United States Office of Air Quality
Environmental Protection Planning and Standards
Agency Research Triangle Park NC 27711
EPA-450/4-84-007e
March 1984
Air
Locating And
Estimating Air
Emissions From
Sources Of
Formaldehyde
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EPA-450/4-84-007e
March 1984
Locating And Estimating Air Emissions
From Sources Of Formaldehyde
U.S. Environmental Protection Agency
Region V, Library
230 South Dearborn Street
Chicago, UUnoU 60604
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office Of Air And Radiation
Office Of Air Quality Planning And Standards
Research Triangle Park, North Carolina 27711
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This report has been reviewed by the Office Of Air Quality Planning And Standards, U.S. Environmental
Protection Agency, and has been approved for publication as received from GCA Technology. Approval does
not signify that the contents necessarily reflect the views and policies of the Agency, neither does mention of
trade names or commercial products constitute endorsement or recommendation for use.
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CONTENTS
Figures 1V
Tables v
1. Purpose of Document 1
2. Overview of Document Contents 3
3. Background 5
Nature of Pollutant 5
Overview of Production and Uses 8
4. Formaldehyde Emission Sources 14
Formaldehyde Production 14
Urea-Formaldehyde and Melamine-Formaldehyde
Resin Production 28
Phenol-Formaldehyde Resin Production 40
Polyacetal Resin Production 48
Hexamethylenetetramine Production 53
Pentaerythritol Production 57
1,4-Butanediol Production 61
Trimethylolpropane Production 63
4,4'-Methylenedianiline Production 65
Phthalic Anhydride Production 67
Use of Formaldehyde Based Additives (FBA's) in
Solid Urea and Ureaform Fertilizer Production. . 70
Miscellaneous Resin Applications 74
Manufacturing of Minor Products Using
Formaldehyde as a Feedstock 77
Miscellaneous Commercial/Consumer Uses
of Formaldehyde 81
Combustion Sources 83
Oil Refining 91
5. Source Test Procedures 102
References 104
Appendix A - Calculations of Process Fugitive .Emissions A-l
References for Appendix A ......... A-9
111
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FIGURES
Number Page
1 Common reactions of formaldehyde 7
2 General reactions of formaldehyde 9
3 Chemical use tree of formaldehyde 12
4 Basic operations that may be used for formaldehyde
production by the silver catalyst process 15
5 Basic operations that may be used for formaldehyde
production by the metal oxide process 18
6 Basic operations that may be used in urea-formaldehyde
and melamine-formaldehyde resin manufacture 29
7 Basic operations that may be used for phenol -
formaldehyde resin manufacturing 41
8 Basic operations that may be used for the production
of polyacetal resins 50
9 Basic operations that may be used in the production of
hexamethylenetetramine 54
10 Basic operations that may be used in the production of
pentaerythritol 58
11 Basic operations that may be used in the production of
phthalic anhydride 68
12 Basic flowsheet for a refinery 92
13 Method 5 sampling train modified for the measurement of
formaldehyde 103
A-l Process flow diagram for metal oxide process A-3
A-2 Process flow diagram for silver catalyst process .... A-6
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TABLES
Numbei
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
r
Physical Properties of Monomeric Formaldehyde
Uncontrolled and Controlled Formaldehyde Emission
Factors for a Hypothetical Formaldehyde Production
Plant (Silver Catalyst Process)
Uncontrolled and Controlled Formaldehyde Emission
Factors for a Hypothetical Formaldehyde Production
Plant (Metal Oxide Catalyst Process)
Production of Formaldehyde
Production of Urea-Formaldehyde Resins
Production of Melamine-Formaldehyde Resins
Production of Phenol -Formaldehyde Resins
Production of Polyacetal Resins
Production of Hexamethylenetetramine
Production of Pentaerythritol
Production of 1 ,4-Butanediol
Production of 4,4' -Methylenedianiline
Production of Phthalic Anhydride
Formaldehyde Emission Factors for Solid Urea Production. .
Standard Industrial Classification Codes for Manufacturing
Processes Engaged in Resin Applications
Manufacturers of Minor Products Using Formaldehyde
as a Feedstock
Formaldehyde Emissions from Stationary Fuel Combustion
Sources
Page
6
19
21
25
31
36
44
52
56
60
62
66
69
72
76
77
84
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Tables (continued)
Number Page
18 Formaldehyde Emissions from Stationary Internal
Combustion Engines 87
19 Total Aldehyde Emissions from Incineration and Open
Burning 87
20 Formaldehyde Emissions from Transportation Sources .... 89
21 Formaldehyde Emissions from Construction and Farm
Equipment 90
22 Formaldehyde Emissions from Petroleum Refining 96
23 Petroleum Refineries 97
VI
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SECTION 1
PURPOSE OF DOCUMENT
EPA, States and local air pollution control agencies are becoming
increasingly aware of the presence of substances in the ambient air that
may be toxic at certain concentrations. This awareness, in turn, has led
to attempts to identify source/receptor relationships for these substances
and to develop control programs to regulate emissions. Unfortunately,
very little information is available on the ambient air concentrations of
these substances or on the sources that may be discharging them to the
atmosphere.
To assist groups interested in inventorying air emissions of various
potentially toxic substances, EPA is preparing a series of documents such
as this that compiles available information on sources and emissions of
these substances. This document specifically deals with formaldehyde.
Its intended audience includes Federal, State and local air pollution
personnel and others who are interested in locating potential emitters of
formaldehyde and making gross estimates of air emissions therefrom.
Because of the limited amounts of data available on formaldehyde
emissions, and since the configuration of many sources will not be the
same as those described herein, this document is best used as a primer to
inform air pollution personnel about 1) the types of sources that may
emit formaldehyde 2) process variations and release points that may be
expected within these sources, and 3) available emissions information
indicating the potential for formaldehyde to be released into the air
from each operation.
The reader is strongly cautioned against using the emissions
information contained in this document to try to develop an exact assessment
of emissions from any particular facility. Since insufficient data are
available to develop statistical estimates of the accuracy of these
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emission factors, no estimate can be made of the error that could result
when these factors are used to calculate emissions from any given facility.
It is possible, in some extreme cases, that orders-of-magnitude differences
could result between actual and calculated emissions, depending on differences
in source configurations, control equipment and operating practices.
Thus, in situations where an accurate assessment of formaldehyde emissions
is necessary, source-specific information should be obtained to confirm
the existence of particular emitting operations, the types and effectiveness
of control measures, and the impact of operating practices. A source
test and/or material balance should be considered as the best means to
determine air emissions directly from an operation.
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SECTION 2
OVERVIEW OF DOCUMENT CONTENTS
As noted in Section 1, the purpose of this document is to assist
Federal, State and local air pollution agencies and others who are interested
in locating potential air emitters of formaldehyde and making gross
estimates of air emissions therefrom. Because of the limited background
data available, the information summarized in this document does not and
should not be assumed to represent the source configuration or emissions
associated with any particular facility.
This section provides an overview of the contents of this document.
It briefly outlines the nature, extent and format of the material presented
in the remaining sections of this report.
Section 3 of this document provides a brief summary of the physical
and chemical characteristics of formaldehyde, its commonly occurring
forms and an overview of its production and uses. A chemical use tree
summarizes the quantities of formaldehyde consumed in various end use
categories in the United States. This background section may be useful
to someone who needs to develop a general perspective on the nature of
the substance and where it is manufactured and consumed.
Section 4 of this document focuses on major industrial source categories
that may discharge formaldehyde air emissions. This section discusses
the manufacture of formaldehyde, its use as an industrial feedstock,
applications of resins produced from formaldehyde, and formaldehyde
production as a byproduct of combustion. For each major industrial
source category described in Section 4, example process descriptions and
flow diagrams are given, potential emission points are identified, and
available emission factor estimates are presented that show the potential
for formaldehyde emissions before and after controls employed by industry.
Individual companies are named that are reported to be involved with
either the production and/or use of formaldehyde, based primarily on trade
publications.
3
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The final section of this document summarizes available procedures
for source sampling and analysis of formaldehyde. Details are not prescribed
nor is any EPA endorsement given or implied to any of these sampling and
analysis procedures. At this time, EPA generally has not evaluated these
methods. Consequently, this document merely provides an overview of
applicable source sampling procedures, citing references for those interested
in conducting source tests.
This document does not contain any discussion of health or other
environmental effects of formaldehyde, nor does it include any discussion
of ambient air levels or ambient air monitoring techniques.
Comments on the contents or usefulness of this document are welcomed,
as is any information on process descriptions, operating practices,
control measures and emissions information that would enable EPA to
improve its contents. All comments should be sent to:
Chief, Source Analysis Section (MD-14)
Air Management Technology Branch
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
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SECTION 3
BACKGROUND
NATURE OF POLLUTANT
Formaldehyde is a colorless gas at normal temperatures with a pungent,
irritating odor. It is the simplest member of the family of aldehydes and
has the following structure:
0
II
/\
H H
Formaldehyde gas is soluble in water, alcohols, and other polar solvents.
Physical properties of pure monomeric formaldehyde are presented in Table 1.
The GANAF Interim Thermochemical Tables list thermodynamic properties data
2
for formaldehyde for temperatures ranging from 0 to 6000 K.
In the presence of air and moisture at room temperature, formaldehyde
readily polymerizes to paraformaldehyde, a solid mixture of linear poly-
oxymethylene glycols containing 90 to 99 percent formaldehyde. Another form
of formaldehyde is its cyclic trimer, trioxane (CgHgO.,). In aqueous solutions,
formaldehyde reacts with water to form methylene glycol. Reactions which
form methylene glycol, trioxane, and paraformaldehyde are illustrated in
Figure 1. As shown in the figure, these reactions are reversible.
Pure, dry formaldehyde gas is stable from 80 to 100°C and decomposes
very slowly up to 300°C. Polymerization takes place slowly below room
temperature but is accelerated by the presence of impurities. Warming
pure liquid formaldehyde to room temperature in a sealed container causes
rapid polymerization and the evolution of heat (63 kj/mole). Decomposition
produces carbon monoxide and hydrogen gas. When catalyzed by certain
metals (platinum, copper, or chromia and alumina), formaldehyde decomposition
can produce methanol, methyl formate, formic acid, carbon dioxide, and methane.
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TABLE 1. PHYSICAL PROPERTIES OF MONOMERIC FORMALDEHYDE
1
Synonyms
Chemical Formula
CAS Registry Number
Molecular Weight
Boiling Point (at 101.3 kPa), °C
Melting Point, °C
Density at -20°C, g/ml
Density at -80°C, g/ml
Antoine Constants for Determining
Vapor Pressure
A
B
C
Vapor Density
Heat of Vaporization, AHV
at 19°C, kJ/mol
at -109 to -22°C,
J/mol
Heat of Formation, AHf at 25°C,
kJ/mol
Gibbs Free Energy, AGj at 25°C,
kJ/mol
Heat Capacity, Cp, J/(mol-K)
Entropy, S°, J/(mol-K)
Heat of Combustion, kJ/mol
Heat of Solution in Water and
Lower Aliphatic Alcohols, kJ/mol
Critical Constants
Temperature, °C
Pressure, MPa
Flammability in Air
Lower/Upper Limits, mo! %
Ignition Temperature, °C
Methanal, methyl aldehyde,
methylene oxide, formic aldehyde,
oxomethane, oxymethane,
oxymethylene
HCHO
50-00-0
30.03
-19
-118
0.8153
0.9151
9.28176
959.43
243.392
1.067 (air = 1)
23.3
27,384 + 14.56T - 0.1207T2 (T = K)
-115.9
-109.9
35.4
218.8
561 - 571
63
137.2 - 141.2
6.784 - 6.637
7.0/73
430
aLogio P - A-(B/(C+t)); where P = vapor pressure in pascals (Pa) and
t = temperature in °C.
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As a result of its unique structure, formaldehyde has a high degree of
chemical reactivity and good thermal stability in comparison with other
carbonyl compounds. This structural uniqueness is due to the attachment of
the carbonyl directly to two hydrogens. As a result, formaldehyde is
capable of undergoing a wide variety of chemical reactions, many of which are
useful in commercial processes. The commercial forms of formaldehyde include
formaldehyde/water solutions, polymers, and derivatives.
Because of its high chemical reactivity and good thermal stability,
formaldehyde is used as a reactant in numerous commercial processes to
synthesize a wide variety of products. These reactions fall into three
categories:
• oxidation-reduction reactions,
• addition or condensation reactions with organics and inorganics, and
• self polymerization reactions.
A general description of these reactions applicable to formaldehyde is
represented in Figure 2.
The residence time of formaldehyde in the atmosphere has been estimated
4
at between 0.1 and 1.2 days. Residence time is defined as the time
required for the concentration to decay to 1/e of its original value. The
major mechanisms of destruction are reaction with hydroxyl radicals (OH-)
and photolysis. The removal rates by physical processes such as deposition
and removal in rain are considered minor.
OVERVIEW OF PRODUCTION AND USES
Formaldehyde was first produced in the United States in 1901 chiefly
c
for use as an embalming agent and disinfectant. It is now a high volume
commercial chemical. Formaldehyde is available in several different forms
to fit users' needs, but is not available commercially in the form of the
anhydrous monomer. Aqueous solutions, often called formalin, are available
containing 37 to 50 percent formaldehyde by weight. These solutions may
contain 6 to 15 percent stabilizer, usually methanol, to prevent polymerization,
Solutions of formaldehyde in alcohol are available for processes that require
high alcohol/low water content. These solutions, called Formcels*, are
*Registered trademark of Celanese Corporation
8
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Oxidation - Reduction
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2CH.O + OH" ^HCOO" + CH3OH
CH20 + RCHO + OH" »HCOO" + RCH?0"
Addition
CH20 + CM" + H
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Crossed Canmzzaro Reaction
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Condersat'0r with Annes
Condensation with Ar-d?;
Acetai For~ation
^ Condensation
Man^ich Reaction
Methyl! Formation
Gngnard
Formation cf BO" vcx
Figure 2. General reactions of formaldehyde.3
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prepared with methanol, n-propanol, n-butanol, or isobutanol. Formaldehyde
is also.available in its polymeric forms of trioxane and paraformaldehyde.
Currently, there are 13 formaldehyde producers in the United States
operating at 48 locations. Most of the formaldehyde produced is consumed in
captive uses at the producer plant site. The large number of plants
results from the high expense associated with transport of aqueous solutions.
Production figures quoted for formaldehyde generally are expressed on
the basis of 37 weight percent formalin solution. The 37 percent solution
figure includes all aqueous and alcoholic solutions, paraformaldehyde, and
3
trioxane. The product mix produced is dependent on fluctuating captive
needs and customer requirements. Production of formaldehyde in 1982 was
estimated to be 2.18 x 10 megagrams on a 37 percent solution basis.
Exports were approximately 9.1 x 10 megagrams in 1982 and imports were
negligible.
Formaldehyde is produced in the United States by two methods: the
metallic silver catalyst process and the metal oxide process. The silver
catalyst process is the predominant process, accounting for 75 percent of
formaldehyde manufactured; while the metal oxide process accounts for the
remaining 25 percent. Both production methods use methanol as the starting
* • i 8
material.
In the silver catalyst process, a methanol-rich air mixture is passed
over a stationary silver catalyst. The reaction products are formaldehyde
and water vapor. Reaction conditions are approximately atmospheric pressure
and temperatures of 450 to 650°C. The product gases are cooled and absorbed
in water. Excess methanol is removed by distillation and returned to the
process. Yields are typically 83 to 92 percent.
The formation of formaldehyde in the silver catalyst process is
thought to follow a two-step process involving the dehydrogenation of
methanol followed by combustion of the hydrogen product. Alternatively, a
combination of single-step processes has been proposed involving the
simultaneous dehydrogenation and oxidation of formaldehyde. A number of
variations of the basic silver catalyst process have been developed in
order to increase yield, decrease side product formation, conserve energy
and reduce emissions.
10
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The metal oxide catalyst process is licensed in the United States by
Reichhold and Lummus. In this process, methanol is converted to formaldehyde
by oxidation of methanol. The catalysts employed in this selective oxidation
process are usually iron molybdenum oxide mixtures. The reactant mixture is
rich in air, containing only 5 to 10 volume percent methanol. As in the
silver catalyst process, the product gases are cooled and absorbed in water.
The formaldehyde yield for the metal oxide process is higher than that for
the silver catalyst process. Thus, the formaldehyde solution formed contains
only a small amount of methanol, usually less than one percent, and does not
require purification by distillation.
Paraformaldehyde is normally produced from formalin solutions. These
solutions are vacuum-distilled until polymer precipitation occurs. Commercial
paraformaldehyde-water solutions are available with formaldehyde contents
ranging from 91 to 99 percent.
Trioxane is prepared from formalin solution by distillation in the
presence of either sulfuric acid or acidic sulfonate ion-exhange resin. The
distillate is an azeotrope of trioxane, formaldehyde, and water, boiling at
about 90°C. Trioxane is separated from the distillate by extraction with
methylene chloride or a-chloronaphthalene. The trioxane is then recovered by
distillation or crystallization.
Formaldehyde is one of the most widely used industrial chemicals. The
current uses of formaldehyde are listed in Figure 3, along with the percentage
of the total product devoted to each use. Over 50 percent of the formaldehyde
produced is used in the manufacture of resins such as urea-formaldehyde
resins, phenol-formaldehyde resins, acetal resins, and melamine-formaldehyde
resins. Other important uses of formaldehyde include the synthesis of
hexamethylenetetramine, pentaerythritol, 1,4-butanediol and other acetylenic
chemicals, chelating agents, urea-formaldehyde concentrates, trimethylol
propane, 4,4-methylenedianiline, acrylic esters, pyridine compounds, and
nitroparaffins. Formaldehyde is also used in textile treating applications,
910
dyes, disinfectants, and preservatives.
11
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Resins that are produced from formaldehyde are used primarily as binders
for particle board and plywood. Other uses for the resins are as molding
compounds for dinnerware, appliances, electric controls, telephones, and
wiring services; foundry resins; and adhesives for thermal and sound
insulation. Butanediol produced from formaldehyde is used mainly to produce
tetrahydrofuran which is used as a solvent for vinyl resins and as an
intermediate in the synthesis of other chemicals. Methylenedianiline is
converted to methylenediphenyl isocyanate which is used in the production of
polyurethanes for reaction injection molding in automobiles.
13
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SECTION 4
FORMALDEHYDE EMISSION SOURCES
This section discusses formaldehyde emissions from direct sources such
as production of formaldehyde, production of chemicals using formaldehyde
as a feedstock and miscellaneous uses of formaldehyde. Indirect emission
sources in which formaldehyde is formed as a byproduct also are discussed.
Indirect sources of formaldehyde include refineries and combustion processes,
Process and emissions information are presented for each source for which
data are available.
FORMALDEHYDE PRODUCTION
Formaldehyde is produced in the United States by two processes. In
the predominant process, methanol is dehydrogenated and oxidized in the
presence of a silver catalyst to produce formaldehyde, hydrogen, and
water. In the other process, formaldehyde and water are formed by the
oxidation of methanol in the presence of a metal oxide catalyst.
Process Descriptions
Silver Catalyst Process --
The major products of the silver catalyst process are formaldehyde,
hydrogen, and water. Basic operations that may be used in a silver
catalyst process are shown in Figure 4. Actual flow diagrams for production
facilities will vary. In Figure 4, compressed air (Stream 1), which has
been scrubbed to remove traces of sulfur dioxide, hydrogen sulfide, and
other impurities, is passed through a vaporizer column where it is heated
and saturated with methanol vapor (Stream 2). The heated stream must
maintain a methanol concentration greater than 37 volume percent in order
to be above the upper explosive limit of methanol.
The mixture (Stream 3) then enters a battery of converters which are
maintained at a temperature of approximately 635°C. The hot effluent gases
(Stream 4) are cooled rapidly to prevent decomposition of the product
14
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formaldehyde. Cooling is accomplished by indirect heat interchange with
the feed mixture in the vaporizer and by then introducing the gas into the
primary absorber.
The primary absorber liquid is an aqueous solution of formaldehyde and
methanol. A portion of this liquid is withdrawn from the bottom of the
absorber column and recirculated to the top. The remainder (Stream 5) is
pumped to the product fractionation column. The uncondensed vapors and
noncondensable gases (Stream 6) are withdrawn from the top of the primary
absorber column and fed to a secondary absorber. The major portion of the
uncondensed vapors is recovered in the secondary absorber column through
contact with demineralized water, and the off-gas, consisting mostly of
nitrogen with some entrained volatile organic compounds, is vented (Vent A).
The weak formaldehyde/methanol solution (Stream 7) withdrawn from the
bottom of the secondary-absorber column is pumped to the primary-absorber
column and used as makeup solution.
The methanol-containing formaldehyde solution (Stream 5) is pumped to
a fractionation column, where methanol is recovered. This vacuum distillation
step yields an overhead product of approximately 99 percent methanol for
recycle to the reactor and a bottom product of formaldehyde solution
containing less than 1 percent methanol. The methanol vapor from the top
of the column is condensed and recycled to the vaporizor (Stream 8).
11 12
Uncondensed vapors (Stream 10) are vented (Vent B) or fed to the absorber. '
The formaldehyde solution from the bottom of the fractionation column
(Stream 9) is pumped to product storage tanks. When required by customer
specifications, the solution is treated in an ion exchange system for removal
of trace amounts of formic acid before being stored.
As a final step, water is added to provide a suitable concentration
for storage and shipping. Reported yields for the metallic silver catalyst
process range from 83 to 92 percent.
All product storage tanks are heated to prevent polymer formation and
precipitation in storage. A series of tanks are used to blend and adjust
the solution to the desired formaldehyde and methanol concentrations
before it is shipped to the customer.
16
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Metal Oxide Catalyst Process --
In the metal oxide catalyst process, the major products are formaldehyde
and water. The catalyst system most often used is ferric molybdate.
Figure 5 presents basic operations that may be used in a metal oxide
catalyst process. Actual flow diagrams for production facilities will
vary. The process begins with incoming air (Stream 1), which has been
scrubbed to remove dust and trace impurities, being mixed with oxygen-lean
recycle gas (Stream 5) from the process to lower the oxygen content of the
air feed stream below 10.9 percent. This keeps the methanol concentration
below the lower explosive limit when a portion of the air feed stream is
saturated with methanol (Stream 2) in the vaporizer column. The methanol saturated
air is then mixed with the remaining air and preheated by heat exchange
with the product gas (Stream 4) leaving the converter. The feed gas mixture
(Stream 3) then enters the converter, which is maintained at 345°C by the
exothermic oxidation reaction.
The product gas (Stream 4) is cooled by heat exhange with the feed gas
mixture and then quenched in the absorber column. The formaldehyde and
methanol are removed from the gas stream by absorption in the aqueous
solution. The unabsorbed gases and vapors exit at the top of the absorber
column. A portion of this gas is recycled (Stream 5) and the remaining gas
(Stream 6) is vented. The product solution drawn from the bottom of the
absorber column contains approximately 0.8 percent methanol and 0.005
percent formic acid. The solution generally is treated in an ion exchange
system to reduce the acidity and is then stored. As a final step, water
(Stream 7) is added to provide a suitable concentration for storage and
shipping. Process yields of 91 to 93 percent are reported for the metal
oxide catalyst process.
Emissions
Uncontrolled formaldehyde emission factors for the silver catalyst
process and the metal oxide catalyst process are listed in Table 2 and
Table 3, respectively, with potential control techniques and associated
emission factors for controlled emissions. These emission factors have
been developed based on hypothetical plants for each of the two processes
with total formaldehyde production capacities of 45,000 Mg/yr.
17
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Process Emissions --
Silver catalyst process -- The primary source of formaldehyde process
emissions is the purging of gases from the secondary absorber (Vent A in
Figure 4). The product fractionator is another possible source of formaldehyde
process emissions (Vent B). However, most producers report that gases from
12
the fractionator are fed to the absorber before venting. Formaldehyde
emissions also occur during plant startup. Formaldehyde plants are normally
operated at design conditions to achieve highest yields, and are shut down when
product inventories are filled. The silver catalyst process operates
above the upper explosive limit of methanol. Thus, plant startup procedures
must be handled carefully. Unstable conditions are often encountered, and
explosions can occur in the methanol vaporizer and the reactor.
Various startup procedures are used in the industry. During startup,
the output from the reactor may be vented until stable operation
is achieved and an acceptable yield ratio is obtained. The flow is then
switched into the absorber. Most formaldehyde producers report that
12
startup vents go through the absorber before venting to the atmosphere.
Total startup time is usually 1 to 2 hours. The reactor feed rate varies
as the startup proceeds. Initially, the reactor produces mainly carbon
dioxide and water vapor. As the temperature rises, the formaldehyde yield
increases, thereby increasing the amount of formaldehyde in the vented
gas. Startup emissions, when venting through the absorber, are reported
to be 0.1 kg/mg12 (see Table 2).
Metal oxide catalyst process -- The metal oxide catalyst process
operates below the explosive limit of methanol with an excess of air
resulting in stable conditions during startup. Thus, venting of the
reactor during startup is not required as it was for the silver catalyst
process and there are no intermittent startup emissions.
Formaldehyde process emissions result from the venting of gases from
the product absorber (Vent A in Figure 5). The emission composition and
flow rates are affected by the percent of absorber gas recycled. By
recycling a portion of the oxygen-lean vent gas, the oxygen concentration
in the reactor feed mixture can be reduced, making it possible for the
23
-------
concentration of methanol to be increased without an explosive mixture
being formed. This reduces the' volume of reaction gases and thus reduces
the emission rate of formaldehyde from the absorber.
Storage Emissions --
Formaldehyde emissions (Vent D in Figures 4 and 5) result from the
storage of formaldehyde product. Formaldehyde storage emissions were estimated
based on an average of four tanks per plant, a tank size of 190 cubic meters,
45 turnovers per year, and a bulk liquid temperature of 54°C. The tanks were
assumed to be fixed-roof, half full, and subject to a diurnal temperature
variation of 11.1°C.15
Handling Emissions --
Emission factors from the handling of formaldehyde product were calculated
assuming submerged-fill-pipe loading into trucks and tank cars.
Fugitive Emissions —
Fugitive emissions of formaldehyde and other volatile organics result
from leaks in process valves, pumps, compressors, and pressure relief
valves. The rate of fugitive emissions of formaldehyde from these sources
was calculated from the number of pumps, valves, compressors and relief
valves in formaldehyde service, the estimated formaldehyde concentration
in streams in contact with these sources, and emission factors for fugitive
sources. The numbers of pumps, valves, compressors and relief valves in
formaldehyde service were estimated from the process flow diagrams and the
total number of fugitive sources in VOC service for the hypothetical
45,000 Mg/yr plant. Refer to Appendix A for fugitive emission rate calculations
Source Locations
Major formaldehyde producers and production locations are listed in
Table 4.
24
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UREA-FORMALDEHYDE AND MELAMINE-FORMALDEHYDE RESIN PRODUCTION
Urea-formaldehyde (U-F) and melamine-formaldehyde (M-F) resins are
the most commonly used amlno resins. They are produced domestically by
the addition of formaldehyde (Ch^O) to urea (NH2CONH2) or melamine (C3N
to form methylol monomer units, and subsequent condensation of these units
to form a polymer. U-F resins are used in the production of home insulation
and as adhesives in the production of particleboard, fiberboard, and
interior plywood. M-F resins are used for high pressure laminates such as
counter and table tops, and are compression molded to form dinnerware.
Process Description
The major products of the U-F and M-F resins production processes are
U-F or M-F resins and water. Basic operations that may be used in U-F
and M-F resin manufacture are shown in Figure 6. Amino resins generally
are produced in a batch reactor. The first reaction of the process, the
addition of formaldehyde to the ami no compound to form methylol compounds,
is carried out under alkaline conditions. Caustic, formaldehyde, and the
amino compound (Streams 1-4) are charged to the heated reaction vessel.
Next, the reactor conditions are altered to favor the second reaction,
the condensation of the methylol compounds to form a polymer chain. The
condensation reaction is carried out under acidic conditions and is
stopped at the desired degree of polymerization by lowering the temperature
and raising the pH.
At high degrees of polymerization, a solid polymer is produced. At
low degrees of polymerization, a stable syrup is produced which can be
used as an adhesive or laminating resin. The syrup can be combined with
a filler to make a molding compound or used with other polymers in coatings
formulations. The syrup can also be spray dried to form a powder for
17 18
convenient storage and handling. ' However, some producers of U-F and
M-F resins report that there are no spray drying operations at their
12
production facilities.
28
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Emissions
Formaldehyde emissions from the polymerization process occur while
water is being removed from the reactor under vacuum (Vent A in Figure 6)
and during the cleaning of the reactor kettles between batches. Fugitive
gaseous emissions may occur from relief valves, pumps, valves and flanges.
Potential formaldehyde emission sources in spray drying operations are belt
driers, continuous drum dryers and continuous screen dryers which are
18
vented to the atmosphere (Vent B).
Uncontrolled formaldehyde emissions from U-F and M-F resin manufacture
8 12
have been estimated as follows: '
• Process -- 0.15 - 1.5 kg/Mg of 37% formaldehyde used
• Formaldehyde Storage -- 0.03 - 0.2 kg/Mg of 37% formaldehyde used
• Fugitive — 0.03 - 0.2 kg/Mg of 37% formaldehyde used
U-F and M-F production plants may vary in configuration and level of control.
The level of control on formaldehyde storage emissions should be equivalent
12
to that for formaldehyde production. The reader is encouraged to contact
plant personnel to confirm the existence of emitting operations and control
technology at a particular facility prior to estimating emissions therefrom.
Source Locations
Major urea-formaldehyde resin producers and production locations are
listed in Table 5. Table 6 lists major melamine-formaldehyde resin producers
and production locations.
30
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TABLE 5. PRODUCTION OF UREA-FORMALDEHYDE RESINS
16
Manufacturer
Location
Allied Corp.
The Bendix Corp., subsid.
Friction Materials Div.
American Cyanamid Co.
Polymer Products Div.
American Hoechst Corp.
Indust. Chems. Div.
Apex Chem. Corp.
Auralux Chem. Associates, Inc.
Borden Inc.
Borden Chem. Div.
Adhesives and Chems. Div.
Cargill, Inc.
Chem. Products Div.
Green Island, N.Y.
Mobile, AL
Wallingford, CT
Charlotte, NC
Mount Holly, NC
Elizabethport, NJ
Hope Valley, RI
Demopolis, AL
Diboll, TX .
Fayetteville, NC
Fremont, CA
Kent, WA
La Grande, OR
Louisville, KY
Missoula, MT
Sheboygan, WI
Springfield, OR
Carpentersville, IL
Forest Park, GA
Lynwood, CA
Celanese Corp.
Celanese Plastics & Specialties Co., Div.
Celanese Specialty Resins, Div. Louisville, KY
Clark Oil & Refining Corp.
Clark Chem. Corp., subsid.
C.N.C. Chem. Corp.
Blue Island, IL
Providence
(CONTINUED)
31
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TABLE 5. (continued)
Manufacturer
Location
Commercial Products Co., Inc.
Consolidated Papers, Inc.
Consoweld Corp., subsid.
Glasvrit America, Inc.
•
Cook Paint and Varnish Co.
Crown-Metro, Inc.
Dan River, Inc.
Chem. Products Div.
De Soto, Inc.
Dock Resins Corp.
Eastern Color & Chem. Co.
Georgia-Pacific Corp.
Chem. Div.
Getty Oil Co.
Chembond Corp., subsid.
Hawthorne, NJ
Wisconsin Rapids, WI
Detroit, MI
North Kansas City, MO
Greenville, SC
Danville, VA
Garland, TX
Linden, NJ
Providence, RI
Albany, OR
Columbus, OH
Conway, NC
Coos Bay, OR
Crossett, AR
Eugene, OR
Louisville, MS
Lufkin, TX
Newark, OH
Peachtree City, GA
Port Wentworth, GA
Richmond, CA
Russellville, SC
Taylorsville, MS
Ukiah, CA
Vienna, GA
Andalusia, AL
Springfield, OR
Winnfield, LA
(CONTINUED)
32
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TABLE 5. (continued)
Manufacturer
Location
Guardsman Chems., Inc.
Gulf Oil Corp.
Gulf Oil Chems. Co.
Indust. Chems. Div,
Millmaster Onyx Group, subsid,
Lynda! Chem. Div.
Hanna Chem. Coatings Corp.
Hercules Inc.
H & N Chem. Co.
Libbey-Owens-Ford Co.
LOF Plastic Products, subsid.
Mobil Corp.
Mobil Oil Corp.
Mobil Chem. Co. , Div.
Chem. Coatings Div.
Monsanto Co.
Monsanto Plastics & Resins Co,
National Casein Co.
National Casein of California
National Casein of New Jersey
Adhesives Div.
Grand Rapids, MI
High Point, NC
West Memphis, AR
Lyndhurst, NJ
Columbus, OH
Chicopee, MA
Hattlesburg, MS
Milwaukee, WI
Portland, OR
Savannah, GA
Totowa, NO
Auburn, MA
Kankakee, IL
Addyston, OH
Chocolate Bayou, TX
Eugene, OR
Santa Clara, CA
Springfield, MA
Chicago, IL
Tyler, TX
Santa Ana, CA
Riverton, NJ
(CONTINUED)
33
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TABLE 5. (continued)
Manufacturer
Location
National Starch and Chem. Corp.
Proctor Chem. Co., Inc., subsid,
Perstorp Inc.
Plaskon Products Inc.
Plastics Mfg. Co.
PPG Indust., Inc.
Coatings and Resins Div.
Reichhold Chems., Inc.
Varcum Div.
Scott Paper Co.
Packaged Products Div.
Southeastern Adhesives Co.
The Standard Oil Co. (Ohio)
Sohio Indust. Products Co., Div,
Dorr-Oliver Inc., unit
Sun Chem. Crop.
Chems. Group
Chems. Div.
SUS Chem. Corp., Inc.
Salisbury, NC
Florence, MA
Toledo, OH
Dallas, TX
Oak Creek, WI
Andover, MA
Detroit, MI
Moncure, NC
South San Francisco, CA
Tacoma, WA
Tuscaloosa, AL
White City, OR
Niagara Falls, NY
Chester, PA
Everett, WA
Fort Edward, NY
Marinette, WI
Mobile, AL
Lenoir, NC
Niagara Falls, NY
Chester, SC
East Providence, RI
Rock Hill, SC
(CONTINUED)
34
-------
TABLE 5. (continued)
Manufacturer Location
Sybron Corp.
Chem. Div.
Jersey State Chem. Co., Div. Haledon, NJ
Synthron, Inc. Ashton, RI
Morganton, NC
Tyler Corp.
Reliance Universal Inc., subsid.
Specialty Chems. and Resins Div. Louisville, KY
United Merchants & Mfgs., Inc.
Valchem - Ch-em. Div. Langley, SC
Valspar Corp.
McWhorter, Inc., subsid. Baltimore, MD
West Point-Pepperell, Inc.
Grifftex Chem. Co., subsid. Opelika, AL
Weyerhaeuser Co. Marshfield, WI
Note: This listing is subject to change as market conditions change,
facility ownership changes, plants are closed down, etc. The
reader should verify the existence of particular facilities by
consulting current listings and/or the plants themselves. The
level of formaldehyde emissions from any given facility is a
function of variables such as capacity, throughput and control
measures, and should be determined through direct contacts with
plant personnel.
35
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TABLE 6. PRODUCTION OF MELAMINE-FORMALDEHYDE RESINS16
Manufacturer
Location
American Cyanamid Co.
Polymer Products Div.
Formica Corp., subsid.
American Hoechst Corp.
Indust. Chems. Div.
Auralux Chem. Associates, Inc.
Borden Inc.
Borden Chem. Div.
Adhesives and Chems. Div.
Cargill, Inc.
Chem. Products Div.
Celanese Corp.
Celanese Plastics & Specialties Co., div,
Celanese Specialty Resins, div.
Chagrin Valley Co. Ltd.
Nevamar Corp., subsid.
Clark Oil & Refining Corp.
Clark Chem. Corp., subsid.
C.N.C. Chem. Corp.
Glasvrit America, Inc.
Cook Paint and Varnish Co.
Crown-Metro, Inc.
Dan River, Inc.
Chem. Products Div.
Dock Resins Corp.
Kalamazoo, MI
Mobile, AL
Wallingford, CT
Charlotte, NC
Evandale, OH
Mount Holly, NC
Hope Valley, RI
Diboll, TX
Kent, WA
Sheboygan, WI
Springfield, OR
Carpentersville, IL
Forest Park, GA
Lynwood, CA
Louisville, KY
Odenton, MD
Blue Island, IL
Providence, RI
Detroit, MI
North Kansas City, MO
Greenville, SC
Danville, VA
Linden, NJ
(CONTINUED)
36
-------
TABLE 6. (continued)
Manufacturer
Location
Eastern Color & Chem. Co.
Gen. Electric Co.
Engineered Materials Group
Electromaterials Business Dept.
Georgia-Pacific Corp.
Chem. Div.
Getty Oil Co.
Chembond Corp., subsid.
Guardsman Chems., Inc.
Hanna Chem. Coatings Corp.
Libbey-Owens-Ford Co.
LOF Plastic Products, subsid.
Mobil Corp.
Mobil Oil Corp.
Mobil Chem. Co., div.
Chem. Coatings Div.
Monsanto Co.
Monsanto Polymer Products Co.
National Starch and Chem. Corp.
Proctor Chem. Co., Inc., subsid.
Providence, RI
Coshocton, OH
Schenectady, NY
Albany, OR
Columbus, OH
Conway, NC
Coos Bay, OR
Crossett, AR
Eugene, OR
Louisville, MS
Lufkin, TX
Newark, OH
Port Wentworth, GA
Richmond, CA
Russellville, SC
Taylorsville, MS
Ukiah, CA
Vienna, GA
Springfield, OR
Winnfield, LA
Grand Rapids, MI
Columbus, OH
Auburn, ME
Kankakee, IL
Santa Clara, CA
Springfield, MA
Salisbury, NC
(CONTINUED )
37
-------
TABLE 6. (continued)
Manufacturer
Location
Perstorp Inc.
Plastics Mfg. Co.
PPG Indust., Inc.
Coatings and Resins Div.
Reichhold Chems., Inc.
Scott Paper Co.
Packaged Products Div.
Sun Chem. Corp.
Chems. Group
Chems. Div.
Sybron Corp.
Chem. Div.
Jersey State Chem. Co., div.
Synthron, Inc.
Florence, MA
Dallas, TX
Circleville, OH
Oak Creek, WI
Andover, MA
Detroit, MI
South San Francisco, CA
Tacoma, WA
Tuscaloosa, AL
White City, OR
Chester, PA
Mobile, AL
Chester, SC
Haledon, NJ
Morganton, NC
Tyler Corp.
Reliance Universal Inc., subsid.
Specialty Chems. and Resins Div.
United Merchants & Mfgs., Inc.
Valchem - Chem. Div.
U.S. Oil Co.
Southern U.S. Chem. Co., Inc.
Valspar Corp.
McWhorter, Inc., subsid.
Westinghouse Electric Corp.
Insulating Materials Div.
subsid.
Louisville, KY
Langley, SC,
East Providence, RI
Rock Hill, SC
Baltimore, MD
Manor, PA
(CONTINUED)
38
-------
TABLE 6. (continued)
Manufacturer Location
West Point-Pepperell, Inc.
Grifftex Chem. Co., subs id. Opelika, AL
Note: This listing is subject to change-as market conditions change,
facility ownership changes, plants are closed down, etc. The
reader should verify the existence of particular facilities by
consulting current listings and/or the plants themselves. The
level of formaldehyde emissions from any given facility is a
function of variables such as capacity, throughput and control
measures, and should be determined through direct contacts with
plant personnel.
39
-------
PHENOL-FORMALDEHYDE RESIN PRODUCTION
Phenol-formaldehyde resins are formed by polymerization of phenol and
formaldehyde. There are two major resin types: resols and novolaks.
Resols are formed in an alkaline medium with an excess of formaldehyde and
are marketed as thermosetting resins, bonding resins, varnishes, and laminates.
Novolaks are formed in an acid medium deficient in formaldehyde. These are
thermoplastic resins which require mixing with formaldehyde or a formaldehyde
donor such as hexamethylenetetramine to produce a thermosetting product.
18
Novalak products include thermosetting resin powders, varnishes, and laminates.
Process Descriptions
Resol Production Process --
Resols are commonly produced in a batch process. Major products of
the resol production process are phenol-formaldehyde resin and water. Basic
operations that may be used in a resol production process are shown in
Figure 7.
Phenol (Stream 1), formaldehyde (Stream 2), and sodium hydroxide
(Stream 3) are charged to an agitating reactor. Steam is then fed to the
kettle jacket and to internal coils to initiate the reaction. As the
exothermic reaction begins, cooling water is supplied to the kettle to
maintain temperature control. Additional cooling is accomplished by
1 o
using a reflux condenser.
The degree of polymerization is monitored by withdrawing samples and
testing them. The degree of polymerization determines the physical properties
of the product. The reaction can be halted at a point where the polymer is
still water soluble enough that it can be incorporated into bonding resins.
Alternatively, the reaction can be allowed to progress to the point at which
the polymer precipitates. In this case the water is removed, and an organic
solvent can be added to form a varnish. If the polymerization reaction is
allowed to continue until the resin reaches a brittle stage, a thermosetting
molding powder can be produced.
40
-------
FORMALDEHYDE STORAGE
SCALE
REACTOR
STEAM
COLD WATE
pH MODIFIER
COOLING
CARRIAGE
RESIN M
TROUGrlW
RESIN
RECEIVER
COOLING
BELT
MILL
NOTE: The numbers in this figure refer to process
streams, as discussed in the text, and the
letters designate process vents. The heavy
lines represent final product streams through
the process.
Figure 7. Basic operations that may be used for phenol-
formaldehyde resin manufacturing."^
41
-------
The polymerization reaction is stopped by rapid cooling and
neutralization with sulfuric acid. The mixture is then distilled in the
reactor kettle to purify the resin. If the resin application requires a
1 o
low concentration of water, the resin is dehydrated, often under vacuum.
The production of dry product requires discharge of the resin from the
reactor through a special quick-discharge valve to prevent it from becoming
an insoluble, infusible solid. Cooling must be accomplished by spreading the
material in thin layers because of its low thermal conductivity. Cooling
devices include water-cooled or air-cooled floors, trays in racks, and
moving belts. After cooling, the solid is ground, screened, and packaged.
Some of the solid resols require several water washing steps. This procedure
necessitates drying the resin before it is packaged. The solid resin may
18
be blended with fillers and additives before it is readied for marketing.
Novolak Production Process --
The production of novolak resins is also commonly performed by a
batch process. Figure 7 presents a flow diagram describing basic operations
that may be used in this process. As in the production of resols, phenol
(Stream 1) and formaldehyde (Stream 2) are charged to a jacketed batch-
reactor. However, sulfuric or hydrochloric acid (Stream 3) is added
instead of a base. The temperature is raised to initiate the reaction.
If strongly acid conditions are used, a vacuum reflux system must be
employed for cooling; but in many cases atmospheric reflux is sufficient.
Additional cooling is provided by circulating cooling water in the jacket
and in the internal coils of the reactor. When the reaction is completed,
the resin is purified by distillation in the reactor kettle and subsequent
dehydration. In some cases, the polymer is neutralized before it undergoes
further processing.
In solid resin production, the reactor charge is dumped onto cooling
surfaces in thin layers. Water-cooled or air-cooled floors, trays in racks,
and moving belts are used for rapid cooling. The solid resin is then ground
and screened. Fillers, coloring agents, and hexamethylenetetramine may be
blended with the resin, which can then be fused on hot rollers, ground and
packaged as .a finished thermosetting resin product.
42
-------
During the production of solutions used in varnishes and laminating
agents, solvent is also added in the reactor. The solutions are packaged in
18
drums or tanks.
Emissions
Formaldehyde emissions from the production of resols and novolaks may
result from the storage of formaldehyde (Vent A) before it is charged to
the reactor, and from the distillation and dehydration (Vents B and C) of
the reaction mixture. Carbon adsorption or liquid extraction is used to
control emissions from these operations. Fugitive gaseous emissions may
occur at the condenser, vacuum line, sample ports, and vents of both
processes. Intermittent formaldehyde emissions occur at safety blow-off
valves. Formaldehyde emissions also may result from the washing of
reactor kettles. Water washing of some resols during product preparation
18
may produce formaldehyde emissions.
Uncontrolled formaldehyde emission factors for the production of
812
phenol-formaldehyde resins have been estimated as follows: '
• Process -- 0.15 - 1.5 kg/Mg of 37% formaldehyde used
• Formaldehyde Storage -- 0.03 - 0.2 kg/Mg of 37% formaldehyde used
• Fugitive — 0.3 - 0.2 kg/Mg of 37" formaldehyde used
Phenol-formaldehyde production plants may vary in configuration and level of
control. The level of control on formaldehyde storage emissions should be
12
equivalent to that for formaldehyde production. The reader is encouraged
to contact plant personnel to confirm the existence of emitting operations
and control technology at a particular facility prior to estimating emissions
therefrom.
Source Locations
Major phenol-formaldehyde resin producers and production locations are
listed in Table 7.
43
-------
TABLE 7. PRODUCTION OF PHENOL-FORMALDEHYDE RESINS16
Manufacturer
Location
Allied Corp.
The Bendix Corp., subsid.
Friction Materials Div.
American Cyanamid Co.
Formica Corp., subsid.
American Hoechst Corp.
Indust. Chems. Div.
AMETEK, Inc.
Haveg Div.
Ashland Oil, Inc.
Ashland Chem. Co., subsid,
Chem. Systems Div.
Foundry Products Div.
Borden Inc.
Borden Chem. Div.
Adhesives and Chems. Div.
Brand-S Corp.
Cascade Resins, Div.
Chagrin Valley Co., Ltd.
Nevamar Corp., subsid.
Clark Oil & Refining Corp.
Clark Chem. Corp., subsid.
Core-Lube, Inc.
Green Island, NY
Evendale, OH
Mount Holly, NC
Wilmington, DE
Columbus, OH
Calumet City, IL
Cleveland, OH
Demopolis, AL
Diboll, TX
Fayetteville, NC
Fremont, CA
Kent, WA
La Grande, OR
Louisville, KY
Missoula, MT
Sheboygan, WI
Springfield, OR
Eugene, OR
Odenton, MD
Blue Island, IL
Danville, IL
(CONTINUED)
44
-------
TABLE 7. (continued)
Manufacturer
Location
CPC Internet1! Inc.
CPC North America, Div.
Indust. Diversified Unit
Acme Resin Corp.
The Dexter Corp.
Midland Div.
Gen. Electric Co.
Engineered Materials Group
Electromaterials Business
The P.D. George Co.
Georgia-Pacific Corp.
Chem. Div.
Dept.
Getty Oil Co.
Chembond Corp., subsid,
Gulf Oil Corp.
Gulf Oil Chems. Co.
Indust. Chems. Div.
Heresite-Seekaphen, Inc.
Forest Park, IL
Waukegan, IL
Coshocton, OH
Schenectady, NY
St. Louis, MO
Albany, OR
Columbus, OH
Conway, NC
Coos Bay, OR
Crossett, AR
Eugene, OR
Louisville, MS
Lufkin, TX
Newark, OH
Peachtree City, GA
Port Wentworth, GA
Russellville, SC
Taylorsville, MS
Ukiah, CA
Vienna, GA
Andalusia, AL
Spokane, WA
Springfield, OR
Winnfield, LA
Alexandria, LA
Manitowoc, WI
(CONTINUED)
45
-------
TABLE 7 (continued)
Manufacturer
Location
Hugh J.-Resins Co.
Inland Steel Co.
Inland Steel Container Co., Div.
The Ironsides Co.
Koppers Co., Inc.
Organic Materials Group
Lawter Internet11, Inc.
Libbey-Owens-Ford Co.
LOF Plastic Products, subsid.
Masonite Corp.
Alpine Div.
Minnesota Mining and Mfg. Co.
Chem. Resources Div.
Mobil Corp.
Mobil Oil Corp.
Mobil Chem. Co., Div.
Chem. Coatings Div.
Monogram Indust., Inc.
Spaulding Fibre Co., Inc., subsid,
Monsanto Co.
Monsanto Plastics & Resins Co.
Miles Chem. Paint Co.
Kordell Indust., Div.
The O'Brien Corporation-Southwestern
Region
[CONT
Long Beach, CA
Alsip, IL
Columbus, OH
Bridgeville, PA
Moundsville, AL
Auburn, ME
Gulfport, MS
Cordova, IL
Cottage Grove, MN
Kankakee, IL
Rochester, PA
De Kalb, IL
Tonawanda, NY
Addyston, OH
Chocolate Bayou, TX
Eugene, OR
Santa Clara, CA
Springfield, MA
Mishawaka, IN
Houston, TX
INUED)
46
-------
TABLE 7. (continued)
Manufacturer
Location
Occidental Petroleum Corp.
Hooker Chem. Corp., subsid.
Plastics & Chem. Specialties Group
Durez Materials Resins & Molding
Owens-Corning Fiberglas Corp.
Resins and Coatings Div.
Plastics Engineering Co.
Polymer Applications Inc.
Polyrez Co., Inc.
Raybestos-Manhattan, Inc.
Adhesives Dept.
Reichhold Chems., Inc.
Vacuum Div.
Rogers Corp.
Schenectady Chems., Inc,
The Sherwin-Williams Co.
Chems. Div.
Kenton, OH
North Tonawanda, NY
Barrington, NJ
Kansas City, KS
Newark, OH
Waxahacie, TX
Sheboygan, WI
Tonawanda, NY
Woodbury, NJ
Stratford, CT
Andover, MA
Carteret, NJ
Detroit, MI
Kansas City, KS
Moncure, NC
South San Francisco, CA
Tacoma, WA
Tuscaloosa, AL
White City, OR
Niagara Falls, NY
Manchester, CT
Oyster Creek, TX
Rotterdam Junction, NY
Schenectady, NY
Fords, NJ
(CONTINUED)
47
-------
TABLE 7. (continued)
Manufacturer Location
Simpson Timber Co.
Oregon Overlay Div. Portland, OR
The Standard Oil Co. (Ohio)
Sohio Indust. Products Co., Div.
Dorr-Oliver Inc., unit Niagara Falls, NY
Union Carbide Corp.
Coatings Materials Div. Bound Brook, NJ
Elk Grove, CA
United Technologies Corp.
Inmont Corp., subsid. Anaheim, CA
Cincinnati, OH
Detroit, MI
Valentine Sugars, Inc.
Valite Div. Lockport, LA
West Coast Adhesives Co. Portland, OR
Westinghouse Electric Corp.
Insulating Materials Div. Manor, PA
Micarta Div. Hampton, SC
Weyerhaeuser Co. Longview WA
Marshfield, WI
Note: This listing is subject to change as market conditions change,
facility ownership changes, plants are closed down, etc. The
reader should verify the existence of particular facilities by
consulting current listings and/or the plants themselves. The
level of formaldehyde emissions from any given facility is a
function of variables such as capacity, throughput and control
measures, and should be determined through direct contacts with
plant personnel.
48
-------
POLYACETAL RESIN PRODUCTION
Acetal resins are produced by the polymerization of anhydrous formaldehyde
or its trimer, trioxane. Formaldehyde and trioxane homopolymers and
copolymers of these compounds and other monomers are produced. The homopolymer
is a chain of repeating oxymethylene structures (-OCHL-) while the copolymer
has the oxymethylene structure occasionally interrupted by a comonomer
18 20
unit such as ethylene. ' Polyacetal resins are used to produce a
variety of parts for automobiles, plumbing fixtures, hardware, lawn and
garden equipment, and sporting goods.
Process Description
Basic operations that may be used in the production of polyacetal resins
from formaldehyde and trioxane are shown in Figure 8. Where formaldehyde is
to be polymerized, the first step in the process is the production of anhydrous
formaldehyde vapor from formaldehyde solution. Water is first evaporated from
aqueous formaldehyde solution to form semi-formals, paraformaldehyde, and
polyoxymethylene which are purified and thermally decomposed to produce
anhydrous formaldehyde. Impurities such as methanol, formic acid, and water
are removed by washing with non-volatile polyols or by freeze-trapping slightly
18
above the boiling point of formaldehyde.
Anhydrous formaldehyde monomer is then fed to an agitated batch reactor
with an inert diluent, initiators, and dispersants, where it is polymerized at
a low temperature. The polymer molecular weight is controlled by the addition
of chain-termination and transfer agents. The reaction is terminated by
stopping the flow of monomer. The solid polymer is separated from the diluent
by filtration and centrifugation. Chain ends are stabilized by treatment with
acetic anhydride and refluxing to form acetyl groups. The final product is
18
then washed and dried.
In trioxane polymerization, trioxane is prepared from aqueous formaldehyde
by acidification and distillation. The trimer is then separated from the
aqueous distillate by extraction or crystallization before it is further
purified by fractional distillation. Trioxane may then be polymerized by
bulk, suspension, or solution methods in the production of the copolymer.
18
Stabilization is accomplished by copolymerization with cyclic ethers.
49
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Extruded molten polymer strands are quenched directly in a water bath and then
1 g
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Emissions
Formaldehyde emissions may result from the storage of aqueous formaldehyde
solution (Vent A in Figure 8) prior to feed preparation. The major source of
process and fugitive emissions is the feed preparation step (Source B).
Formaldehyde emission factors from the production of polyacetal resins have
12 14
been reported as follows: '
• Process — 0.09 - 0.37 kg/Mg of 37% formaldehyde used
• Formaldehyde Storage -- 0.02 - 0.03 kg/Mg of 37% formaldehyde used
• Fugitive -- 0.02 - 0.36 kg/Mg of 37% formaldehyde used
No information was available on the basis of these estimates or types of
controls involved. Polyacetal resin production plants may vary in configuration
and level of control. The reader is encouraged to contact plant personnel to
confirm the existence of emitting operations and control technology at a
particular facility prior to estimating emissions therefrom.
Source Locations
Major polyacetal resin producers and their locations are listed in
Table 8.
51
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HEXAMETHYLENETETRAMINE PRODUCTION
The main use of hexamethylenetetramine is in the production of
cyclonite explosives for the military. Other uses are as curing agents
for phenolic thermosetting resins, and as components in the production of
pneumatic tire rubbers, insecticides, Pharmaceuticals, and textile treating
agents.
Process Description
The major products of the hexamethylenetetramine production process
are hexamethylenetetramine and water. Basic operations that may be used
in the production of hexamethylenetetramine are shown in Figure 9. Aqueous
formaldehyde solution is first charged to a reaction kettle, followed by
ammonia gas in a 3:2 formaldehyde/ammonia mole ratio. During addition of
21
the reactants, the temperature is maintained at about 20 to 30°C.
The reaction mixture is then fed to a vacuum evaporator where it is
maintained at a temperature between 30 and 50°C and at a pH of 7 to 8. As
water is removed, the reactants condense to form hexamethylenetetramine.
After most of the water has been removed the product forms crystals, which
are centrifuged, washed with water, and dried to yield the final product.
The water from the centrifuge and the wash water are recycled to the
21 22
system. The process yield is 97 percent.
Emissions
Formaldehyde emission sources include off-gases from the reactor,
22
waste water from the centrifuge wash bleed line, and the drier vent.
Formaldehyde emissions factors from the production of hexamethylenetetramine
g
have been estimated as follows:
• Process — ^0.39 kg/Mg of 37% formaldehyde used
t Formaldehyde Storage -- 0.05 kg/Mg of 37% formaldehyde used
• Fugitive -- 0.11 kg/Mg of 37% formaldehyde used
53
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No information was available on the basis of these estimates or types of
controls involved. Reference 12 reports that there are virtually no process
formaldehyde emissions and that storage and fugitive losses total approximately
0.05 kg/Mg.
Hexamethylenetetramine production plants may vary in configuration and
level of control. The reader is encouraged to contact plant personnel to
confirm the existence of emitting operations and control technology at a
particular facility prior to estimating emissions therefrom.
Source Locations
Major producers of hexamethylenetetramine and their production locations
are listed in Table 9.
55
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56
-------
PENTAERYTHRITOL PRODUCTION
Pentaerythritol is used in the production of alkyd resins and oil
base paints. Other uses include the manufacturing of some synthetic
lubricants for the automobile industry.
Process Description
Major products of the pentaerythritol production process are pentaerythritol,
alkali formate, and water. Basic operations that may be used in the production
of pentaerythritol are shown in Figure 10. Formaldehyde is produced on site
12
at some plants for direct use as a feedstock in this process. Pentaerythritol
is made by the condensation reaction of formaldehyde and acetaldehyde in the
21
presence of an alkali solution. Most plants use a batch process.
A sodium hydroxide solution or a calcium hydroxide slurry is added to
a formaldehyde solution in a reactor in which the temperature is controlled
at 15 to 20°C. Liquid acetaldehyde is then added to the mixture and an
exothermic reaction takes place. External cooling is used to control the
temperature at about 25°C for several hours, and is then raised to about
60°C.21
When the aldehyde content of the mixture is less than 0.1 percent,
the reaction mixture is fed to the neutralizer tank where formic acid,
sulfuric acid, or oxalic acid is added to neutralize the excess alkali.
The acid also reacts with the metallic ion of the alkali solution to form
21
a salt which can be removed by filtration.
Next, the solution is fed to an evaporator where water is removed to
achieve a specific gravity of about 1.27. Lowering the temperature
results in the crystallization of pentaerythritol which is removed from
21
the slurry by filtration. The mother liquor is fed to a recovery system.
The filter cake can be dried to yield a technical grade of the
product or it may be purified further by conventional methods. Byproducts
of the reaction include polypentaerythritols (mainly dipentaerythritol and
tripentaerythritol) and linear and cyclic formals of the various pentaerythritols.
Based on acetaldehyde, the process yield is 85 to 90 percent pentaerythritol
21
including polypentaerythritols.
57
-------
.
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58
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Emissions
Formaldehyde may be emitted from formaldehyde storage (Vent in Figure 10),
23
from the evaporator (Vent B) and from the drier vents (Vent C). Formaldehyde
emission factors from the production of pentaerythritol have been estimated
as follows:8'12
• Process — 1.3 - 2.7 kg/Mg of 37% formaldehyde used
• Formaldehyde Storage -- 0.002 - 0.33 kg/Mg of 37% formaldehyde used
• Fugitive -- 0.14 - 0.15 kg/Mg of 37% formaldehyde used
No information was available on the basis of these estimates or types of
control involved. Pentaerythritol production plants may vary in configuration
and level of control. The reader is encouraged to contact plant personnel
to confirm the existence of emitting operations and control technology at
a particular facility prior to estimating emissions therefrom.
Source Locations
Major producers of pentaerythritol and their production locations are
listed in Table 10.
59
-------
TABLE 10. PRODUCTION OF PENTAERYTHRITOL16
Manufacturer Location
Celanese Corp.
Celanese Chem. Co., Inc. Bishop, TX
Hercules Inc.
Operations Div. Louisiana, MO
Internat'l Minerals & Chem. Corp.
IMC Chem. Group
Indust. Chems. Div. Seiple, PA
Perstorp Inc. Toledo, OH
Note: This listing is subject to change as market conditions change,
facility ownership changes, plants are closed down, etc. The
reader should verify the existence of particular facilities
by consulting current listings and/or the plants themselves.
The level of formaldehyde emissions from any given facility is
a function of variables such as capacity, throughput and
control measures, and should be determined through direct
contacts with plant personnel.
60
-------
1,4-BUTANEDIOL PRODUCTION
1,4-Butanediol is used primarily in the production of tetrahydrofuran and
polybutylene terephthalate.
Process Description
1,4-Butanediol, also known as 1,4-butylene glycol, is produced by a
two-step process. The first step involves the high-pressure reaction of
24
acetylene and aqueous formaldehyde solution to form 1,4-butynediol . In
the second step, 1,4-butynediol is hydrogenated to form 1,4-butanediol.
Excess hydrogen is added during the exothermic hydrogenation reaction to
25
control the reaction temperature.
Emissions
Formaldehyde emission factors from the production of 1,4-butanediol
8 12
have been estimated as follows: '
• Process -- _f_0.74 kg/Mg of 37% formaldehyde used
• Formaldehyde Storage — 0.005 - 0.2 kg/Mg of 37% formaldehyde used
t Fugitive — 0.005 - 0.2 kg/Mg of 37% formaldehyde used
No information was available on the basis of these estimates or types of
controls involved. Reference 12 indicates that process emissions will be
eliminated if flared.
1,4-Butanediol production plants may vary in configuration and level of
control. The reader is encouraged to ccntact plant personnel to confirm the
existence of emitting operations and control technology at a particular
facility prior to estimating emissions therefrom.
Source Locations
Major producers of 1,4-butanediol and their locations are listed in
Table 11.
61
-------
TABLE 11. PRODUCTION OF 1 ,4-BUTANEDIOL16
Manufacturer Location
BASF Wyandotte Corp.
Indust. Chems. Group
Intermediate Chems. Div. Geismar, LA
E.I. duPont de Nemours & Co., Inc.
Chems. and Pigment's Dept. La Porte, TX
GAF Corp.
Chem. Products Calvert City, KY
Texas City, TX
Note: This listing is subject to change as market conditions change,
facility ownership changes, plants are closed down, etc.
The reader should verify the existence of particular facilities
by consulting current listings and/or the plants themselves.
The level of formaldehyde emissions from any given facility is
a function of variables such as capacity, throughput and control
measures, and should be determined through direct contacts
with plant personnel.
62
-------
TRIMETHYLOLPROPANE PRODUCTION
Trimethylolpropane is used primarily in the production of urethane
coatings and resins. It is also used in some synthetic lubricants.
Process Description
Trimethylolpropane is also known as hexaglycerol. There is little
published information available on the processes used in the production of
this chemical. Trimethylolpropane can be produced by the reaction of
n-butyraldehyde with formaldehyde and alkali.
Emissions
Formaldehyde emission factors from the production of trimethylolpropane
g
have been estimated as follows:
• Process -- 0.074 kg/Mg of 37% formaldehyde used
• Formaldehyde Storage -- 0.01 kg/Mg of 37% formaldehyde used
• Fugitive -- 0.01 kg/Mg of 37% formaldehyde used
No information was available on the basis of these estimates or types of
controls involved. Trimethylopropane production plants may vary in configuration
and level of control. The reader is encouraged to contact plant personnel
to confirm the existence of emitting operations and control technology at
a particular facility prior to estimating emissions therefrom.
Source Locations
Major producers of trimethylolpropane which are published in the SRI
Directory of Chemical Producers for 1983, are listed below:
t Witco Chem. Corp.
Organics Div. Houston, TX
• Atlantic Richfield Co.
Anaconda Indust. Div.
Aluminum Div. West Chester, PA
63
-------
This listing is subject to change as market conditions change, facility
ownership changes, plants are closed down, etc. The reader should verify
the existence of particular facilities by consulting current listings
and/or the plants themselves. The level of formaldehyde emissions from
any given facility is a function of variables such as capacity, throughput
and control measures, and should be determined through direct contacts
with plant personnel.
64
-------
4,4-METHYLENEDIANILINE PRODUCTION
i
4,4-Methylenedianiline (MDA) is formed by condensation of aniline and
formaldehyde. MDA is usually converted into methylenediphenyl isocyanate
o
10
23
(MDI) by phosgenation of the MDA salt. MDI is used in the production of
polyurethanes for reaction injection molding in the automobile industry.
Process Description
The production of MDA is a two stage process. First, aniline is
neutralized with concentrated hydrochloric acid in aqueous solution at
100°C to form aniline hydrochloride. This solution is cooled to 15°C, a
40 percent formaldehyde solution is added, and the resulting mixture is then
heated at 55 to 60°C for four hours. The reaction mixture is chilled again,
and the product precipitated out with dilute ammonium hydroxide. The product
22
may be purified further by recrystallization from alcohol or water.
Emissions
No formaldehyde emission sources or formaldehyde emission factors are
reported in the available literature for the MDA production process.
Source Locations
Major producers of MDA and their production locations are listed in
Table 12.
65
-------
TABLE 12. PRODUCTION OF 4,4'-METHYLENEDIANILINE14'16
ICI Americas Inc.
Rubicon Chems. Inc., subsid. Geismar, LA
01 in Corp.
01 in Chems. Group Moundsville, WV
Uniroyal, Inc.
Uniroyal Chem., div. Naugatuck, CT
The Upjohn Co.
Polymer Chems. Div. La Porte, TX
NOTE: This listing is subject to change as market
conditions change, facility ownership changes,
plants are closed down, etc. The reader should
verify the existence of particular facilities by
consulting current listings and/or the plants
themselves. The level of formaldehyde emissions
from any given facility is a function of variables
such as capacity, throughput and control measures,
and should be determined through direct contacts
with personnel.
66
-------
PHTHALIC ANHYDRIDE PRODUCTION
Production of phthalic anhydride is achieved by the catalytic air oxidation
of o-xylene or naphthalene. Formaldehyde and other oxygenated compounds are
produced as a byproduct of this reaction.
Process Description
Basic operations that may be used for the production of phthalic anhydride
?fi
are presented in Figure 11. Either naphthalene or o-xylene is fed to a
reactor and converted, with air, to phthalic anhydride by vapor-phase oxidation
22
in the presence of a vanadium pentoxide catalyst. The gaseous product is
condensed and dehydrated to remove water formed during the reaction. The
crude phthalic anhydride is then stripped of light ends and distilled under
vacuum for final purification.
Emissions
The main process waste gas from the phthalic anhydride condensers (Source A
in Figure 11) may contain a small amount of formaldehyde and is controlled
either by a scrubber-incinerator combination or by direct incineration. The
latter method has the advantage of providing control of carbon monoxide as
well as the organic species in the waste gas. Use of direct incineration has
27
been reported at an o-xylene based plant.
The uncontrolled formaldehyde emission factor from the phthalic anhydride
switch condensers.and the controlled formaldehyde emission factor from the
27
direct incineration control system are estimated as follows:
t Uncontrolled -- 2.1 kg/Mg of phthalic anhydride
t Controlled — 0.074 kg/Mg of phthalic anhydride
Phthalic anhydride production plants may vary in configuration and level of
control. The reader is encouraged to contact plant personnel to confirm the
existence of emitting operations and control technology at a particular
facility prior to estimating emissions therefrom.
Source Locations
Major phthalic anhydride producers and their locations are listed in
Table 13.16
67
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69
-------
USE OF FORMALDEHYDE-BASED'ADDITIVES (FBAs) IN SOLID UREA AND UREAFORM FERTILIZER
PRODUCTION
Formaldehyde is used in the production of conditioning agents for solid
urea and in the production of ureaform fertilizers. Solid urea is used as a
fertilizer, as a protein supplement in animal feeds, and in plastics manufacturing.
Solid urea is produced by first reacting ammonia and CO^ to form an
aqueous urea solution. This solution is sold as an ingredient in nitrogen
solution fertilizers or further concentrated to produce solid urea. Urea
solids are produced from the concentrated solution by two methods: prilling
28
and granulation. Prilling is a process by which solid, nearly spherical
particles are produced from molten urea. Molten urea is sprayed from the top
of a prill tower, and as the droplets fall through a countercurrent air flow,
they cool and solidify into nearly spherical particles. There are two types
of prill towers, fluidized bed and nonfluidized bed. The major difference
between these towers is that a separate solids cooling operation may be
required to produce agricultural grade prills in a nonfluidized bed prill
29
tower.
Granulation is more popular than prilling in producing solid urea for
fertilizer. There are two granulation methods, drum granulation and pan
granulation. In drum granulation, solids are built up in layers on seed
granules in a rotating drum granulator/cooler approximately 14 feet in diameter.
Pan granulators also form the product in a layering process, but different
30
equipment is used. Pan granulators are not common in this country.
Just prior to solids formations, formaldehyde-based additives (FBAs) are
injected into the liquid or molten urea to harden the product, reduce dust
generation during handling, and provide anticaking properties for storage.
The two most commonly used FBAs in the fertilizer industry are formalin and
urea-formaldehyde (UF) concentrates. Formalin is an aqueous formaldehyde
solution stabilized with methanol, whereas UF-concentrates are a solution of
25 weight percent urea, 60 weight percent formaldehyde, and 15 weight percent
water. Upon injecting FBA into the liquid or molten urea, formaldehyde
reacts with urea to form methylenediurea (MDU), which is the true conditioning
agent. FBA is usually added to urea at a level of 0.3 to 0.5 weight percent
formaldehyde.
70
-------
Ureaform is a slow release fertilizer produced from a mixture of urea,
UF-concentrate, sodium hydroxide, and water. The reaction to produce ureaform
is initiated by addition of acid, forming a wide distribution of methyleneurea
polymers, similar to the MDU in solid urea. The initial concentration of
formaldehyde in the ureaform process is much higher than in solid urea production.
Test data have indicated that formaldehyde is emitted during the urea
32 33
solids production process as presented in Table 14.Jt>-^ However, these data
were collected by the chromotropic analysis method which is not selective for
free formaldehyde. Thus, the test results show the total formaldehyde present,
whether in free form or tied up in chemical compounds such as MDU. Reference 31
indicates that some free formaldehyde may be emitted during the transfer of
FBAs to the urea process or during maintenance operations on equipment
containing or contaminated with FBAs.
Emission sources include fluidized bed prilling and drum granulation
operations. Uncontrolled emission rates from prill towers may be affected by
factors such as product grade being produced (agricultural or feed grade), air
flow rate through the tower, type of tower bed, and ambient temperature and
humidity. Uncontrolled emissions per unit of production are usually lower for
29
feed grade prills than for agricultural grade prills, due to lower airflows.
Emission rates from drum granulators may be affected by parameters such
as rotation rate of the drum, product size, recycle rate of seed material, bed
temperature, solution spray pressure, and airflow rates through the drum.
Controlled emission factors in Table 14 are for prill towers and granulators
33
controlled with wet scrubbers.
Emission estimates for formaldehyde from ureaform production were not
available. Producers of urea-formaldehyde concentrates, which are used in the
manufacture of solid urea and ureaform, were reported for 1978 as follows:
t Getty Oil Co. (Hawkeye Chemical Co.)
• Hercules Inc.
• Kaiser Aluminum & Chemical Corp.
• Lebanon Chemical Corp.
• O.M. Scott & Sons
• W.R. Grace & Co.
-------
TABLE 14. FORMALDEHYDE EMISSION FACTORS FOR SOLID UREA PRODUCTION32'33'3
Emission source
Uncontrolled
formaldehyde .
emission factor '
(kg/Mg)
Control
efficiency
Controlled
formaldehyde .
emission factor 'c
(kg/Mg)
Fluidized bed
prilling
agricultural grade
feed grade
Drum granulation
0.0095
0.0020
0.0055
95.4
74.8
50.2
0.0004
0.0005
0.0027
Any given solid urea production plant may vary in configuration and level
of control. The reader is encouraged to contact plant personnel to confirm
the existence of emitting operations and control technology at a particular
facility prior to estimating emissions therefrom.
"'These data were collected by the chromotropic analysis method which is not
selective for free formaldehyde. Thus, these emission factors are for
total formaldehyde present, whether in free form or tied up in chemical
compounds such as methylenediurea (MDU).
'Emission factors refer to kilograms of formaldehyde emitted per megagram of
solid urea produced.
Control efficiencies are for wet scrubbers.
72
-------
Producers of formaldehyde, which is usually sold as an aqueous solution
called formalin, are listed previously in Table 4.
73
-------
MISCELLANEOUS RESIN APPLICATIONS
General
Resins produced from formaldehyde find a wide range of applications.
Over 65 percent of urea-formaldeyde (U-F) resins are used as adhesives in the
production of particleboard, medium-density fiberboard, and interior plywood.
U-F resins are also used to produce home insulation. Insulation accounted
for over 6 percent of the resin use in 1977. Other uses of U-F resins are in
the textile, paper, and coatings industries, and for adhesives for other than
construction industry applications. These other uses each account for less
34
than 5 percent of the U-F resins produced.
Almost 50 percent of phenol-formaldehyde (P-F) resins are used in the
production of outdoor plywood and molding compounds. About 17 percent of P-F
resins are used as binders in the production of insulation. Other uses are
in the production of foundry molds, laminates, particleboard, friction materials,
and abrasives. Each of these other uses accounts for less than 8 percent of the
P-F resin produced.
Polyacetal resins are used to produce a large variety of parts for
automobiles, plumbing fixtures, hardware, lawn and garden equipment, and
sporting goods. A new area of possible application is molding for seat
backs in automobiles.
Approximately 60 percent of the melamine-formaldehyde (M-F) resins
produced are used for high pressure laminates such as counter and table
tops. M-F resins are also compression molded to form dinnerware. M-F
resins are used in coatings for automobiles, appliances, and metal surfaces
of other products. There is increasing use of methylated and butylated
M-F resins in place of solvent-based coatings.
Emissions
Phenol-formaldehyde and polyacetal resins are fairly stable in the
presence of normal heat and water. Urea-formaldehyde resins have a
tendency to decompose in the presence of normal heat and moisture to produce
formaldehyde gas. No information was available on the stability of
melamine-formaldehyde resins.
74
-------
Formaldehyde emissions occur during resin applications in production
processes as well as during use of products which contain these resins. For
example, use of U-F resins in the production of paneling and furniture often
results in emissions of formaldehyde in the factories where these products
are made. Offgasing of formaldehyde may also occur during use of these
products by consumers. One source reports that most of the unreacted formaldehyde
35
is removed during the manufacture of the products; however, chronic emissions
may occur after the excess free formaldehyde is removed as the urea formaldehyde
resins hydrolyze slowly in contact with moisture. ' A series of tests on
various consumer products showed the most potential for formaldehyde release
from pressed wood products (particle board, plywood and paneling), and much
less potential from new unwashed clothes, fiberglass insulation products
containing formaldehyde resins, paper products, fabrics (cotton, nylon,
olefin, and blended), and foam-backed carpets.
Formaldehyde may evolve from urea-formaldehyde foam insulation (UFFI)
used in residential applications. The insulation is formed by the combination
of the resin with a foaming agent and air, producing a liquid foam that is
sprayed into the outer walls of existing homes. The foam fills the space
g
between the walls and hardens in less than a minute. Formaldehyde is released
during foaming due to excess formaldehyde in the U-F resins and continues to
be emitted long after hardening due to hydrolytic decomposition of the UFFI.
One series of tests demonstrated significant potential for formaldehyde
emissions at least 16 months after initial UFFI installation. In 198
Consumer Products Safety Commission (CPSC) placed a ban on the use of UFFI.
How
it.
emissions at least 16 months after initial UFFI installation. In 1982, the
Consumer Products Safety Commission (CPSC) placed a ban on the use of UFFI.
However, the ban was overturned in August 1983, and CPSC declined to appeal
38
Sufficient information was not found to estimate emission rates from
resin and resin product uses in actual applications.
Source Locations
SIC Codes for miscellaneous manufacturing applications of resins are
listed in Table 15.
75
-------
TABLETS. STANDARD INDUSTRIAL CLASSIFICATION CODES FOR MANUFACTURING
PROCESSES ENGAGED IN RESIN APPLICATIONS39
Resin and use SIC code
Urea-Formaldehyde
Particleboard 2492
Fiberboard 2661
Interior plywood 2435, 2436
Foam insulation 1742, 2899 (Insulating compounds)
Textiles 22, 23
Paper 26
Surface coatings 2641, 2851, 3479
Adhesives 2891
Phenol-Formaldehyde
Outdoor plywood 2435, 2436
Molding compounds 2821
Insulation 2899 (Insulating compounds)
Foundry molds 3565
Laminates 2435, 2436, 2439
Particleboard 2492
Friction materials 3499
Abrasives 3291
Polyacetal
Plumbing fixtures 3079
Hardware 3079
Sporting goods 3949
Mel ami ne-Formaldehyde
Countertops 2541, 2542
Dinnerware 3079 (Dishes, kitchenware)
Surface coatings 2641, 3479
76
-------
MANUFACTURING OF MINOR PRODUCTS USING FORMALDEHYDE AS A FEEDSTOCK
General
Formaldehyde is used in a wide range of industrial and consumer applica-
tions. Because formaldehyde is somewhat unstable in its pure monomeric form,
it is usually converted to a variety of forms including a solid polymer
(paraformaldehyde), formaldehyde/water solutions called formalin, and
®
formaldehyde/alcohol solutions called Formcels. Much of formalin is used by
the textile, leather and dye industries. Because of its lighter weight and
lower shipping costs, much of the paraformaldehyde is used in industrial
applications in plants that are located at long distances from a formaldehyde
producer.
One of the minor uses of formaldehyde is in the production of chelating
agents such as nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid
(EDTA). Chelating agents are chemicals used in the manufacture of consumer
products such as detergents, water softening chemicals, and fertilizers.
Pyridine manufacture is an important consumer of formaldehyde. Pyridine
is used as a solvent in the manufacture of some pharmaceutical and as an
intermediate chemical in the production of other Pharmaceuticals such as
antihistamines. It is also used in the rubber industry as an accelerator and
in the textile industry for waterproofing fabrics. Under normal conditions,
pyridine chemicals will not emit formaldehyde.
Small quantities of formaldehyde are used to convert certain compounds
to diols. A typical example is the condensation of nitromethane with
formaldehyde to give 2-nitropropane-3,3-diol, which can be brominated to
2-bromo-2-nitropropane-l,3-diol, an antimicrobial preservatives used in some
consumer products such as aerosol insecticides. These condensation products
formed from nitroparaffins and formaldehyde would regenerate formaldehyde in
the presence of alkali.
A small amount of formaldehyde is used to produce sodium formaldehyde
bisulfite and sodium formaldehyde sulfoxy!ate for use in the making of dyes
for the textile industry.
77
-------
Emissions
Para-formaldehyde has a tendency to decompose and release formaldehyde
gas. In most other forms, formaldehyde gas will only be release under extreme
conditions such as combustion. No quantitative data are available on
formaldehyde emissions from the manufacture of minor products.
Source Locations
Manufacturers of the chemicals discussed above are listed in Table 16.
78
-------
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80
-------
MISCELLANEOUS COMMERCIAL/CONSUMER USES OF FORMALDEHYDE
General
Formaldehyde is sold directly for consumer or commercial use in
several forms, such as in a 37 percent solution (formalin) and in a solid
form (paraformaldehyde).
Although only a small amount of formaldehyde use is devoted to consumer
and commercial products, its low cost and unique capabilities cause it to
be used in a wide variety of products. Formaldehyde is an excellent
embalming agent and its preserving capabilities cause it to be routinely
used in almost every high school and college biology laboratory. Its
capability to control the growth of bacteria is important to many consumer
products, and manufacturers add trace amounts of formaldehyde to products
that would otherwise support bacterial growth. Formaldehyde is added to
cosmetics such as mascara to prevent bacteria from the eye from growing in
the unused product.
In the South, where temperatures and humidity are high, paraformaldehyde
in small cloth bags is hung in closets to release formaldehyde gas which
prevents growth of molds (mildew). Barber shops frequently use dilute
solutions of formaldehyde to disinfect scissors and combs. Farmers spray
dilute solutions of formaldehyde on animal feeds and seeds to prevent
bacterial growth. Some agricultural diseases are controlled by spraying
dilute solutions of formaldehyde directly on the ground. Formaldehyde is
added to oil well drilling muds to prevent bacterial growth in starches
which are added as thickening agents. Some room deodorizers use formaldehyde
because of its ability to react with ammonia and hydrogen sulfide and to
reduce the sensitivity of one's sense of smell. Some dry cleaning processes
use formaldehyde dispersed in cleaning solvents for disinfecting.
Emissions
Only about two percent of the paraformaldehyde produced in the United
States is used in consumer products. However, because of the tendency of
paraformaldehyde to decompose and release formaldehyde gas, consumer
81
-------
products containing paraformaldehyde will be a source of formaldehyde emissions
In most other forms, formaldehyde gas will only be released under extreme
conditions such as combustion. No quantitative data was available on
formaldehyde emissions from consumer products.
82
-------
COMBUSTION SOURCES
Introduction
Formaldehyde is a product of incomplete combustion in most fuel burning
operations and is emitted with other combustion products in the exhaust. The
concentration of formaldehyde in exhaust gas from fuel combustion is generally
very low, but because of the large amount of fuel consumed, fuel burning
accounts for a large quantity of formaldehyde emissions. Because formaldehyde
emissions from fuel burning result from incomplete combustion, emissions vary
from source to source depending on a number of parameters, such as excess air
and flame temperature.
Combustion processes have been grouped into five general categories for
the purposes of compiling formaldehyde emission factors. These categories
are: external combustion in boilers and space heaters; external combustion
in industrial process heaters; internal combustion in stationary sources;
incineration and open burning; and internal combustion in mobile sources.
Emissions of formaldehyde from these combustion categories are discussed in
the following subsections.
Combustion sources are listed in most emissions inventories, including
the National Emissions Data System (NEDS). Guidance is available from the
U.S. Environmental Protection Agency on locating combustion sources and
40-44
determining their design combustion rates and operating schedules.
External Combustion — Boilers and Space Heating
The boiler and space heating category includes steam-electric generating
(utility) plants; industrial boilers; and commercial, institutional and
domestic combustion units. These units are mainly fired by coal, oil, and
natural gas. Other fuels used in relatively small quantities include
liquefied petroleum gas, wood, coke, and waste and by-product fuels.
Table 17 presents estimates of formaldehyde emissions from external
combustion sources. The values presented in the table are based on the
results of extensive testing of formaldehyde emissions conducted by the
45
Public Health Service in the early 1960s. As noted above, emissions
vary from source to source depending on a number of parameters. Measurements
83
-------
TABLE 17 . FORMALDEHYDE EMISSIONS FROM EXTERNAL COMBUSTION SOURCES45
Emission factor
(ng/J)
Coal -fired sources
Pulverized coala 0.048
Chain grate stoker 0.060
Spreader stoker0 0.095
Underfed stokerd 0.53
Hand stoked6 0.027
Oil-fired sources
Residual oil 0.069
Distillate oil9 0.10
Natural gas-fired sources
Industrial1"1 0.038
Commercial/institutional 0.095
Domestic3 0.43
aBased on testing of two units with firing rates of 1,640 GJ/hr and 140 GJ/hr.
Based on testing of a unit with a firing rate of 155 GJ/hr.
cBased on testing of a unit with a firing rate of 62 GJ/hr.
Based on testing of two units with firing rates of 4.6 GJ/hr and 3.2 GJ/hr.
eBased on testing of a unit with a firing rate of 0.12 GJ/hr.
Based on testing of a steam-atomized unit with a firing rate of 15 GJ/hr.
%ased on testing of a steam-atomized unit with a firing rate of 22 GJ/hr.
Based on testing of a unit with a firing rate of 9.8 GJ/hr.
on testing of a unit with a firing rate of 1.0 GJ/hr.
JBased on testing of three units with firing rates of 0.19 GJ/hr, 0.18 GJ/hr,
and 0.013 GJ/hr.
84
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of total aldehyde emissions illustrate the variability which can be expected
from source to source in formaldehyde emissions. In comparison with the low
formaldehyde levels presented in Table 17, total aldehyde levels (of which
formaldehyde is estimated to comprise 70 to 100 percent) as high as 33 ng/J
have been reported for coal combustion; up to 40 ng/J for fuel oil combustion
and 7 ng/J for natural gas combustion,
Techniques which are used to mitigate total hydrocarbon and CO emissions
from combustion sources also reduce formaldehyde and other aldehyde emissions.
These techniques include operating measures to assure complete combustion as
well as periodic burner maintenance and tuning.
External Combustion — Industrial Process Heating
In a number of industrial processes, heat requirements are satisfied by
direct firing or by process heaters. In direct firing, hot gases from fuel
combustion are contacted with the material to be heated. Process heaters are
used to heat the material indirectly, either through the walls of a vessel or
through a heat exchanger. Indirect contact process heating units generally
are fired by natural gas, process gas, fuel oil, or oil-gas mixtures. Direct
fired units, such as rotary kilns, may also use coal.
Emissions of total aldehydes from refinery process heaters fired by
49
oil-gas mixtures have been measured at about 2.2 ng/Joule. Aldehyde emissions
from natural gas combustion and oil combustion have been estimated to be
100 percent and 70 weight percent formaldehyde, respectively. Based on
these data, an emission factor of 1.9 ng/Joule heat input has been derived
for formaldehyde emissions for process heaters fueled by oil-gas mixtures-
Data were not available to estimate formaldehyde emissions from direct firing.
Emissions would vary with the material being heated and may differ significantly
from emissions from other combustion sources.
As in the case of other external combustion sources, formaldehyde emissions
from industrial process heating are controlled by the same techniques which
control total hydrocarbon and CO emissions. These include the use of operating
measures that assure complete combustion as well as periodic burner maintenance
and tuning.
85
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Internal Combustion - Stationary Sources
Stationary internal combustion engines are used to generate electricity,
to pump gas or other fluids, to compress air for pneumatic equipment, and to
compress other gases for industrial processes. These engines include gas
turbines and heavy duty reciprocating engines.
Table 18 presents estimates of formaldehyde emissions from stationary
internal combustion engines. Formaldehyde emissions from gas turbines and
gas-fired reciprocating engines were estimated using published hydrocarbon
emission factors and species characterization data for hydrocarbon emissions
from gas turbines and gas-fired reciprocating engines. Emissions from
gasoline and diesel oil-fired industrial equipment were estimated based on a
50
published emission factor for total aldehydes and data showing that formaldehyde
comprises about 70 percent of total aldehyde emissions from oil-fired combustion
sources.
Techniques which are used to mitigate CO and total hydrocarbon emissions
from stationary internal combustion engines would also reduce formaldehyde
emissions. These include periodic engine maintenance and tuning.
Incineration and Open Burning
Table 19 presents total aldehyde emission factors for a number of types
of incinerators and for open burning of waste materials. Data were not
available on the fraction of aldehyde emissions comprised by formaldehyde;
however, formaldehyde has been estimated to make up 70 to 100 percent of
total aldehyde emission from other combustion processes. The data presented
in Table 19 were published between 1959 and 1968. It should be noted that
improved incinerator design may have resulted in a reduction of total aldehyde
and formaldehyde emission factors from some types of incinerators since these
data were collected. Emissions of formaldehyde from incinerators can be
reduced by the use of combustion controls, periodic maintenance, ard the use
of afterburners or additional combustion chambers.
Internal Combustion - Mobile Sources
Mobile internal combustion sources include automobiles, trucks, farm
equipment, construction equipment, airplanes, trains, and other vehicles.
These sources are generally powered by internal combustion engines fired by
gasoline, diesel fuel, or other distillate oil products.
86
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TABLE 18. FORMALDEHYDE EMISSIONS FROM STATIONARY INTERNAL
COMBUSTION rMCTMr<;3.49-bU
Gas turbines
Gas fired reciprocating engines
Gasoline and diesel -powered
industrial equipment
Formal
ng/Joule
heat input
4.0
5.7
13.2
dehyde emissions
g/hp-hr
0.04
0.04
0.15
g/kWhr
0.04 •
0.06
0.21
TABLE 19. TOTAL ALDEHYDE EMISSIONS FROM INCINERATION
AND OPEN BURNING3»3
Aldehyde emissions (g/kg)
Average
value
Range
Apartment incinerators
Domestic incinerators
Backyard burning
2.5
2.0
5.2
1 - 4
0.1 - 8
1 - 14
Data were not available to estimate the fraction of aldehydes comprised by
formaldehyde; however, formaldehyde comprises 70 to 100 percent of aldehyde
emissions from other combustion processes.
87
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Table 20 presents estimates of formaldehyde emissions from automobiles,
locomotives, heavy duty gasoline and diesel-powered vehicles, motorcycles,
snowmobiles, and aircraft. Table 21 lists formaldehyde emission estimates
for diesel and gasoline-powered farm and construction equipment.
Formaldehyde emission values per vehicle mile for automobiles and heavy
duty gasoline and diesel powered vehicles are based on EPA formaldehyde
52 53
emissions test data. ' Emissions per gallon of fuel burned were derived
using average fuel mileages of 16 miles/gallon for automobiles and 50 miles/gallon
54
for motorcycles.
Emission factors for locomotives, motorcycles, snowmobiles, aircraft,
and farm and construction equipment were derived from total aldehyde emissions
data. ' It has been estimated that formaldehyde makes up 70 percent of
total aldehyde emissions from fuel oil combustion and 60 percent of total
3
aldehyde emissions from gasoline and diesel fuel combustion.
Techniques which are used to mitigate total hydrocarbon and CO emissions
from mobile fuel combustion sources also reduce formaldehyde and other aldehyde
emissions. These techniques include carburetion adjustment and catalytic
conversion of exhaust gas.
88
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TABLE 20. FORMALDEHYDE EMISSIONS FROM TRANSPORTATION SOURCES
Automobiles3
Catalyst
Non-catalyst '
Diesel
Other ground transportation
Heavy duty gasoline vehicles
Heavy duty diesel vehicles
Locomotives
e f
Motorcycles: 2-cycle '
4-cycle '
Snowmobiles^
Aircraft
Jet9
g
Turboprop or piston
Formaldehyde
g/gal
0.05-0.83
0.83
0.33
0.64
0.55
1.5
3.3
1.4
5.9
1.9
1.6
emissions
mg/km
2-32
32
13
76
55
41
17
aAn average fuel mileage for automobiles of 16 miles/gallon was used to
convert from mg/km to g/gal.
Use lower value for newer, low mileage cars and higher-value for high
mileage cars. »53
Reference 52.
i CO
All cars were tuned to manufacturer's specifications. Malfunctioning
vehicles may emit considerably higher levels.5°
Emissions were calculated using aldehyde emission data and assuming
aldehyde emissions are 60 percent formaldehyde.
An average fuel mileage for motorcycles of 50 miles/gallon was used to
convert from mg/km to g/gal.54
a 55
Emissions were calculated using aldehyde emission data and assuming
aldehyde emissions are 70 percent formaldehyde.3
89
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TABLE 21. FORMALDEHYDE EMISSIONS FROM CONSTRUCTION AND FARM EQUIPMENT3
Formaldehyde emissions
Gasoline powered construction equipment
Wheeled tractor
Motor grader
Wheeled loader
Roller
Miscellaneous
Gasoline powered farm equipment
Tractor
Miscellaneous
Diesel powered construction equipment
Track! aying tractor
Wheeled tractor
Wheeled dozer
Scraper
Motor grader
Wheeled loader
Tracklaying loader
Off -highway truck
Roller
Miscellaneous
Diesel powered farm equipment
Tractor
Miscellaneous
g/gai
1.6
1.6
1.3
1.3
1.2
1.9
1.1
1.7
2.8
1.6
2.6
1.2
2.0
1.0
2.1
1.7
1.8
3.3
2.8
g/hr
4.8
5.2
5.8
4.5
5.4
4.2
2.8
7.4
8.1
17
39
3.3
11
2.4
31
4.5
8.3
9.8
4.3
g/hp-hr
0.15
0.17
0.13
0.15
0.13
0.18
0.13
0.10
0.17
0.096
0.17
0.073
0.012
0.06
0.13
0.12
0.12
0.20
0.18
Emissions were calculated using aldehyde emissions data50and the
assumption that aldehyde emissions are 60 percent formaldehyde.3
90
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OIL REFINING
Formaldehyde is produced as a combustion product in a number of refinery
operations. The major sources of formaldehyde emissions from oil refining
are catalytic cracking, coking operations and fuel combustion.
Process Description
Figure 12 shows a basic flow diagram for an oil refinery. Refining
operations which are major sources of formaldehyde emissions are described
briefly below.
Fuel Combustion --
Process heaters are used in almost every refinery unit operation to heat
feed materials or to supply heat in distillation operations. They are designed
to provide temperatures up to 51Q°C, and can be fired by refinery fuel gas
(usually CO rich), natural gas, fuel oil, or oil/gas mixtures.
Heat for refinery operations is also provided by steam which is produced
in boilers in the refinery utilities plant. These boilers generally are
fired by fuel oil or oil/gas mixtures.
At older refineries, high pressure compressors are often run by natural
gas fired internal combustion engines. High pressure compressors are used in
hydrodesulfurization, reformation, and other refinery unit operations.
Because of their greater reliability, electric motors and steam engines are
used at most newer refineries in place of gas-fired engines.
The total amount of fuel burned at a refinery is dependent on the size
and complexity of the refinery. The breakdown of fuel use between fuel oil
and gas depends on the availability of fuels, the particular requirements of
various burners or engines, and applicable environmental (e.g., fuel sulfur)
regulations. It is estimated that for a large complex refinery, the total
fuel requirement is 230 Gigajoules (GO) heat input per barrel (bbl) of crude
feed, of which on the average about 70 percent is provided by fuel oil combustion
and 30 percent by fuel gas combustion.
91
-------
o
tn
O)
S-
s-
o
QJ
OJ
-C
t/1
o
o
• p—
LO
ro
CQ
HI
i-
3
Ol
92
-------
Catalytic Cracking --
In catalytic cracking, catalysts are used to break down heavy oils to
lighter products. Feedstocks to catalytic cracking typically have a boiling
range of 340 to 540°C. Catalytic cracking processes currently in use can be
classified as either fluidized catalytic cracking (FCC) units or moving-bed
49 50
catalytic cracking units. ' In both processes, fresh and recycled oil are
fed to a cracking reactor with hot regenerated catalyst. The reactor
temperature for both processes is 470 to 525°C.
In the FCC process, the oil vaporizes and the catalyst, made up of very
fine particles, becomes entrained in the vapor. The cracking reaction takes
place as the fluidized-catalyst/oil-vapor stream flows up a riser in the
center of the reactor. The catalyst and oil vapor are separated by cyclones
at the top of the reactor. Spent catalyst from the cyclones falls to the
reactor bottom where it is steam stripped to remove adsorbed hydrocarbons
before flowing out of the reactor.
In the moving-bed process, catalyst beads (about 0.5 cm in diameter) are
fed to the top of the reactor along with a mixed phase oil feed. Cracking
occurs as the catalyst and oil move concurrently downward through the reactor.
Hydrocarbons are separated from the catalyst in a zone near the reactor
bottom. Spent catalyst is then steam stripped of adsorbed hydrocarbons and
flows out of the reactor.
Oil removed from the FCC catalytic cracking process is fed to a fractionation
column, where it is split into gas and liquid product streams and a recycle
stream. Spent catalyst in both processes is transferred to a regenerator,
where coke deposits are removed from the catalyst surface by partial combustion
with air at 590 to 675°C. Regenerated catalyst is separated from combustion
products by cyclones and returned to the cracking reactor.
Because the combustion process in the regenerator is incomplete, flue
gas from the regenerator generally has a high carbon monoxide (CO) concen-
tration. Emissions of CO generally are controlled using CO waste heat
boilers. Entrained catalyst particles are generally controlled by electrostatic
precipitators (ESPs).
93
-------
Coking --
Coking involves the thermal cracking of heavy residual oil to form
lighter products and petroleum coke. Two types of coking processes are
currently in use: fluid coking and delayed coking.
In delayed coking, feed oil is heated to 480 to 580°C in a process
heater and then fed to one of two coke drums. Cracking occurs as the oil
flows through the heater, and light products are removed as an overhead vapor
stream from the drum. Heavy liquids remain in the drum to form coke. The
delayed coking process is a batch process. When the drum in use is filled to
capacity with coke, the stream from the process heater is fed to the second
drum. Meanwhile, coke is removed from the first drum with high pressure
water jets.
In the fluid coking process, feed oil is contacted with hot pellets or
seed coke particles in a fluidized bed reactor. The feed oil cracks, forming
coke, which remains on the particles, and light products, which flow out of
the reactor in an overhead stream. Fluid bed particles are removed continuously
from the reactor, and circulated through a burner. In the burner, the coke
is partially combusted with air. A portion of the coke leaving the burner is
removed as product, and the remainder is returned to the reactor. The continuous
circulation of reactor bed material through the burner provides heat for the
cracking reaction, transferred as sensible heat in the bed material. The
reactor temperature is maintained at 525 to 590eC. Flue gas from the fluid
coker burner offgas contains incomplete combustion products including a large
amount of carbon monoxide. Carbon monoxide emissions generally are controlled
CO
by passing the flue gas through a CO waste heat boiler.
Emissions
Formaldehyde is emitted with combustion products from refinery process
heaters, boilers, and internal combustion compressor engines. These combustion
sources are located throughout the refinery. Process vent streams from
catalytic cracking and fluid coking operations also contain formaldehyde.
These streams are discharged from boilers used to burn CO rich waste gas
streams. In catalytic cracking, the CO rich waste stream results from the
94
-------
partial air oxidation of catalyst coke deposits; while in fluid coking, the
CO stream results from the partial oxidation of the coke burned to provide
process heat. There is no corresponding process vent stream from the delayed
coking operation. Refinery unit operations include valves, pumps, flanges,
and other hardware, all of which emit fugitive hydrocarbons. These hydrocarbons
are not, however, expected to contain large amounts of formaldehyde.
Table 22 presents emission factors for catalytic cracking and fluid
49
coking. Emissions from external combustion sources (boilers and process
heaters) and internal combustion engines are discussed in the section of this
report entitled COMBUSTION SOURCES.
Formaldehyde emission factors presented in Table 22 were derived from
49
emission test data for total aldehydes, using published estimates of the
fraction of formaldehyde in aldehyde emissions from various combustion processes,
Based on the processes by which aldehydes are formed and the nature of the
fuels, aldehyde emissions from natural gas combustion have been estimated in
published literature to be 100 percent formaldehyde, and aldehyde emissions
from oil combustion have been estimated to be 70 percent formaldehyde.
Because the streams entering CO boilers in fluid coking and catalytic cracking
operations result from the partial combustion of petroleum coke, aldehyde
emissions from these sources are expected to have a formaldehyde content
similar to that in aldehyde emissions from oil combustion.
Formaldehyde emissions from all of the above sources result from
incomplete combustion. Emissions of formaldehyde differ from source to
source depending on burner operating conditions, such as excess air and flame
temperature. Formaldehyde emissions from combustion sources, like total
hydrocarbon emissions, can be mitigated to a certain extent by maintenance of
proper operating conditions, including periodic burner maintenance and
tuning.
Source Locations
A list of active refineries in the United States is given in Table 23,
showing the location of each refinery as well as the total crude oil refining,
and catalytic cracking and fluid coking capacities, in barrels per stream
day.59
95
-------
TABLE 22. FORMALDEHYDE EMISSIONS FROM PETROLEUM REFINING
49,a
Source
Emission factor
Combustion Sources
Gas fired external combustion
Oil fired external combustion
Gas fired reciprocating engine
Oil/gas mixture fired process heater
See COMBUSTION SOURCES
Catalytic Cracking
FCC regenerator with CO boiler/ESP
Moving bed (TCC) regenerator with
CO boiler/ESP
Coking
Fluid coker burner with CO boiler/scrubber
2.2 kg/1000 bbl fresh feed
1.0 kg/1000 bbl fresh feed
0.54 kg/1000 bbl fresh feed
Petroleum refineries may vary in configuration and level of control.
The reader is encouraged to contact plant personal to confirm the
existence of emitting operations and control technology at a particular
facility prior to estimating emissions therefrom.
96
-------
TABLE 23. PETROLEUM REFINERIES
59
(bbl
caa-ic; !/
(bb> *r-sn
Hur: Oil Co.--Tus«laow
Lou suns Land and E*olor3tian
Co. --Sjra land.
Mar-on Cj"3- --Theodorf
Mo2 is 3ay 3e*-ning Ci —CVcfca
Warrror Assnalt Co. of AUoama
At'anfc ^ic^field Cera --Prydhoe Say
Chevrjn U.S.A. Inc.--Kena.
Her".- 30je ^e*lrnr-i 0lv> Of
«7 .SuO
81,300
37.SCO
JO, 300 :
6,000
20.500.
46.SCO
Ar* ::"a "uel s Co'*?, --f^ecsnia
Be*""/ 'st-cl;jj~, Division of
Crssi 3ii S ie-'-mng :0. a'
H,gras:rCo,. c=.-
Tosc: CsP3.--tl Dorado
Cal • *:-• "a
Arc"3r ?ef-nng CJ--*c;:r
in,':cc 2s, 30:
30, SCO
S4.7C3
n,=3c
17,200
53,2:3
7, SCO —
'"""
29,500
23,000
20,303
130.300
23,300
5.000
48.CC3
45,303"
46.300
14 ,000
94.3CC —
113,300
15,300
78, WC
40,300 7 .M3
126, OCO1 37,303
111.000
117.300
30.300
40, SCC
33.500
14.00C
'".
l6,:-oa
S3";c:3
30,3COa
...
62,3:=a
63.30C3
—
—
50~300a
toicoo1
—
—
15, SCO3
—
— .
—
... .
51 ,30Ca
...
—
•-*
""""
13, sac
.--
6Q,:OG3
3S.2C3
...
28 . jCC.
12 ,CCO
47.JOO
4S.3C33
---
s, oca3
is.ooc'1
-•-
JCONIINUED)
97
-------
TABLE 23. (continued)
Company and location
refi ning
casac»ty
(bo I/strea
day)
COfeinq charge
capacity
(bbl *resh
feed/s:ream day)
Catalytic
cracxm^ c*arge
caoacity
(bbl fresh
feed/stream day)
Getty Re Tin ing and Marketing Cc.--
DeU-are City
Ajnoco Oil Co.--Savannah
Young Sffimng Corp.--0o,uglasvi 1 le
150,COO
27,000
Chevron U.S.A. Inc.—Sarb-r's Point
Hawaiian Inaeoenaent Refinery
inc.--t"a Seacft
C'jpK OH i defining Corp...
Slue island
Ha-tford
warathon Oil Co.--Re5i"SOn
Mobile Oil COPS.—Joint
Shell Oil Ca.—Woos River
Texaco Inc.--Lawrenceville
union Oil Co. of CallfO'-nla--Le'T1ont
Anoco Oil Co.—Whiting
Gladieux Refinery Inc.--Ft. Wayne
Incnana Para Bureau Cooperative
Association Inc.--Ht. Vetion
tafcetan Refining Cor^.— UVe"n
Rocit Island Re'imng Corp.—
Inaiantooli s
i
Oeray Re'imng Ca.--Wichita
Famland Industries Inc.—
Ccffeyville
Getty Refimng & *Ur(teting Co.--
£1 Dorado
Mobile Oil Cora.—Augusta
National Cooperati-'e Refinery
'ester Re'-ning C3.---1 Dorado
Total Pet*o!eum—Arkansas CUy
Asnland Petrolewi! Co.--Catlettsaurg
lauisvi"le
Soferjet Refinery Inc.--Somerset
Atlas Processing Co., Division of
Penizoi1--Shreveaort
Calianet Defining C0.--princst3n
Canal Refining Co.--Churcn ooint
Celeron Oil & G*s—Mernentau
Cities Service Co.--t.aite Charles
Claioome Gasoline Co.--Lisbon
Coroca Inc.-Lake Charles
Cotton Valley Refinery (Kerr-HcGee
Kefinin? Carp.)—Cattan Valley
C?I Refining Inc.—U»e Charles
£**on Co.*-flaton Rouge
Gulf Oil Corp.--8elle Chasse
Hill Petroltm C0---Kr3tl Springs
Kerr McGe« Corp.—DuOach
Marathon Oil Ca.--Garyvilie
Kurpny Oi! Co.'-Hfaux
Placid Refining Ca.--'ort Allen
Port Petraieu* inc --S:one*aH
Shell Oi' :o.--Norca
"enneco Qi• Ca.--Chalmecce
Texaco Inc.--Convent
67,900
60,000
so,:oo
22,100
s,=:o
30,000
60,723
82,000
Si.500
57,:oo
«7;;5o
220.000
25,::o
6,050
82,500
6.S30
7,353
15.000
330,000
6,:oo
164,000
17,500
474,000
205.000
50.000
11.0:0
6,000:
263.000
95.400
5S.OOO
4.CCO
225.000
120,:00
147,000
22,000*
25,00-"
27,:::'
38.00='
98.0CC'
58,000'
150.000*
a,oooa
19,000'
31.000"
20.0:0'
H.500J
i8,c:o'
150,000
30,SOS'
iss.occ'
75.000°
3S.30C'
18.5COJ
100.000'
22.500'
70,000'
(CONTINUED!
98
-------
TABLE 23. (continued)
Comoany and location
Crude
day)
FUiJ
coking charge
caoacity
feed/stream day)
Cf.l'j'-^
feed.'s:--;- ::^3'
Chevron U.S.A. Inc.—Baltimore
Mieniojn
Crystal Refining Co.--Carson City
Lakeside 3eMmng Ca.--Kalamazoo
Marathon Oil Co.--Detroit
local Petroleum Inc.--Alma
14,3
6 ,:o:,
5.5CC"
71 ,000
42,000
Asnland Petroleum Co.—St. Paul Park
Kocl Refining Co.— Roser'lount
69,300
137,3CS
23.:::J
53.:::=
Amerada-^sss Cars.—Purvis
Chevc'' 'J.S.A. Inc.-Pascacoula
£rqon Be-'-.nin^ Inc.—Vlcitsaurg
Natr'ier Re'imng Inc. —Vatc'ie:
Soutr/.jna or, Cs.— LuBoe'tan
Sanoe'svi 1T«
zso.:cc-
22.300
22,300
S.500
U.SCO
7,300
Cenex—Laur«l
Conoco Inc.--3lllings
Exxcn Ca.—Billings
Flying J rnc.--CuC Sank
Kenca Refining Inc.—^ol* Point
Siimons Refining Co.--Great Falls
Bevada
Nevada Refining Co.—Tonooah
Sew Jg--sey
so,:::
*6.0CO
6.ZK
».9=:-
6,SCO
7,000
is:=:oa
21 ,:co-
Chevpon U.S.A. —Perth Amooy
Exxon Co.--i.lnden
Hooil Oil Cora. — Paulsboro
Scaview Petroleum Inc.—
Thorofare
Texaco Inc. — Uestvi lie
Giant Industries Inc.— Cfniza
Famington
Navajo ^e'lning Co.—Artesia
Plateau Inc. — Sloomfie'd
Southern Union Refining Co- —
Lovinqton
Thnftxay Co.—31oomffe!d
Nortl Oakota
Amoco Oil Co.--«snt!an
flying J Inc. — Ullllston
OMo
Ashland Petroleum Co.— Canton
Standard Oil Co. of Ohio— lima
Toledo
Sun CI—Toledo
Oklahoma
Allied Material Coro.—Stroud
Chamolin Petroleum Co.— Enid
Conoco Inc. — Ponca City
Kerr-«cS« Sefming Coro,—
Wynne«*ood
Oklahoma Refining Co.— Cyi!
CusteP Country
Sun CI--"uHa
16a.3CCs
110,300
102.200 —
45 ,OCC:
95,300
19,000
H.OCO
29.93C
18,100
36 .300
7.500-
58,300
5,400
68.000
45 ,300 —
177,000
126, COO
124,000
8,500
56.000
133,000
43,000"
15.500
12.SOC
90,300
33.:::
120,000
34,"0-
..-
40, ,1.0
7.2001
---
17 .3"
5,^CC
— -
*"
2s.:coa
_--
|: 1
55! :•:'
50. 3Ca
— a
19. 5:0
45. :c:
.
20,300'
7,3::
--- ,
:o,.v3
(COnTINUED)
99
-------
TABLE 23. (continued)
Company and location
Crude
refining
capacity
(bbl/stream
day)
coking, charge
capacity
(bbl fresn
feeti/strearr day)
Catalytic
cracking charge
capacity
(bbl fresh
feed/stream day)
Oklahoma fcon't)
Tonkawa Refining Co-—Arnett
Tosco—Duncan
Total Petroleum Corp.--Are-nore
Oregon
Chevron U.S.A. Inc.--Portland
Pennsylvania
Atlantic Richfielc" Co.--Philadelphia
BP Oil Corp.--Marcus Hood
Gulf Oil Co.--Pni1adel2hia
Kendall-Amai ie Divsion
Uitco enemies! Co.--8rad'ord
Penzoil Co.—Rouseville
Quaker State Oil Re*:m*g
Corp.--Farmers Valley
Sun CI--Marcus HOOK
United Seining Co.--Warren
Valvcline Oil Co., Division
of Ashland Oil Co.--freedom
13.000
49,500
64,500
15,799
131,000
177,000
180,000
9,000
16,500
6,800
165,000
62,000
7,000
25,000a
J2.0003
29,000a
48.DOOa
85,300*
75,:cc°
18.3C04
Delta Refining Co.--Memohis
Texas
49,300
30.00C4
Amber Refining Co. --Fort Worth
American Petrofma Inc.--
Big Spring
Port Arthur
Amoco Oil Co. --Texas City
Atlantic Richfield Co. --Houston
Chaff-plin Petroleum Co.--
Corpus C>in$t*
Charter International Q} 1
Co.— Houston
Chevron U.S.A. Inc.--£l Paso
Coastal States Petroleum Ca.«
Corpus Cnnst!
Crown Central Petroleum
Corp. --Houston
Diamond Shamrock Corp.--Sunray
Dorchester Refining Co.«
Ht. Pleasant
Eddy Refining Co -—Houston
Exxon Co. U.S.A.--Baytown
Flint Chemical Co. --San Antonio
Gulf Oil Co. --Port Arthur
Howell HyCrocartons Inc. --San Antonio
Koch Re'imng Co. --Corpus Christi
I*fi7or?« Oil i Gas Co.--T.vJe*'
Licuid Energy Corp.— Sridoepo-t
Marathon Oil Co. --Texas City
Hooil Oil Corp.— Seaurtont
Phillips Petroleum Co.—
Borger
Sweeny
Pride Refining Inc. --Abilene
Quintan* Petrochemical Co.--
Corpus Christl
Saber Energy Inc. --Corpus Christi
Shell Oil Co.— Deer Park
Odessa
Sigmor Refining Co.— Three Rivers
South Hampton Refining Co.— Silsbee
Southwestern Refining CI--
Corpus Christ!
Tesoro Petroleum Corp.--
Carrizo Springs
Texaco Inc.— Amarillo
El Paso
Port Arthur
Port Neches
Texas Citv Refimnq Inc --Texas City
Uni Ref'ning I nc. --Ingleside
Union Oil Co. of Califorma--
(Beaumont) , Neder^na
20.500
60,000
110,000
432. :oo
244,000
179,000
7c,:oc
76,wCjC
95,000C
103, OCO
76,440
26, SCO
3,500C
525,000
1,400
424,000
10,000
108,000
70,000
10,300
72,000
335,000
100,000
195,000
36,500
34,000
21 .300
310,000
33,500
49,500
17,500
104,000C
27,474
21 ,000
18,000
425,000
32 ,600
130,000
45,000
126,300
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
—
...
—
...
...
...
...
...
».
...
—
...
...
...
...
...
...
5,OOCa
23, 500 a
34 , jCO*
194,000a
78,000*
69,000a
50,000a
22,OOCa
19,500a
56,CCCa
45 .000*
K
9,600"
...
T55.30C*
...
no.ooo3
27.000*
17,OCCa
38,OOCa
100,500*
18,300s
60,000a
87,OOCa
—
65,000*
10,500a
17,000*
*.-
47.000*
.--
8,OCCa
7,OOCd
135,000*
40,QCOa
—
38,000
(CONTItiUEO)
100
-------
TABLE 23. (continued)
Company and location
Crude
refining
capacity
(bbl/stream
day)
Fluid
coking charge
capacity
(bbl fresh
feed/stream day)
Catalytic
cracking charge
capacity
fbbl fresh
feed/stream day)**'
Utah
Amoco Oil Co.--Salt Lake City
Caribou Four Corners Inc.--Woods Cross
Chevron U.S.A.--Salt Lake City
Crysen Refining Co.--Woods Cross
Husky Oil CO.—North Salt Laice City
Phillips Petroleum Co.—*«food$ Cross
Plateau Inc.—Roosevelt
Virginia
Amoco Oil Co.— Yortctown
Washington
Atlantic Richfield Co.-~remdale
Chevron U.S.A. Inc.— Seattle
Mobile Oil Corp.— Ferndale
Shell Oil Co.—Anacortes
Sound Refining Inc. — Tacoma
Texaco Inc.— Anacortes
U.S. Oil & Refining Co.— Tacoma
West ^Virginia
Quaker State Oil Refining Core.—
Newell
St. Mary's
Wisconsin
Murphy Oil Corp. --Superior
41,500
8,400
45,000C
12,500C
26,000
25,000
8,500
55,000
131,000
5,500C
75,000
94,000
11,700C
82,000
24,000C
12,000
5,000
42,000
18,000*
11, MM3
7,000
3,400°
6,000*
28,000*
25"500^
30,300*
9,700*
ftmocs 011 Co. —Casper
Husky Oil Co. —Cheyenne
Little America Refining Co.— Casper
Mountaineer Refining CI— LaBarge
Sinclair Oil Corp. — Sinclair
Wyoming Refining Co. —Newcastle
49,000
30,000
24,500C
700
54,000
13.500
9,000
13.000*
12,000*
12.50C?
21.000*
4,000°
NOTE. This listing is suoject to change as market conditions change, facility ownership changes, olants are
closed down, etc. The reader should verify the existence of particular facilities by consulting
current listings and/or the plants themselves. The level of formaldehyde emissions from any given
facility is a function of variables such as capacity, throughput and control measures, and should be
determined through direct contacts with plant personnel.
ariuid oed catalytic cracking.
Moving bed catalytic cracking.
'Capacity in bbl/calendar day.
101
-------
SECTION 5
SOURCE TEST PROCEDURES
There is no EPA Reference Method for source sampling and analysis of
formaldehyde; however the EPA Industrial Environmental Research Laboratory
has published a recommended Level 2 sampling and analysis procedure for
aldehydes including formaldehyde. This method involves the reaction of
formaldehyde with 2,4-dinitrophenylhydrazine (DNPH) in hydrochloric acid
(HC1) to form 2,4-dinitrophenylhydrazone. The hydrazone is then analyzed by
high performance liquid chromatography (HPLC).
Exhaust containing formaldehyde is passed through impingers or bubblers
containing DNPH in 2N HC1 (Figure 13).60~62 The molar quantity of DNPH in
the impingers must be in excess of the total molar quantity of aldehydes and
ketones in the volume of gas sampled. Formaldehyde, higher molecular weight
aldehydes, and ketones in the gas react with DNPH to yield hydrazone derivatives,
which are extracted from the aqueous sample with chloroform. The chloroform
extract is washed with 2N HC1 followed by distilled water, and is then evaporated
to dryness. The residue is dissolved in acetonitrile. The solution is then
analyzed by HPLC with an ultraviolet (UV) detector set at a wavelength of
254 microns. The mobile phase is 62 percent acetonitrile/38 percent water.
The recommended column is a 4.6 mm by 25 cm stainless steel 5 micron Zorbax
ODS (Dupont) reverse phase column, and the flow rate is 1.5 ml/min. Under
the above conditions, the residence time of formaldehyde is 4.46 minutes.
The detection limit of the method is 0.1 ng to 0.5 ng. Aldehydes have been
recovered from air sample spikes with an average efficiency of 96 percent
(+5.5 percent).60
Modifications of this general method have been applied for low level
ambient air measurements of formaldehyde. In estimating low levels by this
procedure precautions must be taken to insure that degradation of the absorbing
reagent does not occur. One measure found to be helpful consists of conditioning
the glass samplers by rinsing them with dilute sulfuric acid followed by
rinsing with the 2,4-DNPH absorbing solution.
102
-------
.TEMPERATURE
SENSOR
HEATED AREA
THERMOMETER
FILTER HOLDER
r
REVERSE-TYPE
SILICA GEL
IMPINGER
CHECK
VALVE
PITOT TUBE
PITOT
MANOMETER
2-LITER IMPtNGERS
WITH DNPH 8 2N HC1
THERMOMETERS
ORIFICE
VACUUM
LINE
VACUUM
BY-PASS GAUGE
VALVE
DRY GAS'
METER
MAIN VALVE
•AIR-TIGHT
PUMP
Figure 13. Method 5 sampling train modified for the measurement
of formaldehyde.60"62
103
-------
Because higher molecular weight aldehydes and ketones also react with
DNPH, they may interfere with the analysis of formaldehyde at some chromato-
graphic conditions. Thus, it may be necessary to adjust the chromatographic
conditions in order to give adequate separation of the formaldehyde-DNPH
derivative (2,4-dinitrophenylhydrazone) from the hydrazone derivatives formed
co
by higher molecular weight aldehydes and ketones. It may also be necessary
to adjust the acetonitrile/water ratio to avoid interference with residual
DNPH.
•
When sulfur dioxide is present in the emission stream, it can dissolve
in the absorbing solution to produce sulfite ion, which reacts rapidly with
formaldehyde to form bisulfite. This side reaction should not be a problem
as long as the absorbing solution is kept acidic (pH<3). However, the
affect of high sulfur dioxide concentrations on the accuracy of the method
has not been tested.
It should also be noted that unpredictable deterioration has been observed
for some samples analyzed by this method. Samples should therefore be analyzed
within a few hours after collection. Finally, the method does not apply
when formaldehyde is contained in particulate matter.
104
-------
REFERENCES
1. Encyclopedia of Chemical Technology, Kirk-Othmer, 3rd Edition, Volume 11.
Wiley-Interscience Publication, New York, New York. 1980. p. 231-247.
2. JANAF Interim Thermochemical Tables. Midland Michigan, The Dow Chemical
Company, March 1961.
3. Kitchens, J.F., et al. Investigation of Selected Potential Environmental
Contaminants: Formaldehyde. U.S. Environmental Protection Agency.
Washington, DC. Publication No. EPA-560/2-76-009. August 1976.
4. Cupitt, L.T. Fate of Toxic and Hazardous Materials in the Air Environment.
U.S. Environmental Protection Agency, Research Triangle Park, NC.
Publication No. EPA-600/3-80-084, August 1980. p. 23.
5. Morris, R. and F. Higgins. Engineering and Cost Study of Air Pollution
Control for the Petrochemical Industry Volume 5: Formaldehyde Manufacture
with the Mixed Oxide Catalyst Process. U.S. Environmental Protection
Agency. Research Triangle Park, N.C. Publication No. EPA-450/3-73-006e.
March 1975.
6. Synthetic Organic Chemicals, United States Production and Sales, 1982.
U.S. International Trade Commission. Washington, DC. 1983. p. 259.
7. Key Chemicals-Formaldehyde. Chemical and Engineering News. 60:26.
March 29, 1982.
8. Human Exposure to Atmospheric Concentrations of Selected Chemicals,
Volume 2. U.S. Environmental Protection Agency. Research Triangle
Park, N.C. February 1982. Appendix A-15.
9. Chemical Producers Data Base System-Formaldehyde. U.S. Environmental
Protection Agency. Cincinnati, Ohio. July 1981.
10. Sheldrick, J. and T. Steadman. Product/Industry Profile and Related
Analysis for Formaldehyde and Formaldehyde-Containing Consumer Products.
Part 1-Overview of Formaldehyde Production and Markets. U.S. Consumer
Product Safety Commission. Washington, D.C. February 1979. p. 9-24.
11. Lovell, R.J. Report 1: Formaldehyde. In: Organic Chemical Manufacturing
Volume 9: Selected Processes. U.S. Environmental Protection Agency.
Research Triangle Park, N.C. Publication No. EPA-450/3-80-028d.
December 1980. pp. III-l to III-9.
105
-------
12. Hewlett, C.T., Formaldehyde Institute, Scarsdale, NY. Letter to
Tom Lahre, Office of Air Quality Planning and Standards, U.S. Environmental
Protection Agency, September 29, 1983.
13. "Thermal Incinerator Performance for NSPS." Memo and addendum from Mascone,
D., EPA to Farmer, J., EPA. June 11, 1980.
14. Gilby, P.G., E.I. DuPont DeNemours & Company, Inc., Wilmington, Delaware.
Letter to Tom Lahre, Office of Air Quality Planning and Standards,
U.S. Environmental Protection Agency, July 29, 1983.
15. Reference 11, pp. IV-1 to IV-12.
16. 1983 Directory of Chemical Producers, United States of America. SRI
International. Menlo Park, California. 1983.
17. Encyclopedia of Chemical Technology, Kirk-Othmer, 3rd Edition, Volume
2. Wiley-Interscience Publication, New York, New York. 1978.
p. 440-469.
18. Wilkins, G.E. Industrial Process Profiles for Environmental Use.
Chapter 10 - Plastics and Resins Industry. U.S. Environmental
Protection Agency. Cincinnati, Ohio. Publication No. EPA-600/2-77-023J.
February 1977.
19. Knob, A. and W. Scheib. Chemistry and Application of Phenolic Resins.
New York, Springer-Uerlag, 1979. p. 61.
20. Encyclopedia of Chemical Technology, Kirk-Othmer, 3rd Edition, Volume 1.
Wiley-Interscience Publication, New York, New York. 1978. p. 112-123.
21. Faith, W.L., D.B. Keyes, and R.L. Clark. Industrial Chemicals, 4th Edition.
John Wiley and Sons, New York. 1975.
22. Liepins, R. and F. Mixon. Industrial Process Profile for Environmental
Use. Chapter 6 - The Industrial Organic Chemicals Industry. U.S.
Environmental Protection Agency. Cincinnati, Ohio. Publication
No. EPA-600/2-77-023f. February 1977.
23. Hedley, W.H., et al. Potential Pollutants from Petrochemical Processes.
Monsanto Research Corporation. Dayton, Ohio. December 1973.
24. Walker, J.F. Formaldehyde. 3rd Edition. New York, Reinhold Publishing
Corporation, 1964.
25. Encyclopedia of Chemical Technology, Kirk-Othmer, 3rd Edition,
Volume 1. Wiley-Interscience Publication, New York, New York.
1978. pp. 256-259.
106
-------
26. Shreve, R.N. and J.A. Brink. Chemical Process Industries, Fourth
Edition. McGraw-Hill, Inc. New York, New York. 1977. pp. 599-601.
27. Serth, R.W. and T.W. Hughes. Source Assessment: Phthalic Anhydride
(Air Emissions). U.S. Environmental Protection Agency. Research
Triangle Park, N.C. Publication No. EPA-600/2-76-032d. December 1976.
pp. 3-7.
28. Urea Manufacturing Industry - Technical Document. U.S. Environmental
Protection Agency, Research Triangle Park, NC. Publication No.
EPA-450/3-81-001. January 1981. p. 2-4.
29. Reference 1, pp. 3-10 to 3-20.
30. Reference 1, pp. 3-21 to 3-27.
31. Report of the Fertilizer Institute's Formaldehyde Task Group. The
Fertilizer Institute, Washington, DC, February 4, 1983. 10 pages.
32. Reference 1, pp. 3-5.
33. Reference 1, p. 4-28.
34. Sheldrick, J. and T. Steadman. Product/Industry Profile and Related
Analysis for Formaldehyde and Formaldehyde-Containing Consumer
Products. Part II - Products/Industry Profile on Urea Formaldehyde.
U.S. Consumer Product Safety Commission. Washington, D.C. February 1979.
35. Urea-Formaldehyde Foam Gets the Axe For Home Insulation. Chemical
Week, Volume 130, No. 9, pp. 12-13, March 1982.
36. Hawthorne, A.R. and R.B. Gammage. Formaldehyde Release from
Simulated Wall Panels Insulated with Urea-Formaldehyde Foam Insulation.
Journal of the Air Pollution Control Association, Volume 32, No. 11,
pp. 1126-1131, November 1982.
37. Pickrell, J.A., et al., "Formaldehyde Release Rate Coefficient from Selected
Consumer Products." Environmental Science and Technology. Vol. 17, No. 12.
1983. pp. 753-757.
38. Marshall, Walt. Consumer Products Safety Commission, Washington, DC.
Personal communication with D.C. Misenheimer, GCA, November 23, 1983.
39. Statistical Policy Division, Office of Management and Budget. Standard
Industrial Classification (SIC) Manual. 1972.
40. Procedures for Emission Inventory Preparation, Volume I: Emission
Inventory Fundamentals. EPA-450/4-81-026a, U.S. Environmental
Protection Agency, Research Triangle Park, NC, September 1981.
41. Procedures for Emission Inventory Preparation, Volume II: Point
Sources. EPA-450/4-81-026b, U.S. Environmental Protection Agency,
Research Triangle Park, NC, September 1981.
107
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42. Procedures for Emission Inventory Preparation, Volume III: Area
Sources. EPA-450/4-81-026c, U.S. Environmental Protection Agency,
Research Triangle Park, NC, September 1981.
43. Procedures for Emission Inventory Preparation, Volume IV: Mobile
Sources. EPA-450/4-81-026d, U.S. Environmental Protection Agency,
Research Triangle Park, NC, September 1981.
44. Procedures for Emission Inventory Preparation, Volume V: Bibliography.
EPA-45Q/4-81-Q26e, U.S. Environmental Protection Agency, Research
Triangle Park, NC, September 1981.
45. Hangebrauk, R.P., D.J. Von Lehmden, and J.E. Meeker. Emissions of
Polynuclear Hydrocarbons and Other Pollutants from Heat Generation
and Incineration Processes. Journal of the Air Pollution Control
Association, Volume 14, No. 7, pp. 267-278, July 1964.
46. Hovey, H.H., A. Risman, and J.F. Cumman. The Development of Air
Contaminant Emission Tables for Nonprocess Emissions. Paper No. 65-17
presented at the 58th Annual Meeting, Air Pollution Control Association,
Toronto, Canada, June 20-24, 1965.
47. Smith, W.S. Atmospheric Emissions from Fuel Oil Combustion, An
Inventory Guide. AP-2, U.S. Department of Health, Education, and
Welfare Public health Service, Cincinnati, Ohio, November 1962.
48. Natusch, D.F.S. Potentially Carcinogenic Species Emitted to the
Atmosphere by Fossil-Fueled Power Plants. Environmental Health
Perspectives. Volume 22, pp. 79-90, 1978.
49. Wetherold, R.G. and D.D. Rosebrook. Assessment of Atmospheric
Emissions from Petroleum Refining. Volume 1. Technical Report.
EPA-600/2-80-075a, U.S. Environmental Protection Agency, Research
Triangle Park, NC, April 1980.
50. Compilation of Air Pollution Emission Factors. Third Edition.
AP-42. U.S. Environmental Protection Agency. Research Triangle
Park, N.C. August 1977.
51. Volatile Organic Compound (VOC) Species Data Manual, Second Edition.
EPA-450/4-80-015, U.S. Environmental Protection Agency, Research
Triangle Park, NC, July 1980.
52. Carey, P.M. Mobile Source Emissions of Formaldehyde and Other
Aldehydes. EPA/AA/CTAB/PA/81-11, U.S. Environmental Protection
Agency, Ann Arbor, Michigan, May 1981.
108
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53. Memo from J.E. Sigsby, Environmental Sciences Research Laboratory, U.S.
Environmental Protection Agency, Research Triangle Park, NC, to J.H.
Southerland, Office of Air Quality Planning and Standards, U.S. Environmental
Protection Agency, Research Triangle Park, NC regarding air emissions of
formaldehyde from mobile sources. June 27, 1983.
54. Highway Statistics, 1982. U.S. Dept. of Transportation. Federal
Highway Administration.
55. Mayer, M. A Compilation of Air Pollutant Emission Factors for Combustion
Processes, Gasoline Evaporation, and Selected Industrial Processes.
Public Health Service, Cincinnati, Ohio, 1965.
56, Charles Urban. Unregulated Exhaust Emissions from Non-Catalyst Baseline
Cars Under Malfunction Conditions. EPA-460/3-81-020. U.S. Environmental
Protection Agency. Ann Arbor, MI. May 1981.
57. Radian Corp. Assessment of Atmospheric Emissions from Petroleum Refining:
Volume 4 - Appendices C, D, and E. EPA-600/2-80-75d, U.S. Environmental
Protection Agency, Research Triangle Park, NC, July 1980.
58. PEDCo Environmental, Inc. Petroleum Refinery Enforcement Manual.
EPA-340/1-80-008, U.S. Environmental Protection Agency, Washington, DC,
March 1980.
59. Cantrell, A. Annual Refining Survey. Oil and Gas Journal. March 2T, 1983,
pg. 128.
60. Thrun, K.E., J.C. Harris, C.E. Rechsteiner, and D.J. Sorlin. Methods
for Level 2 Analysis by Organic Compound Category. EPA-600/7-81-029,
U.S. Environmental Protection Agency, Research Triangle Park, NC, March 1981.
61. Harris, J.C., M.J. Hayes, P.L. Levins, and D.B. Lindsay. EPA/IERL-RTP
Procedures for Level 2 Sampling and Analysis of Organic Materials.
EPA-600/7-79-033, U.S. Ervironmental Protection Agency, Research Triangle
Park, NC, February 1979.
62. Method 5 - Determination of Particulate Emissions from Stationary Sources.
Federal Register. 42(160): 41776, 1977.
63. Letter from Victor Elia, National Council of the Paper Industry for Air
and Stream Improvement (NCASI) to Thomas Lahre, U.S. Environmental
Protection Agency providing comments on source test procedures. May 4, 1983.
109
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APPENDIX A
CALCULATIONS OF PROCESS FUGITIVE EMISSIONS
Fugitive emissions of formaldehyde and other volatile organics result
from leaks in process valves, pumps, compressors, and pressure relief valves.
For formaldehyde production processes, the formaldehyde emission rates from
these sources are based on process flow diagrams, process operation data,
fugitive source inventories for typical plants, and EPA emission factors for
2
process fugitive sources.
The first step in estimating fugitive emissions of formaldehyde is to
list the process streams in the representative plant. Their phases are then
identified from the process flow diagram and their compositions are estimated.
For a reactor product stream, the composition is estimated based on reaction
completion data for the reactor and on the plant product slate. For a stream
from a distillation column or other separator, the composition is estimated
based on the composition of the input stream to the unit, the unit description,
and the general description of stream of interest (i.e., overheads, bottoms, or
sidedraw).
After the process streams are characterized, the number of valves per
stream are estimated by dividing the total number of valves at the plant
equally among the process streams. Similarly, pumps are apportioned equally
among liquid process streams, and relief valves are apportioned equally among
all reactors, columns, and other separators. The locations of any compressors
are determined from the process flow diagram.
Emissions are then calculated for pumps, compressors, valves in liquid
and gas line service, and relief valves. Emissions from flanges and drains
are minor in comparison with these sources and are, therefore neglected.
Fugitive emissions from a particular source are assumed to have the same
composition as the process fluid to which the source is exposed. For valves
in liquid service, for instance, formaldehyde emissions are determined by
taking the product of: (1) the total number of liquid valves in formaldehyde
A-l
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service; (2) the average formaldehyde content of the streams passing through
these valves; and (3) the average fugitive emission rate per valve per unit
time as measured by EPA. Emissions from valves in gas service, pumps and
compressors are calculated in the same manner. For relief valves, fugitive
emissions are assumed to have the composition of the overhead stream from the
reactor or column served by the relief valve. Emissions from the various
fugitive source types are summed to obtain total process fugitive emissions of
formaldehyde.
Because emissions from process fugitive sources do not depend on their
size, but only on their number, total process fugitive emissions are not
dependent on plant capacity. Thus, the overall emissions are expressed in
terms of kilograms per hour of operation.
FORMALDEHYDE METAL OXIDE CATALYST PROCESS
Representative plant fugitive source inventory --
177 process valves (in hydrocarbon service)
4 pumps (not including spares)
4 safety relief valves
Process line composition--
Of the total process lines in hydrocarbon service, only 4 are in
formaldehyde service, from the formaldehyde converter to formaldehyde storage
(see Figure A-l). Compositions are estimated as follows:
Composition (wt. percent)
Stream number Phase CHi=0_ Water
4
5
6
7
Valves--
177 valves = 22 valves per process stream
8 streams
Gas
Liquid
Liquid
Liquid
29
37
37
37
71
63
63
63
A-2
-------
o o
3 <
o a:
E
UJ
CO
en
-------
Assuming 22 valves in each of the above lines, and averaging the
formaldehyde contents for gas and liquid lines, total plant valve emissions
are estimated as follows:
Component
emissions factor Valves in Average CH2=0 Emissions
(kg/hr-valve)2 CH^=Q service content (percent) (kg/hr)
Liquid valves 0.0071 66 37 0.173
Gas valves 0.0056 22 29 0.036
0.209
Pumps —
5 ?iq£id lines ~' } pumP Per I1^u1d Process 1ine
For one pump in each of the six liquid lines in formaldehyde service, an
2
emission factor of 0.05 kg/hr/pump, and average formaldehyde concentration of
37 percent, pump emissions from the model plant are estimated at:
1 pumps/line x 3 lines x 0.05 kg/hr x 0.37 = 0.056 kg/hr
Compressor--
There are no compressors in formaldehyde service.
Relief vslves—
It is assumed that two of the four relief valves are applied to the
converter and two to the vaporizer. The converter overheads contain about
100 percent formaldehyde, while the vaporizer is not in formaldehyde service.
2
Using an emission factor of 0.104 kg/hr-valve, emissions from the converter
relief valves can be estimated as follows:
2 relief valves x 0.104 kg/hr-valve = 0.208 kg/hr
Total process fugitive emissions--
Total process fugitive emissions of formaldehyde from the metal oxidation
process representative plant are as follows:
Valves-liquid 0.173
- gas 0.036
Pumps 0.056
Compressors
Relief valves 0.209
Total 0.47 kg/hr
A-4
-------
Controls which can be used to reduce fugitive emissions include rupture
disks on relief valves, pumps with double mechanical seals, and inspection and
maintenance of pumps and valves. Double mechanical seals and rupture disks
are approximately 100 percent efficient in reducing emissions from pumps and
relief valves. Monthly inspection and maintenance (I/M) is about 73 percent
efficient for valves in gas service, 59 percent efficient for valves in liquid
service, and 61 percent efficient for pumps; while quarterly I/M is about
64 percent efficient for gas valves, 44 percent efficient for liquid valves,
2
and 33 percent efficient for pumps.
Overall efficiences were calculated for three control options. The
first, quarterly I/M for pumps and valves, has an overall efficiency for
formaldehyde emissions of about 53 percent. Monthly I/M for pumps and
valves has an overall efficiency of about 73 percent. The use of double
mechanical seal pumps, application of rupture disks to relief valves,
and monthly I/M for other valves has an overall efficiency of about
2
79 percent.
FORMALDEHYDE METALLIC SILVER PROCESS
Model plant fugitive source inventory --
214 process valves
7 pumps (not including spares)
6 safety relief valves
Process line composition—
Of the total 23 process lines, about 13 are in formaldehyde service, from
;onverters reactor to
are estimated as follows:
the converters reactor to formaldehyde storage (see Figure A-2). Compositions
A-5
-------
W> ^
s. a>
(1)
(J
o
Q.
re
-4->
re
5-
O)
i.
O
IB
Cl
re
•a
o
to
to
O)
O
o
CL.
CM
I
OJ
3
cn
A-6
-------
Composition (_wt. percent)
Stream number
3a-f
4
5
6
7
9
n
12
Phase
Gas
Gas
Gas
Liquid
Liquid
Liquid
Liquid
Liquid
CH2=0
20
20
20
10
30
37
37
37
H?0
-
-
85
55
63
63
63
CHqOH
-
-
5
15
30
-
-
Other
80
80
80
0
-
-
-
-
Valves —
214 valves
23 lines
= 9 valves per process line
Assuming 9 valves in each of the above lines, and averaging the
formaldehyde contents for gas and liquid lines, total plant valve emissions
are estimated as follows:
Component Valves in
emission factor CH2=0
(kg/hr-valve)2 service
Liquid valves 0.0071
Gas valves 0.0056
45
72
Average CH2=0
content (percent)
30
20
Emissions
(kg/hr)
0.096
0.081
0.177
Pumps--
6 liquid lines ~~ } pump per liquid process line
Assuming an average of one pump for each of the 15 liquid process
o
lines in formaldehyde service, an emission factor of 0.05 kg/hr-pump and
average formaldehyde content of 30 percent, pump emissions from the model
plant are estimated as follows:
1 pump /line x 7 lines x 0.05 kg/hr x 0.30 = 0.105 kg/hr
There are no compressors in formaldehyde service.
A-7
-------
Relief valves--
It is assumed that 2 relief valves are applied to the vaporizer and
4 to the bank of converters. The converter overheads contain about
20 percent formaldehyde, while the vaporizer is not in formaldehyde
service. Using an emission factor of 0.104 kg/hr, emissions from the
converter relief valves are estimated as follows:
4 relief valves x 0.104 kg/hr-valve = 0.416 kg/hr
Total process fugitive emission rate—
Total process fugitive emissions of formaldehyde for the silver
catalyst process:
Valves - liquid 0.096
- gas 0.081
Pumps 0.105
Relief valves 0.416
Total 0.70 kg/hr
Controls which can be used to reduce fugitive emissions include rupture
disks on relief valves, pumps with double mechanical seals, and inspection
and maintenance of pumps and valves. The efficiencies of these controls
for individual components are given in the previous section on metal
oxide catalyst process fugitive emissions.
The first control option, quarterly I/M for pumps and valves, has an
overall efficiency for formaldehyde emissions of about 57 percent. Monthly
I/M for pumps and valves has an overall efficiency of about 69 percent; and
the use of double merchanical pumps, application of rupture disk to relief
valves, and monthly I/M for other valves has an overall efficiency of about
2
91 percent.
A-8
-------
REFERENCES FOR APPENDIX A
1. Organic Chemical Manufacturing, Volume 9. EPA-450/3-80-028d, U.S.
Environmental Protection Agency, Research Triangle Park, NC. 1980.
2. Fugitive Emission Sources of Organic Compounds - Additional Information
on Emissions, Emission Reductions, and Costs. EPA-450/3-82-010,
U.S. Environmental Protection Agency, Research Triangle Park, NC.
1982.
A-9
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1 REPORT NO.
EPA-450/4-84-007e
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
LOCATING AND ESTIMATING AIR EMISSIONS FROM SOURCES OF
FORMALDEHYDE
5. REPORT DATE
March 1984
6. PERFORMING ORGANIZATION CODE
7 AUTHOR(S)
GCA Corporation
213 Burlington Road, Bedford, MA 01730
8. PERFORMING ORGANIZATION REPORT NO.
9 PERFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
Office Of Air Quality Planning And Standards
U. S. Environmental Protection Agency
MD 14
Research Triangle, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
EPA Project Officer: Thomas F. Lahre
16. ABSTRACT
To assist groups interested in inventorying air emissions of various
potentially toxic substances, EPA is preparing a series of documents such
as this to compile available information on sources and emissions of these
substances. This document deals specifically with formaldehyde. Its
intended audience includes Federal, State and local air pollution personnel
and others interested in locating potential emitters of formaldehyde and in
making gross estimates of air emissions therefrom.
This document presents information on 1) the types of sources that may
emit formaldehyde, 2) process variations and release points that may be
expected within these sources, and 3) available emissions information
indicating the potential for formaldehyde release into the air from each
operation.
KEY WORDS AND DOCUMENT ANALYSIS
a DESCRIPTORS
Formaldehyde
Air Emission Sources
Locating Air Emission Sources
Toxic Substances
!
18 DISTRIBUTION STATEMENT
1
I
b. IDENTIFIERS/OPEN ENDED TERMS
19. SECUR'TY CLASS /This Report
20 SECUP;TV CLASS < Tn-.s pjge;
c. COSAT! Heid/Group
21 NC OF PAGES
124
22 PRICE
EPA Form 2220-1 ''Rev. 4-77)
^Di^'ON S OBSOLETE
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U.S. Environmental Protection Agency
Rtglon V, Library
230 South Dearborn Street
Chicago, Illinois 60604
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