EPA-450/4-91-012
LOCATING AND ESTIMATING AIR EMISSIONS
FROM SOURCES OF FORMALDEHYDE
(REVISED)
By
Emission Inventory Branch
Technical Support Division
EPA Project Officer: Dallas Safriet
U. S. Environmental Protection Agency
Office Of Air And Radiation
Office Of Air Quality Planning And Standards
Research Triangle Park, NC 27711
March 1991
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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. Any mention of
trade names or commercial products is not intended to constitute endorsement or
recommendation for use.
EPA-450/4-91-012
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CONTENTS
Figures iv
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 13
Formaldehyde Production 13
Urea-Formaldehyde and Mel amine-Formaldehyde
Resin Production 23
Phenol-Formaldehyde Resin Production 29
Polyacetal Resin Production 41
Hexamethylenetetramine Production 49
Pentaerythritol Production 52
1,4-Butanediol Production 57
Trimethylolpropane Production 57
4,4-Methylenedianiline Production 59
Phthalic Anhydrine Production . . 60
Use of Formaldehyde-Based Additives (FBA's) in
Solid Urea and Ureaform Fertilizer
Production 63
Miscellaneous Resin Applications 67
Manufacturing Minor Products Using Formaldehyde
as a Feedstock 73
Miscellaneous Commercial/Consumer Uses
of Formaldehyde 75
Combustion Sources 78
Oil Refining 84
Asphaltic Concrete Production and Use 92
Formaldehyde Production in the Atmosphere via
Photo-Oxidation 98
5. Source Test Procedures 100
References 103
Appendix A - Calculations of Process Fugitive Emissions A-l
References for Appendix A A-8
iii
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FIGURES
Number Page
1 Common reactions of formaldehyde ...... 7
2 General reactions of formaldehyde . .... 9
3 Chemical use tree for formaldehyde 12
4 Basic operations that may be used for formaldehyde
production by the silver catalyst process 14
5 Basic operations that may be used for formaldehyde
production by the metal oxide process 16
6 Basic operations that may be used in urea-formaldehyde
and melamine-formaldehyde resin manufacture 27
7 Basic operations that may be used for phenol-
formaldehyde resin manufacturing ..... 39
8 Basic operations that may be used for the production
of polyacetal resins 48
9 Basic operations that may be used in the production of
hexamethylenetetramine 51
10 Basic operations that may be used in the production of
pentaerythritol 54
11 Basic operations that may be used in the production of
phthalic anhydride 62
12 Basic flowsheet for a refinery 85
13 Method 5 sampling train modified for the measurement
of formaldehyde 102
A-l Process flow diagram for metal oxide process A-3
A-2 Process flow diagram for silver catalyst process A-6
iv
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TABLES
Number Paoe
1 Physical Properties of Monomerlc Formaldehyde 6
2 Uncontrolled and Controlled Formaldehyde Emission
Factors for a Hypothetical Formaldehyde Production
Plant (Silver Catalyst Process) 18
3 Uncontrolled and Controlled Formaldehyde Emission
Factors for a Hypothetical Formaldehyde Production
Plant (Metal Oxide Catalyst Process) 20
4 Production of Formaldehyde 24
5 Production of Urea-Formaldehyde Resins 30
6 Production of Mel amine-Formaldehyde Resins 35
7 Production of Phenol-Formaldehyde Resins 42
8 Production of Polyacetal Resins 50
9 Production of Hexamethylenetetramine 53
10 Production of Pentaerythritol 56
11 Production of 1,4-Butanediol 58
12 Production of 4,4-Methylenedianiline 61
13 Production of Phthalic Anhydride 64
14 Formaldehyde Emission Factors for Solid Urea Production 66
15 Standard Industrial Classification Codes for Manufacturing
Processes Engaged in Resin Applications 74
16 Manufacturers of Minor Products Using Formaldehyde
as a Feedstock 76
17 Formaldehyde Emissions From External Combustion Sources 80
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TABLES (continued)
Number Page
18 Formaldehyde Emissions From Stationary Internal
Combustion Engines .... 83
19 Total Aldehyde Emissions From Incineration and Open
Burning 83
20 Formaldehyde Emissions From Transportation Sources 86
21 Formaldehyde Emissions From Construction and Farm
Equipment 87
22 Formaldehyde Emissions From Petroleum Refining 91
23 Petroleum Refineries 94
vi
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SECTION 1
PURPOSE OF DOCUMENT
The 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 amount of data available on formaldehyde
emissions, and since the configuration of many sources is not 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 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
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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 from these sources. 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 Us 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.
The final section of this document summarizes available procedures for
source sampling and analysis of formaldehyde. Details are not prescribed, nor
does EPA endorse any of these sampling and analysis procedures. At this time,
EPA generally has not evaluated these methods. Consequently, this document
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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 welcome, 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
C
/ \
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 JANAF Interim Thermochemical Tables list thermodynamic properties data 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
polyoxymethylene glycols containing 90 to 99 percent formaldehyde. Another
form of formaldehyde is its cyclic trimer, trioxane (CjHgO,). In aqueous
solutions, formaldehyde reacts with water to form methylene glycol. Reactions
that 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.
As a result of its unique structure, formaldehyde has a high degree of
chemical reactivity and good thermal stability in comparison to 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.*
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TABLE 1. PHYSICAL PROPERTIES OF MONOMERIC
FORMALDEHYDE17
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 Vaporation, AH
V
at 19*C, kJ/mol
at 109 to -22'C, j/mol
Heat of Formation, AH*- at 25'C,
kJ/mol r
Gibbs Free Energy, AG'r at 25*C,
kJ/mol r
Heat Capacity, C' , 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, mol %
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
A-(B/(C+t)); where P - vapor pressure in pascals (PA) and
t - temperature in 'C.
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-
^
o
V
01
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Because of Its high chemical reactivity and good thermal stability,
formaldehyde 1s 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 that apply to formaldehyde is
presented in Figure 2.
The residence time of formaldehyde in the atmosphere has been estimated
at between 0.1 and 1.2 days. Residence time 1s 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 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 prepared with methanol, n-propanol, n-butanol, or
isobutanol. Formaldehyde is also available in its polymeric forms of trioxane
and paraformaldehyde.
Currently, 13 formaldehyde producers in the United States operate 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.
'Registered trademark of Celanese Corporation.
a
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A. CH20 + 30H'
Oxidation - Reduction
» HCOO" + ZHO + 2e"
B. CH20 + 2Ag(NH3)2 + 30H" - »-2Ag + HCOO" +
C. 2CH20 + OH"
•HCOO" + CH3OH
D. CH20 + RCHO + OH"
E. CH20 + CN" + H
F. CH20 + Na HSO,"
G. 2CH20 + 2HC1'
H. 6CH20 + 4NH--
HCOO" + RCH2OH
Addition
H
I
I
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H
I
• H-C-SO,"Na
(
OH
J. CH20 + RjNH-
K.
RCONH
2
» R-NHCH2OH
R
I
•R-N-CH2OH
-RCONHCH2OH
1. CH20 + ROH H » RO-CH20!' H
R'O
M.
H R'O
i I n
HOC-C-C-R
I i
H R"
2e"
Toll ins Reaction
Cannizzaro Reaction
Crossed Cannizzaro Reaction
Cyanohydrin Formation
Addition of Bisulfite
Bi s(chloromethyl )ether Fo mat ion
Hexanethylenetetrarine For— atior
Condensation with Arines
Condensation with Amines
Condensation with Anide;
Acetal Formation
Aldol Condensation
N. CH,0 + RNH + R'-C-C-R"1
i i
R"
•RNCH.-C-C-R"'
«
H-0
'•
Reaction with Active H
OH OH
0. CH20
acid orr
base
• - CHjOH
Mannich Reaction
Methylol Formation
P. CH20 + RMgX——»RCH2(OMgX) ——wRCHjOH + XMgOH
nH,C(OH),»=*HO-(CH,0) -H + (n-l)H.O
t t t n t
Grignard
Formation of polyoxmethylene
Figure 2. General reactions of formaldehyde.3
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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 trioxane.
The product mix produced depends on fluctuating captive needs and customer
requirements. Production of formaldehyde in 1982 was estimated to be
2.18 x 10 megagrams on the basis of a 37 percent solution. 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
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
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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.
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.
10
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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-exchange 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 cr-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
9 10
textile treating applications, dyes, disinfectants, and preservatives.
Resins that are produced from formaldehyde are used primarily as
binders for particleboard 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.
11
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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 1s 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 that are
maintained at a temperature of approximately 635*C. The hot effluent gases
(Stream 4) are cooled rapidly to prevent decomposition of the product
formaldehyde. Cooling 1s 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
13
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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 demineral1 zed water, and the off-gas, consisting mostly of
nitrogen with some entrained volatile organic compounds (VOC's), 1s vented
(Vent A). The weak formaldehyde/methanol solution (Stream 7) withdrawn
from the bottom of the secondary absorber column 1s 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 vaporizer (Stream
8). Uncondensed vapors (Stream 10) are vented (Vent B) or fed to the
11 12
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 add before being
stored.11
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.
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 as incoming air (Stream 1), which has been
scrubbed to remove dust and trace impurities, is mixed with oxygen-lean
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recycle gas (Stream 5) from the process to lower the oxygen content of the
air feed stream below 10.9 percent. This low oxygen content 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 exchange 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.
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 fractlonator is another possible source of
formaldehyde process emissions (Vent B). However, most producers report
that gases from 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
17
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process operates above the upper explosive limit of methanol. Thus, plant
startup procedures must be handled carefully. Unstable conditions are
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 1s
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 venting 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
concentration of methanol to be increased without forming an explosive
mixture. 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 storing
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.TC.15
22
-------
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 organlcs
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.
UREA-FORMALDEHYDE AND MELAMINE-FORMALDEHYDE RESIN PRODUCTION
Urea-formaldehyde (U-F) and melamine-formaldehyde (M-F) resins are
the most commonly used amino resins. They are produced domestically by
adding formaldehyde (CH20) to urea (NH2CONH2) or melamine (C3N3(NH2)3) to
form methylol monomer units, and subsequent condensation of these units
to form a polymer. Urea-formaldehyde resins are used in the production
of home insulation and as adhesives in the production of particleboard,
fiberboard, and interior plywood. Melamine-formaldehyde resins are used
for high-pressure laminates such as counter and table tops, and are
Q
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 but some are produced in closed
continuous systems. The first reaction of the process, the addition of
formaldehyde to the amino compound to form methylol compounds, is carried
23
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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 1s 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 1s produced that 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
17 18
powder for convenient storage and handling. ' However, some producers
of U-F and M-F resins report that there are no spray drying operations at
12
their production facilities.
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
18
dryers that are vented to the atmosphere (Vent B).
Uncontrolled formaldehyde emissions from U-F and M-F resin
8 12
manufacture have been estimated as follows.
• Process--0.15 to 1.5 kg/Mg of 37 percent formaldehyde used;
• Formaldehyde Storage--0.03 to 0.2 kg/Mg of 37 percent
formaldehyde used;
and
• Fugitive--0.03 to 0.2 kg/Mg of 37 percent formaldehyde used;
Urea-formaldehyde and M-F production plants may vary in configuration and
level of control. The level of control on formaldehyde storage emissions
12
should be 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 its emissions.
28
-------
Source Locations
Major U-F resin producers and production locations are listed in
Table 5. Table 6 lists major M-F resin producers and production locations.
PHENOL-FORMALDEHYDE RESIN PRODUCTION
Phenol-formaldehyde resins are formed by polymerization of phenol and
formaldehyde. The two major resin types are 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 that require mixing with formaldehyde or a
formaldehyde donor such as hexamethylenetetramine to produce a
thermosetting product. Novolak products Include thermosetting resin
18
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 I), 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 using
18
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.
29
-------
TABLE 5. PRODUCTION OF UREA-FORMALDEHYDE
RESINS1*
Manufacturer
Location
Allied Corp.
The Bendlx Corp., subsld.
Friction Material 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 Chem. Div.
Cargill, Inc.
Chem. Products Div.
Celanese Corp.
Celanese Plastics & Specialties Co., div.
Celanese Specialty Resins, div.
Clark Oil & Refining Corp.
Clark Chem. Corp., subsid.
C.N.C. Chem. Corp.
Green Island, N.Y.
Mobile, AL
Wallingford, CT
Charlotte, NC
Mount Holly, NC
Elizabethport, NJ
*>
Hope Valley, RI
Demopolis, AL
01 boll, 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
Louisville, KY
Blue Island, IL
Providence, RI
(CONTINUED)
-------
TABLE 5. (continued)
Manufacturer
Location
Commercial Products Co., Inc.
Consolidated Papers, Inc.
Consoweld Corp., subsid.
Glasvrit America, Inc.
Cook Paint and Varnish
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)
31
-------
TABLE 5. (continued)
Manufacturer
Location
Guardsman Chems., Inc.
Gulf Oil Corp.
Gulf Oil Chems. Co.
Indust. Chems. 01v.
Mi 11 master Onyx Group, subsid.
Lyndal 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 Oiv.
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, UI
Portland, OR
Savannah, GA
Totowa, NJ
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)
-------
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 Oiv.
Scott Paper Co.
Packaged Products Oiv.
Southeastern Adhesives Co.
The Standard Oil Co. (Ohio)
Sohio Indust. Products Co., div.
Dorr-Oliver, Inc., unit
Sun Chem. Corp.
Chems. Group
Chems. Div.
SUS Chera. 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)
33
-------
TABLE 5. (continued)
Manufacturer Location
Sybron Corp.
Chem. 01v.
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 - Chem. 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 existance of particular facilities by consulting
current listings and/or the plants themselves. The level of
formaldehyde emissions from any given facility 1s a function of
variables such as capacity, throughput, and control measures and should
be determined through direct contacts with plant personnel.
-------
TABLE 6. PRODUCTION OF ME1AMINE
RESINS"
-FORMALDEHYDE
Manufacturer
Location
American Cynamld Co.
Polymer Products Div.
Formica Corp., subsid.
American Hoechst Corp.
Indust. Chems. Div.
Auralux Chera. Associated, Inc.
Borden Inc.
Borden Chem. Div.
Adheslves and Chems. 01v.
Cargill, Inc.
Chem. Products Div.
Celanese Corp.
Celanese Plastics & Specialties Co., dlv.
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)
-------
TABLE 6. (continued)
Manufacturer
Location
Eastern Color & Chem. Co
Gen. Electric Co.
Engineered Materials Group
Electromaterlals 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
Lufkln, 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)
-------
TABLE 6. (continued)
Manufacturer
Location
Perstorp, Inc.
Plastics Mfg. Co.
PPG Indust., Inc.
Coatings and Resins 01v.
Reichhold Chems., Inc.
Scott Paper Co.
Packaged Products 01v.
Sun Chem. Corp.
Chems. Group
Chems. Dlv.
Synthron, Inc.
Tyler Corp.
Reliance Universal, Inc., subsid.
Specialty Chems. and Resins Dlv.
United Merchants & Mfgs., Inc.
Valchem - Chem. Dlv.
U.S. Oil Co.
Southern U.S. Chem. Co., Inc., subsid.
Valspar Corp.
McWhorter, Inc., subsid.
Westlnghouse Electric Corp.
Insulating Materials D1v.
Florence, MA
Dallas, TX
Clrclevllle, 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
Morganton, NC
Louisville, KY
Langley, SC
East Providence, RI
Rock Hill, SC
Baltimore, MD
Manor, PA
(CONTINUED)
37
-------
TABLE 6. (continued)
Manufacturer Location
West Point-Pepperell, Inc.
Grifftex Chem. Co., subsid. 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.
-------
SCALE
PHENOL STORAGE
FORMALDEHYDE STORAGE
pH MODIFIER-
<*>
REACTOR
STEAM
COLD WATE
COOLING
CARRIAGE
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.^
39
-------
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
18
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 be blended with fillers and additives before it is readied
18
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 acidic conditions are used, a vacuum reflux system must be used
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.
40
-------
During the production of solutions used In varnishes and laminating
agents, solvent is also added in the reactor. The solutions are packaged
18
in 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 washing reactor
kettles. Water washing of some resols during product preparation may
18
produce formaldehyde emissions. Uncontrolled formaldehyde emission
factors for the production of phenol-formaldehyde resins have been
estimated as follows:8'12
• Process--0.15 to 1.5 kg/Mg of 37 percent formaldehyde used;
• Formaldehyde Storage--0.03 to 0.2 kg/Mg of 37 percent formaldehyde
used; and
• Fugitive--0.03 to 0.2 kg/Mg of 37 percent 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 its
emissions.
Source Locations
Major phenol-formaldehyde resin producers and production locations are
listed in Table 7.
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
(-OCH--), while the copolymer has the oxymethylene structure occasionally
18 20
interrupted by a comonomer unit such as ethylene. ' Polyacetal resins
41
-------
TABLE 7. PRODUCTION OF PHENOL
RESINSIb
-FORMALDEHYDE
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)
-------
TABLE 7. (continued)
Manufacturer
Location
CPC Internat'l Inc.
CPC North America D1v.
Indust. Diversified Unit
Amce Resin Corp.
The Dexter Corp.
Midland D1v.
General Electric Co.
Engneered Materials Group
Electromaterlals Business Dept.
The P.D. George Co.
Georgia-Pacicfic Chemical Group
Getty Oil Co.
Chembond Corp., subsid
Gulf Oil Corp.
Gulf Oil Chems. Co.
Indust. Chems. Div.
Hereslte-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
Lufkln, TX
Newark, OH
Peachtree City, GA
Port Wentworth, GA
Russellvllle, SC
Taylorville, MS
Uklah, CA
Vienna, GA
Andalusia, AL
Spokane, WA
Springfield, OR
Winnfleld, LA
Alexandria, LA
Manltowoc, WI
(CONTINUED)
43
-------
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 Internat'l Inc.
Libby-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.
Nies Chem. Paint Co.
Kordell Indust., div.
The O'Brien Corporation-Southwestern
Region
Long Beach, CA
Alsip, IL
Columbus, OH
Bridgeville, PA
Moundsville, AL
Auburn, ME
Gulfport, MS
Cordova,IL
Cottage Grove, MN
Kankakee, IL
Rochester, NY
De Kalb, IL
Tonawanda, NY
Addyston, OH
Chocolate Bayou, TX
Eugene, OR
Santa Clara, CA
Springfield, MA
Mishawaka, IN
Houston, TX
(CONTINUED)
44
-------
TABLE 7. (continued)
Manufacturer
Location
Occidental Petroleum Corp.
Hooker Chem. Corp., subsid.
Plastics & Chem. Specialties Group
Durez Materials Resins & Molding
Owens-Corning Fiberglass Corp.
Resins & Coatings Oiv.
Plastic Engineering Co.
Polymer Applications, Inc.
Polyrez Co., Inc.
Raybestos-Manhattan, Inc.
Adhesives Oept.
Reichhold Chems., Inc.
Vacuum Div.
Rogers Corp.
Schenectady Chems., Inc.
The Sherwin-Williams Co.
Chems. Oiv.
Kenton, OH
North Tonawanda, NY
Barrlngton, NJ
Kansas City, KS
Newark, OH
Uaxahacie,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)
45
-------
TABLE 7. (continued)
Manufacturer
Location
Simpson Timber Co.
Oregon Overlay Div.
The Standard Oil Co. (Ohio)
Sohio Indust. Products Co., div.
Dorr-Oliver Inc., unit
Union Carbide Corp.
Coatings Materials Div.
United Technologies Corp.
Inmont Corp., subsid.
Valentine Sugars, Inc.
Valite Oiv.
West Coast Adhesives Co.
Vlestinghouse Electric Corp.
Insulating Materials Div.
Micarta Div.
Weyerhaeuser Co.
Portland, OR
Niagara Falls, NY
Bound Brook, NJ
Elk Grove, CA
Anaheim, CA
Cincinnati, OH
Detroit, MI
Lockport, LA
Portland, OR
Manor, PA
Hampton, SC
Longview, WA
Marshfield, WI
Note: This listing is subject to change as market conditions change, facility
ownerships change, 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.
46
-------
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
semiformals, 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 nonvolatile
polyols or by freeze-trapping slightly above the boiling point of
18
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
18
groups. The final product is 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. Stabilization is accomplished by copolymerization with
18
cyclic ethers.
The final polymer is extruded. Additives may be added during
extrusion. Extruded molten polymer strands are quenched in a water bath and
then pelletized and stored.
Emissions
Formaldehyde emissions may result from the storage of aqueous
formaldehyde solution (Vent A, Figure 8) prior to feed preparation. The
major source of process and fugitive emissions is the feed preparation step
47
-------
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(Source B). Formaldehyde emission factors from the production of polyacetal
12 14
resins have been reported as follows: '
• Process -- 0.09 to 0.37 kg/Mg of 37 percent formaldehyde used;
• Formaldehyde Storage--0.02 to 0.03 kg/Mg of 37 percent formaldehyde
used; and
• Fugitive--0.02 to 0.36 kg/Mg of 37 percent 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 its emissions.
Source Locations
Major polyacetal resin producers and their locations are listed in
Table 8.
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 a component 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 to
produce 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 the reactants, the
21
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.
49
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Emissions
Formaldehyde emission sources Include off-gases from the reactor,
22
waste water from the centrifuge wash bleed line, and the drier vent.
Formaldehyde emission factors from the production of hexamethylenetetramine
o
have been estimated as follows:
• Process--0.38 kg/Mg of 37 percent formaldehyde used;
• Formaldehyde Storage--0.05 kg/Mg of 37 percent formaldehyde used;
and
• Fugitive--0.11 kg/Mg of 37 percent formaldehyde used.
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 the emissions.
Source Locations
Major producers of hexamethylenetramine and their production locations
are listed in Table 9.16
PENTAERYTHRITOL PRODUCTION
Pentaerythritol is used in the production of alkyd resins and oil-
based 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
12
produced onsite at some plants for direct use as a feedstock in this process.
Pentaerythritol 1s made by the condensation reaction of formaldehyde and
acetaldehyde in the 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
52
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exothermic reaction takes place. External cooling is used to control the
temperature at about 25"C for several hours, and it 1s 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 a salt, which can
21
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 the
21
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 including
21
polypentaerythri tol s.
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 to 2.7 kg/Mg of 37 percent formaldehyde used;
• Formaldehyde Storage--0.002 to 0.33 kg/Mg of 37 percent formaldehyde
used; and
• Fugitive--0.14 to 0.15 kg/Mg of 37 percent 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 its emissions.
Source Locations
Major producers of pentaerythritol and their production locations are
listed in Table 10.
55
-------
TABLE 10. PRODUCTION OF
PENTAERTHRITOL™
Manufacturer Location
Celanese Corp.
Celanese Ceh. Corp., Inc. Bishop, TX
Hercules Inc.
Operations Div. Louisana, MO
Internat'l Minerals & Chem. Corp.
IMC Chem. Group
Indust. Chems. 01 v.
Perstorp Inc.
Seiple, PA
Toledo, OH
Note: This listing 1s subject to change as market conditions change,
facility ownerships change, 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.
-------
1,4-BUTANEDIOL PRODUCTION
1,4-Butanediol 1s 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 1s added during the exothermic hydrogenation reaction to control the
25
reaction temperature.
Emissions
Formaldehyde emission factors from the production of 1,4-butanediol have
8 12
been estimated as follows: '
• Process--Z-0.74 kg/Mg of 37 percent formaldehyde used;
• Formaldehyde Storage--0.005 to 0.2 kg/Mg of 37 percent formaldehyde
used; and
• Fugitive--0.005 to 0.2 kg/Mg of 37 percent 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 contact plant personnel to confirm the
existence of emitting operations and control technology at a particular
facility prior to estimating its emissions.
Source Locations
Major producers of 1,4-butanediol and their locations are listed in
Table 11.
TRIMETHYLOLPROPANE PRODUCTION
Trimethylolpropane is used primarily in the production of urethane
coatings and resins. It is also used in some synthetic lubricants.10
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.24
57
-------
TABLE 11. PRODUCTION OF
M-BUTANEDIOL™
Manufacturer Location
BASF Wyandotte Corp.
Indust. Chems. Group
Intermediate Chems. Div. Geismar, LA
E.I. DuPont de Nemours & Co., Inc.
Chems. and Pigments 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
ownerships change, 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.
-------
Emissions
Formaldehyde emission factors from the production of trimethylolpropane
o
have been estimated as follows:
• Process--0.074 kg/Mg of 37 percent formaldehyde used;
• Formaldehyde Storage--0.01 kg/Mg of 37 percent formaldehyde used; and
• Fugitive--0.01 kg/Mg of 37 percent 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 its emissions.
Source Locations
Major producers of trimethylolpropane, which are published in the SRI
Directory of Chemical Producers for 1983, are listed below:
• Uitco Chem. Corp.
Organics Div. Houston, TX
• Atlantic Richfield Co.
Anaconda Indust. Div.
Aluminum Div. West Chester, PA
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.
4,41-METHYLENEDIANILINE PRODUCTION
4,41 -Methylenedianiline (MDA) is formed by condensation of aniline and
formaldehyde. MDA is usually converted into methylenediphenyl isocyanate (MDI)
23
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 4 hours. The reaction mixture is chilled again, and
59
-------
TABLE 12. PRODUCTION!)^,.
4,4-METHYLENDIANILINE1^'10
Manufacturer Location
ICI Americas Inc.
Rubicon Chems. Inc., subsld. Geismar, LA
011n Corp.
011n Chems. Group Moundsvilie, WV
Un1royal Inc.
Uniroyal Chem., Dlv. Naugatuck, CT
The Upjohn Co.
Polymer Chems. Dlv. La Porte, TX
Note: This listing is subject to change as market conditions change,
facility ownerships change, 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.
-------
the product is 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.
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
26
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 been
27
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:
• Uncontrolled -- 2.1 kg/Mg of phthalic anhydride
• 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 its emissions.
60
-------
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Source Locations
Major phthalic anhydride producers and their locations are listed In Table
13.16
USE OF FORMALDEHYDE-BASED ADDITIVES (FBA's) IN SOLID UREA AND UREAFORM
FERTILIZER PRODUCTION
Formaldehyde 1s used 1n the production of conditioning agents for solid
urea and 1n the production of ureaform fertilizers. Solid urea Is used as a
fertilizer, as a protein supplement 1n animal feeds, and In plastics
manufacturing.
Solid urea is produced by first reacting ammonia and C0~ to form an
aqueous urea solution. This solution 1s 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 equipment is used. Pan granulators are not common in this country.
Just prior to solids formation, formaldehyde-based additives (FBA's) 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 FBA's in the fertilizer industry are formalin and urea-
formaldehyde (U-F) concentrates. Formalin is an aqueous formaldehyde solution
stabilized with methanol, whereas U-F-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
63
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Is usually added to urea at a level of 0.3 to 0.5 weight percent
formaldehyde.
Ureaform Is a slow-release fertilizer produced from a mixture of urea,
U-F-concentrate, sodium hydroxide, and water. The reaction to produce ureaform
is Initiated by adding acid, forming a wide distribution of methylene-urea
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.-"-»-"' 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,
both 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
FBA's to the urea process or during maintenance operations on equipment
containing or contaminated with FBA's.
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
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:
• Getty Oil Co. (Hawkeye Chemical Co.)
• Hercules, Inc.
• Kaiser Aluminum & Chemical Corp.
• Lebanon Chemical Corp.
• O.M. Scott & Sons
• W.R. Grace & Co.
65
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TABLE 14. FORMALDEHYDE EMISSIONS.FACTORS FOR
SOLID UREA PRODUCTION"'•"'*
Emission source
Uncontrolled
formaldehyde
emission
factorP>c (kg/Mg)
Percent
control
efficiency"
Controlled
formaldehyde
emission factor"'c
(Kg/Mg)
Fluidized bed
prilling
agricultural grade
feed grade
0.009S
0.0020
95.4
74.8
0.0004
0.0005
Drum granulation
0.0055
50.2
0.0027
aAny 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 its emissions.
"These data were collected by the chromotropic analysis method, which is not
selective for free formaldehyde. Thus, these emissions factors are for
total formaldehyde present, whether in free form or tied up in chemical
compounds such as methylenediurea (MDU).
cEmission factors refer to kilograms of formaldehyde emitted per megagram of
solid urea produced.
dControl efficiencies are for wet scrubbers.
-------
Producers of formaldehyde, which is usually sold as an aqueous solution called
formalin, are listed previously in Table 4.
MISCELLANEOUS RESIN APPLICATIONS
General
Resins produced from formaldehyde find a wide range of applications. Over
65 percent of U-F resins are used as adhesives in the production of
particleboard, medium-density fiberboard, and hardwood plywood. The U-F resins
are also used to produce home insulation, which 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 applications outside the construction
industry. These other uses each account for less than 5 percent of the U-F
34
resins produced.
Almost 50 percent of phenol-formaldehyde (P-F) resins are used in the
production of structural wood panels (soft plywood, oriented strandboard) 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 me!amine-formaldehyde (M-F) resins
produced are used for high-pressure laminates such as counter and table tops.
The M-F resins are also compression molded to form dinnerware. The 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. The U-F 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 M-F resins.
Formaldehyde emissions occur during resin applications in production
processes as well as during the use of products that contain these resins. For
example, the use of U-F resins in the production of paneling and furniture
67
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often results In emissions of formaldehyde in the factories where these
products are made. Offgasing of formaldehyde may also occur during the use of
these products by consumers. One source reports that most of the unreacted
formaldehyde 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 (particleboard and plywood) 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.
Pressed-wood Manufacturing--
Emissions from pressed-wood products result as compounds in the resin used
to bind the chips evaporate when heated. These emissions usually exit through
exhaust fans mounted on the roof above the presses. Georgia Pacific's
hardboard plant in Lebanon, Oregon, is the only plant in the country attempting
to control emissions from the press vents. A spray chamber containing 80 spray
nozzles continuously sprays the exiting press vent gases with water to remove
fine particulate matter from the exhaust gas. The spray chamber, installed in
1972, has never been tested, so no information is available regarding pollutant
removal efficiencies.
The type of resin used and, thus, the compounds present in its formulation
vary depending upon the type of panel being manufactured. The U-F resins are
primarily used in the production of particleboard and medium-density
fiberboard. These panels typically contain 8 to 9 percent (w/w) resin. The
U-F resin is used in applications where the final product will not be subject
to weathering. The P-F resins are used in the production of particleboard,
waferboard (WB), and oriented strand board (OSB). Structural particleboard
made with P-F resins contains approximately 7 percent (w/w) resin, and WB and
OSB contain approximately 2 percent (w/w) resin. The P-F resins are more
resistant to moisture than U-F resins.
The National Council of the Paper Industry for Air and Stream Improvement
(NCASI) published two technical bulletins in 1986 that investigated the release
38 39
of formaldehyde from press vents in the wood panel board industry. ' One
NCASI study concluded that three major factors affect the release of
formaldehyde from press vents: (1) the excess formaldehyde content of the
68
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resin, (2) the amount of resin used, and (3) the press temperature.38 jhese
factors are discussed below.
Excess formaldehyde Is the amount of formaldehyde in the resin in excess
of the amount required for stolchlometrlc reaction with the urea or phenol In
the resin. The emission rates have been shown to Increase in proportion to the
Increase In the free formaldehyde content of the resin. The excess or free
formaldehyde contents of resins are often held proprietary by resin
manufacturers. NCASI showed that where such Information was available, the
data Indicated that 5 to 15 percent of the excess formaldehyde in the
38
panelboard was emitted during the pressing and board cooling operations.
One method to determine the potential of resins to emit formaldehyde
during partlcleboard manufacture would be to use the excess formaldehyde
content of the resin (calculated on the basis of the amount of formaldehyde In
excess of the amount needed to react stolchlometrlcally with the other reactive
constituents in the resins). However, resin manufactures will not divulge
sufficient Information about their resins to allow these calculations to be
made.
The NCASI study showed that the emission rate of formaldehyde Increased In
proportion to the amount of resin used In the panelboard and the press
temperature. The formaldehyde emission factors ranged between 0.30 and 0.75
38
lb/thousand square feet of product using U-F resin.
The NCASI study also showed that the formaldehyde emissions from
partlcleboard press vents are related to the amount of excess formaldehyde In
the unpressed boards loaded Into the press. It would appear that formaldehyde
emission rates could be reduced by using less excess formaldehyde In the resin.
The Industry has already decreased the amount of excess formaldehyde In resins
In order to reduce the emissions of formaldehyde from the finished product into
the living or work space. This reduction of excess formaldehyde in the resin
also resulted in longer press times and, hence, reduced production rates.
In an effort to eliminate the potential for formaldehyde emissions,
methylene diphenyldiisocyanate (MDI) resins have been used by some
manufacturers. The MDI resins produce a higher-strength panel than do the U-F
or P-F resins. Therefore, manufacturers are able to use less MDI resin to meet
the industry's product standards. However, MDI resins are much more expensive
than U-F or P-F resins, and panels produced with MDI resins tend to stick to
the presses. Two approaches have been used to prevent the panels from
69
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sticking. One is to spray the presses lightly with an antisticking agent
between press cycles. Another approach 1s to use U-F or P-F resins to blind the
material on the two outer surfaces of the panel. The core of the panel is
bound with the MDI resin. This reduces the amount of formaldehyde available to
volatilize, and the panel retains the structural strength provided by the MDI
resin.
Two recent tests for VOC emissions at Louisiana Pacific plants shed
some light on the level of VOC emissions that might be expected from press
vents.40
VOC EMISSION FACTORS FOR PRESS VENTS40
VOC emission
factor, Ib
Plant Resin VOC/ton product.
Hayward, Wis. 100 percent MDI 0.36
Sagola, Mich. 50 percent liquid P-F for 0.56
surface and 50 percent
MDI for the core
This data can be used to estimate VOC emissions for 100 percent P-F resin,
since data collected by Interpoll Labs has shown that the MDI is not
volatilized. This being the case, the 100 percent MDI test VOC emission factor
is indicative of the VOC's emitted from the wood itself (EJ, and the 50:50
test corresponds to the VOC's emitted from the wood and from the P-F resin in
the surface (E ). The general relationship 1s shown below:
Et * Ew+Ec+Es*EMDI>
where:
E. - total VOC emission factor;
E • VOC emission factor due to VOC's emitted from the wood;
E. - VOC emission factor due to VOC's emitted from P-F resin in the
core;
VOC ei
surface; and
E - VOC emission factor due to VOC'S emitted from P-F resin on the
70
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EMDI - VOC emission factor due to volatilization of MDI - 0.
In the case where 100 percent MDI was used:
and thus:
Ec - Es ' EMDI
0.36 - Ew+0+0+0
Ew - 0.36 Ib VOC/ton product.
This is equivalent to saying that the use of 100 percent MOI allows estimation
of the base VOC emission factor for the wood in the board. A plant using 50
percent MDI (in the core) and 50 percent P-F resin (on the surface) is
represented in terms of the general equation as follows:
0.56
Since E - 0.36 and E - 0 because MDI was used in the core, then:
0.56 - 0.36+0+ES, and
Es - 0.20 Ib VOC/ton product.
Now, if it may be assumed that EC =s E$ (which is a very safe assumption, since
loss of P-F from the core is much less likely than loss of P-F from the surface
of the waferboard), then the total VOC emission factor where 100 percent P-F is
used may be calculated as follows:
Et * Ew"l"Ec"*"Es *
where:
Ew - 0.36;
Es - 0.20;
Ec «;0.20;
Et - 0.36+0.20-^20.20, and
Et <; 0.76 Ib VOC/ton product.
This analysis suggests that use of MDI resins instead of P-F resins would
result in a reduction of at least 50 percent in VOC emissions.
In addition to press vents, wood furnish dryers are also sources of
formaldehyde emissions. In a study by NCASI designed to determine the emission
rates of formaldehyde and other compounds emitted from wood furnish dryers, a
range of typical emission factors were developed for use in preparing emission
41
estimates for air discharge permits. The study indicates that the
concentration of formaldehyde in the dryer exhaust is a function of the dryer
inlet temperature. The formaldehyde emission rate at dryer inlet temperatures
71
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below 900*F was less than 0.085 Ib/ton of product. At Inlet temperatures; above
1000'F, the formaldehyde emission rates ranged from 0.01 to 1.1 Ib/ton of
product.
Furniture Manufacturing--
In the absence of furniture plant formaldehyde emissions data, the
available range of partlcleboard manufacturing formaldehyde emissions data may
be used to predict a worst-case formaldehyde emissions estimate for furniture
manufacturing. This estimate 1s possible because both Industries use similar
U-F adhesive resins and both utilize board pressing operations at elevated
temperatures and pressures.
However, in furniture plants It 1s possible that a smaller percent of the
excess formaldehyde in the adhesive resin 1s emitted than In partlcleboard
plants. Formaldehyde emissions from furniture plants are probably lower
because: (1) presses In furniture plants operate at much lower temperatures,
(2) furniture presses have somewhat shorter cycle times than those In
partlcleboard plants, and (3) the physical configuration of furniture pieces Is
different than that of particleboards. (In a furniture piece, a veneer barrier
protects the major glue surface from direct exposure to air, while no such
continuous barrier inhibits formaldehyde evaporation during the particleboard
42
pressing cycle.)
Urea-Formaldehyde Foam Insulation Manufacturing--
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 between the
g
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 1982, the Consumer
Products Safety Commission (CPSC) placed a ban on the use of UFFI. However,
44
the ban was overturned in August 1983 and CPSC declined to appeal it.
Sufficient information was not found to estimate emission rates from resin
and resin product uses in actual applications.
72
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Source Locations
SIC codes for miscellaneous manufacturing applications of resins are
listed in Table 15.
MANUFACTURING MINOR PRODUCTS USING FORMALDEHYDE AS A FEEDSTOCK
General
Formaldehyde 1s used in a wide range of Industrial and consumer
applications. Because formaldehyde 1s 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 1s used by
the textile, leather, and dye industries. Because of Us lighter weight and
lower shipping costs, much of the paraformaldehyde 1s 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
1s used as a solvent in the manufacture of some Pharmaceuticals 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 1s the condensation of nltromethane with formaldehyde
to give 2-nitropropane-3, 3-diol, which can be brominated to
2-bromo-2-nitropropane-l, 3-diol, an antimicrobial preservative used in some
consumer products such as aerosol insecticides. These condensation products
formed from nltroparaffins and formaldehyde regenerate formaldehyde in the
presence of alkali.
A small amount of formaldehyde is used to produce sodium formaldehyde
bisulfite and sodium formaldehyde sulfoxylate for use in making dyes
for the textile industry.
73
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TABLE 15. STANDARD INDUSTRIAL CLASSIFICATION CODES
MANUFACTURING PROCESSES ENGAGED IN RESIN APPLICATIONS
Resin and use SIC code
Urea-Formaldehyde
Particleboard 2492
Fibreboard 2661
Interior plywood 2435, 2436
Foam Insulation 1742,2899(1nsulat1ng compounds)
Textiles 22, 23
Paper 26
Surface coatings 2641, 2851, 3479
Adhesives 2891
Phenol-Formaldehyde
Outdoor plywood 2435, 2436
Molding compounds 2821
Insulations 2899 (Insulating compounds)
Foundry molds 3565
Laminates 2435, 2436, 2439
Particleboard 2492
Friction materials 3499
Abrasives 3291
Polvacetal
Plumbing fixtures 3079
Hardware 3079
Sporting goods 3949
Mel ami ne-Formaldehvde
Countertops 2541, 2542
Dinnerware 3079 (dishes, kitchenware)
Surface coatings 2641, 3479
70.
-------
Phenolic resins containing formaldehyde are an additive used in the
production of tires. The formaldehyde is believed to remain in the tire as
45
part of the product.
Emissions
Paraformaldehyde has a tendency to decompose and release formaldehyde gas.
In most other forms, formaldehyde gas will only be released 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.
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 that 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. The textile
75
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industry uses finishing agents containing formaldehyde to treat fabric and give
it a desired surface effect (i.e., flame resistance, crease-proofing, moth-
45
proofing, water repellency, shrink-proofing).
Electro!ess plating is a process used for plating surfaces with nickel,
copper, or silver that does not employ the use of electrolysis. The process
includes etching, neutralizing, catalysis, acceleration, and electro!ess bath.
The electroless bath for copper and silver usually contains formaldehyde which
acts as an oxidizing agent. Among the products produced by electroless plating
are auto parts, circuit boards, mirrors, and architectural reflective glass.
Mirror production is the largest application for electroless silver. There are
also a few specialty applications in the electronics industry for electroless
gold and platinum. In a 1985/1986 metal finishing industry job shop industry
profile the information collected indicated that 22 percent of all job shops in
the U.S., or approximately 885 shops, offered electroless plating of one type
or another.
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 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 or commercial uses of formaldehyde.
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.
78
-------
Combustion processes have been grouped into five general categories for
the purposes of compiling formaldehyde emission factors. These categories are
(1) external combustion in boilers and space heaters, (2) external combustion
in industrial process heaters, (3) internal combustion in stationary sources,
(4) incineration and open burning, and (5) internal combustion in mobile
source. 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 EPA on
locating combustion sources and 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 unit 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 Public Health
Service in the early 1960's. As noted above, emissions vary from source to
source depending on a number of parameters. Measurements of total aldehyde
emissions illustrate the variability that 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
52-54
natural gas combustion.
A few studies have been performed to measure formaldehyde emissions from
domestic wood-burning fireplaces and stoves. Current best estimates
indicate that approximately 23.3x10 metric tons of wood are burned annually in
fireplaces and wood stoves. A few formaldehyde measurements were made by
DeAngelis et al. on wood-burning fireplaces and stoves. Their data indicated
that formaldehyde emissions ranged between 0.1 and 0.4 g/kg of wood burned.
They found that wood type and combustion equipment design had very little
79
-------
TABLE 17. FORMALDEHYDE EMISSIONS,FROM EXTERNAL COMBUSTION
SOURCES31
Emission factor
(ng/J)
Coal fired sources
Pulverized coa1a 0.048
Chain grate stoker" 0.060
Spreader stoker0. 0.095
Underfed stokerd 0.53
Hand stoked6 0.027
Oil-fired sources
Residual o11f 0.069
Distillate oil9 0.10
Natural oas-flred sources
Industrial*1 . 0.038
Commercial/Institutional1 0.095
Domestic^ 0.43
jBased on testing of two units with firing rates of 1,640 GJ/hr and 140 GJ/hr.
bBased on testing of a unit with a firing rate of 155 GJ/hr.
'•Based on testing of a unit with a firing rate of 62 GJ/hr.
dBased on testing of two units with firing rates of 4.6 GJ/hr and 3.2 GJ/hr.
|Based on testing of a unit with a firing rate of 0.12 GJ/hr.
'Based on testing of steam-atomized unit with a firing rate of 15 GJ/hr.
jjBased on testing of 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.
BBased on testing of a unit with a firing rate of 1.0 GJ/hr.
JBased on testing of three units with a firing rates of 0.19 GJ/hr,
0.18 GJ/hr, and 0.013 GJ/hr.
80
-------
effect on formaldehyde release. In another study, Snowden et al. reported
emissions of 0.3 to 11 g of formaldehyde/kg of wood burned. A study
performed by the General Motors Research laboratory Indicated that total
aldehyde emissions from wood-burning fireplaces varied by a factor of 4 from
0.6 to 2.3 g/kg of wood burned and that formaldehyde emissions ranged from 21
to 42 percent of the total aldehyde emissions. This body of information
suggests that nationwide formaldehyde emissions from domestic wood-burning
fireplaces and stoves may range from 2.33x10 to 2.56x10 metric tons per year.
Techniques that 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 ensure 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 are generally
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
CO
oil-gas mixtures have been measured at about 2.2 ng/J. Aldehyde
emissions from natural gas combustion and oil combustion have been
estimated to be 100 percent and 70 percent by weight formaldehyde,
respectively. Based on these data, an emission factor of 1.9 ng/J 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
that control total hydrocarbon and CO emissions. These techniques include the
use of operating measures that ensure complete combustion as well as periodic
burner maintenance and tuning.
81
-------
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
59
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
eg
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 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 various incinerators
and for open burning of waste materials. Data were not available on the
fraction of aldehyde emissions made up of formaldehyde; however, formaldehyde
has been estimated to comprise 70 to 100 percent of total aldehyde emissions
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 with
combustion controls, periodic maintenance, and 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.
82
-------
TABLE 18. FORMALDEHYDE EMISSIONS FROM STATIONARY INTERNAL
COMBUSTIONS ENGINES5*'60
Formaldehyde emissions
Gas turbines
Gas fired reciprocating engines
Gasoline and diesel -powered
industrial equipment
ng/Joul e
heat input
4.0
5.7
13.2
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 BURNING4'3
Apartment incinerators
Domestic incinerators
Backyard burning
Aldehyde emissions
(9/kg)
Average Range
value
2.5 1-4
2.0 0.1-8
5.2 1-14
aData 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.
83
-------
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
61 62
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 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
aldehyde emissions from gasoline and diesel fuel combustion.
Techniques 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.
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 that 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 510*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.
84
-------
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35
-------
TABLE 20. FORMALDEHYDE EMISSIONS FROM TRANSPORTATION SOURCES
Formaldehyde emission;;
g/gal mg/km
Automobiles8
Catalyst5 . 0.05-0.83 2-32
Noncatalystc'd 0.83 32
Diesel0 0.33 13
Other ground transportation
Heavy-duty gasoline vehicles0 0.64 76
Heavy-duty diesel vehicles0 0.55 55
Locomotives6 1.5
Motorcycles: 2-cycleeȣ 3.3 41
4-cyclee»f 1.4 17
Snowmobiles6 5.9
Aircraft
Jet9 1.9
Turboprop or piston^ 1.6
aAn average fuel mileage for ay
.convert from mg/km to g/gal.63
tomobiles of 16 miles/gal was used to
5Use lower value for newer, low-milage cars and higher value for
high-milage cars 61»6Z
^Reference 61.
"All cars are tuned to manufacturer's specifications.51 Malfunctioning
vehicles may emit considerably higher levels.65
Emissions were calulated using aldehyde emissions data64 and assuming
aldehyde emissions are 60 percent formaldehdye.3
'An average fuel mileage for motorcycles of 50 mpg was used to
convert from mg/km to g/gal.63
^Emissions were calculated using aldehyde emissions data64 and assuming
aldehyde emissions are 70 percent formaldehyde.3
86
-------
TABLE 21. FORMALDEHYDE EMISSIONS FROM CONSTRUCTION AND FARM
EQUIPMENT8
Formaldehyde emissions
Gasoline-Dowered construction eau lament
Wheeled tractor
Motor grader
Wheeled loader
Roller
Miscellaneous
Gasoline-powered farm eauipment
Tractor
Miscellaneous
Diesel -oowered construction eauioment
Tracklaylng tractor
Wheeled dozer
Scraper
Motor grader
Wheeled loader
Tracklaying loader
Off -highway truck
Roller
Miscellaneous
Diesel -cowered farm eauioment
Tractor
Miscellaneous
g/gai
1.6
1.6
1.3
1.3
1.2
1.9
1.1
1.7
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
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
0.096
0.17
0.073
0.012
0.06
0.13
0.12
0.12
0.20
0.18
Emissions were calculated using aldehdye emissions data59 and the
assumption that aldehyde are 60 percent formaldehyde.3
Q7
-------
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
59
most newer refineries in place of gas-fired engines.
The total amount of fuel burned at a refinery depends 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 (GJ) 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.
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
58 59
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
59
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
59
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 CO concentration. Emissions of CO
generally are controlled using CO waste heat boilers. Entrained catalyst
59
particles are generally controlled by electrostatic precipitators (ESP's).
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 580*C. Flue gas from the fluid
coker burner off-gas contains incomplete combustion products including a large
amount of CO. Carbon monoxide emissions generally are controlled by passing
the flue gas through a CO waste heat boiler.
89
-------
Emissions
Formaldehyde 1s 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
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
58
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
58
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.
90
-------
TABLE 22. FORMALDEHYDE EMISSIONS FROM PETROLEUM
REFINING58'3
Source Emission factor
Combustion Sources
Gas-fired external combustion
011-fired external combustion
Gas fired reciprocating engine see COMBUSTION SOURCES
01I/gas mixture fired process heater
Catalytic Cracking
FCC regenerator with CO boiler/ESP 2.2 kg/1000 bbl fresh feed
Moving bed (TCC) regenerator with 1.0 kg/1000 bbl fresh feed
CO boiler/ESP
Coking
Fluid coker burner with CO boiler/scrubber 0.54 kg/1000 gal bbl fresh feed
aPetroleura refineries may vary 1n 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 establishing its emissions.
91
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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 per
day.66
ASPHALTIC CONCRETE PRODUCTION AND USE
Asphalt plants or asphaltic concrete plants are used to produce hot mix
asphalt paving. This product is a mixture of well graded, high quality
aggregate and liquid asphaltic cement which is heated and mixed in measured
quantities to produce bituminous pavement material. Hot mix asphalt paving can
be manufactured by batch mix, continuous mix, or drum mix process.
In recent years, recycling of old asphalt paving has been initiated in the
asphaltic concrete industry. In recycling, old asphalt pavement is broken up
at a job site and is removed from the road base. This material is then
transported to the plant, crushed, and screened to the appropriate size for
further processing. The paving material is then heated and mixed with new
aggregate, to which the proper amount of new asphaltic cement is added, to
produce a grate of hot asphalt paving suitable for laying.
The most significant source of emissions from asphalt plants is the rotary
dryer. Dryer fuels are typically natural gas and oil, including recycled or
waste oil. Dryer emissions contain the fuel combustion products of the burner
and aggregate dust carried out of the dryer by the moving gas stream. These
emissions consist of a substantial amount of particulate matter and lesser
amounts of gaseous volatile organic compound (VOC) of various species,
including formaldehyde. The formaldehyde emissions are from the incomplete
combustion of the dryer fuel and possibly from the liquid asphaltic cement.^
Source tests obtained from a single asphatlic concrete plant indicated
that asphalt plants with scrubbers have an average emission factor of
0.00015 pounds per ton of asphaltic concrete produced.^ For asphalt plants
with baghouses an emission factor was developed from four stack tests performed
in Wisconsin in 1989. During two of these tests, drum mix asphalt plants were
using 40 percent recycle and burning waste oil. For the other two tests,
stationary batch plants were using 20 percent recycle with one burning waste
oil and the other burning No. 2 oil. The emission rate from these plants
ranged from 0.0024 pounds per ton to 0.0071 pounds per ton and averaged
0.0036 pounds per ton.45
92
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TABLE 23. PETROLEUM REFINERIES68
Company «nd location
Alabama
Hum Oil Co. - Tuecafoooe
LouWene Und end Exploration Co. - Seraland
Morion Corp. - Theodore
MoMo Boy Refining Co. - Chkkaaew
Worrior Aephelt Co. of Mobomo Inc. - Hott
Atlanta
Atlantic RichfieU Corp. - Prudhoe Boy
Chovron U.S.A.. Inc. - Konoi
North Polo RofMng. Otv. of Mopeo - North Pete
Toooro Petroleum Corp- - Konoi
Ariiono
Arizona Fuoto Corp. - Fredenia
Arkaneaa
flii.ii Hall II|BI mi nil ilaiin. ^ l~ri i«l •! ("Ill t*n ntmiimtM
Borry I'airwoum. untoion o? i*ryetai UN (.0. — stevene
CroM Oil 4 Refining Co. of Arkaneae - Smackover
MacmiMan Ring-Free 04 Co. - Norphlot
Tosco Corp. - B Dorado
Colifemio
Anchor Refirvng Cl *• McKittrick
Atlantic RichfieU Co. - Coroon
Booeon Oil Company - Monford
Chomolin Polroloum Co. - Wilmington
Chowon U.3.A. Inc. - Bokannald
BSagtndo
Mctwwfo^
Douglao OH Co. - Santa Mario
Eeo Potroloum Inc. - Signal HW
Edgington Oil CI - Long Booeh
Exxon Co. - BanWo
Rotehor Oil * RofMng Co. - Coroon
Qotty RofMng 4 Marketing Co. - Bekorafiold
Oaldan Boor DivWon. Whoa Gnomical Carp. - Oridalo
OuM Oil Co. - Santa Fo Springe
Huntway Refining Co. - Bencio
inramingtoci
Independent Valley Energy Co. - BakoraneM
Kem Ca«My Refinery Inc. - Bakerefiold
Mariex OH 4 RofMng Inc. - Long Beach
Mob* Oil Corp. - Torranee
NewhoV Refining a - Newhetf
Oxnwd Refinery - Oxnard
Pacific Oaele - Parameuil
Poofie RofMng Ce. - Herculoo
Pewerino Oil Co. - Santo Fa Springs
S0Of9 nflnflefflQ Inc. "• Bo^MaWfMld
Shel Oil Co. - MortMn
Wilmington
Suiiand Refining Corp. - BokerafioU
Texaco Inc. - WUmingten
Toaco Carp. - Bakerefield
Mertinei
Union Oil Co. of CaMfemie - Lao Angalao
Rodeo
USA Petrechem Corp. - Ventura
Colorado
Aeamera Oil U.S. Inc. - Commerce City
Conoco Inc. - Commerce City
Gary Refining Co.- Frufte
(bW/atraam/dav)
47.600
11.300
27,000
30,000°
8.000
20.000
22,200e
46.600
61.063
6.600
A eUV)
•*t*r*«W
•,•60
8.000
48.000
• • /VVa
1 1 (wOU
213.000
18,230
62.600
26,000°
406,000°
366,000°
10.000
7,000°
44.730
112.000
30.600
64,700
11,600
17,200
63.800
7,600
8,000
28,600
23,000
20,000
130,000
23,000
6,000
48,000
46,000°
46,000
14,000
•4,000
113,000
16,000
78,400
40.000
128.000°
111,000
117.300
30,000
40,000
33,600
14.000
Rud coking charge
feed/stream/dayl
-
-
_
-
-
—
-
-
-
_
-
-
_
-
_
_
_
-
_
-
-
26,000
-
-
_
_
-
-
_
_
_
-
-
-
_
_
-
_
-
-
_
_
7.000
37,000
-
_
—
_
_
-
Catalytic cracking charge
fiw^atv ll^/fr^ah
G^P^Hty UMMfTT^OTl
feed/etream/davr
-
-
_
-
-
..
-
-
-
_
-
16,000*
68.00O*
_
30.000*
_
63,000*
63.000*
_
-
_
50,000*
10,000*
-
_
16,600*
_
_
-
_
_
61,000*
-
_
..
—
13, BOO*
_
60.OOO*
36.000*
_
28,000*
12,000B
47,000*
46.000*
_
-
8,000*
16.000*
-
(CONTINUED)
-------
TABLE 23. (continued)
Company •nd (ocMMfi
Oal«V»ara
OMty Rafining and Marketing Co. - Delaware CMy
Qeorni*
Amoco Oil C«. - Savannah
Young Booing Corp. - DouglaavHIe
Hawaii
Chevron U.S.A. Inc. - Barber'. Point
Hawaiian Independent Refinery Inc. - Ew« Such
IIHnoii
BkioMand
Hartford
Marathon OH Ca. - Robineon
Mobito Oil Corp. - Jokot
ShaN Oil Co. - Wood River
Toxoeo Inc. - LawieiiBovilli
Union Oil Co. of CaKfomie - LomoM
Indlono
Amoco Oil Co. - Whiting
OladMux Rofinory Inc. - Ft. Woyna
Indian* Form Buroou Cooporotivo
Aeeocietion Ine. - Mt. Vomon
Laketon Refining Corp. - Laketon
Rock Mend Refinng Corp. - IncKonopolio
Kana*»
Dwby RWWWIQ Co. •• WncnnA
FormUnd Induotrio* Inc. - CoffoyviNo
Qotty (Uflning A Morkotfng Co. - B Oorodo
Mobil* OH Corp. - AujuM
Pootor RonViing Co. - B Oorodo
Total Potroloum - Ariunso* City
Kontuefcv
A*Mand PMroloum Co. - Codottoburg LouwviH*
somonMf rWiHiory inc. ^ SMmonMt
Louioiono
Ad«B Pruroning Co., Drvioion of Ponraoil - Shrovoport
Cokjmot Rofkiing Co. - Princeton
C*nol Refining Co. - Chrich Point
Cotoron Oil 4 Qm - Mormontou
CHM Sonrieo Co. - L«k« Chonoo
Conoco Inc. - Lak* Chonoo
Cotton Voltey Hofinory Korr-McGo*
fWMng Corp.) - Cotton VoKoy
CPI RofMng Inc. - Late Ghana*
Exxon Co. - Baton fteuga
OUf OH Carp. - BoNo Chaaa*
Hi* Potroloum Ca. - Krott Spring*
rUrr McOaa Carp. - Dubaoh
Mallard Oaioureaa Inc. - Ouaydon
Marathon OH Co. - OaryviM*
Murphy OH Ca. - Marauc
Pladd RafMng Co. - Part AN*n
Pan Potroloum Inc. - StanawaH
Shal OH Ca. - Narea
Tamaca OH Co. - Chaknacta
Taxaeo Ine. - Convent
Crude refMng capacity
IbW/atraam day)
160.000
27,000
-
4«.000e
•7.000
60,000
80.000
2O6.000
200.000
296.000
M.OOO
167.000
400.000
20.000
22.100
1.600
44,600
30.000
80.723
•2,000
64,600
67,000
32.000
47.200
220,000
26,000
S.OOO
•2,600
•.600
7,»M
16,000
330.000
8,700
184,000
6,000°
17,600
474,000
206,000
60,000
11,000
8.000°
283.000
•6,400
66,000
4,000
226,000
120,000
147,000
Fluid caking oharg*
capacity IbW fraah
faad/atraam day)
44.000
-
-
-
_
_
_
_
_
_
-
-
-
-
-
-
—
_
_
_
,.
-
-
-
-
-
-
-
-
_
w
-
-
-
_
_
-
-
_
_
-
-
_
_
_
~
Catalytic cracking charge
capacity IbM froah
faad/etream day)**0
82.00O*
-
22.000*
-
26,000*
27,000*
M.OOO*
M.OOO*
•4.000*
34,000*
61,000*
160,000*
-
•.000*
_
18.000*
b
10,800
23,000*
31,000*
22,100
20,000*
14,600*
18,000*
80,000*
10,000
-
-
-
-
-
160,000*
_
30,800*
-
-
166,000*
•8.000*
22,600*
-
_
76,000*
36,300*
18,600*
.
100.000*
22.600*
70.000*
(CONTINUED)
94
-------
TABLE 23. (continued)
Company and location
Maryland
Chavron. U.3.A., Inc. - BoWmoro
Michigan
CryMat Rofining Co. - Careen City
Lakeeida Refining Co. - Kalemoioo
Marathon Q» Col. - Detroit
Total Petroleum Inc. - Alma
Mlnnoaota
AaNend Petroleum Co. - SI. Paul Park
Koch Refining Co. - RoaamourK
Amor and* Maaa Corp.. - Purvia
Chevron, U.S.A. Inc. - Paecageulo
Ergon Refining. Inc. - Vkkoburg
Natchez Retiring Inc. - Natchez
SautNand Oil Co. - Lumborton
SendenvMe
Montana
Comex - Laurel
Canoeo. Inc. - BiMinqa
Exxon Co. - Olllinqa
Frying J Inc. - Cut Bank
Koneo RefMng. Inc. - Watf Point
Navada
Novada Rofining Co. - Tonopah
Now Joraov
Chavron U.S.A. - Perth Amboy
Exxon Co. - Undan
Mob* ON Corp. - Pautobaro
Saavtaw Palralaum Inc. - Thorofara
Toxaeo, Inc. - WaotvMa
Now Maxlce
Giant Induatriaa Inc. - CMzo
Fwnwx)ton
Navajo Rofining Co. - Artoaia
Plataau. Inc. - Bloomnald
Southom Union IWming Co. - Lovingtan
Thnftway Ca. - BloomfWd
North Dakota
Amoco Oil Ca. - Mandan
Hying J Inc. - WHIiatan
aas
AaMand Patralaum Co. - Canton
OuN Oil Co. - Cincinnati
Standard Oil Co. of Ohio - Lima
Tolodo
SunCI-Tolada
Oklahoma
ANiad Matariol Carp. - Straud
Cnarnplin Fall alami Co - Enid
Conoco, Inc. - Ponea Ctty
Oklahoma narirang Ca. - Cyril
Cuatar Country
SunO-Tukjo
Tonkowa Rafimng Ca. - Amatt
Toaeo- Duncan
Total Patrolaum Corp. - Ardmoro
Cruda ralinir^ capacity
IbM/atraam day!
14,847
8,200
S.oOO0
71.00O
42,000
««.ooo
137,000
30,OOOC
280,000°
22,000
22,000
8,600
12.600
42.600
60.000
48,000
8,200
4.960°
8,600
4.700
188,000°
110,000
102,200
4C.0000
88,600
18,000
14,000
28,830
18,100
38.000
7,600°
68,000
8.400
88.000
46,000
177,000
128.000
124,000
8,600
68,000
138,000
43.000°
16.600
12,600
90.000
13,000
48,600
84,600
Huid coking charge
capacity
-------
TABLE 23. (continued)
Company end location
Oregon
Chevron U.S.A. Inc. - Portend
nmnnmtthiMftlM
imSSSSX£££SX
Atlantic NcMWd C«. - Philadelphia
BP OK Cere. - Marcus Hood
Ou» Oil Co, - Philadelphia
KandeK-Amalie Division. VMtee Chemical Co - Bradford
Pomes' Co. - •.ousoviio
Quaker SUM OK Manning Corp. - Farmers VeHey
Sun 0 - Marcus Hook
VetvoHne OK Co., Division of AoN«nd OH Co. - Freedom
Ddte Refining Co. - Memphis
IHH
Amorieon Petrofine, Inc. -
M« Spring
Port Arthur
Amoco Oil Co. - Texas City
Atlantic McNond Co. - Houoton
Chemctin Pouoloum. Co. - Corpus Chrieti
Chortor InMmodonol OH Co. - Houston
Chovron U.SJk. Inc. - B POM
Cooftol Stotoi rotirtoun Co — Corpus Chriotf
Crown Control Potroloum Corp. - Houoton
Diomond Shomrook Corp. - Sunroy
Eddy RofMng Co. - HouMon
Exxon C. U.S.A. - Houston
r%« Chomkol Co. - Sw Antonio
Our) OH Co. - Port Arthur
Howoll Hydrocarbons. Inc. - Son Antonio
Koch RofMng Co. - Corpus Christf
UOtorio OH It Qos Co. - Tytar
Liquid Enorgy Corp. - Bridgeport
Morothon Oil Co. - Toxos City
MobU Oil Corp. - Booumonf
Ptwps Pctfowunt Co. *•
Borgor
Swoony
Quintono Potroohomicol Co. - Corpus Christi
Sooor Enorgy. Inc. - Corpus Christi
Shot Oil Co. - Door Pork
Odioss
Tosoro Potroloum Corp. - Corrao Springs
Toxoco, Inc. - Amenta
BPsse
Port Arthur
PortNechss
Texas Ctty Refining. Inc. - Texaa City
Uni FwnninQf Inc* •• InQwtitM
Union Oil Co. of Crfforrea - Booument, Noderiond
Crude refining capacity
(bbVetreom deyl
18.7M
131,000
177,000
igo,ooo
•.000
ia.foo
•.•00
1M.OOO
•2.000
7,000
48.000
20.600
•0.000
110,000
432,000
244,000
179.0OO
70.000
76,000°
•6,000°
103.000
78.440
2W.OO
3.600°
626,000
1,400
424.000
10,000
10S.OOO
70,000
10,800
72.000
336.000
100.000
196.000
3«.6OO
34.000
21.000
310.000
33.800
4C.600
17.600
104.00OC
27.474
21.000
18.000
426,000
32,800
130,000
46,000
128,300
Fluid ookino charge
capacity Ml fresh
feed/stream day)
-
.
-
Catalytic crocking durge
capacity HI frech
food/stream day)"'
28.0OO*
48,000*
86.300*
76,000*
18.00(1*
30,000*
6.000*
23,60(1*
34.600*
1 94.0OO*
78.00(1*
88.00(1*
60,000*
22,000*
ia.600*
68,000*
46.0OO*
8.8OO
166.000*
1 10,000*
27.000*
17,000*
38.000*
18.000b
60,000*
87.000*
66.OOO*
1 0,600 *
17,000*
47.000*
8.00(1*
7.000*
136,000*
40.000*
38.0CO
(CONTINUED)
96
-------
TABLE 23. (continued)
CoflThfMny And toctMMfi
Amoco OH Co. - Soft Late City
Caribou Four Comoro, Ine. - Wooda Craaa
Chavran U.SJk. - Soft Loko City
Cryoon RefMng Co. - Wood* Croaa
Huoky OH Ca. - North Sort Loko City
PhiWpo Petroleum Co. - Woodo Croaa
Plateau, Ine. - Reeeovoft
Amoco OH Co. - Yorktown
Chovron U.S.A., Inc. - Saattia
MobHa OH Carp. - Fomdolo
Shall OH Ca. - Anaorette
Sound fWining, Ine. - Tacomo
Taxoco, Inc. - Anacortaa
U.S. OH ft Refining Co. - Toeomo
WeetvlrflWe,
Ouokor Stoto OH Refining Corp. -
NowoH
St. Marya
Murphy OH Corp. - Superior
Amoco OH Co. - Cooper
Huoky OH Ca. - Choyamo
UMe America Refining Ca. - Cooper
Sinclair OH Corp. - Sinclair
... , _ ._ . _ ._, _^,_
Crude refining capacity
IbbUMream deyl
41.800
1.400
46.000°
12.600°
26.000
26.000
(.600
66.000
13 OOO
6.600°
76,000
•4,000
11.700°
•2,000
24,000°
12,000
6.000
42.000
48.000
30,000
24.600°
64.0OO
13.600
Fluid coking charge
capacity (bbl froah
feed/etreem day)
_
-
_
w
_
-
^
_
_
_
_
_
-
-
-
8,000
_
_.
-
Catalytic cracking charge
capacity BM freah
feod/Mream day)*'
18.000*
_
11,000*
7.000
_
4,400°
8,400
6,000*
28,000*
_
26,600°
36,000*
_
30.000*
-
-
8.700*
13.000*
12.000*
12.600*
6,600°
21,000*
4,000°
Now:
TNi Doting I* mbjoet to chongo « morkot eondWoni chongo. facility exnorahip cnongoa, pUnt* ora cloud dawn. ate. Tha raodar ahouU varify tha axiataneo
of portkUor facHWaa by conaurttng currant Uatinga and/or tha plonta thamaorva*. Tha lovoi o4 formoWahydo anwaiona from any givan facility ia o function of
vorioMa* ouch aa capacity, throughput, ond control maoauraa and ahauld ba datarmlnod through diroct conucta with plonta poroonnal.
*FUd bad catalytic crocking.
Moving bod cotarytfe crocking.
'Capacity In bU/colondor day.
97
-------
In addition to formaldehyde emissions from the production of asphalt, the
application of asphalt cement results 1n the emission of 0.0040 pounds of
formaldehyde per ton of asphalt.45
FORMALDEHYDE PRODUCTION IN THE ATMOSPHERE VIA PHOTO-OXIDATION
Just as formaldehyde Is produced in combustion processes from Incomplete
oxidation, It Is also formed In the atmosphere when gaseous organic materials
69
are oxidized, usually with the aid of sunlight. Several reaction paths exist
from such formation. It should be noted that as formaldehyde Is produced In
the atmosphere, It 1s also destroyed. This Is because formaldehyde Is also
consumed by photo-oxidation, with the oxidation products eventually becoming
carbon dioxide and water.
Since formaldehyde Is produced by photo-oxidation in the atmosphere, there
are no definable sources of these emissions. The sources of the organic
precursors are any and all sources of organic emissions. This list includes,
but is not limited to:
- Combustion processes;
- Surface coating applications;
- Pesticide application; and
- Solvent and other VOC evaporative losses.
Prediction or estimation of the amount of formaldehyde produced by
photo-oxidation is a complex task. There are several reaction paths, and
complex equilibria are involved in each reaction path. Sunlight aids the
production of formaldehyde, as does the presence of other atmospheric
69
contaminants such as NO . Studies to date have not succeeded in
n
accurately modeling these phenomena. Rather, the studies have used what little
experimental data are present to estimate formaldehyde conversion "efficiency
factors." These factors represent the fraction of VOC that is converted into
formaldehyde. At best, this type of technique yields very approximate
estimates. The formaldehyde conversion efficiency factors available in the
69
literature are summarized below:
1. From photo-oxidation of automobile exhaust--formaldehyde formation is
calculated by assuming a 30 to 60 percent increase in the initial concentration
of formaldehyde (i.e., concentration exiting the exhaust pipe);
2. For California only—technique assumes 1,262 metric tons/day of
"reactive organic gas" and a formaldehyde conversion factor range of 0.06 to
0.12; and
98
-------
3. Nationwide—technique assumes hydrocarbon emissions total 26,400,000
metric tons/yr and a formaldehyde conversion factor of 0.075. Based on the
latter two figures, it seems reasonable to expect that nationwide formaldehyde
o
production due to atmospheric photo-oxidation may be in the range of 500 x 10
9 69
to 2 x 10 kg per year. The wide range is indicative of the uncertainty
associated with this estimate.
99
-------
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).70~72 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).
Modifications of this general method have been applied to low-level
ambient air measurements of formaldehyde. In estimating low levels by this
procedure, precautions must be taken to ensure 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.
Because higher molecular weight aldehydes and ketones also react with
DNPH, they may interfere with the analysis of formaldehyde at some
chromatographic conditions. Thus, it may be necessary to adjust the
chromatographic conditions in order to give adequate separation of the
100
-------
., HEATED AREA
TEMPERATURE /^x-THERMOMETER
, SENSOR / /\x-FILTER HOLDER
^ _»ffl£j
STACK
WALL
REVERSE-TYPE
PITOT TUBE
*'
PITOT
MANOMETER
2-LITER IMPINGERS
WITH DNPH 8 2N HCI
THERMOMETERS
ORIFICE
SILICA GEL'
IMPINGER
VACUUM
BY-PASS GAUGE.
VALVE
CHECK
VALVE
VACUUM
LINE
MAIN VALVE
DRY GAS
METER
AIR-TIGHT
PUMP
Figure 13. Method 5 sampling.tea in modified for the measurement
of formaldehyde. 70-72
101
-------
formaldehyde-DNPH derivative (2,4-dinitrophenylhydrazone) from the hydrazone
derivatives formed 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.
102
-------
REFERENCES
1. Encyclopedia of Chemical Technology, Kirk-Othmer, 3rd Edition,
Volume II. New York, Wiley-Interscience Publication. 1980. p.
231-247.
2. JANAF Interim Thermochemical Tables. Midland, MI. 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, NC.
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. 6_Q:26.
March 29, 1982.
8. Human Exposure to Atmospheric Concentrations of Selected Chemicals,
Volume 2. U.S. Environmental Protection Agency. Research Triangle
Park, NC. February 1982. Appendix A-15.
9. Chemical Producers Data Base System--Formaldehyde. U.S.
Environmental Protection Agency. Cincinnati, OH. 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, DC.
February 1979. p. B-24.
11. Lovell, R.J. Report 1: Formaldehyde. In: Organic Chemical
Manufacturing Volume 9: Selected Processes. U.S. Environmental
Protection Agency. Research Triangle Park, NC. Publication No.
EPA-450/3-80-028d. December 1980. pp. III-l to III-B.
103
-------
12. Letter from Hewlett, C.T., Formaldehyde Institute, to Lahre, T.,
September 29, 1983. EPA/OAQPS.
13. Memo and addendum from Mascone, 0., EPA, to Farmer, J., EPA. June
11, 1980. Thermal Incinerator Performance for NSPS.
14. Letter from Gilby, P.G., E.I. OuPont De Nemours & Company, Inc., to
Lahre, T., EPA:OAQPS. 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, CA. 1983.
17. Reference 1, pp. 440-469.
18. Wilkins, G.E. Industrial Process Profiles for Environmental Use.
Chapter 10--Plastics and Resins Industry. U.S. Environmental
Protection Agency. Cincinnati, OH. Publication No. EPA-600/
2-77-023J. February 1977.
19. Knob, A., and U. Scheib. Chemistry and Application of Phenolic
Resins. New York, Springer-Uerlag, 1979. p. 61.
20. Reference 1, pp. 112-123
21. Faith, U.L., O.B. Keyes, and R.L. Clark. Industrial Chemicals, 4th
Edition. New York, John Wiley and Sons. 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, OH.
Publication No. EPA-600/2-77-023f. February 1977.
23. Hedley, W.H., et al. Potential Pollutants from Petrochemical
Processes. Monsanto Research Corporation. Dayton, OH.
December 1973.
24. Walker, J.F. Formaldehyde. 3rd Edition. New York, Reinhold
Publishing Corporation. 1964.
25. Reference 1, pp. 256-259.
26. Shreve, R.N., and J.A. Brink. Chemical Process Industries, Fourth
Edition. New York, McGraw-Hill, Inc. 1977. pp. 588-601.
27. Serth, R.W., and T.W. Hughes. Source Assessment: Phthalic Anhydride
(Air Emissions). U.S. Environmental Protection Agency. Research
Triangle Park, NC. Publication No. EPA-600/2-76.032d. December
1976.
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.
104
-------
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, pp. 4-28.
34. Sheldrick, J., and T. Steadman. Product/Industry Profile and Related
Analysis for Formaldehyde and Formladehyde-Containing Consumer
Products. Part II--Products/Industry Profile on Urea Formaldehyde.
U.S. Consumer Product Safety Commission, Washington, DC.
February 1979.
35. Urea-Formaldehyde Foam Gets the Axe for Home Insulation. Chemical
Week. J2p_(9):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.
12(11):1126-1131. November 1982.
37. Pickrell, J.A., et al. Formaldehyde Release Rate Coefficient From
Selected Consumer Products. Environmental Science and Technology.
17(12):753-757. 1983.
38. A Survey of Formaldehyde and Total Gaseous Nonmethane Organic
Compound Emissions From Particleboard Press Vents. NCASI Technical
Bulletin No. 493. June 1986.
39. Formaldehyde, Phenol, and Total Gaseous Nonmethane Organic Compound
Emissions From Flakeboard and Oriented-Strand Board Press Vents.
NCASI Technical Bulletin No. 503. September 1986.
40. Vaught, C.C. (Midwest Research Institute). Evaluation of Emission
Control Devices at Waferboard Plants. U.S. Environmental Protection
Agency Control Technology Center. EPA-450/3-80-002. October 1988.
41. A Survey of Emissions From Dryer Exhausts in the Wood Panel board
Industry. NCASI Technical Bulletin No. 504. September 1986.
42. Radian Corporation. Evaluation of Emission Factors for Formaldehyde
From Certain Wood Processing Operations. U.S. Environmental
Protection Agency Control Technology Center. EPA-450/3-87-023.
October 1987.
43. Marshall, Walt. Consumer Products Safety Commission, Washington, DC.
Personal communication with D.C. Misenheimer, GCA, November 23, 1983.
44. Statistical Policy Division, Office of Management and Budget.
Standard Industrial Classification (SIC) Manual. 1972.
105
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45. Formaldehyde Special Study. Wisconsin Department of Natural
Resources, Bureau of Air Management. Publication No. AM-048-090.
November 21, 1990.
46. Procedures for Emission Inventory Preparation, Volume I: Emission
Inventory Fundamentals. U.S. Environmental Protection Agency
Research Triangle Park, NC. EPA-450/4-81-026a. September 1981.
47. Procedures for Emission Inventory Preparation, Volume II: Point
Sources. U.S. Environmental Protection Agency. Research Triangle
Park, NC. EPA-450/4-81-026b. September 1981.
48. Procedures for Emission Inventory Preparation, Volume III: Area
Sources. U.S. Environmental Protection Agency, Research Triangle
Park, NC. EPA-450/4-81-026c. September 1981.
49. Procedures for Emission Inventory Preparation, Volume IV: Mobile
Sources. U.S. Environmental Protection Agency. Research Triangle
Park, NC. September 1981.
50. Procedures for Emission Inventory Preparation, Volume V:
Bibliography. U.S. Environmental Protection Agency. Research
Triangle Park, NC. EPA-450/4-81-026e. September 1981.
51. 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, H(7):267-278. July 1964.
52. 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.
53. 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, OH. November 1962.
54. Natusch, D.F.S. Potentially Carcinogenic Species Emitted to the
Atmosphere by Fossil-Fueled Power Plants. Environmental Health
Perspectives 22:79-90. 1978.
55. Lipari, L., et al. Aldehyde Emissions From Wood-Burning Fireplaces.
Environmental Science and Technology. 1£(5). May 1984.
56. DeAngells, D.G., et al. (Monsanto). Preliminary Characterization of
Emissions From Wood-Fired Residential Combustion Equipment. U.S.
Environmental Protection Agency, Research Triangle Park, NC.
EPA-600/7-80-040. NTIS P880-182066. March 1980.
57. Snowden, W.D., et al. Source-Sampling Residential Fireplaces for
Emission Factor Development. U.S. Environmental Protection Agency
Research Triangle Park, NC. EPA-450/3-76-010. 1975.
106
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58. Wetherold, R.G., and 0.0. Rosebrook. Assessment of Atmospheric
Emissions from Petroleum Refining. Volume 1. U.S. Environmental
Protection Agency. Research Triangle Park, NC. Technical Report
EPA-600/2-80-075a. April 1980.
59. Compilation of Air Pollution Emission Factors. Third Edition. AP-42
U.S. Environmental Protection Agency, Research Triangle Park, NC.
August 1977.
60. Volatile Organic Compound (VOC) Species Data Manual, Second Edition.
U.S. Environmental Protection Agency. Research Triangle Park, NC.
EPA-450/4-80-015. July 1980.
61. Carey, P.M. Mobile Source Emissions of Formaldehyde and Other
Aldehydes. EPA/AA/CTAB/PA/81-11. U.S. Environmental Protection
Agency, Research Triangle Park, NC. Ann Arbor, MI. May 1981.
62. Memo from J.E. Sigsby, EPA/Environmental Sciences Research
Laboratory, to J.H. Southerland, EPA/OAQPS. June 27, 1983.
Discussion air emissions of formaldehyde from mobile sources.
63. Highway Statistics, 1982. U.S. Department of Transportation.
Federal Highway Administration.
64. Mayer, M.A. Compilation of Air Pollutant Emission Factors for
Combustion Processes, Gasoline Evaporation, and Selected Industrial
Processes. Public Health Service, Cincinnati, OH. 1965.
65. Urban, C. Unregulated Exhaust Emissions From Non-Catalyst Baseline
Cars Under Malfunction Conditions. U.S. Environmental Protection
Agency. Ann Arbor, MI. EPA-460/3-81-020. May 1981.
66. Radian Corporation. Assessment of Atmospheric Emissions From
Petroleum Refining: Volume 4 - Appendices C, 0, and E. U.S.
Environmental Protection Agency. Research Triangle Park, NC.
EPA-600/3-81-020. July 1980.
67. PEDCo Environmental, Inc. Petroleum Refinery Enforcement Manual.
U.S. Environmental Protection Agency. Washington, DC.
EPA-340/1-80-008. March 1980.
68. Cantrell, A. Annual Refining Survey. Oil and Gas Journal. March
21, 1983. pp. 128.
69. Phillips, M.U., and G.E. Wilkins. Source Assessment of Formaldehyde
Emissions. U.S. Environmental Protection Agency, Pollutant Analysis
Branch. September 3, 1985.
107
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70. Thrun, K.E., J.C. Harris, C.E. Rechsteiner, and O.J. Sorlin. Methods
for Level 2 Analysis by Organic Compound Category. U.S.
Environmental Protection Agency, Research Triangle Park, NC.
EPA-600/7-81-028. March 1981.
71. Harris, J.C., M.J. Hayes, P.L. Levins, and O.B. Lindsay.
EPA/IERL-RTP Procedures for Level 2 Sampling and Analysis of Organic
Materials U.S. Environmental Protection Agency. Research Triangle
Park, NC. EPA-600/7-78-033. February 1981.
72. Method 5--Determination of Partlculate Emission From Stationary
Sources. Federal Register. 12(160):41776. 1977.
73. Letter From Victor Elia, National Council of the Paper Industry for
Air and Stream Improvement (NCASI), to Thomas Lahre, EPA. Providing
comments on source test procedures. May 4, 1983.
108
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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
service, (2) the average formaldehyde content of the streams passing through
A-l
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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 four are in
formaldehyde service, from the formaldehyde converter to formaldehyde storage
:ed as follows:
Composition fwt. percent)
(see Figure A-l). Compositions are estimated as follows:
Phase
Gas
Liquid
Liquid
Liquid
CHg*
29
37
37
37
Water
71
63
63
63
Stream number
4
5
6
7
Valves--
177 valves » 22 valves per process stream
8 Streams
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:
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Component
emissions factor Valves in Average CH2»0 Emissions
fkq/hr-valve)2 CH:»0 service content (percent) fkq/hr)
Liquid valves 0.0071 66 37 0.173
Gas valves 0.0056 22 29 0.036
0.209
Pumps--
4 Pumps
5 liquid lines
1 pump per liquid process line
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 valves--
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
Controls that 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
A-4
-------
relief valves. Monthly Inspection and maintenance (I/M) 1s about 73 percent
efficient for valves 1n 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 efficiencies 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
2
other valves has an overall efficiency of about 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
the converters reactor to formaldehyde storage (see Figure A-2) .
Compositions are estimated as follows:
Composition (wt. percent)
Stream number
3a-f
4
5
6
7
9
11
12
Phase
Gas
Gas
Gas
Liquid
Liquid
Liquid
Liquid
Liquid
CH3-0
20
20
20
10
30
37
37
37
H20
.
.
-
85
55
63
63
63
CH?OH
.
-
-
5
15
30
-
-
Other
80
80
80
0
-
-
-
-
Valves--
214 valves rt . ,.
23 ,. <" 9 valves per process line
A-5
-------
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at vi
in «i
VI U
3 a.
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3 *•» U
5-S 2
0- 010.
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4^
VI £
e w en
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VI ••"» k
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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 Average CH2-0 Emissions
(kg/hr-valve)2 service content (percent) (kg/hr)
Liquid valves 0.007 45 30 0.096
Gas valves 0.0056 72 20 0.081
0.177
Pumps--
7 Pumps
1 pump per liquid process line
6 liquid lines
Assuming an average of one pump for each of the 15 liquid process
2
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.
Relief valves--
It is assumed that two relief valves are applied to the vaporizer and
four to the bank of converters. The converter overheads contain about 20
percent formaldehyde, while the vaporizer 1s 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
0.70 kg/hr
A-7
-------
Controls that 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 mechanical pumps, application of rupture disk to relief
valves, and monthly I/M for other valves has an overall efficiency of about 91
2
percent.
REFERENCES FOR APPENDIX A
^*
1. Organic Chemical Manufacturing, Volume B. 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-8
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing/
1. REPORT NO.
EPA-450/4-91-012
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Locating and Estimating Air Emissions From Sources of
Formaldehyde (Revised)
5. REPORT DATE
March 1991
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Chuck Vaught
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Midwest Research Institute
401 Harrison Oaks Blvd., Suite 350
Gary, NC 27513
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 Aaency
MD-14
Research Triangle, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
EPA Project Officer: Dallas Safriet
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
This document updated a report published in 1984.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Formaldehyde
Air Emission Sources
Locating Air Emission Sources
Toxic Substances
18. DISTRIBUTION STATEMENT
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123
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