion of n-pentane in a schock
tube. Combustion Science and Technology. 6(3):143-150. 1972.
2. Hughes, K.J., R.W. Hum, and F.G. Edwards. Separation and Identification
of Oxygenated Hydrocarbons in Combustion Products from Automotive Engines.
In: International Symposium on Gas Chromatography (2nd, 1969; Michigan
State University). New York, NY. Academic Press. 1961. p.171-182.
3. Bogyo, D.A., S.S. Lande, W.M. Meylan, P.H. Howard, and J. Santodonato.
Investigation of Selected Environmental Contaminants: Epoxides. Office
of Toxic Substances, U.S. Environmental Protection Agency. Washington,
D.C. EPA-56U/11-80-005. March 1980. p.12,26-28,30,67,68.
4. Rigby, L.J. The Collection and Identification of Toxic Volatiles from
Plastics under Thermal Stress. Ann. Occup. Hyg. (United Kingdom).
24(4):331-345. 1981.
b. Grayson, M., ed. Kirk-Othmer Encyclopedia of Chemical Technology,
3rd edition, Vol 19. New York, NY. John Wiley and Sons, 1982. p.249-
258,262,263.
6. SRI International. 1985 Directory of Chemical Producers. Menlo Park,
CA. 1985. p.844.
7. Hancock, E.G., ed. Propylene and Its Industrial Derivatives. New York,
NY. John Wiley and Sons. 1973. p.276-279.
8. Peterson, C.A. (IT Enviroscience) Propylene Oxide Product Report.
In: Organic Chemical Manufacturing, Volume 10: Selected Processes.
Office of Air Quality Planning and Standards, U.S. Environmental
Protection Agency. Research Triangle Park, NC. EPA-450/3-8U-028e.
December 1980. p.III-1, III-3-III20.
9. Hydroscience, Inc. Trip Report to Oxirane, Channel view, TX, October 18,
1978. In: Hydroscience files, Emission Standards and Engineering Divison,
Office of Air Quality Planning and Standards, U.S. Environmental Protection
Agency, Research Triangle Park, NC.
10. Hydroscience, Inc. Trip Report to Dow, Plaquemine, LA. November 16-17,
1977. In: Hydroscience Files, Emission Standards and Engineering
Division, Office of Air Quality Planning and Standards, U.S. Environmental
Protection Agency, Research Triangle Park, NC.
11. Mannsvilie-Chemical Products Corporation. Chemical Products Synopsis:
Propylene Oxide. Cortland, NY. February 1984.
12. Propylene Oxide puts its Waste to Work. Chemical Week. April 5,
1978. p.33-34.
2-5
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3.0 PROPYLENE OXIDE USES
Propylene oxide was the 40th highest volume chemical produced in
1979.1 In 1987, propylene oxide had the 38th highest production volume.b3
Its primary function is that of a chemical intermediate in the manufacture
of other chemical compounds. Most of the propylene oxide produced is
used to manufacture polyether polyols for use in urethane foams, functional
fluids and surface-active agents (surfactants). Another major derivative
of propylene oxide is propylene glycols and the associated dipropylene
and tripropylene glycols. Propylene oxide is used to manufacture glycol
ethers, isopropanol amines, nonpolyolbased surfactants, and propylene
carbonate. Approximately 170 Mg per year, or 0.02 percent of total annual
production of propylene oxide is used as a fumigant or a steri lant.1*2
It should be noted that the categories of use for propylene oxide are
not clearly defined. For example, polypropylene glycol might be considered
to be in the category of polyether polyols for non-urethane applications.
It might also be considered part of the propylene glycol category or even
in the miscellaneous category. The existence of this ambiguity is most
significant for the production estimates of the emission source categories.
(see Appendix G).
3-1
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3.1 POLYETHER POLYULS
A polyol Is the product of a reaction between an epoxlde and a compound
which contains active hydrogens such as glycols, amines, acids or water.
Polyether polyol s are polymers with the characteristic ether linkage
(R-O-R) which are based upon tri- or polyhydric alcohols. A compound with
two hydroxyl groups (-OH) is commonly referred to as a diol. A polyol has
three or more hydroxyl groups.-* The molecular weight of a polyol can
range from 200 to 7,000.4
3.1.1 Urethane Applicatons
The production of polyether polyol s for urethane applications is the
largest use category for propylene oxide. The basic reaction is shown below.
H 0
i H
RN<*0 + R'OH >RN-COR'
Isocyanate Polyol Urethane group
Polyol, Isocyanate Reaction3*5
The hydrogen atom that becomes attached to the nitrogen is active and
may provide a reactive point for additional crosslinking. Isocyanates
react with water to form an amine and carbon dioxide. This reaction can be
used to cause foaming while polymerization continues. In this manner,
flexible and rigid polyurethane foams can be manufactured.
Flexible and semiflexible foams are used in furniture, transportation,
rugs and underlays, bedding, packaging and textile laminates. Of the total
domestic consumption of polyether polyol s for urethane applications, 74 percent
was used for flexible foams in 1979.7
Rigid foams are manufactured using lower ratios of polyol to isocyanate.
These foams form the second largest urethane usage group. They are used in
building construction, appliances, packaging, transportation, furniture and
marine flotation.15
3-2
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Urethane foams are usually manufactured In a one-shot process. That
is, all raw materials are combined in a single step.7
The urethane reaction can also be used for nonfoam products. These can
be microcellular or noncellular. Nonfoam uses include surface coatinys,
elastomers, fibers and thermosetting resins.13 Elastomers may be
manufactured by mixing the polyols and isocyanates and then pouring or
injecting them into the mold. They may also be manufactured by reaction-
injection molding (RIM) in which the feedstreams are separately metered to
a mixing head, then injected directly into the mold.7 Elastomers are used
for shoe uppers and heels, encapsulating electronic parts, films, linings,
and adhesives.1
3.1.2 Non-Urethane Applications
Polyether polyols are also used in non-urethane applications.
Approximately 4U percent of these polyols are used as surface active agents
(surfactants). Surfactant polyols may be used as dispersants, defoamers,
oil-field chemicals, such as crude oil demulsifiers, power transmission
fluids, lubricants, greases, and wetting agents.7 These polyols can be in
the configuration of random or block copolymers of polypropylene glycol and
polyethylene glycol.
Another 41) percent of these polyether polyols are used as lubricants
and functional fluids. The remaining 2U percent are used in Pharmaceuticals,
cosmetics, toiletries, and the plasticizer industries.8*9
3-3
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3.2 PROPYLENE GLYCOLS
The source category "Propylene Glycols," includes propylene glycol
dipropylene glycol (DPG), and tripropylene glycol (TPG). Propylene Glycol
is considered nontoxic. It is classified as a generally recognized as safe
(GRAS) chemical by the Food and Drug Administration.10 This non-toxicity
allows it to be used in a variety of phamaceutical, cosmetic, food, and
drug processes and formulas. Propylene glycol is primarily used to produce
unsaturated thermoset polyester resins. Propylene glycol is also used in
antifreezes, hydraulic fluids, pet foods, functional fluids (including heat
transfer fluids and brake fluids), paints and coatings, plasticizers, and
as a tobacco humectant and cellophane softening agent.8 Oipropylene glycol
is used in hydraulic fluids, cutting oils, textile lubricants, ink formulations,
industrial soaps, and solvents and it is an indirect food additive.11
Tripropylene glycol is used in cleansing creams, textile soaps, lubricants,
and cutting oil concentrates.4
DPG and TPG are coproducts of propylene glycols. The relative capacity
for these three glycols can be manipulated by the reaction conditions but
they are usually present as 1U percent and 1 percent (respectively for DPG
and TPG) of the propylene glycol product.8
Propylene glycol is produced under pressure, at temperatures up to
200ฐC, without a catalyst, by reacting 15-20 moles of water for every
mole of propylene oxide.3ป4 The reaction is carried out in a jacketed
pipe system. Water and propylene oxide are added and the dilute mixed
glycol solution is withdrawn at a rate that will maintain a constant com-
position along the pipe. The product is dehydrated in a vacuum evaporator
and the glycols are separated in a multicolumn distillation system.3 Approxi-
mately U.8 Ib propylene oxide are consumed for each pound of propylene glycol
produced.7
Propylene glycol is easily biodegraded by many micro-organisms. In
fresh water or salt water, 55 percent or more of the original propylene
glycol is bio-oxidized after 5 days.10
3-4
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3.3 GLYCOL ETHERS
Glycol ethers are obtained from the reaction of an epoxide and an
alcohol or phenol.4 They are used primarily in formulations of mixed
solvents for paints, resins and inks.3 Glycol ethers are miscible in
water so they can be used in aqueous solvent systems. Glycol ethers are
also used as synthetic lubricants, hydraulic and automotive brake fluids,
coupling agents, and heat transfer fluids.4
Specific chemical names for some widely used glycol ethers are listed
in Table 3-1.
Table 3-1 Names of Glycol Ethers*
Common Name
Propylene Glycol Monomethyl Ether
Dipropylene Glycol Monomethyl Ether
Tripropylene Glycol Monomethyl Ether
Chemical Name
1 methoxy-2-propanol
3-(3-methoxypropoxy) propanol
3-(3-(3-methoxypropoxy) propoxy)
propanol
* SRI International. Chemical Economics Handbook. Menlo Park, CA.
1978-1980. P.69U.8022T.
3-b
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3.4 MISCELLANEOUS
Propylene oxide is used to produce a variety of chemicals other than
polyether polyols, propylene glycols and glycol ethers. These chemicals
include isopropanolamines, propylene carbonate, polypropylene glycol, and
nonpolyol based surfactants. Some propylene oxide is used directly as a
sterilant or fumigant for food and other products.9
3.4.1 Isopropanolamines
Isopropanolamines, l-amino-2-propanols, are the result of the reaction
of propylene oxide, ammonia, and water.4 These products can react chemically
as both amines and alcohols. They are used with fatty acids in emulsifiers,
detergents, foam stabilizers and shampoos.
Although propylene oxide and ammonia can react spontaneously at room
temperature, the industrial process usually occurs in a tube reactor with
aqueous ammonia at temperatures up to 100ฐC and pressures up to 300 psi.3
An estimated 10-15 million Ibs of propylene oxide were consumed in 1979 to
produce mono-, di-, and tripropanolamines.**
3.4.2 Propylene Carbonate
Propylene carbonate is manufactured by reacting propylene oxide with carbon
dioxide. It is used as a solvent for organic and inorganic gases and as a
gas conditioner for removal of hydrogen sal fide, carbon dioxide, and mercap-
tans. An estimated 2 million Ibs of propylene oxide were consumed for this
use in 1979.4ป8
3.4.3 Nonpolyol based Surfactants
Surface active agents, surfactants, which are not based upon polyether
polyols provide another market for the consumption of propylene oxide.
Table 3-2 gives specific examples of these chemicals. These surfactants are
usually propoxylated compounds.
3-6
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Mixed linear propoxylated alcohols is the most siynificant of these
compounds. Propylene oxide/ethylene oxide block copolymer surfactants are
used as crude oil demulsifiers and for breaking water-in-oil emulsions.y
Table 3-2 Nonpolyol based Surfactants*
Type
Amphoteric
Characteristics
anionic or cationi c
notable for mildness
personal care products
Example
oleic acid-ethylenediamine
condensate, propoxylated,
sodium sal t
Anioni c
positive charge
disinfectant,
fabric softener
hexyloxy propyl sulfate,
sodium salt
Cationi c
negative charge
.high sudsing
[coconut oil alkyljamine,
pro poxy1ated
Nonionic
contains neither anions
nor cations
mild, low sudsing
mixed linear alcohols,
ethoxylated and propoxylated
*SRI International .Chemical Economics Handbook. Menlo Park, CA. 1978-1980
editions. p.690.8U22 U.
3.4.4 Fumigant/Sterilant
Although the use of propylene oxide for fumigation does not consume
large amounts of propylene oxide, this minor use category is of special
interest because of a number of considerations. When used as a fumigant,
unless emission control devices are used at the facility,all of the
propylene oxide consumed will probably be emitted to the atmosphere. The
propylene oxide which remains in the food product might react to form
propylene glycol or it might form propylene chlorohydrin. The Food and
Drug Administration (FDA) regulates the amounts of residues that can remain
in foods that are designated for consumption.
3-7
-------
Propylene oxide nas been studied for use as a sterilant for therapeutic
immunoadsorbents.12 The sterilization use may allow some replacement of
ethylene oxide which is generally the preferred sterilant. Propylene oxide
is less toxic than ethylene oxide but it is also substantially less anti-
microbial.
Because of the greater toxicity of ethylene oxide, propylene oxide has
been considered as an alternative fumigant. Use of propylene oxide is
limited by the necessity of heating it to 35ฐC (95ฐF) to reach the gaseous
phase. This heating can reduce the quality of some products, such as
spices.13 It also makes the residues more difficult to remove. During the
fumigation of a few foods, e.g. cocoa beans, propylene oxide is pref-
erentially used because ethylene oxide causes quality deterioration.
Propylene oxide is allowed by the FDA as a package fumigant for dried
prunes and glace fruit. A residue of 700 ppm propylene glycol is allowed.
Propylene oxide is also allowed as a bulk fumigant for foods such as cocoa,
gums, spices, starch and nutmeats (except peanuts) that are to be further
processed. The residue limit is 300 ppm of propylene oxide. Propylene
oxide can also be used in modified food starch. Residue is limited to 5 ppm
of propylene chlorohydrin.14
Residues of the epoxides, propylene oxide and ethylene oxide, have
been studied.^ The propylene oxide combines with the elements of water to
form propylene glycols or it combines with the elements of hydrochloric
acid to form propylene chlorohydrin.16 One reference estimated that the
intake of as much as 21 mg of propylene chlorohydrin can result from the
fumigation of 1 Ib of food.*
*Reference 17. The calculations that obtained this result were not included
in the paper. It should also be noted that the calculations were made in
1975 and were probably made without regard to U.S. FDA regulations as it
was not a domestic study.
3-8
-------
Residual propylene oxide has been found on fumigated foods in
other studies. Various plastics and cellulose products used as
food wrappings and containers also have been found to contain propylene
oxide residue. 6tl8,19
3.4.5 Other
Propylene oxide was used as a raw material for the production of
glycerin, but this Bayport, Texas, plant was shut down by FMC in 1982.7
Propylene oxide is a stabilizer for fuel and heating oils, methylene
chloride, and vinyl resin lacquers. It is a solvent for various resins,
commercial gums, hydrocarbons, and cellulose derivatives.11
Besides being used as an intermediate chemical, propylene oxide can
also be used as a process chemical, that is, not used directly as an
ingredient of the final product but used to facilitate or catalyze the
necessary reactions. 20,21
3-9
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3.5 REFERENCES
1. Hawley, G.G., ea. The Condensed Chemical Dictionary, 10th edition,
New York, NY. Van Nostrand Reinhold Company. 1981. p.839, 840,
865.
2. Windholz, M., ed. The Merck Index, 10th edition. Rayway, New Jersey,
Merck and Company, Inc. 1983, p.7764.
3. Hancock, E. G., ed. Propylene and Its Industrial Derivatives. New York
NY, John Wiley and Sons. 1973. p.287,288,292-295.
4. Grayson, M., ed. Ki rk-Othmer Encyclopedia of Chemical Technology, 3rd
edition. Vol 19. New York, NY. John Wiley and Sons, 1982. p.249-251,
264,267,268.
5. Considine, D.M., ed. Chemical and Process Technology Encyclopedia.
New York, NY. McGraw Hill Book Company. 1974. p.1121.
6. Society of the Plastics Industry (SPI). Quarterly Polyols and Isocyanates
Reports. In: Facts and Figures of the U.S. Plastics Industry, 1985 ed.
New York, NY. p.31,50,51.
7. Mannsville Chemi cal Products Corporation. Chemical Products Synopsis:
Propylene Oxide. Cortland, New York. February 1984.
8. SRI International. Chemical Economics Handbook. Menlo Park, CA.
1978-1980. p.688.3500A, 69U.6050C, J, 690.8022U.
9. Bogyo, D.A., S.S. Lande, W.M. Meylan, P.H. Howard, and J. Santodonato.
Investigation of Selected Potential Environmental Contaminants: Epoxides.
Office of Toxic Substances, U.S. Envi ronemntal Proteaction Agency.
Washingto, D.C. EPA 560/I1-80-DO5. March 1980. p.46.
10. Miller, L.M. Investigation of Selected Potential Environmental
Contaminants: Ethylene Glycol, Propylene Glycols, and Butylene Glycols.
U.S. Environmental Protection Agency. Washington, D.C. EPA-560/11-79-
006. May 1979, p.i, 62,63.
11. Occupational Health Guidelines for Propylene Oxide. National Institute
for Occupational Safety and Health, U.S. Department of Health and
Human Services and Occupational Safety and Health Administration, U.S.
Department of Labor. Washington, D.C. September 1978.
9
12. Sato. H., T. Kidaka, and M. Hori. The Sterilization of Therapeutic
Immunoadsorbents with Aqueous Propylene Oxide Solution. Inter. T. Artif.
Organs. 8(2):109-14. 1985.
3-10
-------
13. Memorandum from Belolan, A., Benefits and Use Division, Office of
Pesticides and Toxic Substances (OPTS), U.S. EPA to Lapsley, P.
Special Review Branch Reyistration Division. OPTS, USEPA. June 11,
1986. Ethylene Oxide: Nonmedical uses.
14. Food Chemical News, Inc. The Food Chemical News Guide. June 28, 1982.
p.374.1,374.2.
16. Lindgren, D.L., W.B. Sinclair, and I.E. Vincent. Residues in raw and
processed foods resulting from post-harvest insecticidal treatment.
Residue Reviews. 21:93-96. 1968.
16. Wesley, F., B. Rourke, and 0. Darbishire. The Formation of persistent
toxic chiorohydrins in foodstuffs by fumigation with ethylene oxide and
with propylene oxide. Journal of Food Science. 30: 1037-1042. 1965.
17. Rosenkranz, H.S., T.J. Wlodkowski, and S.R. Bodine. "Chloropropanol,
a Mutagenic Residue Resulting from Propylene Oxide Sterilization. Mutation
Resarch 30:303-304.1975.
18. International Agency for Research on Cancer (IARC), World Health
Organization. Propylene Oxide. In: Cadmium, Nickle, Some Epoxides,
Miscellaneous Chemicals, and General Considerations on Volatile
Anaesthetics. Lyon, France. 11:191-199. 1976.
19. Kereluk, K., Propylene Oxide. In: Gaserous Sterilization: Methylne
Bromide, Propylene Oxide, and Ozone. Prog. Inc. Microbiol. 10:117-
-125. 1971.
20. Large, G.B. and Buren, L.L. Phosphonium Salts of N-phosphonomethylglycine
and their use as herbicides and plant growth regulators. Patent pending.
U.S. Application No. 295345 (810824) or 374539 (820505).
21. Chemical and Engineering News, Top bO Chemicals Production Turned Back
Up in 1987. Vol.66, no. 15, April 11, 1988. p.31.
3-11
-------
-------
4. INDUSTRIAL GRUWTH
4.1 HISTORY
Propylene oxide was first identified in 1860. It was first manufactured
in Germany during World War I. Propylene oxide became a major industrial
chemical soon after World War II.1ป2,3
The process used for production was the chlorohydrin process. This
process was also used for production of ethylene oxide. Around 1940, Union
Carbide Corporation began producing ethylene oxide by direct oxidation.
The direct oxidation of ethylene oxide gradually became the preferred
process for production of ethylene oxide. This made available chlorohydrin
plants which could be easily converted to the production of propylene
oxide.1ป4
In the I9601 s, propylene oxide demand increased Ib percent per year,
from 1970-1979, demand increased 7 percent per year.^
In 1968, Atlantic Richfield Corporation (ARCO) and Hal con International
formed Oxi pane, and commercialized the hydroperoxidation process for propylene
oxide production. The isobutane peroxidation process was an economically
competitive process and small producers who used the chlorohydrin process
began dropping out of the market. In 1977, Oxiranes ethyl benzene peroxiaation
plant came on line. The economics of the peroxidation process depend upon
the coproduct markets as well as the propylene oxide market because of the
large amount of coproducts produced.lป2ป5
In 1980, ARCO purchased Hal con's share of the Oxi rane facilities. In
this same year, an economic recession began which reduced automobile produc-
tion and housing starts. Propylene oxide consumption shrank 26 percent
from 2.11 billion Ibs in 1979 to 1.56 billion Ibs in 1982.3 The existence
of the rival peroxidation process and the decreased demand for propylene
oxide were contributing reasons for the remaining small producers to shut
down their facilities.
Only Dow and ARCO, with two plants each, continued to produce
propylene oxide for the years from 1983 to 1986. Propylene oxide demand
has increased steadily during this time. These two companies remain the
only domestic producers of propylene oxide.
4-1
-------
4.2 OUTLOOK
Demand for propylene oxide is primarily dependent upon the demand for
polyurethane polyols and propylene glycols. Demand for these products is
dependent upon their end product markets, such as the transportation and
construction markets.
Demand for the major consumers of propylene oxide will probably increase
from 4 percent to 7 percent from 1984 to 1989. Propylene oxide production
is expected to increase by approximately 4 percent per year during the same
period. 3
Production facilities are currently operating at 73 percent of capacity.
(See Appendix B.) Additional demand is more likely to be satisfied by
expansion of the Dow and ARCO facilities than by new plant startups.
4-2
-------
4.3 REFERENCES
1. Hancock, E.G., ed. Propylene and Its Industrial Derivatives. New York,
NY. John Wiley land Sons. 1973. p.273,274,282.
2. Grayson, M., ed. Kirk-Othmer Encyclopedia of Chemnical Technology,
3rd edition, Vol 19. New York, NY. John Wiley and Sons. 1982.
p.253,257.
3. Mannsville Chemical Products Corporation. Chemical Products Synopsis:
Propylene Oxide. Cortland, NY. February 1984.
4. Peterson, C.A. (IT Enviroscience). Propylene Oxide Product Report.
In: Organic Chemical Manufacturing Volume 10: Selected Processes.
Office of Air Quality Planning and Standards. U.S. EPA. Research
Triangle Park, NC. EPA-450/3-80-028e. December 1980. p.III-2.
5. Bogyo, D.A., S.S. Lande, W.M. Meylan, P.M. Howard, and J. Santodonato.
Investigation of Selected Potential Environmental Contaminants: Epoxides.
Office of Toxic Substances, U.S. EPA. Washington, D.C. EPA-560/11-80-005,
March 1980. p.30.
4-3
-------
-------
5. PROPYLENE OXIDE EMISSIONS
This section of thr; r-jvjrt contains emission estimates and related
data for production and consumption facilities. Most of the emissions
are annual averages. The only information available on short term, or
peak emissions, is for use of propylene oxide as a fumigant at an Illinois
facility. Further information and calculations regarding this usage can
be found in Appendix J.
Some of the annual emission estimates in this report were calculated
using emission factors. An emission factor is "an average value which
relates the quantity of a pollutant released to the atmosphere with the
activity associated with the release of that pollutant."1 Emission factors
used here relate the total annual quantity of emissions to the total
annual quantity of propylene oxide or other chemical produced.
The emission factor for a process emission or emission point was given
in other references or was based upon emission factors or emission rates
given in other references. For example, a reference might give total VOC
from a propylene oxide process unit, for the industry or at a specific
facility. That total YOC could be divided by the total propylene oxide
produced or consumed at the facility. The number would then be multiplied
by an estimate or calculation of the propylene oxide fraction in. the VOC.
The resulting number is a propylene oxide emission factor for the process
emissions.
The fugitive emissions, or equipment leaks, for those facilities were
not determined using emission factors. Equipment leaks are not proportional
to production volume. They are a function of the complexity of a process.
In other words, the quantity of emissions from equipment leaks depends
upon the number of process components, such as valves and pumps, that
could leak. For most of the facilities, the size of a typical production
unit and the ratio of propylene oxide to total VOC were based upon available
data, such as process flow diagrams available in general references.
5-1
-------
Depending upon the available data, different levels of error and
uncertainty are present in the final estimates. The approximations and
assumptions are chosen so that the emission estimates, and subsequent
concentration estimates, will err by being too high, rather than too low.
Applying this rule to calculations is referred to as choosing the conserva-
tive assumption.
The bases, calculations, assumptions, and references for specific
emission estimates are given in the appendices.
5.1 Domestic Production, Consumption, Imports, and Exports
In 1986, an estimated 950 Gg (2100 mil Ibs) of propylene oxide was
produced in the U.S. Approximately 860 Gg (1900 mil Ibs) is estimated
to have been consumed. The amount of propylene oxide produced and consumed
In recent years is given in Table 5.1-1
TABLE 5.1-1 PROPYLENE OXIDE SUPPLY AND DEMAND
(millions of lbs)a
Year
Capacity
Production
Imports
Exports
Demand
1981
2760
1831
89
17K
1742
1982
276U
1660
51
1.46
1565
1983
2860
1840
32
166
17U6
1984
2860
1900C
26b
180C
1750C
1985
2870
2000C
30^
200C
1800C
1986
2870
2100C
30C
210C
1900C
a Unless otherwise noted, values are from:
Mannsville Chemical Products Corporation. Chemical Products
Synopsis: Propylene Oxide. Cortland, NY. February 1984.
b Chemical Imports in 1984. Chemical Week. February 20, 1985. p.36.
c Estimated values. For method of calculation, see appendix A.
5-2
-------
Propylene oxide is domestically produced at four facilities. There are
36 production sites for the manufacture of polyether polyols, the largest
consumption category for propylene oxide. Table 5.1-2 indicates the number of
companies and the number of major facilities for all the emission source
categories.
TABLE 5.1-2 NUMBER OF MAJOR FACILITIES3
Source category
Production
Polyether Polyols
Propylene Glycols
Glycol Ethers
No. of companies
2
22
4
4
No. of facilities
4
36
5
7
a. SRI International. 1985 Directory of Chemical Producers. Menlo
Park, CA. 1985.
5-3
-------
b.2 PRODUCTION FACILITIES
Based upon the total capacity and estimated total production, it was
calculated that each facility would operate at 73 percent capacity.
Production estimates for each site are given in Table 5.2-1. Appendix B
contains calculations for this section.
TABLE 5.2-1 PRODUCTION ESTIMATES FOR MANUFACTURING FACILITIES
Company
ARCO
Dow
Location
Bayport, TX
Channel view, TX
Freeport, TX
Plaquemine, LA
1
J1986 Capacity3
Process 1 (mil Ibs)
1
isobutane j 1020
peroxidation j
ethyl benzene j 500
peroxidation j
chlorohydri nation] 950
chl o rohyd ri nati on | 400
i
i
Estimated
1986 Production5
(mil Ibs) (Gg)
740 340
360 160
690 310
290 130
a SRI International. 1985 Directory of Chemical Producers. Menlo Park,
CA. 1985.
b See Appendix B for calculations
Emission estimates and emission stream characteristics which were
developed in this source assessment, are appropriate for use in the Human
Exposure Model (HEM).
The Human Exposure Model is a screening model which uses (1) emission
estimates for point sources, (2) meteorological data for locations near
these sources, (3) population data from the census, and (4) risk factors
which are developed from health assessments for the specific chemical to
calculate potential levels of exposure and estimate the number of people
who might be exposed. HEM values for the production facilities are
given in Table 5.2-2.
Notes concerning plant location data, zone characterization, and
other information in the HEM input tables may be found in Appendix C.
Appendix E contains information concerning the equipment leak emission
estimates. Storage and transportation related emission estimates are
treated in Appendix F.
5-4
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5.3. USER FACILITIES
It was necessary to estimate the amount of propylene oxide which would
be consumed In 1986 by each major source categories. The calculations and
assumptions used to determine these estimates can be found In Appendix G.
The results are displayed in Table 5.3-1.
TABLE 5.3-1 PRUPYLENE OXIDE CONSUMPTION ESTIMATES
1986 DOMESTIC CONSUMPTION
(%) (mil Ibs) (Gy)
Polyether Polyols for
Urethane Applications 56 1,050 480
Polyether Polyols
for non-Urethane
applications 11 200 luo
Propylene Glycol,
Di propylene Glycol,
Tripropylene Glycol 24 450 210
Glycol Ethers 1 20 10
Miscellaneous uses 8 150 70
Capacity estimates for specific facilities in 1985 were available.6
These capacities were used to prorate the total consumption for each source
category to give an estimate of the propylene oxide usage at each facility.
Occasionally, capacities were given as a company total for two or more
sites. In these cases, it was assumed that the capacities of all facilities
were equal.
5-6
-------
b.3.1 Polyether Polyols
The emission factors for propylene oxide in the production of polyether
polyols were assumed to be the same for urethane and non-urethane polyols.
This assumption was necessary because no other data were available.
5.3.1.1 Urethane Applications
Table 5.3.1-1 lists the 1985 capacities and the estimated 1986 consumption
values for facilities which manufacture polyether polyols for urethane
applications. The emission estimates for these facilities are also given
in the table. Appendices D, ฃ, F, and H contain pertinent values and
cal culations.
5.3.1.2 Non-Urethane Appl i cations
Estimated 1986 consumption values and emission estimates for non-urethane
polyether polyol facilities are given in Table 5.3.1-2.
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-------
5.3.2 Propylene Glycols
For facilities lacking explicit dipropylene glycol and tripropylene
glycol capacity vaUius, these values were assumed to be 10 percent and
1 percent, res^ctively, of the propylene glycol product.8
Table 5.3.2-1 lists capacities, consumption, and emissions for non-
urethane polyether polyol facilities. Appendices D, E, F, and H contain
calculations and assumptions made to obtain these values.
5-lb
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5.3.3. Glycol Ethers
To obtain emission estimates for this category, it was necessary
to assune that the propylene glycol emission factors were applicable
for this source cateytry,^
Table 5.3.3-1 lists capacities, consumption, and emission data
tor this category.
5-17
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5.3.4 Miscellaneous
The propylene oxide emissions information was available which allowed
short-term modeling data to be developed for the minor use of fumigation or
sterilization. This minor use is one of the few direct uses of propylene
oxide. In 1986, 170 Mg (380,000 Ibs) of propylene oxide was used domestically
for fumigation.12
5.3.4.1. Site Specific Data
Direct use of propylene oxide includes * variety of categories. These
uses were discovered through site specific data requests to state agences.
Propylene oxide is used as a solvent or stabilizer in paint mixtures.
Propylene oxide also serves an unknown function in ski go
-------
TABLE 5.3.4-1 EMISSION PARAMETERS
Height (m) 12.
Diameter (m) 0.08
Temperature (K) 370.
Velocity (m/s) 16.
Propylene oxide comprises only 10 wt percent of the total annual
gaseous fumigant usage. For the short-term calculations, it was assumed
that pure propylene oxide was used simultaneously in the retorts.
The average sterilization cycle lasts 8 hours. The total emissions
time during this cycle is ?:> minutes. The emission time is not continuous
A break is necessary for the intake of air. The length of time of this
break is unknown. For modeling purposes, the emission time was assumed
continuous for 60 minutes.
The total amount of propylene oxide emitted in that hour is 170 kg.
The emission rate is 47 g/s. Appendix I contains the details of tne
calculation.
Additional work was done to refine this emission estimate. These
calculations and comments are given in Appendix J.
5-21
-------
5.4 REFERENCES
1. Office of Air Quality Planning and Standards, U.S. Environmental Protection
Agency. Compilation of Air Pollution Emission Factors, 4th edition,
Vol I, Stationary Point and Area Sources. Research Triangle Park, NC.
r 1985. p.l.
2. Mannsville Chemical Products Corporation. Chemical Products Synopsis:
Propylene Oxide. Cortland, NY. February 1984.
3. Chemical Imports *n 1984. Chemical Week. Februa-y 20, 1985. p. 36.
4. SRI International. 1985 Directory of Chemical Producers. Menlo Park,
CA. 1985. p. 550, 623, 827-830, 844, 950.
5. Ibid, p. 844.
6. Ibid, p,5SO, 623, 827-830, 844, 950.
7. Ibid. p. 829, 830.
8. SRI International, Chemical Economics Handbook. Menlo Park, CA.
August 1980, p. 690. 6050C.
9. Systems Applications, Inc. (SAI). Appendix A-26: Propylene Oxide. In:
Human Exposure to Atmospheric Concentrations of Selected Chemicals,
Vol II. Prepared for Office of Air Quality Planning and Standards, U.S.
Environmental Protection Agency. Research Triangle Park, NC. Contract
No. 68-02-306.. February 1982.
10. Reference 4. p. 623.
11. Bogyo, D.A., S.S. Lande, W.M. Meylan, P.H. Howard, and J. Santodonato,
Investigation of Selected Potential Environmental Contaminants:
Epoxides. Office of Toxic Substances, U.S. Environmental Protection
Agency, Washington, D.C. EPA-560/11-80-005. March 1980. p. 156.
12. Letter and attachments from M. Warren, ABERCO, Inc. to G. Hume,
U.S. EPA, September 4, 1986. Fumigation with Propylene Oxide.
13. Information obtained through Air Pollution Control Office, New York
State Department of Environmental Conservation, Albany, NY. 1986.
14. Lazenka, C.A., N.J. Ciciretti, R.T. Ostrowski , and W. Reilly.
Experiences with Tox^c Air Contaminant Control in Philadelphia. In:
76th Annual Meeting of the Air Pollution Control Association, Atlanta,
GA. June 1983. Paper No. 83-46.3.
15. Information obtained through Air Pollution Control Division, Illinois
Environmental Protection Agency, Springfield, 111. 1986.
5-22
-------
6. OTHER INFORMATION
6.1. AQUEOUS EMISSIONS
Generally, organic emissions are not transferred from air to water.1
This might not be the case for propylene oxide because propylene oxide is
water soluble and, at ambient conditions, it exists in the liquid phase.
Propylene oxide can be discharged from facilities into effluent water.
This occurrence has been discovered at at least one facility.2 quantifying
data were not available for this discharge.
Because propylene oxide is not completely soluble in water, and because
it has a high vapor pressure, propylene oxide might evaporate from effluent
emissions. This evaporation rate has been estimated to be approximately
equal to the hydrolysis rate of propylene oxide.3 Information on effluent
streams was not available for any of the source categories. Therefore,
estimates of secondary emissions were not made.
6.2. AMBIENT AIR CONCENTRATIONS
No literature was found in which propylene oxide had been measured in .
ambient air. This might be due to any of a number of factors. The most
obvious explanation is that it might not be emitted in detectable quantities
Propylene oxide is highly reactive. This reactivity could prevent
it from accumulating in measurable quantities. Rapid dispersion in areas
where propylene oxide is emitted might also reduce the probability of
measurement.
Propylene oxide is a volatile organic chemical which patticipates in
the photochemical smog cycle.4'5
6-1
-------
6.3. ENVIRONMENTAL FATE
Epoxides, such as propylene oxide, neither persist in the environment
nor accumulate in the food chain. They are rarely identified in monitoring
studies, but their degradation products have been identified.3
Epoxides are likely to migrate rapidly in soil. They have significant
mobility in both water and air. This results from the combination of high
water solubility and high vapor pressure.6 Propylene oxide can degrade
to a glycol or a halohydrin, or it can be biodegraded or evaporated from
water.
In water, the evaporation rate is thought to be competitive with the
hydrolization rate. Table 6. 3-1 lists estimated half lives for propylene
oxide degradation in water. The values in this table do not take biodegradation
routes into account. An estimated 70 percent of propylene oxide biodegrades
in 30 days in water.3*6
TABLE 6.3-1 PROPYLENE OXIDE DEGRADATION IN WATER a
AT A TEMPERATURE OF 25ฐC
Half life (hrs)
Fresh water
Marine water
Chlorohydrin rat-in
Glycol
169
36.3
3-4
279
99
4.3
279
99
4.3
a Bogyo, D.A., S.S. Lande, W.M. Meylan, P.H. Howard, and J. Santodonato.
Investigation of Selected Potential Environmental Contaminats:
Epoxides. Office of Toxic Substances, U:.S. Environmental Protection
Agency. EPA-b60/ll~80-OOb. March 1980. p. 84.
6-2
-------
One reference estimated that in the atmosphere, the residence time
for propylene oxide is 8.9 days. The residence time is not a concentration
lifetime but the time required for a quantity of the pure chemical to be
reduced to 1/e, approximately 0.37, of its original value.7 Other atmospheric
degradation pathways include free radical oxidation in reactions with ozone,
03, or the hydroxyl radical, 'OH.9 Table 6.3-2 lists possible atmospheric
degradation products of propylene oxide.
TABLE 6.3-2 ATMOSPHERIC DEGRADATION PRODUCTS OF PRQPYLENE OXIDE3>bปc
Name Chemical Formula
Tsopropyl alcohol C^CHOHCHq
n-propyl alcohol CH3CH2CH2OH
propion aldehyde CH3CH2CHO
acetone CH3COCH3
formaldehyde CH20
2-oxo-pro pa nal CH3COCHO
methyl ester acetate CH3COOCHO
methanoic anhydride CHOOCHO
a Cupitt, L.T. Fate of Toxic and Hazardous Materials in the Air
Environment. Office of Research and Development. U.S. Environmental
Protection Agency, Washington, D.C. EPA-600/3-80-084. August 1980.
p.19-21.
b Gritter, K.J. and E.G. Sabatino. Free Radical Chemistry of Cyclic
Ethers. VII. Ultraviolet Photolysis of Epoxides and Porpylene
Sulfide in the Liquid Phase. Journal of Organic Chemistry.
29;. 1966-1967. 19b4.
c Nitrogen containing species are also possible degradation products.
6-3
-------
6.4. OCCUPATIONAL EXPOSURE DATA
In its 1986-1986 pamphlet, the American Conference of Governmental
Industrial Hygienists (ACGIH) set a Threshold Limit Value-Time Weighted
Average (TLV-TWA) of 20 ppm or 50 mg/m3 for propylene oxide.
The people most likely to be exposed to this chemical are the process
operators, maintenance personnel, tank car loaders and others who work with
it directly. Exposure data which were readily available are given in
tables 6.4-1, 2 and 3.
TABLE 6.4-1 MAXIMUM PEAK CONCENTRATIONS3*5
Worst Case Typical with
Activity 1979 (ppm) Controls (ppm)
Process sampling I,0b0 <1
Tank car sampling 460 1
Tank car disconnect 150
Gas chromatograph
work 10 4
Other lab work 25 <1
Maintenance 3,800 <1
Exposure duration < 1 minute.
Flores, G.H. Controlling Exposure to Al kene Oxides.
Chemical Engineering Progress. 79:39-43. March 1983
TABLE 6.4-2 TIME WEIGHTED AVERAGE EXPOSURE*
Typical daily *
exposure, 1979
(ppm)
Process operator 2.0
Tank car leader 2.0
Maintenance u.2
*Flores, G.H. Controlling Exposure to Al kene Oxides.
Chemical Engineering Progress. 21:39"43ซ March 1983
6-4
-------
TABLE 6.4-3 8-HOUR TIME WEIGHTED AVERAGE EXPOSURE. 1979*
Activity
Loading/drumming
Process operator
Maintenance
Laboratory Technician
Tank farm operator
High
Dow
8.5
2.4
8.3
-
*~
(ppm)
AKCO
9.5
1.1
-
10.6
8.7
Low (ppm)
Dow ARCU
2.4 1.1
1*3 0.1
2.8
1.0 0.7
0.8
*Assessment of Testing Needs: Propylene Oxide, Support Document for
Proposed Health Effects Test Rule. Office of Toxic Substances.
U.S. Environmental Protection Agency, Washington, D.C.- 1983. p.16
6-5
-------
6.5 REGULATIONS
At least three StatesConnecticut, Nevada, and New York, have limits
for the allowed concentration of propylene oxide in ambient air.11 These
limits are based upon health considerations, not upon monitoring data.
Some offices of the Federal Government have regulations concerning
specific aspects of propylene oxide production and use.
The Department of Transportation (DOT) has issued various regulations
cocnerning the labeling of containers and acceptable transportation vehicles
(see Appendix F). The Occupation Safety and Health Administration (OSHA)
has issued a permissible exposure level (PEL) for this chemical. To comply
with this regulation may require the use of personal protective equipment,
local exhaust ventilation, general dilution ventilation, and other
measures.3*12
Within the Environmental Protection Agency (EPA), the Office of Pesticide
Programs (OPP) regulates the amount of propylene oxide used for fumigation.
This office can grant low volume (LV)-minor use wafvers to allow this use.
As has been discussed (see Section 3.4.4), the FDA also regulates the use
of propylene oxide for fumigation of food.3*13
6-6
-------
6.6 REFERENCES
1. Sittig, M., Environmental Sources Emissions Handbook. Prk Ridge, NJ.
Noyes Data Corporation. 1975.
2. Schackelford, W. M. and L.H. Keith Frequency of Organic Compounds
Identified in Water. Officse of Research and Development, U.S.
Environmental Protection Agency, Athens, GA. EPA-600/4-76-U62.
December 1976. p.2U8.
3. Bogyo, D.A., S.S. Lande, W.M. Meylan, P.H. Howard, and J. Santodonato.
Investigation of Selected Potential Environmental Contaminants: Epoxides
Office of Toxic Substances, U.S. Environmental Protection Agency. EPA-
560/11-8U-U05. March 1980. p.72, 73, 96, 150, 151.
4. Pitts, J.N., Jr., G.J. Doyle, A.C. Lloyd, and A.M. Winer. Chemical
Transformations in Photochemical Smog and Thei r Applications to Air
Pollution Control Strategies. National Scinee Foundation. National
Technical Information Service (NTIS).
5. Akimoto, H., M. Hoshimo, G. Inoue, F. Sakamaki, H. Bandow, and M. Okuda.
Formation of Propylene Glycol 1,2-Dinitrate in the Photo-oxidation of a
Propylene-Nitrogen Oxide-Air System. Journal of Envi ronmental Science
and Health. A/3(9):677-686. 1978.
6. Assessment of Testing Needs: Propylene Oxide, Support Document for
Proposed Health Effects Test Rule. Office of Toxic Substances. U.S.
Environmental Protection Agency, Washington, D.C. 1983. p.31
7. Cupitt, L.T. Fate of Toxic and Hazardous Materials in the Air
Environment. Office of Research and Development. U.S. Environmental
Protection Agency, Washington, D.C. EPA-60U/3-8U-U84. August 1980.
p.19-21.
8. Gritter, R.J. and E.G. Sabatino. Free Radical Chemistry of Cyclic
Ethers. VII. Ultraviolet Photolysis of Epoxides and Porpylene Sulfide
in the Liquid Phase. Journal of Organic Chemistry. 2^:1965-1967.
1964.
9. Radding, S.B. Review of the Environmental Fate of Selected Chemicals.
Office of Toxic Substances. U.S. Environmental Protection Agency.
Washington, D.C. EPA-560/5-75-001. January 1975. p.8.
6-7
-------
1U. Flores, G.H. Controlling Exposure to AT kene Oxides. Chemical
Engineering Progress. 2i:3y-43ซ March 1983.
11. Information obtained through National Air Toxics Information Clearing
House (NATICH) Data Base. September 1985. Office of Air Quality
Planning and Standards. U.S. Environmental Protection Agency. Research
Triangle Park, NC. EPA No. 68-02-3889, WA 2b.
12. Occupational Health Guidelines for Propylene Oxide. National Institute
for Occupational Safety and Health (NIOSH), U.S. Department of Health
and Human Services, and Occupational Safety and Health Administration
(OSHA), U.S. Department of Labor. September 1978.
13. The Food Chemical News Guide. Ford Chemical News, Inc. June 28, 1982.
p.374.1-374.2
6-8
-------
Appendix A P.O. Production, Consumption, Import, Export
Production1
1983 estimated P.O. production = 1,840 mil. Ibs.
1983-1989 estimated growth rate - 4% per year.
(100 (----r-H/89-83 = 4%
1.8
estimated production 1984 = (1,840) (1.04) = 1,900 mil. Ibs.
1985 = 2,000 mil. Ibs.
1986 = 2,100 mil. Ibs.
Imports
1. Imports are typically a minor share of total P.O. supply.2
2. Most imports come from Canada.3
3. In 1984, sizeable exports were made to Canada.4
Based upon these three facts, imports were assumed to be constant near their
1983, 1984 levels of 30 million Ibs. per year.
Exports
1980 total exports = 131 mi 1 lion Ibs. 5
1984 total exports * 180 million Ibs.4
180-131
Annual Growth Rate: (--")/84-80 = 9%
1985 estimated exports * (180) (1.09) * 200 mil. Ibs.
.1986 estimated exports ป 210 mil. Ibs.
Consumption
Assuming the amount of P.O. in surplus or storage remains constant,
Production + Imports - Exports a Consumption
For 1986: 2,100 + 30 - 210 = 1,900 mil. Ibs. (860 Gg)
A-l
-------
1. Mannsville Chemical Products Corporation. Chemical Products Synopsis:
Propylene Oxide. Cortland, New York, February 1984.
2. Assessment of Testing Needs: Propylene Oxide. Support Document for
Proposed Health Effects Test Rule. Office of Toxic Substances. U.S.
Environmental Protection Agency. Washington, D.C. 1983, p.8.
3. Bogyo, DA, SS Lande, WM Mcylan, PH Howard, and J. Santodonato.
Investigation of Selected Potential Environmental Contaminants: Epoxides.
Office of Toxic Substances, U.S. Environmental Protection Agency.
Washington, D.C. EPA 560/11-80-005. March 1980. p. 15.
4. US Exports, Schedule B, Commodity by Country. Bureau of the Census,
US Department of Commerce. Washington, D.C. FT 446. June 1985. p. 1-121.
5. US Exports, Schedule B, Commodity by Country. Bureau of the Census,
US Department of Commerce. Washington, D.C, FT 446. April 1981. p. 1-138.
A-2
-------
Appendix B Production Facilities
Utilization Factor:
2,100 mil Ibs propylene oxide (PO) produced = 73 percent utilization factor
2,870 mils Ibs capacity
Process Vent Emissions:
Process vent parameters were only available for two process vents of the
chlorohydrination process. Since no other data were available, it was assumed
that two process vents existed for both the chlorohydri nation and the
peroxidation processes and their parameters would be the same.
Table B - 1 - Process Vent Parameters1
Height(m) Diameter(m) Temperature(K) Velocity(m/s)
Reactor Vent 23. 0.30 289 1.5
Condenser Vent 14. 0.08 294 17.
Chlorohydrin Vent Emissions:
Table B - 2 Chlorohydri nation - Model Facility Vent Emissions2
Process Ventd Emission Source VOC Emissions PO wt.% in VQC PQ Emission
:' (g/kg)bFactor(g/kg)c
Reactor Vent Saponification .043 90. .039
Column
Condenser Vent PO Stripping .006 89.9 j .Olb
Lignt Stripping .006 79.9 j
PO distillation .006 100. 1
^ The stripping column and distillation emissions are all assumed to
be emitted from the condenser vent because vent parameters were
available only for one reaction vent and one condenser vent.
b g VOC emitted/kg PO produced
c PO emission factor for reactor vent ป (VOC emissions)(PO wt %) -
. (.043) (.90) ซ 0.039 g/kg
condenser vent s (VOC emissions)(PO wt%)
= .006(.899) + .006(.799) + .006(1.00) ซ .016 g/kg
B-l
-------
Table B - 3 Emissions from Chi orohydri nation Process Vents
Vent
Company Location Type
Dow Freeport, TX Reactor
Condenser
Plaquemlne, LA Reactor
Condenser
Prod(Gg)
310.
310.
130.
130.
Emission
Factor
(g/kg)
0.039
.016
.039
.016
Annual
Emissions
(kg/yr)a
12,200
5,000
5,200
2,100
Emission
Rate
(g/s)b
.39
.16
.16
.07
(1,000 kg/Gy)
a. Annual Emissions * (Production)(Emission Factor) * Ig/kg
12,200 kg * (310)(.039)(1,000)
b. Emission Rate s
(n)(3.!7 x UT5)g/s
(n)kg
yr
^
8,
/r
ho
|
1 3
hr
,600
s
|1
j
,000
kg
g
(12,200)(3.17 x 10~5) * 0.39 g/s
Peroxidation Vent Emissions:
Tabl e
Press
Vent*
Reactor Vent
Condenser Vent
B - 4 Peroxidation -
Emission VOC
Source^
PO Stripping
Crude TBA
Recovery0
Solvent Scrubber
Model Facility
Emissions
(g/kg)bd
.0185
.0155
.63
Vent Emissions
PO wt% in
vocb
100
trace j
i
0.5 j
2
PO Emission
Factor (g/kg)
.019
.0003
The recovery and scrubber column emissions were assumed to be emitted from
the condenser vent because vent parameters were only available for one
reactor and one condenser vent.
b Ref. g. Separate tables were given in this reference for the isobutane and
ethyl benzene peroxidation process. The values for ethyl benzene peroxidation
yielded PO emission factors 100 times smaller than the total emission factors
for isobutane peroxidation and chlorohydination. It was assumed that the best
estimate of PO emissions could be obtained by using the isobutane values for
both peroxidation processes.
c Tertiary butyl alcohol = TBA
d g VOC emitted/kg PO produced
e Calculated in same manner as Table 7.2-2, footnote d.
B-2.
-------
Table B - 5 Emissions From Peroxlelation Process Vents
Company
Arco
Location
Bayport.TX
Channel view, TX
Vent
Type
Reactor
Condenser
Reactor
Condenser
Prod
(Gg)
337
337
16b
165
Emission
Factor
(g/kg)
.019
.003
.019
.003
Annual a
Emissions
(kq/yr)*
6,4UO
1,000
3,100
5UO
Emission8
Rate
(g/s)ซ
.20
.03
.10
.03
a Calculated in same manner as corresponding columns in Table B-3.
B-3
-------
REFERENCES
Hydroscience, Incorporated. Trip Report to Dow
November 16-17, 1977. In: Hydroscience Files,
and Engineering Division, Office of Air Quality
Standards, U.S. Environmental Protection Agency
Park, North Carolinal
in Plaquemine, LA.
Emission Standards
Planning and
Research Triangle
2.
Peterson, CA (IT Enviroscience). Propylene Oxide Product Report.
In: Organic Chemical Manufacturing Volume 10: Selected Processes,
Office of Air Quality Planning and Standards, U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina.
EPA 4bO/3-80-U28e. December 1980. p. IV-2, IV-6.
B-4
-------
Appendix C Comments Regarding HEM Input Tables
For all HEM Input tables, the following options apply:
Zone -
Emission
Type -
Area -
Vent
Type -
Urban = 0, rural = 1.
Where the zone was unknown, it was assumed to be rural.
Process vent = P, equipment leaks = E, storage = S
Equipment leaks may also be referred to as fugitive emissions.
For vent or stack emissions - cross sectional downwash area,
for equipment leaks = floor area. Where specific data was
unavailable, these areas were based upon estimated dimensions of
a manufacturing, facility.
Vertical - 0, nonvertical = 1
Process vents were assumed to be vertical. All other vents and emissions
were assumed non vertical.
Duration - Continuous emissions = 24 hrs/day x 365 days/yr
= 8,760
Plant
Location - The address given in Reference 1U was assumed correct for manufacturing
facilities.
Latitude,
Longitude - The latitudes and longitudes given are those corresponding to the
city name as listed in Reference 11. The precision of this Reference
is 0.1 minutes (6 seconds). The accuracy of the values is a function
of this precision and is dependent upon the actual location of the
facility relative to the location of the city center. The following
cities were not listed in Reference 11. Their angular measurements
were obtained from various sources.
C-l
-------
REFERENCES
1. SRI International. 1985 Directory of Chemical Producers. Menlo Park,
California, 1985. p. 550, 623, 827-830, 844, 950.
2. Gerlach, AC ed. The National Atlas of the United States of America.
Geological Survey, U.S. Department of the Interior. Washington,
D.C. 1970.
C-2
-------
Appendix D - Approximations of Stream Compositions
Notes from teleconference with West Viryinia Environmental
Protection Agency personnel, May 1, 1986.
Data in Table D~l are from equipment leak estimates, Option #1 - Pump
Seal Counts and Mass Balances for Union Carbide Corporation Facilities
Option #1 was one option used in developing the inventory for the state
in which an average factor relating the number of equipment components per
pump seal was used to derive total equipment counts based on multiplying the
pump seal count for the process unit by this factor.
Table D~l Stream Compositions
Corresponding
Sou rce
Location
South Charleston,
West Vi rginia
Institute, WV
Process VOC(lb/yr)
Flexible
Polyols
Phase 4
Ucon
Lubricants
Flexible
Polyols
Rigid Polyols
Hydroxypropyl
Met hi sop ropy 1 ami ne
Butoxyethoxy
Polyoxy
47 ,2UU
36,900
116,000
73,800
18,000
828
1,180
384
43,700
P0(lb/yr) Category*'5 Wt. % POC
1,660
2,340
3,8bO
12,600
1,130
738
499
32b
1,760
PP
PG
PP
PP
PP
PG
MI
PG
MI
3.6
6.4
3.3
17.1
6.3
89.1
42.2
84.6
4.0
average for all streams 28.5
PP - Polyether Polyols, PG - Propylene Glycol, MI - Miscellaneous
This correspondence was assumed based upon product information for
these facilities (see Table D-2).
100 ((P.O. lb/yr)/(VOC lb/yr)) * wt% P.O.
D-l
-------
Appendix D - Approximations of Stream Compositions (cont'd)
Table D-2 Possible Products from Process Streams Propylene Oxide
Products in South Charleston and Institute, WV
Location
South Charleston, WV
Institute, W Va
Products8
Polyether polyols for urethane applications
Polyether polyols for non-urethane applications
Propylene Glycol
Dipropylene Glycol
Polypropylene Glycol
n~P ro poxy pro pan ol
Polyether polyols for urethane applications
Polyether polyols for non-urethane applications
l-Butoxyethoxy~2-propanol
a SRI International. 1984 Directory of Chemical Producers, Menlo Park,
California. 1984
Telecon. Dale Farley, West Virginia EPA, to G. Hume U.S. EPA on May
Ul, 1986. Propylene Stream Compositions at Industrial Consumption
Sites.
D-2
-------
Appendix E Equipment Leaks
A correlation relating production rate to equipment leaks has not been
found. Fluid vapor pressure, which is high for P.O., is a "primary fa.ctor
influencing the equipment leak emission sources." 1 The complexity of a
process unit influences the amount of equipment leak emissions. This
complexity is indicated by the number of pump seals a facility has. Thus,
the total equipment leak emissions of a specific VOC is a function of the
number of pump seals in the facility. 2
Table E-l Baseline VOC Emissions3
A
Model Plant Pump Seals in
Light Liquid Service13 8
VOC Emissions (Mg/yr)c 28.06
B
29
106.42
C
91
331.49
a "Baseline" means uncontrolled. A VOC is a volatile organic compound.
b Office of Air Quality Planning and Standards, U.S. Environmental
Protection Agency. VOC Fugitive Emissions in Synthetic Organic-
Chemicals Manufacturing Industry - Background Information for Promulgated
Standards. Research Triangle Park, North Carolina!. EPA 450/3-80-033b.
June 1982. p.3-14.
c Office of Air Quality Planning and Standards, U.S. Environmental Protection
Agency. Fugitive Emission Sources of Organic Compounds-Additional
Information on Emissions, Emission Reductions and Costs, EPA 450/3-82-010.
April 1982. P B-3.
Table E-2 Emission Stream Parameters3
Source
Category
Production
Polyether polyols
Popylene glycols
Release
height (m)
3.0
3.0
3.0
Diameter
(m)
0.0
0.0
0.0
Temp
00
300
300
300
Velocity
(m/s)
0.01
0.01
0.01
a Values given are default values which were used because specific
information was not available.
E-l
-------
P roducti on Faci 1 i ties
For the p. o. production facilities, flow sheets of model plants were
available. These flow sheets indicated that 31, 74 and 57 pumps were used
at the chlorohydrin and peroxidation facilities.3 All of these pumps were
assumed to be in light liquid service. It was assumed that there was a
spare in place for each pump located on the flow sheet. All production
facilities were assumed to be of the same complexity. The best model for
these plants was determined by averaging the number of pumps in the facilities
2(31) + 2(74) + 2(57) s 1U8 average number of pumps
The number of pumps corresponds to the number of pump seals. Model plant C,
with 91 light liquid pump seals, was chosen as the best model for equipment
leaks in p.o. production facilities.
To determine the amount of p.o. emissions, it was necessary to obtain
an indication of the composition of the VOC streams. Available information
indicated that 28.5 wt% would be a reasonable estimate, (see Appendix D).
Model C, VOC equipment leaks x wt % of PO = PO equipment leaks
(331.49 Mg/yr) x .286 * 945UO kg/yr
Emission rate ป (945UU kg/yr)(3.17 x 10~5 g/s ) = 3.00 g/s
kg/yr
Polyether Polyol
Process descriptions of polyether polyol urethane production were the
basis for deciding that a model-unit B was most appropriate for equipment
leak estimates in urethane application.4*^
Because there is not a foaming process or urethane addition involved
in non-urethane polyether polyol production, these non-urethane production
units are believed to be less complex than the urethane processes. No
data was available on which to base estimates of equipment leaks. Based
upon a general understanding of process reactions and products, the model
unit A facility was used to estimate equipment leaks for non-urethane
production units.
ฃ-2
-------
A composition factor was determined using available data (see Appendix U)
Based on information indicating production units at specific facilities
(see Appendix D, table D-2), The following streams were assumed to be
associated with the polyether polyol process units.
Flexible Polyols 3.5 wt % PO in VOC
Flexible Polyol s 17.1
Rigid Polyols 6.3
Ucon Lubricants 3.3
Avg. HTwt %
(YOC emissions from Model Plant)(P.O. fraction) - PO emissions
Model Plant A: (28.U6 Mg/yr)(.076) = 2.1 Mg/yr
Model Plant B: (1U6.42 Mg/yr)(.076) * 8.1 Mg/yr
Based upon a flow diagram and description of the hydration process,
Model A was assumed to be the best model for equipment leaks from these
processes.^ Available data were used to determine stream composition
(see Appendix D).
Phase 4 6.4 wt-% PO/VOC
Hyd roxyp ropy lene 89
Butoxyethoxy 85
Avg 60 wt %
P.O. emissions = (28.06 Mg VOC/yr) (.60) * 16800 kg PO/yr
E-3
-------
REFERENCES
1. Office of Air Quality Planning and Standards, U.S. Environmental
Protection Agency. Fugitive Emission Sources of Organic Compounds-
Additional Information on Emissions, Emission Reductions and Costs,
EPA 450/3-82-010. Apri1 1982. P B-3.
2. Memorandum from Stalling, J. Radian to Evans, L.B., Office of Air
Quality Planning and Standards, Environmental Protection Agency.
April 15, 1986. Fugitive Emission Estimates - Kanawha Valley.
3. Peterson, CA (IT Enviroscience). Propylene Oxide Product Report. In:
Organic Chemical Manufacturing Volume 10: Selected Processes. Office
of Air Quality Planning and Standards, U.S. Environmental Protection
Agency, Research Triangle Park, North Carolina. EPA 450/2-80-028e.
December 1980. P. III-5,6,11-14,23-25. IV-2,6.
4. Mark, M.F., J.J. McKetta, D.F. Othmer, eds. Kirk-Othmer Encyclopedia
of Chemical Technology, 2nd ed. vol 21, John Wiley and Sons, New York.
1975. P 60-62, 80-94.
5. Considine, D.M. ed., Chemical and Process Technology Encyclopedia.
McGraw-Hill Book Company. New York. 1974. 1121-1125.
6. Lowenheim, F.A. and M.K. Moran, Faith, Keyes, and Clark's Industrial
Chemicals, 4th edition. John Wiley and Sons. New York. 1975.p.688,689,
E-4
-------
APPENDIX F - STORAGE AND TRANSPORTATION EMISSIONS
Transportation
A primary consideration in the storage and transportation of propylene
oxide (PO) is this compound's flammability. The high reactivity of PO is
another important consideration.
The Department of Transportation (DOT) has developed regulations for
this chemical.1 PO may be transported by a variety of vehicles. It may
be conveyed by ship or barge. Railroad tankers, holding 10.000 to 20,000
gallons, may be used. PO may also be transported in tnk trucks or in b5
gal Ion drums.2
Emissions data were not available for any of these modes of transportation
Storage
The parameters in Table F-l were used for storage emissions at all
facilities. Storage emissions are not associated with an emission area.
Table F-l. Storage Emission Parameters3
Height Diameter Velocity Temperature
_iฃ
6.0
(m) (m) (m/s) 00
inn or 300
a Systems Applications, Inc. (SAI). Appendix A-26: Propylene Oxide.
In: Human Exposure to Atmospheric Concentrations of Selected Chemicals.
Vol. II. Office of Air Quality Planning and Standards, U.S. Environ-
mental Protection Agency. Research Triangle Park, North Carolina.
No. 6b~02-306. February 19b2.
Storage at Production Facilities
The only data for storage emissions of PO indicated that a single fixed
roof tank (heights46 feet, diameters62 feet) at a production facility
emitted 1 ton (1 Mg) of PO per year. It was implied that this was the
only storage device used for PO. There was no indication of how frequently
the tank was emptied and refilled.4 A storage emission factor from
another source3 was used for the following calculations.
F-l
-------
Table F-2. Storage Emissions at Production Facilities
Company Location
Arco Bay port, Texas
Channel view, Texas
Dow Freeport, Texas
Plaquemine, Louisiana
Estimated
1986
Production
(Gg)
34U
160
310
130
Annual PO
Storage Emissions3
(kg)
10,400
5,100
9,700
4,100
Emission
Rateb
(g/s)
0.33
0.16
0.31
0.13
a Systems Applications, Inc. (SAI). Appendix A-26: Propylene Oxide.
In: Human Exposure to Atmospheric Concentrations of Selected Chemicals.
Vol. II. Office of Air Quality Planning and Standards, U.S. Environ-
mental Protection Agency. Research Triangle Park, North Carolina.
No. 68-02-306. February 1982.
b Emission factor*0.000031 Ib P.O. emitted/lb P,0, produced.
Storage at User Sites
The only available source3 gave an emission factor of .000001 Ib PO
emitted/lb of PO consumed. This number probably represents an assumed
reasonable value rather than calculations from actual data.
Nothing in the available literature suggested that storage techniques
or storage emission factors would vary greatly from production and user
facilities. Since the emission factor used for production facilities
was 0.000031 Ib PO emitted/lb PO produced, it was considered more reason-
able to use an estimated emission factor of 0.00001 Ib PO emitted/lb PO
consumed.
F-2
-------
STORAGE OF PROPYLENE OXIDE
Propylene oxide is a liquid under ambient conditions (20ฐC, latm). It
has a low boiling point (34.2ฐC) and a high vapor pressure (445 mm Hg at
20ฐC). This means that it must be stored under pressure or in a manner
which will minimize loss. Propylene oxide is also toxic and flammable.
These characteristics encourage industrial consumers to minimize the amount
or propylene oxide stored on the premises.
One example of storage of propylene oxide is given below. This example
is considered typical for industry.5
The tanks used to store propylene oxide are blanketed with nitrogen.
They are kept at a pressure slightly above atmospheric. The propylene oxide
is kept cool by refrigerated vent condensers. Vapors emitted from the
condensers go to a scrubber. Scrubber emissions are vented to a biological
oxidation unit.
These storage tanks are on the premises of a propylene oxide production
facility. The propylene oxide is pumped directly from the product distillation
column. Most of the product is pumped from the tank directly to a propylene
glycol production unit.
F-3
-------
REFERENCES
1. Grayson, M., ed. Ki rk-Othmer Encyclopedia of Chemical Technology,
3rd Edition. Volume 19. New York, New York. John Wiley and Sons.
p. 263.
2. Bogyo, DA, SS Lande, WM Mcylan, PH Howard, and J. Santodonato.
Investigation of Selected Potential Environmental Contaminants:
Epoxides. Office of Toxic Substances, U.S. Environmental Protection
Agency. Washington, D.C. EPA 560/11-80-005. March 1980. p. 62.
3. Systems Applications, I:nc. (SAI. Appencix A-26: Propylene Oxide.
In: Human Exposure to Atmospheric Concentrations of Selected Chemicals.
Vol. II. Office of Air Quality Planning and Standards, U.S.
Environmental Protection Agency. Research Triangle Park, North
Carolina. No. 68-02-306. February 1982.
4. Hydroscience, Incorporated. Trip Report to Dow in Plaquemine, LA.
November 16-17, 1977. In: Hydroscience Files, Emission Standards and
Engineering Division, Office of Air Quality Planning and Standards,
U.S. Environmental Protection Agency. Research Triangle Park,
North Carol ina.
5. Telecon. G. Hume, Emission Standards and Engineering Division, U.S.
Environmental Protection Agency, to Mike Nevill, Dow Chemical. July 24,
1986. Propylene Oxide Storage File 86/22.
F-4
-------
APPENDIX G - CONSUMPTION ESTIMATES FOR USE CATEGORIES
The estimation of current consumption of PO was complicated by the
fact that different references list different categories of use. It is not
always clear which of these categories refer to the same use.
Table G-l PQ Usage3
1983 1985b
(% of consumption) (% of consumption)
Polyurethane
Flexible Foams 40 41
Rigid Foams 7 7
Noncellular 10 11
Coatings and Adhesives 7 6
Polyols for Specialty Surfactants 4 4
Propylene Glycol 22 22
Detergents 4 4
Other 6 5
aMannsville Chemical Products Corporation. Chemical Products Synopsis:
Propylene Oxide. Cortland, New York, February 1984.
Estimates made using 1983 estimates and growth predictions from Reference 1.
Table G~2. PO Usage*
1*78 x tai 1983
(% of consumption) (% of consumption)
Polyurethane Polyols 62 64
Flexible Foams (71)
Rigid Foams (9)
Non-Foam (10)
Export (10)
Propylene Glycol 21 21
Dipropylene Glycol 3 3
Glycol Ethers 1 1
Miscellaneous 12 11
*SRI International Chemical Economics Handbook, Menlo Park, California.
1978-1980. p.690. 8021C,b90 .8022K.
G-l
-------
The reference lists were reorganized into the desired categories
From this information, the current use categories were estimated.
Table G-3. PO Consumption Estimates
Polyether Polyols
for Urethane
Applications
Polyether Polyols
for Nonurethane
Applications
Propylene Glycols
Glycol Ethers
Miscellaneous
1983 . 1985 % , 1986
(% of consumption) (% of consumption) (% of consumption)
5769 56
24
1
11
12
22
7
11
24
1
8
G-2
-------
REFERENCE G
1. Mannsville Chemical Products Corporation. Chemical Products Synopsis;
Propylene Oxide. Cortland, New York, February 1984.
2. SRI International. Chemical Economics Handbook. Menlo Park,
California. 1978-1980. p.690.8021C, 690.8022K.
(i-3
-------
-------
APPENDIX H - PROCESS VENT PARAMETERS
Table H-l Process Vent Parameters3
Source
Polyether
Polyols
P ropyl ene
Glycols
Release
Height
(m)
13
27
Diameter
(m)
0.03
O.Ob
Temperature
(K)
300
278
Velocity
(ra/s)
1.1
3.3
Emission
Factor5
.00013
.000028
a Systems Applications, Inc. (SAI). Appendix A-26: Propylene Oxide.
In: Human Exposure to Atmospheric Concentrations of Selected Chemicals,
Vol. II. Office of Air Quality Planning and Standards, U.S. Environ-
mental Protection Agency. Research Triangle Park, North Carolina.
No. 68-02-306. February 1982.
b Lb PO emitted/1b PO consumed
H-l
-------
-------
APPENDIX I - SHORT TERM EMISSIONS DATA
The following information was obtained for a sterilization facility.1
In 1984, the facility reported using 18,326 pounds (8,000 kg) of PO.
This was 10 percent by weight of the total gaseous sterilants. The
example situation desired for the emissions estimate was the use of 100
percent PO. Although the facility has six separate retorts, the emissions
calculations were made assuming simultaneous emissions, which is calculated
in the same way as assuming a single retort.
Table 1-1. Emission Parameters
Release Height (m)
Vent Diameter (m)
Emission Velocity (m/s)
Temperature (K)
Event Duration (min/cycle)
Average Events/Day
Operating Hours
Total Emissions Per Event:
12
.08
16
370
75
l.b
52 weeks/year, 5 days/week
18,326
Ibs PO/yr
.10 fraction of sterilants
year
52 weeks
week
5 days
day
1.5 events
Emission Rate:
213 kg PO
event
event
7b minutes
1,000 g
kg
1 minute s 47
60 seconds
= 469.9 Ib PO/event
For modeling purposes, total emissions for a 1 hour time period were
calculated.
= 170 kg/hr
47 g
s
3,600 s
hr
kg
1,000 g
1-1
-------
-------
J. SHORT-TERM EMISSIONS ESTIMATES
Additional information was sought to recheck the assumptions which
were used to calculate short-term emission rates. The information used for
these emission estimates came from permit applications filed with the
Illinois Environmental Protection Agency.1 The permits were granted for
the Micro-Biotrol, Incorporated sterilization facility in Willowbrook,
Illinois. The additional information obtained2 clarified facility operations
and the methods of calculation which were given in the permit applications.
Two methods of calculation for short-term emission rates were used.
The first method used past annual consumption to estimate current consumption.
The annual consumption was converted to peak hourly rates using facility
operation information contained in the permits. The second method used an
average quantity of propylene oxide consumed per cycle to determine the
peak hourly emissions. The peak emission rates obtained from these methods
were both 0.2 Mg/hr.
The methods of calculation are given in Sections J.2 and J.3.
Section J.I.I contains general information about the use of propylene oxide
as a fumigant.
J.I Propylene Oxide Fumigation
Every year, a small amount of propylene oxide is used as a fumigant.
Regulations concerning this use are promulgated by the Food and Drug
Administration (FDA). These regulations restrict the products on which
propylene oxide may be used, limit the amount of residue, and set forth
process restrictions. Propylene oxide may be used to fumigate dried prunes,
glace fruit, cocoa, gums, spices, starch, and processed nut meats (except
peanuts). The regulations establish acceptable residue levels of propylene
oxide or of its reaction products propylene glycol or propylene chlorohydrin.3
Industry sources indicate that propylene oxide is used primarily to
fumigate cocoa powder and shelled walnuts, almonds, and pecans.4ป^ Propylene
oxide disinfests and destroys microorganisms in these foods. It is the only
J-l
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effective and allowed fumigant for these processed nuts and cocoa powder.^
Other fumigants may be used on nuts before they are shelled.
Methyl bromide has been used for dIsInfestation but It is not as
effective against microorganisms.4 Propylene oxide is superior to
ethylene oxide on these foods for a number of reasons. Ethylene oxide
can react with chemicals in the foods and degrade the quality of that
product. This is the case with cocoa powder. Ethylene oxide would be a
more effective fumigant because it is a more effective antimicrobial agent.
However, it is also more toxic to humans, which means allowed residue would
be smaller and worker contact would be a greater concern. Propylene oxide
is less reactive with salts so it is less likely to form chlorohydrin than
is ethylene oxide. Finally, both of these oxides can react to form their
glycbls. Ethylene glycol is toxic but propylene glycol is a chemical which
is classified as Generally Recognized As Safe (GRAS) by the FUA.b
Two companies sell propylene oxide for fumigant uses. These companies
are Union Carbide Corporation and ABERCO, Incorporated. They sold a combined
total of 170 Mg (380.UOO. Ibs) of propylene oxide for fumigation in 1986.5ป7
Propylene oxide demand for this consumption category is expected to increase
because of increased demand for nuts in breakfast cereals.4
Propylene oxide is a liquid at ambient conditions. Its boiling point
at atmospheric pressure is 34ฐC (94ฐF). To be used as a fumigant it must
be in the vapor phase. This is accomplished by using vacuum chambers or
by heating the fumigant or by doing both of these things. Applying too much
heat to the system could cause product degradation.
For fumigation, propylene oxide is usually used in its 99.9 percent
pure form. It can also be used in an 8 percent propylene oxide mixture
with carbon dioxide. The mixture is generally not as effective as pure
propylene oxide.4
During the process, the product usually sits in the fumigant for two
to four hours at a temperature of bOฐC (121) op).11 After this time the
steriliation chamber is evacuated to the atmosphere. If the facility
uses ethylene oxide and if this fumigant is emitted from the same point as
J-2
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the propylene oxide, there might be an air pollution control device for the
ethylene oxide. This might also reduce propylene oxide emissions. One such
control device is the scrubbing unit which has been installed at the fumigation
facility in Willowbrook, Illinois.2'13
This scrubbing unit has a removal efficiency of 99.8 to 99.99 percent
for ethylene oxide. It has an efficiency of 98 to 99 percent for propylene
oxide. If desired, the system removal efficiency for propylene oxide
could be increased. This would simultaneously increase the efficiency for
ethylene oxide.8
Emission rates from ethylene oxide sterilization chambers have been
modeled. The rate is an exponentially decaying function of the chamber
volume, mass flow rate and time. The modeling indicates that 8U percent
of the sterilant is emitted during the first 10 minutes of the emission
phase.9 it is reasonable to assume that propylene oxide emission rate is
an exponentially decaying function. To obtain accurate peak emission
rates for a shorter time period than the 1-hour basis used, it would be
necessary to have more detailed information about process cycles and the
timing of emission phases of different sterilization chambers.
Most propylene oxide fumigation facilities consume between 3 and
5 Mg (6,000 to 12,000 Ibs) of propylene oxide annually. Industry sources
indicated that the contract sterilization facility in Willowbrook, Illinois,
is the largest single consumer for this use. This facility consumes 10 Mg
(20,000 Ibs) of propylene oxide annually. Industry sources felt that
specific locations of propylene oxide fumigation facilities is confidential
information. Some locations were assumed for modeling purposes
(see Table 8.1). Since the Micro-Biotrol facility has the largest annual
consumption, it was assumed that a peak hourly rate of emissions for that
facility would be a reasonable peak hourly rate for tjie other facilities.4*6*7
J-3
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TABLE J-l PROPYLENE OXIDE FUMIGATION
Location
State
California
Georgia
1111noi s
New Jersey
Pennsylvania
City*
Fresno
Los Angeles
Total
Albany
Total
Chi cago
Total
Boundbrook0
Newark
Union0
Total
Hers hey
Total
Percent Annual
Fumiyation Consumption**
35
2.5
15
45
2.b
Annual Consumption6
(Mg/yr)
20
17
9
6
65
6
aThe locations of fumigation facilities in the given cites were assumed unless
otherwise noted. These general locations were checked with regional and State
agencies. Reference 12.
Reference 1
clndustry sources
^Reference 5
e (1) Percent consumption by State x total consumption - annual consumption
by State.
(2) (annual consumption by State - known facility consumption) - estimated
city consumption assumed number of city locations.
J-4
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J.2 Annual Consumption Method
This method was used for the emission estimate given in Section 7.9
of this document.1^ The method is repeated in this section in more detail
to explicate the calculations, data, and assumptions.
The company uses three gases for sterilization. In 1984, the facility
consumed 1UU,UUU Ibs of ethylene oxide, 18,000 Ibs. of propylene oxide, and
62,000 Ibs of 12/88 (Freon). Ethyl ene oxide is used in pure form or in a
mixture with Freon. Propylene oxide is used only in the pure form. Propylene
oxide comprises 5 percent of the annual usage of gaseous sterilants.
The annual percentage gives no indication of the maximum number of
retorts that may be using propylene oxide at a particular time. There are
eight retorts at the facility. In order to calculate the maximum amount of
p.o. emissions it was assumed that, at some time, propylene oxide could be
in use in all of the retorts.
It was also assumed that all eight retorts could be in the emission
stages of their cycles simultaneously. The average cycle length is 8
hours. During the cycle emissions occur in two phases. These phases
average 46 minutes and 30 minutes for a total emission time of 1.2b hours.
They are separated by an unspecified amount of time while the retort is
filled with air up to atmospheric pressure. The amount of time necessary
for the air influx would probably be minimal. Therefore, the short-term
modeling could be based upon a single continuous one hour emission period.
In the original calculations for short-term emissions,*0 it was assumed
that the same amount of p.o. would be consumed in 1986 as was consumed in
1984.
Because of the limits upon the amount of residue allowed on the food, it
is desirable to evacuate as much fumigant as possible from the retort. It
was assumed that all of the propylene oxide consumed would be emitted to
the atmosphere from the retort.
An emission control device, a Best Available Control Technology
(BACT) Oeoxx unit, began operation in November 1987.13 This start up date
was rescheduled from January 1987 due to construction delays. The de-ox
unit converts oxides into glycols. The control device is being installed
primarily to reduce ethyl ene oxide emissions but it will also reduce propylene
oxide emissions.8
J-b
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1986 Emission Estimates
Average use of propyVene oxide per cycle per retort
18326 Ib/yr annual consumption*
18326 1b x 1 yr x IJ* x 1 d x 8 nrs* = 47. Ib po used/ cycle* (26. kg)
yr 52 wk 5 d 12 hrs* 1 cycle
47 Ib po/cycle - 5.9 Ib po/cycle per retort
8 retorts (2.7 kg po/cycle per retort)
2.7 kg po consumed = 2.7 kg po emitted
2.7 kg po x 100% possible usage per cycle x 1 kg emitted - 27 kg po/cycle
cycle 10% average usage per cycle 1 kg used per retort
emitted
Eight retorts are assumed to emit simultaneously.
27 kg po/cycle x 8 retorts = 210 kg po emitted/cycle (564 Ib po/cycle)
retort
Emission rates --
210 kg po x 1 cycle x 1000 g x 1 min - 47 g/s
cycle 75 min kg 60 s
x 3600s_ = 170
1000 g
* Given or calculated as an average.
J-6
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J.3 Consumption Per Cycle Method
The second method for the calculation of propylene oxide emission rate
is based upon the value that Micro~Biotrol, Inc, gave for the average amount
of p.o. used per cycled Mi cro-Biotrol estimated that an average of 154 Ibs
(70 kg) of propylene oxide were consumed per cycle per retort. It was
assumed that all of the propylene oxide consumed would be emitted. Assumptions
regarding the length of time of the emissions during the average cycle were
the same as those given in the previous section.
154. Ib avg po used per cycle (7U kg)
75 min avg evacuation time per cycle
For a single retort ~
70 kg p.o. x cycle a 0.93 kg/min
cycle 75 min
0.93 kg/mi n = 16 g/s = 56 kg/hr
Table J-2 Propylene Oxide Emissions
Number or retorts emitting j emission rate j emissions per hour
p.o. simultaneously j (g/s) j (kg)
1
2
4
16
32
62
56
110
220
Four retorts would be the maximum number emitting simultaneously.2 It was
assumed that all of these retors would be using propylene oxide.
J-7
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References
1. Information obtained through Air Pollution Control Division,
Illinois Environmental Protection Agency, Springfield, Illinois, permit
I.D. No. 043110AAC, November Ib, 1985.
2. Telcon. G. Hume, Emission Standards and Engineering Division,
Environmental Protection Agency to J. Kjellstrand, Micro-Biotrol, Inc.
July 22, 1986 and July 28, 1986. Sterilization with Propylene Oxide. File
86/22.
3. Food Chemical News, Inc., The Food Chemical News Guide, June 28, 1982.
p. 374.1, 374.2
4. Telcon. G. Hume, Emission Standards and Engineering Division,
Environmental Protection Agency to F. Mosebar, Dried Fruit Association of
California. August 15, 1986. Fumigation with Propylene Oxide. File 86/22.
5. Letter and attachments from M. Warren, ABERCO, Inc. to G. Hume,
Emission Standards and Engineering Division, Environmental Protection Agency.
September 4, 1986. Fumigation with Propylene Oxide.
6. Telcon. G. Hume, Emission Standards and Engineering Division,
Environmental Protection Agency to M. Warren, ABERCO, Inc. August 26, 1986.
Fumigation with Propylene Oxide. File 86/22.
7. Telcon. G. Hume, Emission Standards and Engineering Division,
Environmental Protection Agency to C. Woltz, Union Carbide Corporation.
November 16, 1986. Fumigation with Propylene Oxide. File 86/22.
8. Telcon. G. Hume, Emission Standards and Engineering Division,
Environmental Protection Agency to T. Bonicor, Chemrox. August 26, 1986.
Deoxx unit removal of Propylene Oxide. File 86/22.
9. Memorandum from D.L. Newton, Midwest Research Institute, to
D.W. Markwords, Emission Standards and Engineering Division, Environmental
Protection Agency. April 28, 1986. Short Term Emission Parameters for
EU Sterilization Facilities.
10. See Section 5.3.4.2 and Appendix 7.9 of this report; i.e., G. Hume,
Propylene Oxide: Preliminary Source Assessment. Environmental Protection
Agency, Research Triangle Park, N.C., July 1986.
11. Letter and attachments from M. Warren, ABERCO, Inc. to National
Toxicology Program, Research Triangle Park, N.C. November 3, 1986.
Fumigation and Sterilization with Propylene Oxide.
12. Personnel Communication with N. Pate, Strategies and Air Standards
Division, Environmental Protection Agency.
13. Telcon. G. Hume, Emission Standards Division, Environmental Protection
Agency to Jim Cobb, permit section, Illinois Environmental Protection Agency.
May 10, 1988. Deoxx unit at Microbiotrol Facility. File 86/22.
J-8
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-450/3-88-014
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Summary of Emissions Associated with Propylene Oxide
5. REPORT DATE
November 1988
\. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Gretchen Hume, ESD
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
U.S. Environmental Protection Agency
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
10. PROGRAM ELEMENT NO.
1. CONTHACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
IS. SUPPLEMENTARY NOTES
This summary describes the industrial production and uses of propylene oxide
documents the methods of calculation used to estimate emissions, and lists the
major facilities emitting propylene oxide along with their estimated emissions
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Air Pollution
Emission Summary
Propylene Oxide
Air Pollution Estimates
Source Cateaories
8. DISTRIBUTION STATEMENT
Unlimited
SECURITY CLASS (This Report)'
21. NO. OF PAGES
20. SECURITY CLASS (Thispage)
22. PRICE
EPA Form 2220-1 (Rซv. 4-77) PREVIOUS EDITION is OBSOLETE
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