United State*
Environmnntal Protection
Agency
Office of Air Quality
Planning And Standard*
Rumarch Trianglo Park, NC 27711
EPA-454/R-93-041
September I993
AIR
PRELIMINARY DATA SEARCH REPORT
FOR LOCATING AND ESTIMATING
AIR EMISSIONS FROM SOURCES OF
CYANIDE COMPOUNDS
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EPA-452/R-93-041
September 1993
PRELIMINARY DATA SEARCH REPORT FOR
LOCATING AND ESTIMATING AIR TOXIC EMISSIONS
FROM SOURCES OF CYANIDE COMPOUNDS
Prepared for:
Anne Pope
Office of Air Quality Planning and Standards
Technical Support Division
U. S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
Prepared by:
Midwest Research Institute
401 Harrison Oaks Boulevard, Suite 350
Cary, North Carolina 27513
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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. Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
EPA 454/R-93-041
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TABLE OF CONTENTS
Section Page
1 PURPOSE OF DOCUMENT 1-1
2 OVERVIEW OF DOCUMENT CONTENTS 2-1
3 BACKGROUND 3-1
3.1 NATURE OF THE POLLUTANT 3-1
3.1.1 Hydrogen Cyanide 3-1
3.1.2 Sodium Cyanide 3-3
3.1.3 Potassium Cyanide 3-3
3.1.4 Other Cyanide Compounds 3-3
3.2 OVERVIEW OF PRODUCTION, USE, AND EMISSIONS OF
CYANIDES 3-6
3.2.1 Production 3-6
3.2.2 Uses 3-7
3.2.3 Emissions 3-9
4 EMISSIONS FROM PRODUCTION OF MAJOR CYANIDE COMPOUNDS 4-1
4.1 HYDROGEN CYANIDE PRODUCTION 4-1
4.1.1 Process Descriptions 4-3
4.1.2 Emission Control Measures 4-11
4.1.3 Emissions 4-12
4.2 SODIUM CYANIDE PRODUCTION 4-12
4.2.1 Process Description 4-14
4.2.2 Emission Control Measures 4-16
4.2.3 Emissions 4-16
4.3 POTASSIUM CYANIDE 4-17
5 EMISSIONS FROM MAJOR USES OF CYANIDE COMPOUNDS . . . 5-1
5.1 ADIPONITRILE PRODUCTION 5-1
5.1.1 Process Description 5-2
5.1.2 Emission Control Measures 5-4
5.1.3 Emissions 5-4
5.2 ACETONE CYANOHYDRIN 5-5
5.2.1 Process Description 5-6
5.2.2 Emission Control Measures 5-8
5.2.3 Emissions 5-8
5.3 CYANURIC CHLORIDE 5-9
5.3.1 Process Description 5-10
5.3.2 Emission Control Measures 5-10
5.3.3 Emissions 5-12
5.4 CHELATING AGENTS PRODUCTION 5-12
5.4.1 Process Descriptions 5-12
5.4.2 Emission Control Measures 5-14
5.4.3 Emissions 5-15
5.5 CYANIDE ELECTROPLATING 5-16
5.5.1 Process Description 5-16
5.5.2 Emission Control Measures 5-23
5.5.3 Emissions 5-23
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TABLE OF CONTENTS (continued)
6 CYANIDE COMPOUND EMISSIONS FROM MISCELLANEOUS
SOURCES 6-1
6.1 IRON AND STEEL PRODUCTION 6-1
6.1.1 Emission Control Measures 6-4
6.1.2 Emissions 6-4
6.2 CARBON BLACK PRODUCTION 6-4
6.2.1 Process Description 6-6
6.2.2 Emission Control Measures 6-9
6.2.3 Emissions 6-9
6.3 CARBON FIBER PRODUCTION 6-10
6.3.1 Process Description 6-11
6.3.2 Emission Control Measures 6-12
6.3.3 Emissions 6-12
6.4 PETROLEUM REFINING 6-12
6.4.1 Process Description 6-12
6.4.2 Emission Control Measures 6-15
6.4.3 Emissions 6-16
6.5 MOBILE SOURCES 6-16
7 SOURCE TEST PROCEDURES 7-1
7.1 INTRODUCTION 7-1
7.2 STATIONARY SOURCE SAMPLING METHODS 7-2
7.2.1 CARB Method 426, "Determination of
Cyanide Emissions from Stationary Sources" . . 7-2
7.3 AMBIENT AIR SAMPLING METHODS 7-2
7.3.1 NIOSH Method 7904, "Determination of Cyanide
Concentrations in Workplace Atmosphere" 7-2
7.4 ANALYTICAL METHODS 7-4
7.4.1 EMSLC, 335.1, "Cyanides, Amenable to Chlorination
(Titrimetric and Spectrophotometric)" 7-4
7.4.2 EMSLC, 335.2, "Cyanide, Total (Titrimetric and
Spectrophotometric)" 7-4
7.4.3 EMSLC, 335.3, "Cyanide, Total (Colorimetric,
Automated UV) " 7-6
7.4.4 OSW, 9010A, "Method 9010A, Total and
Amenable Cyanide" 7-6
7.4.5 OSW, 9012A, "Method 9012A, Total and
Amenable Cyanide (Colorimetric, Automated UV)" 7-7
IV
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TABLE OF CONTENTS (continued)
7.5 COMBINED SAMPLING/ANALYTICAL METHODS 7-7
7.5.1 Fourier Transform Infrared Spectroscopy (FTIR) 7-7
7.5.2 ASTM, D4490, "Standard Practice for Measuring the
Concentration of Toxic Gases or Vapors
Using Detector Tubes" 7-8
7.6 SUMMARY 7-8
REFERENCES 8-1
APPENDIX A NATIONWIDE EMISSION ESTIMATES A-l
APPENDIX B ELECTRIC ARC FURNACES IN IRON AND STEEL
PRODUCTION AND CRUDE OIL DISTILLATION
CAPACITY B-l
v
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LIST OF FIGURES
Page
3-1 End uses of hydrogen cyanide 3-8
4-1 Andrussow HCN production process with
ammonia recycle 4-4
4-2 Andrussow HCN production process without
ammonia recycle 4-5
4-3 Blausaure Methane Anlage HCN production
process 4-8
4-4 Sohio production process for
acrylonitrile/HCN production 4-10
4-5 Sodium cyanide neutralization production
process 4-15
5-1 Process flow diagram for production of adiponitrile by
hydrocyanation of butadiene 5-3
5-2 Process flow diagram for production of
acetone cyanohydrin 5-7
5-3 Process flow diagram for production of
cyanuric chloride 5-11
5-4 Flow diagram for a typical electroplating
process 5-18
6-1 Process flow diagram for carbon black
manufacturing process 6-8
7-1 Schematic of CARB Method 426 sampling
train 7-3
7-2 Schematic of NIOSH Method 7904 sampling
train 7-5
VI
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LIST OF TABLES
Page
3-1 PHYSICAL AND CHEMICAL PROPERTIES OF
HYDROGEN CYANIDE 3-2
3-2 PHYSICAL AND CHEMICAL PROPERTIES OF SODIUM
CYANIDE 3-4
3-3 PHYSICAL AND CHEMICAL PROPERTIES OF
POTASSIUM CYANIDE 3-5
3-4 SIC CODES ASSOCIATED WITH HYDROGEN CYANIDE
AND OTHER CYANIDE COMPOUND EMISSIONS 3-11
3-5 ESTIMATED 1991 NATIONWIDE CYANIDE COMPOUND
EMISSIONS FOR SELECTED POINT SOURCE
CATEGORIES 3-14
4-1 DOMESTIC PRODUCERS OF HYDROGEN CYANIDE 4-2
4-2 HYDROGEN CYANIDE PRODUCERS REPORTING
HYDROGEN CYANIDE EMISSIONS IN THE 1991
TOXICS RELEASE INVENTORY 4-13
4-3 DOMESTIC PRODUCERS OF SODIUM CYANIDE 4-14
4-4 HYDROGEN CYANIDE AND SODIUM CYANIDE
EMISSIONS FROM NaCN PRODUCTION FACILITIES .... 4-17
5-1 DOMESTIC ADIPONITRILE PRODUCERS 5-2
5-2 ADIPONITRILE PRODUCERS REPORTING CYANIDE
COMPOUND OR HYDROGEN CYANIDE EMISSIONS IN
THE 1991 TOXICS RELEASE INVENTORY 5-5
5-3 DOMESTIC ACETONE CYANOHYDRIN PRODUCERS 5-6
5-4 ACETONE CYANOHYDRIN PRODUCERS REPORTING
CYANIDE COMPOUNDS OR HYDROGEN CYANIDE
EMISSIONS IN THE 1991 TOXICS RELEASE
INVENTORY 5-9
5-5 U.S. PRODUCERS OF HCN-USING CHELATING
AGENTS 5-13
5-6 PRODUCERS OF CHELATING AGENTS REPORTING
CYANIDE COMPOUND OR HYDROGEN CYANIDE
EMISSIONS IN THE 1991 TOXICS RELEASE
vii
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INVENTORY 5-15
5-7 ESTIMATED NUMBER OF METAL FINISHING JOB
SHOPS PERFORMING SELECTED PLATING
OPERATIONS 5-17
5-8 COMPOSITION AND OPERATING PARAMETERS OF
A TYPICAL COPPER CYANIDE PLATING BATH 5-20
5-9 COMPOSITION AND OPERATING PARAMETERS OF
A TYPICAL ZINC CYANIDE PLATING BATH 5-20
5-10 COMPOSITION AND OPERATING PARAMETERS OF
A TYPICAL CADMIUM CYANIDE PLATING BATH 5-21
5-11 COMPOSITION AND OPERATING PARAMETERS OF
A TYPICAL SILVER CYANIDE PLATING BATH 5-21
5-12 COMPOSITION AND OPERATING PARAMETERS OF
A TYPICAL GOLD ALKALINE CYANIDE PLATING
BATH 5-22
5-13 COMPOSITION AND OPERATING PARAMETERS OF
A TYPICAL BRASS CYANIDE PLATING BATH 5-22
5-14 COMPOSITION AND OPERATING PARAMETERS OF
A TYPICAL INDIUM CYANIDE PLATING BATH 5-23
6-1 IRON/STEEL AND COKE PRODUCTION FACILITIES
REPORTING CYANIDE COMPOUND EMISSIONS IN
THE 1991 TOXIC RELEASE INVENTORY 6-5
6-2 CARBON BLACK PRODUCTION FACILITIES 6-7
6-3 CARBON BLACK PRODUCERS REPORTING CYANIDE
COMPOUND EMISSIONS IN THE 1991 TOXIC
RELEASE INVENTORY 6-10
6-4 DOMESTIC PRODUCERS OF HIGH PERFORMANCE
CARBON FIBERS 6-11
6-5 CARBON FIBER PRODUCERS REPORTING HYDROGEN
CYANIDE EMISSIONS IN THE 1991 TOXICS
RELEASE INVENTORY 6-13
6-6 FLEET AVERAGE EMISSION FACTORS FOR
HYDROGEN CYANIDE 6-17
7-1 CYANIDE SAMPLING METHODS 7-2
VI11
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SECTION 1
PURPOSE OF DOCUMENT
The U. S. Environmental Protection Agency (EPA), State,
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, little information exists on the ambient air
concentration of these substances or about 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.
Prior documents in the series are listed below:
Substance
EPA Publication Number
Acrylonitrile
Carbon Tetrachloride
Chloroform
Ethylene Bichloride
Formaldehyde
Nickel
Chromium
Manganese
Phosgene
Epichlorohydrin
Vinylidene Chloride
Ethylene Oxide
EPA-450/4-84-007a
EPA-450/4-84-007b
EPA-450/4-84-007C
EPA-450/4-84-007d
EPA-450/4-91-012
EPA-450/4-84-007f
EPA-450/4-84-007g
EPA-450/4-84-007h
EPA-450/4-84-0071
EPA-450/4-84-007J
EPA-450/4-84-007k
EPA-450/4-84-0071
1-1
-------
Chlorobenzene
Polychlorinated Biphenyls(PCB's ;
Polycyclic Organic Matter (POM)
Benzene
Perchloroethylene and
Trichloroethylene
Municipal Waste Combustion
Coal and Oil Combustion
1,3-Butadiene
Chromium (Supplement)
Sewage Sludge
Styrene
Cadmium
Mercury
Methylene Chloride
Medical Waste
TCDD/TCDF
Toluene
Xylenes
Methyl Ethyl Ketone
Methyl Chloroform
Chlorobenzene (Update)
Chloroform (Update)
EPA-450/4-84-007m
EPA-450/4-84-007n
EPA-450/4-84-007p
EPA-450/4-84-007q
EPA-450/2-
EPA-450/2-
EPA-450/2-
EPA-450/2-
EPA-450/2-
EPA-450/2-
EPA-454/R-
EPA-454/R-
EPA-454/R-
EPA-454/R-
Number to
Number to
Number to
Number to
Number to
Number to
Number to
Number to
89-013
89-006
89-001
89-021
89-002
90-009
•93-011
•93-040
•93-023
•93-006
be Assigned
be Assigned
be Assigned
be Assigned
be Assigned
be Assigned
be Assigned
be Assigned
This document differs from the previous locating and
estimating documents listed above because of the lack of
published test data. It is being published to solicit
additional data to allow the document to be finalized. The
document deals specifically with cyanide compounds (e.g.,
hydrogen cyanide, sodium cyanide, potassium cyanide). Sources
of cyanide compound emissions evaluated in this document
include: (1) cyanide compound production; (2) emissions
resulting from major uses of cyanide compounds; and (3)
emissions from miscellaneous sources. Data presented in this
document are total cyanide compound emissions.
In addition to the information presented in this document,
another potential source of emissions data for cyanide
1-2
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compounds is the Toxic Chemical Release Inventory (TRI) form
required by Section 313 of Title III of the 1986 Superfund
Amendments and Reauthorization Act (SARA 313).l SARA 313
requires owners and operators of facilities in certain
Standard Industrial Classification Codes (SIC) that
manufacture, import, process or otherwise use toxic chemicals
(as listed in Section 313) to report annually their releases
of these chemicals to all environmental media. As part of
SARA 313, EPA provides public access to the annual emissions
data. The TRI data include general facility information,
chemical information, and emissions data. Air emissions data
are reported as total facility release estimates for fugitive
emissions and point source emissions. No individual process
or stack data are provided to EPA under the program. The TRI
requires sources to use stack monitoring data for reporting,
if available, but the rule does not require stack monitoring
or other measurement of emissions if it is unavailable. If
monitoring data are unavailable, emissions are to be
quantified based on best estimates of releases to the
environment.
The reader is cautioned that the TRI will not likely
provide facility, emissions, and chemical release data
sufficient for conducting detailed exposure modeling and risk
assessment. In many cases, the TRI data are based on annual
estimates of emissions (i.e., on emission factors, material
balance calculations, and engineering judgment). We recommend
the use of TRI data in conjunction with the information
provided in this document to locate potential emitters of
cyanide compounds and to make preliminary estimates of air
emissions from these facilities.
Cyanide compounds are of particular importance as a result
of the Clean Air Act Amendments of 1990. Cyanide compounds
are included in the Title III list of hazardous air pollutants
and will be subject to standards established under Section
1-3
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112, including maximum achievable control technology (MACT).
These standards are to be promulgated no later than 10 years
following the date of enactment.
1-4
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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 cyanide compounds and estimating 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
document.
Section 3 of this document provides a brief summary of the
physical and chemical characteristics of hydrogen cyanide and
other cyanide compounds and an overview of their production
and uses. This background section may be useful to someone
who wants to develop a general perspective on the nature of
the substance and where it is manufactured and consumed and
reported TRI emissions.
Sections 4 through 6 of this document focus on the major
industrial source categories that may discharge air emissions
containing cyanide compounds. Section 4 discusses the
production of major cyanide compounds. Section 5 discusses
the different major uses of cyanide compounds as an industrial
feedstock. Section 6 discusses emissions from miscellaneous
2-1
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sources. For each major industrial source category described,
process descriptions and flow diagrams are given wherever
possible; potential emission points are identified, and
available emission factor estimates are presented that show
the potential for cyanide compound emissions before and after
controls are employed by industry. Individual companies are
identified that are reported to be involved with the
production and/or use of cyanide compounds based on industry
contacts, the Toxic Release Inventory (TRI), and available
trade publications.
Section 7 summarizes available procedures for source
sampling and analysis of cyanide compounds. Details are not
prescribed nor is any EPA endorsement given or implied for any
of these sampling and analysis procedures. Section 8 presents
the references. Appendix A presents calculations used to
derive the estimated 1990 nationwide cyanide compound
emissions presented in Section 3. Appendix B presents a list
of iron and steel production facilities that use electric arc
furnaces and the crude oil distillation capacity at U.S.
refineries.
This document does not contain any discussion of health or
other environmental effects of cyanide compounds, nor does it
include any discussion of ambient air levels or ambient air
monitoring techniques.
Comments on the content or usefulness of this document are
welcome, as is any information on process descriptions,
operating practices, control measures, and emissions that
would enable EPA to improve its contents. All comments should
be sent to:
Chief, Emission Factor and Methodology Section (MD-14)
Emission Inventory Branch
U. S. Environmental Protection Agency
Research Triangle Park, NC 27711
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SECTION 3
BACKGROUND
This section provides a brief summary of the physical and
chemical characteristics of hydrogen cyanide and other cyanide
compounds. This section also gives an overview of the
production, use, and emissions of hydrogen cyanide and other
cyanide compounds.
3 . 1 NATURE OF THE POLLUTANT
3.1.1 Hydrogen Cyanide
Hydrogen cyanide (CAS 74-90-8), HCN, is a colorless,
poisonous liquid with the characteristic odor of bitter
almonds. It is a low viscosity liquid at 25°C and has a
boiling point of 25.70°C. Hydrogen cyanide is miscible in all
portions in water and alcohol, and is soluble in ether.
Hydrogen cyanide polymerizes spontaneously when not absolutely
pure or stabilized. The stabilizer used is sulfur dioxide and
sulfuric acid. Table 3-1 summarizes the physical and chemical
properties of HCN. Hydrogen cyanide is primarily used as a
basic building block for other chemical products such as
adiponitrile, methyl methacrylate, cyanuric chloride, sodium
cyanide, potassium cyanide, and a variety of chelating
agents . 2~4
Hydrogen cyanide is a very weak acid, having an ionization
constant of the same magnitude as natural amino acids. As the
nitrile of formic acid, HCN undergoes many typical nitrile
reactions. For example, HCN can be hydrolyzed to formic acid
by aqueous sulfuric acid, converted to phenylformamidine with
3-1
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TABLE 3-1. PHYSICAL AND CHEMICAL PROPERTIES OF HYDROGEN CYANIDE
Property
Value
Structural formula: HCN
Synonyms: hydrocyanic acid, prussic acid, formonitrile
CAS Registry No.: 74-90-8
Molecular weight
Melting point, °C
Boiling point, °C
Triple point, °C
Density, liquid, g/ml
0°C
10°C
20°C
Specific gravity, aqueous solution, d1818
10.04% HCN
20.29% HCN
60.23%
Vapor pressure, kPaa
-29.5°C
0°C
27.5°C
Vapor density, at 31 °C (air = 1)
Heat of formation, kJ/molb
Gas
Liquid at 18°C, 100kPaa
Heat of combustion, kJ/molb
27.03
-13.24
25.70
-13.32
0.7150
0.7017
0.6884
0.9838
0.9578
0.829
6.697
35.24
107.6
0.947
-128.6
-10.1
667
Source: Reference 2-5.
a To convert kPa to mm Hg, multiply by 7.5.
b To convert J to cal, divide by 4.184.V
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aniline and hydrogen chloride, or hydrogenated to
methylamine.2'5 It also reacts with the carbonyl group of
aldehydes and ketones to form cyanohydrins. The most
important uses of this type of reaction are in the manufacture
of acetone cyanohydrin (an intermediate in the production of
methyl methacrylate) and in the production of adiponitrile
from HCN and butadiene.5
3.1.2 Sodium Cyanide6
Sodium cyanide (CAS 143-33-9), NaCN, is a white, cubic
crystalline solid and is very soluble in liquid ammonia. It
is odorless when dry but emits an odor of bitter almonds when
damp. Today, NaCN is produced by the neutralization or wet
process, in which liquid HCN and sodium hydroxide solution
react and water is evaporated. Table 3-2 summarizes the
physical and chemical properties of NaCN.
3.1.3 Potassium Cyanide6
Potassium cyanide (CAS 151-50-8), KCN, is a white
crystalline solid that dissolves to liquid by absorbing
moisture from the air. Commercial KCN is currently produced
by the neutralization or wet process, which reacts as aqueous
solution of potassium hydroxide with hydrogen cyanide to
produce KCN at 99 percent purity. Potassium cyanide of 99.5+
percent purity can be prepared by using high-quality HCN and
potassium hydroxide (KOH). Potassium cyanide does not form a
dihydrate. Table 3-3 gives physical and chemical properties
of KCN.
3.1.4 Other Cyanide Compounds6
Other cyanide compounds include lithium cyanide, rubidium
cyanide, cesium cyanide, ammonium cyanide, strontium cyanide,
magnesium cyanide, barium cyanide, and calcium cyanide. Of
these compounds, only calcium cyanide is commercially
3-3
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TABLE 3-2. PHYSICAL AND CHEMICAL PROPERTIES OF SODIUM CYANIDE
Property
Value
Structural formula: NaCN
Synonyms: White cyanide, cyanogran, cyanide of sodium,
sodium salt, cymag, M-44 cyanide capsules
CAS Registry No.: 74-90-8
Molecular weight
Melting point, °C (100%)
(98%)
Boiling point (extrapolated), °C
Density, g/cm3
Cubic
Orthorhombic
Molten, at 700°C
Vapor pressure, kPaa
800°C
900°C
1000°C
1100°C
1200°C
1300°C
1360°C
Heat capacity13, 25-72°C, J/gc
Heat of vaporization, J/gc
Heat effusion, J/gc
Heat of formation, AHf °, NaCN(c), J/molc
Heat of solutiond, AHsoln , J/molc
Hydrolysis constant, Kh , 25°C
Viscosity, 26 wt% NaCN-H2 O, 30°C, mPa«s(=cP)
49.02
563.7 (+1)
560
1500
1.6
1.62-1.624
1.22 (approx.)
0.103
0.4452
1.652
4.799
11.9
27.2
41.8
1.38
3,190
314
-89.9 x103
1,510
2.51 x10'5
4
Source: References 6-8.
3 To convert kPa to mm Hg, multiply by 7.5.
b The heat capacity of sodium cyanide has been measured between 100° and 345° K.
c To convert J to cal, divide by 4.184.
dln200mol H2 O.3
3-4
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TABLE 3-3. PHYSICAL AND CHEMICAL PROPERTIES OF POTASSIUM CYANIDE
Property Value
Structural formula: KCN
Synonyms: Cyanide of potassium, potassium salt
CAS Registry No.: 151-50-8
Molecular weight 65.11
Melting point, °C
100% 634.5
96.05% 622
Density, g/cm3
Cubic at 20°C 1.553
Cubic at 25°C 1.56
Orthorhombic at-60°C 1.62
Specific heat, 25° to 72°C, J/ga 1.01
Heat of fusion, J/mola 14.7x103
Heat of formation, AHf °, J/mola -113 x 103
Heat of soln, AHsoln ° , J/mola +11.7 x 103
Hydrolysis constant, 25°C 2.54 x 10-5
Solubility in water at 25°C, g/100 g H2O 71.6
Resistivity, Q«cm
0.25 normal soln 70
0.5 normal soln 15
1.0 normal soln 10
2.0 normal soln 5
Source: References 6-8.
aTo convert J to cal, divide by 4.184.
3-5
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important, although manufacture has been greatly reduced in
recent years. It is marketed in flake form, as a powder, or
as cast blocks by American Cyanamid Company and is
manufactured in Canada and South Africa.
3.2 OVERVIEW OF PRODUCTION, USE, AND EMISSIONS OF CYANIDES
3.2.1 Production
Hydrogen cyanide--
Hydrogen cyanide production in the United States is
primarily accomplished through either the Andrussow process or
the Blausaure Methane Anlage (BMA) Process by Degussa.2 The
Andrussow process involves the reaction of ammonia, methane
(natural gas), and air over platinum metals as catalysts and
is the dominant commercial process. The BMA process involves
the reaction of ammonia with methane and is not as widely used
as the Andrussow process. The Andrussow process accounts for
74 percent of the total U.S. HCN production. The BMA process
is used at only one facility, which accounts for only 3
percent of U.S. HCN production.4 Hydrogen cyanide is also
produced as a byproduct in the manufacture of acrylonitrile by
the ammoxidation of propylene (Sohio technology).2 The Sohio
process accounts for the remaining 23 percent of HCN
production in the U.S.4 Since storage and shipment of HCN is
difficult, producers are primarily the end users.3
Sodium cyanide--
Sodium cyanide can be prepared by heating sodium amide
with carbon or by melting sodium chloride and calcium
cyanamide in an electric furnace.7 However, almost all of the
NaCN currently manufactured is produced by the neutralization
or so-called wet process, in which liquid hydrogen cyanide
reacts with sodium hydroxide solution.6
3-6
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Potassium cyanide--6
Potassium cyanide is made commercially by the
neutralization or wet process, which reacts aqueous solution
of potassium hydroxide with hydrogen cyanide.
3.2.2 Uses
Hydrogen cyanide--
Forty-three percent of the HCN produced in the United
States is used in the manufacture of adiponitrile (a starting
material of Nylon 6,6). Another 33 percent is used in the
production of acetone cyanohydrin, an intermediate in the
production of methyl methacrylate (MMA) , and an additional 9
percent is used in sodium cyanide production. Cyanuric
chloride production and chelating agents production use 6 and
5 percent of HCN, respectively. The remaining HCN (4 percent)
is used in miscellaneous processes such as methionine and
nitrilotriacetic acid productions. Figure 3-1 illustrates
these uses.9
Historically, the growth in demand for HCN has been 4.8
percent per year from 1980 to 1989. Future demand is expected
to be about 3 percent per year from 1989 through 1994.8
Growth in MMA production and the start-up of at least three
sodium cyanide plants in the United States will require an
increase in HCN capacity.9
Sodium cyanide--
The principal use of sodium cyanide is for the extraction
and recovery of minerals and metals from ores, specifically in
the cyanidation recovery of gold and silver, the froth
flotation beneficiation of sulfide ores, and the refinement of
metal concentrates. Gold recovery by cyanidation is the
single largest mining use for NaCN. Electroplating,
especially for zinc, copper, brass, and cadmium, was the
largest single market for NaCN, but a substantial decline in
use has occurred in recent years due to tighter restrictions
3-7
-------
Adiponitrile 43%
co
I
CO
Methyl MetViacrylate 33%
Miscellaneous 4%
Oh elating Agents 5%
Cyan uric Chloride 6%
Sodium Cyanide 9%
figure 3-1, End uses of.hydroacn cyanide,3
-------
on cyanide discharge and conservation of plating and rinse
solutions. Sodium cyanide is also used for five general
categories of chemical uses (dryers, agricultural chemicals,
Pharmaceuticals, chelating or sequestering agents, and
specialty chemicals). Miscellaneous uses of NaCN include
metal stripping, heat-treating, and compounds used for
cleaning smut (sooty matter). No specific emissions data
exist for NaCN.10
Potassium cyanide--
Potassium cyanide is used primarily for fine silver
plating but is also used for dyes and specialty products.
There are no emissions data specific for KCN.
Other cyanide compounds--6
Of the remaining cyanide compounds, only Ca(CN)2 has any
industrial uses. It is made commercially by heating crude
calcium cyanamide in an electric furnace above 1000°C (1832°F)
in the presence of sodium chloride, and then cooling the
result rapidly to prevent reversion back to calcium cyanamide.
Calcium cyanide is marketed in the form of dark gray flakes
and is used primarily for the extraction or cyanidation of
precious metal ores. It is also used in the froth flotation
of minerals, as a depressant or inhibitor of the flotation of
certain minerals, as a fumigant and rodenticide, and in
limited quantities in the production of prussiates or
ferrocyanides.
3.2.3 Emissions
Two distinct methods were used to develop nationwide
emission estimates for specific source categories. The first
method involved developing source-specific emission factors
and applying those emission factors to estimates of nationwide
source activity to calculate nationwide HCN emission
3-9
-------
estimates. The second method relied on extrapolating emission
estimates from the Toxic Chemicals Release Inventory (TRI) .X1
Hydrogen cyanide is emitted from a number of industrial
processes such as HCN/NaCN/KCN production, adiponitrile
production, acetone cyanohydrin production, cyanuric chloride
production, and production of chelating agents. Other
indirect sources include petroleum refineries and mobile
sources.
Primary sources of information for HCN emission data or
emission factors included ongoing EPA regulatory development
activities, information being collected by EPA to develop
toxic air pollutant emission factors in AP-42, and an EPA data
base on toxic air pollutant emission factors.12'13 With the
exception of mobile sources, no HCN emission factor data were
available. For mobile sources, an emission factor was used to
estimate emissions. For all other potential sources of HCN
emissions, use of emission estimates from the TRI11 and the
EPA study4 were used for estimation of nationwide cyanide
emissions.
Cyanide compounds are emitted from a number of industrial
processes such as NaCN/KCN production, adiponitrile
production, acetone cyanohydrin production, cyanuric chloride
production, and production of chelating agents. Cyanide
compounds are formed as by-products during these processes.
Other operations that emit cyanide compounds include iron and
steel production, carbon black production and electroplating.
For those processes, no HCN emission factor data were
available. For source categories that involve the use of
cyanide compounds, the source of emissions information was TRI
data.11
Table 3-4 presents a compilation of SIC codes that have
been associated with cyanide compound emissions.11'12 This
table lists the SIC codes that were identified as a potential
3-10
-------
TABLE 3-4. SIC CODES ASSOCIATED WITH HYDROGEN CYANIDE AND OTHER CYANIDE
COMPOUND EMISSIONS
SIC Code
Description
2819a
2824b
2833
2834
2865a
2869
Industrial inorganic chemicals
Organic fibers, noncellulosic
Medicinals and botanicals
Pharmaceuticals
Cyclic crudes and intermediates
Industrial organic chemicals
2879
2891
2895
2899a
2911b
3079 & 3089a
3312a
Agricultural chemicals
Adhesives and sealants
Carbon black
Chemical preparations
Petroleum refining
Miscellaneous plastic products
Blast furnaces and steel mills
3313
3315
3316
3334
3339
Electrometallurgical products
Steel wire and related products
Cold finishing of steel
Primary aluminum
Primary nonferrous metals
3341
3351
3355
3357
3398
Secondary nonferrous metals
Copper rolling and drawing
Aluminum rolling and drawing
Nonferrous wire drawing/insulating
Metal heat treating
3429
3432
3452
3471
3482
Hardware
Plumbing fixtures
Bolts/nuts/rivets/washers
Plating and polishing
Small arms ammunition
3-11
-------
TABLE 3.4 (CONTINUED)
SIC
Description
3492
3494
3496
3497
3519
Valves and hose fittings
Valves/pipe fittings
Miscellaneous fabricated wire products
Metal foil and leaf
Internal combustion engines
3562
3566
3610
3624b
3621
3625
Ball and roller bearings
Speed changers/drives/gears
Electrical distributors
Carbon and graphite products
Motors/generators
Relays and industrial controls
3643
3644
3678
3714
3721
Wiring devices
Noncurrent carrying wire devices
Electronic connectors
Motor vehicle parts and accessories
Aircraft
3724
3728
3743
3825
3914
Aircraft engines and parts
Aircraft parts
Railroad equipment
Instruments/transformers
Silverware and plated ware
3949
3963
3964
3965
4925
NA
Sporting and athletic goods
Buttons
Needles/pins/hooks/buttons/etc.
Fasteners/buttons/needles/pins
Gas production/distribution
Mobile sources
aThe HCN emissions reported by facilities belonging to SIC Codes 2879, 2865, 2899, 3079 & 3089, and
3312 in the 1991 TRI collectively constituted approximately 0.3 percent of total HCN emissions reported
in the 1991 TRI.
b The HCN emissions reported by facilities belonging to SIC Codes 2824, 2869, 2911, and 3624
collectively constituted approximately 99.7 percent of total HCN emissions reported in the 1991 TRI.
3-12
-------
source of cyanide emissions, provides a description of the SIC
code, and identifies other emission sources that do not have
an assigned SIC code.11'13
It should be noted that the companies reporting to TRI
specify the type of compound emitted, either HCN or cyanide
compounds in general. Unfortunately, there is not consistent
reporting (e.g., some companies reported their HCN emissions
as HCN emissions, and some companies reported their HCN
emissions as cyanide compound emissions). This primarily
occurs for companies with SIC code 3312, which includes coke
ovens and blast furnaces. Sources indicate that the emissions
from coke ovens/blast furnaces (which are reported in TRI as
cyanide compound emissions) are primarily HCN emissions (see
Section 6).
In selected cases, facilities reported to TRI under
multiple SIC codes. As a result, it was difficult to assign
emissions to a specific SIC code. In those cases, efforts
were made to determine the appropriate SIC codes associated
with the emissions. If appropriate SIC codes could not be
explicitly identified, the data were not used in the analysis.
Table 3-5 provides a summary of the estimated 1991
nationwide cyanide compound emissions for those point source
categories where adequate information was available (i.e.,
emission factors and production data). Appendix A presents
the data used for each of these estimates, assumptions, and
emission calculations for each of these point source
categories. The estimated emissions were based on emission
factors provided in this document or calculated from source
test data and appropriate process information, if available.
From the data shown in Table 3-5 for point source
categories, cyanide emissions from carbon black production
contributed 412 Mg or approximately 47 percent of the total
emissions. Of the remaining point source categories, the next
3-13
-------
TABLE 3-5. ESTIMATED 1991 NATIONWIDE CYANIDE COMPOUND EMISSIONS
FOR SELECTED POINT SOURCE CATEGORIES
Cyanide compound emissions
Point source category
Hydrogen cyanide production
Sodium cyanide production13
Adiponitrile production13
Acetone cyanohydrin production130
Cyanuric chloride13
Chelating agentsd
Electroplating
Iron and steel production
Carbon black production8
Carbon fiber production'
Petroleum refineries9
Mg
154
-
0.013
3.0
-
1.3
10
180
412
74
49
Tons
170
-
0.014
3.3
-
1.4
11
198
454
82
54
Basis3
TRI
TRI
TRI
TRI
TRI
TRI
TRI
TRI
TRI
TRI
TRI
+ EPA
+ EPA
Total
883
974
a TRI = Reference 11; EPA = Reference 4.
b HCN emissions reported under HCN production include HCN emissions for the other
production processes because most facilities that produce HCN also produce the other
products that use HCN.
c These are cyanide compound emission estimates for two of four facilities. There is no basis
to estimate HCN emissions from the other two facilities. Hydrogen cyanide emission
estimates are included in hydrogen cyanide production figures.
d These are emission estimates for only 3 of 22 facilities. Hydrogen cyanide emissions from
3 other facilities are included in hydrogen cyanide production. There is no basis to estimate
HCN emissions from all other facilities producing chelating agents.
8 These emission estimates are for 6 of 24 facilities. There is no basis to estimate cyanide
emissions from the other facilities.
'These emission estimates are for five of eight facilities. There is no basis to estimate cyanide
emissions from the other facilities.
g These emission estimates are for 3 of the 104 petroleum refineries listed in Appendix B. There
is no basis to estimate cyanide emissions from the other facilities.
3-14
-------
four categories having the highest emissions are iron and
steel production (20 percent), hydrogen cyanide production (17
percent), carbon fiber production (8 percent), and petroleum
refineries (6 percent). These five categories constitute
about 98 percent of the total emissions shown in Table 3-5.
All other categories contribute insignificant quantities
compared to the total amount.
3-15
-------
SECTION 4
EMISSIONS FROM PRODUCTION OF MAJOR CYANIDE COMPOUNDS
This section discusses potential emission sources from
production of major cyanide products, hydrogen cyanide (HCN),
sodium cyanide (NaCN), and potassium cyanide (KCN). Process
descriptions, emission control measures, and potential
emissions are provided below for each of the production
processes.
4 . 1 HYDROGEN CYANIDE PRODUCTION
Table 4-1 presents a list of domestic HCN manufacturing
facilities.14 The 1990 annual HCN production capacity was
533 million kilograms (kg) (1,175 million pounds [lb]) and the
estimated demand for 1994 is 590 million kg (1,300 million
lb), respectively.9
Hydrogen cyanide is produced by three different processes:
(1) direct synthesis using methane, ammonia, and oxygen, based
on the Andrussow process, (2) synthesis using methane and
ammonia based on Blausaure Methane Anlage (BMA) process, and
(3) the Sohio process where HCN is obtained as a byproduct of
the reaction between propylene, ammonia, and oxygen. The
Andrussow process accounts for 74 percent of the HCN produced
in the United States. The BMA process is used at one
facility, which accounts for only 3 percent of U.S. HCN
production. The remaining 23 percent is produced by the
Sohio process. A description of each of these production
processes is given below.4
4-1
-------
TABLE 4-1. DOMESTIC PRODUCERS OF HYDROGEN CYANIDE
Facility
Location
1991 Production capacity,
Mg (tons)
American Cyanamid0
BP Chemicals0
BP Chemicals0
CIBA-Geigya
Cyanco Co.a
Degussa Corp.b
Dow Chemical3
DuPonf
DuPont3
DuPont3
DuPont3
FMC Corp.d
Monsanto0
Rohm & Haas3
Sterling Chemicals0
TOTAL
Avondale, LA
Green Lake, TX
Lima, OH
St. Gabriel, LA
Winnemucca, NV
Theodore, AL
Freeport, TX
Beaumont, TX
Memphis, TN
Orange, TX
Victoria, TX
Green River, WY
Alvin, TX
Deer Park, TX
Texas City, TX
29,510(32,500)
27,240 (30,000)
15,890(17,500)
45,400 (50,000)
7,264 (8,000)
24,970 (27,500)
9,080(10,000)
27,240 (30,000)
90,800(100,000)
145,280(160,000)
136,200(150,000)
14,982(16,500)
22,700 (25,000)
90,800(100,000)
38,590 (42,500)
725,946 (799,500)
Source: Reference 14.
3 Hydrogen cyanide is manufactured based on the Andrussow process at these facilities
(Reference 4).
b Hydrogen cyanide is manufactured using the BMA process at these facilities (Reference 4).
0 Hydrogen cyanide is manufactured using the Sohio process at these facilities (Reference 4).
d FMC Corp. manufactures HCN using the Androssow process for captive use within the
facility to produce cyanide.
4-2
-------
4.1.1 Process Descriptions
Andrussow process 4--
A simplified process flow diagram for the Andrussow
process with ammonia recycle is shown in Figure 4-1. The same
process without ammonia recycle is shown in Figure 4-2. In
this process, air and anhydrous ammonia react in the presence
of a platinum/rhodium catalyst at a reaction temperature of
1100°C (2012°F). The reaction heat is supplied by
simultaneous combustion of methane supplied in the form of
natural gas. This reaction is as follows:
2NH3 + 2CH4 + 302 - 2HCN + 6H20
Ammonia Methane Hydrogen
Cyanide
As shown in Figure 4-1, ammonia, air, and natural gas
(CH4)are fed to the reactor. The reactor off-gas, containing
HCN, excess ammonia, water, and excess air, is routed to a
waste-heat-boiler to cool the gas to below 400°C (752°F).
This cooling minimizes decomposition of HCN and ammonia and
also produces steam for energy efficiency. The gas steam then
passes through an ammonia absorber to remove the remaining
ammonia.
If ammonia recycle is used, a monoammonium phosphate
solution can be used to absorb the ammonia and form diammonium
phosphate. The diammonium phosphate solution then passes
through two stripper columns. The ammonia stripper removes
any absorbed NH3 . The NH3 removed from the absorber is
recycled back to the reactor. The second column strips the
HCN stream with steam. The overheads are then fractionated
under pressure to yield ammonia gas for recycle. If ammonia
recycle is not used (Figure 4-2), the ammonia is absorbed
using a sulfuric acid solution to produce ammonium sulfate.
4-3
-------
fiSf»
A-/.
OK4r.
NHft-
PUranCATTC*!
c
1
BOiftfe
S&%afnl£>
RfiACTOR
pinrJ A
WHB
Dilwl*
HCfNgns
ABSORKS
)naW /\ FlnIB
l\^f
*id '.vftRrc
Dihflu MGN liquid^" "yiqfJid rieMpiQdua
ABSORBER
1
WaslA Watu
HCN PURIFICATION
Figure 4-t, Andrussow HCN production process with ammonia recycle,*
-------
Ta (tare (start-up)
I
Cn
•a
1
PJ
|
f
I
Vv_
.
E
a
fflaactor -otf-gaa
*
BOILER
crtw
(C4~ IDT
aeld waste
flan (used when
HON-WKler
• AcW
1
HCN E-tippur
Waste
HON wilh Sp2
inhibitor
HC
—| Steam I
I S02 i
Sleain
Waste walsf
Figure 4-2. Andruss^jw HCN production process without 9 romance
-------
After ammonia absorption, the product gas stream passes
through an HCN absorber where HCN is recovered as a dilute
solution in water. The HCN solution is then purified to over
99-percent purity using conventional stripping and
distillation columns. The off-gas from the HCN absorber,
which contains some HCN, is usually routed to a boiler for
energy recovery. Wastewater resulting from the absorber, HCN
purification, and the ammonia purification process is
collected and treated. Details pertaining to the methods used
for collection, treatment, and ultimate disposal are not
available.
The major emission sources for this process are the
reactor, HCN absorber, and HCN distillation column. The off-
gases from the HCN absorber and the distillation column are
routed to boilers or flares and are shown by solid circles in
Figures 4-1
and 4-2. In addition, the reactor off-gas is routed to a
flare during startup until the reactor reaches its desired
operating range. Depending on the concentration of HCN in the
wastewater resulting from the absorber, HCN purification and
ammonia purification steps, the wastewater treatment operation
may also result in HCN emissions.
Other sources of HCN emissions include fugitive emission
sources such as storage, valves, joints, and other fittings.
Data from the 1991 TRI show nonpoint emissions to be about 10
percent of the total reported emissions.
Blausaure Methane Anlage (BMA) production process 4--
In the BMA process, only methane (as natural gas) and
ammonia are supplied to the reactor. The process reaction is
as follows:
CH4 + NH3 - HCN + 3H2
4-6
-------
The heat of reaction is supplied to the reactor by external
heating of the ceramic or alumina tubes coated with a thin
layer of platinum.
Figure 4-3 presents a simplified flow diagram for this
process. The effluent gas exiting the reactor is cooled and
then routed to an absorber where the ammonia is removed using
a sulfuric acid solution to produce ammonium sulfate. Details
pertaining to the reactor design and the cooling system are
not available. After ammonia absorption, the product gas
passes through the HCN absorber where HCN is absorbed as a
dilute solution in water. The dilute solution is then
enriched in the same fashion as the Andrussow process.
The off-gas from the HCN absorber is mainly hydrogen.
This gas stream is used in other processes. This process also
routes the reactor off-gas to a flare during startup.
Wastewater may be generated as a result of absorption and HCN
distillation. Details pertaining to collection, treatment,
and ultimate disposal of wastewater are not available.
The major advantages of the BMA process compared to the
Andrussow process are higher feedstock yields of HCN and a
relatively pure hydrogen byproduct stream. Higher yields
reduce the size and the cost of the recovery equipment, while
byproduct hydrogen can be used as a fuel for other processes
or used in other processes. However, the BMA process requires
a more complex reactor system.
The major emission sources (shown in Figure 4-3 by solid
circles) are the reactor and HCN distillation column. During
startup, the reactor off-gases are routed through a flare.
Depending on the concentration of HCN in the wastewater
produced from the various process steps, the wastewater
treatment operation may also result in HCN emissions. Other
4-7
-------
I
CO
1
[•\
BOfUER
Slsam
Rwcter
afl-gas
Air
Fuel
REACTOft
FURNACE
V - J
t
MIXER
To flaw
Tail gas
HCN
NH3ABSORBER
*J«JM DISfTAUATIDW
I—Mfi)^
^^ scfubon
Figure 4-3. llausa.Lrfe Methane Aniaae HCN urodyctiofi
-------
sources of HCN emissions include fugitive emission sources
such as valves, joints, and other fittings. However,
information pertaining to these sources is not available.
Sohio production process 4--
All six of the U.S. plants producing acrylonitrile use the
Sohio process. In this process, propylene, anhydrous ammonia,
and air are combined to produce acrylonitrile and byproducts
of HCN and acetonitrile. The reactions which occur in this
process are as follows:
Primary Reaction:
2C3H6 + 2NH3 + 302
Propylene Ammonia
Secondary Reactions:
2CH2 = CHCN + 6H20
Acrylonitrile
C3H6 + 3NH3
30-
3NH-
30-
3HCN + 6H20
Hydrogen
Cyanide
3CH3CN + 6H20
Acetonitrile
Figure 4-4 presents a simplified flow diagram for the
Sohio process. Propylene, ammonia, and air are introduced
into a fluid bed catalytic reactor operating at 35 to
207 kPa (5 to 30 psig) and 400° to 510°C (750° to 950°F). The
reactor off-gas containing the reaction products passes
through a quencher to lower the temperature. Sulfuric acid
may be added in the quencher to neutralize any excess ammonia.
The gas stream then goes to an absorber where the HCN and
other products are absorbed into a dilute solution. The gas
stream from the absorber is then routed to a waste heat boiler
for energy recovery.
4-9
-------
I
h->
o
Veal
t
UquidWaatB
Waste Oxidizsr
Boiler
To Flare
(dart-up only]
PMfl HCN flaa
Air
1
Renctnr
t Dinote€ polmlial
tymtit smisslon souroe
Flare
T I UquW
I HCM
MH k
I
colUmrt
:n_J
UgUta
colurm
Water Tfeattneirt
arid
4-4. SoNo production procsss for accyloriitrifs/HCN production,
-------
The solution containing acrylonitrile and HCN from the
absorber goes to a series of distillation columns where the
acrylonitrile and HCN are separated and purified. The gaseous
streams from the distillation columns, which contain
acetonitrile along with trace amounts of HCN, are routed
through a flare. The Sohio process allows yields of 0.9
pounds of acrylonitrile and 0.1 pounds of HCN per pound of
propylene feed.
The major emission points for this process as denoted on
Figure 4-4 are reactor and distillation column off-gas
streams, which are routed to the flare during startup, and the
absorber off-gas, which is typically routed to a boiler for
energy recovery.
Wastewater resulting from the absorber and distillation
columns is collected, heated, and recycled. Information
pertaining to the treatment methods used is not available.
Depending on the concentration of HCN in the wastewater, the
wastewater treatment system may also potentially emit HCN.
Other sources of HCN emissions include fugitive emission
sources such as valves, joints, and other fittings. No
information is available pertaining to these sources.
4.1.2 Emission Control Measures4
In the Andrussow process, the reactor off-gases are
destroyed in a flare only during startup, until the desired
operating conditions are reached. The emissions from the
absorber are burned in a boiler onsite. Emissions from the
HCN distillation column are routed to a flare. Details
pertaining to the operating conditions of the control systems
and destruction efficiencies of HCN are not available.
Additionally, information pertaining to control of HCN
4-11
-------
emissions resulting from wastewater treatment is not
available.
In the BMA process, the reactor off-gases are also
destroyed in a flare during startup. Information pertaining
to control of HCN emissions from other sources, such as HCN
distillation column and wastewater treatment, is not
available.
In the Sohio process, the reactor off-gases are destroyed
in a flare during startup only. Emission streams containing
trace amounts acetonitrile and HCN from the absorber and
distillation columns are destroyed in a flare. Details
pertaining to destruction efficiency are not available.
4.1.3 Emissions
Test data are not available for HCN emissions occurring
during the different steps of HCN production. However, 12 of
the 15 HCN manufacturing facilities have reported facilitywide
HCN emissions in the 1991 Toxic Chemical Release Inventory
(TRI). The TRI data are presented in Table 4-2."
Hydrogen cyanide emission data for the remaining three
facilities were not contained in the 1991 TRI. The U. S.
Environmental Protection Agency has estimated annual HCN
emissions for all 15 of the domestic HCN producing
facilities.4 Table 4-2 also presents HCN emission data
estimated by EPA for the three remaining facilities for which
1991 TRI data were not available.4
4.2 SODIUM CYANIDE PRODUCTION
Sodium cyanide accounts for 9 percent of HCN use.14
Table 4-3 presents a list of domestic NaCN manufacturers.4'14
This section presents a description of the NaCN production
4-12
-------
TABLE 4-2. HYDROGEN CYANIDE PRODUCERS REPORTING HYDROGEN
CYANIDE EMISSIONS IN THE 1991 TOXICS RELEASE INVENTORY
Emissions, kg (Ib)
Facility
BP Chemicals
Lima, OH
Ciba-Geigy
St. Gabriel, LA
Degussa Corp.
Theodore, AL
Dow Chemical
Freeport, TX
DuPont
Beaumont, TX
DuPont
Memphis, TN
DuPont
Orange, TX
DuPont
Victoria, TX
FMC Corp.
Green River, WY
Monsanto
Alvin, TX
Rohm & Haas
Deer Park, TX
Sterling Chemicals
Texas City, TX
American Cyanamid3
Avondale, LA
BP Chemicals'3
Green Lake, TX
Cyanco
Winnemucca, NY
Nonpoint
998 (2,200)
29 (63)
345 (760)
2(4)
1,360(3,000)
459(1,012)
1,002(2,210)
1 ,038 (2,290)
0(0)
680 (1 ,500)
254 (560)
3,936 (8,680)
727 (1 ,600)
5,909(13,000)
N/E
Point
4,308 (9,500)
93 (204)
771 (1,700)
0(0)
1 ,496 (3,300)
13,224(29,159)
30,970 (68,288)
2,531 (5,580)
36 (79)
635 (1 ,400)
49,887(110,000)
17,451 (38,480)
909 (2,000)
15,000(33,000)
N/E
Total
5,306(11,700)
122(267)
1,116(2,460)
2(4)
2,856 (6,300)
13,683(30,171)
31,972(70,498)
3,569 (7,870)
36 (79)
1,315(2,900)
50,141 (110,560)
21,387(47,160)
1 ,636 (3,600)
20,909 (46,000)
N/E
Source
TRI
TRI
TRI
TRI
TRI
TRI
TRI
TRI
TRI
TRI
TRI
TRI
EPA
EPA
EPA
TOTAL
16,739(36,879) 137,311(302,690) 154,050(339,569)
Source: References 4 and 11.
aThe emission data for American Cyanamid are based on data reported to TRI. However, the year is unknown.
b The basis of estimation of emissions from BP Chemicals is not known.
N/E = Not estimated.
4-13
-------
process, emission control measures, along with a discussion on
emissions resulting from the production process.
TABLE 4-3. DOMESTIC PRODUCERS OF SODIUM CYANIDE
Facility Location 1991 Production capacity,
Mg (ton)
Cyanco Co. Winnemucca, NV 12,712(14,000)
Dow Chemical Freeport, TX N/A
DuPont Memphis, TN 113,500(125,000)
DuPont Texas City, TX N/A
FMC Corp. Green River, WY N/A
Sterling Chemicals Texas City, TX 45,400 (50,000)
Degussa Corp. Theodore, AL 27,240 (30,000)
Source: References 4 and 14.
N/A = not available.
4.2.1 Process Description4
The process description given below is based on very
limited information and references available at this time.
All the facilities listed in Table 4-3 produce NaCN using the
neutralization or wet process. The reaction for this process
is as follows:
NaOH + HCN - NaCN + H20
A flow diagram for this process is shown in Figure 4-5.
Hydrogen cyanide and sodium hydroxide are mixed in a reactor
vessel to produce NaCN and water. Excess sodium hydroxide is
used to maintain an alkaline condition. This prevents
reformation of HCN. Once past the reactor, there is no HCN
remaining in any of the process streams.
4-14
-------
To atenosfBw a
NaGH
HCN
To packing area
wio storage
4jS. Sodium cvinicte neutralization prpclwcticin
-------
The slurry produced by the reaction is typically routed to
a crystallizer and then to a drum filter where the NaCN solids
are separated from the water. The solids are dried and
conveyed pneumatically to a briquetter; then, they are packed
in drums or plastic-lined crates for bulk shipment.
The major cyanide emissions source for this process is the
vent from the crystallizer. This vent typically passes
through water and then a caustic scrubber to recover any
traces of residual HCN. Based on the limited available
information, some facilities vent the reactor to a flare. The
hot air used for drying is recycled so there is no emission
potential. If air is used to convey the NaCN, then the air
exhaust stream becomes a potential emission point of NaCN.
Typically, a cyclone is used to remove NaCN from the airstream
when this is the case.
4.2.2 Emission Control Measures
The main source of NaCN emissions is the crystallizer.
The gases from the crystallizer are vented through a caustic
scrubber to remove the NaCN. In cases where the reactor is
equipped with a vent, the off-gases are routed through a
flare. Information pertaining to cyanide compound reduction
achievable in the caustic scrubber and the flare is not
available. Also, information pertaining to NaCN emissions
resulting from pneumatic conveying and its control are not
available.
4.2.3 Emissions
Test data are not available for cyanide compound emissions
occurring during the different steps of NaCN production.
However, five of the seven NaCN manufacturing facilities shown
in Table 4-4 have reported facilitywide HCN emissions in the
1991 TRI; these five facilities also manufacture HCN. The TRI
data are presented in Table 4-2.ll It is not clear as to what
4-16
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TABLE 4-4. HYDROGEN CYANIDE AND SODIUM CYANIDE EMISSIONS
FROM NaCN PRODUCTION FACILITIES
Facility
Cyanco Co.
Process vent
emissions
40 (88)a
Emissions, kq (Ib)
Fugitive
emissions
NAb
Total
40 (88)a
Winnemucca, NV
DuPont
Memphis, TN
FMC Corp.
Green River, WY
NA
NA
NA
NA
HCN 4,536 (10,000)
NaCN 1,361 (3,000)
NA
Sterling Chemicals
Texas City, TX
Degussa Corp.
Theodore, AL
HCN 9 (20)
NaCN 18(39)
HCN 125(276)
NaCN NA
HCN 49 (108)
NaCN 32 (70)
NA
HCN 58 (128)
NaCN 50 (109)
HCN 125(276)
NaCN NA
Source: Reference 4.
3 Hydrogen cyanide and sodium cyanide emissions combined.
b NA = Not available.
fraction of the HCN emissions result due to the manufacture of
HCN itself, as opposed to the manufacture of NaCN. The EPA
study presented a summary of emissions from NaCN production
for four of the seven producers in 1991.4 These data are
presented in Table 4-4 and, where available, show values for
both HCN and NaCN. No breakdown between process vents and
fugitive emissions were available for the DuPont Memphis
plant.
4.3 POTASSIUM CYANIDE
Two facilities, DuPont, Memphis, TN, and W. R. Grace,
Nashua, NH, manufacture KCN.14 Production capacity data for
these two facilities are not available.
The process used in the manufacture of KCN is similar to
that used in the manufacture of NaCN.15 The only difference
4-17
-------
is that instead of NaOH, KOH is used as the raw material which
is reacted with HCN. The process description for the
manufacture of NaCN is presented in the previous section.
Emission control measures for the control of HCN and KCN
emissions are assumed to be the same as that used during the
manufacture of NaCN. Test data pertaining to emissions of HCN
and KCN resulting from the different steps in the manufacture
of KCN are not available. Table 4-2 presents facilitywide HCN
emissions reported by DuPont in the 1991 TRI. DuPont has also
reported a facilitywide cyanide compound emissions of 1,385 kg
(3,053 Ib) in the 1991 TRI. Details pertaining to the nature
of cyanide compounds are not available. DuPont manufactures
several cyanide compounds at the Memphis, TN, location. W.R.
Grace has reported a facilitywide HCN emission of 1,028 kg
(2,267 Ib) in the 1991 TRI. W.R. Grace also manufactures
other cyanide compounds, in addition of KCN. Therefore, it is
difficult to determine how much of the HCN emissions reported
in the 1991 TRI resulted due to KCN production alone.
4-18
-------
SECTION 5
EMISSIONS FROM MAJOR USES OF CYANIDE COMPOUNDS
Hydrogen cyanide (HCN) is used as a feedstock for
manufacturing adiponitrile, acetone cyanohydrin which is used
in the production of methyl methacrylate, cyanuric chloride,
and chelating agents. In the manufacture of all of these
substances, hydrogen cyanide is used as a raw material which
participates in chemical reactions. In these reactions,
hydrogen cyanide emissions (and emissions of other cyanide
compounds) can be expected to occur during the raw material
preparation steps and product purification steps.
This section presents process information, air pollution
control measures, and estimates of hydrogen cyanide (and other
cyanide compounds) emissions from these sources.
5.1 ADIPONITRILE PRODUCTION
Adiponitrile, which is derived from adipic acid, accounts
for 43 percent of HCN use.9 Adiponitrile is used as an
intermediate for the manufacture of hexamethylenediamine, a
principal component of Nylon 6,6. Three facilities currently
manufacture adiponitrile in the United States (U.S.), as
indicated in Table 5-1.14 DuPont manufactures adiponitrile
by hydrocyanation of butadiene where butadiene is reacted with
HCN. In the DuPont process, unreacted HCN may potentially be
emitted as an air pollutant. Monsanto produces adiponitrile
from electrohydrodimerization of acrylonitrile and does not
involve the use of HCN.
5-1
-------
TABLE 5-1. DOMESTIC ADIPONITRILE PRODUCERS
Facility Location 1991 Production
capacity, Mg (tons)
DuPont
DuPont
Monsanto3
Orange, TX
Victoria, TX
Decatur, AL
220,450 (242,500)
215,910(237,500)
188,640(207,500)
Source: Reference 14.
a Process does not use HCN.
A process description of the hydrocyanation of butadiene
used to manufacture adiponitrile and a discussion of the
emissions resulting from the various operations are presented
below.
5.1.1 Process Description17
Hydrocyanation of Butadiene--
Figure 5-1 presents a process flow diagram for
manufacturing adiponitrile by hydrocyanation of butadiene. In
this process, butadiene is fed to a separator where it is
dried by separating the impurities through molecular sieves.
The dried butadiene is fed into a reactor along with HCN and a
catalyst. As a result of the catalytic reaction,
intermediates consisting of pentenenitriles are formed.
The pentenenitriles stream, consisting of unreacted raw
materials and the catalyst (carried over from the reactor), is
fed into an absorption column where butadiene is used as the
absorbent to recover unreacted butadiene. The pentenenitrile
stream now containing predominantly the catalyst is sent to a
catalyst removal system to recover the catalyst. The purified
pentenenitrile stream continues to a distillation column where
5-2
-------
Cn
I
co
VtemtB
Butadiene
Storage
Ad^pcnidle
Aqueous. VI/QSIB
(ID fr^ociion wMIJ
tc
5
1
m
r;
^L
^
Sump
System
5-1. Process flDrt diagram for production of adlpanitrlle by hydrocvanaticm c* butadiene
-------
low boiling fractions are removed. The bottoms from the
distillation column, containing mononitriles, are passed to a
second-stage reactor where additional HCN is added to convert
the mononitriles to dinitriles. The dinitrile stream is
purified in an additional refining step to separate
adiponitrile.
5.1.2 Emission Control Measures16
Emissions resulting from the butadiene absorption column
may contain HCN and are destroyed in a flare. The gas streams
from the distillation column and the second-stage reactor may
also contain HCN. However, information pertaining to HCN
destruction efficiencies obtained during combustion in the
boiler or flare is not available.
5.1.3 Emissions
Sources of HCN emissions are shown in Figure 5-1 by solid
circles. Hydrogen cyanide emissions can potentially result
from the primary and second stage reactors. Other sources may
include the butadiene absorption column and the pentenenitrile
distillation column. Emissions of HCN may also result from
sources of fugitive emissions such as joints, valves, and
other fittings. However, details pertaining to fugitive
emissions are not available. Hydrogen cyanide may be present
in the aqueous waste from the second stage reaction, which is
sent to an injection well.
Test data pertaining to cyanide emissions from individual
sources at adiponitrile manufacturing facilities are not
available. However, two facilities manufacturing adiponitrile
have reported cyanide compound emissions in the Toxic Release
Inventory (TRI) for the year 1991. The TRI data are presented
in Table 5-2.X1 Both facilities produce multiple derivatives
5-4
-------
of HCN. Therefore, it is not clear which specific sources
emit cyanide compounds and/or HCN.
TABLE 5-2. ADIPONITRILE PRODUCERS REPORTING CYANIDE COMPOUND OR HYDROGEN
CYANIDE EMISSIONS IN THE 1991 TOXICS RELEASE INVENTORY3
Cyanide compound emissions,
kg (Ib)
Facility Nonpoint Point Total
Hydrogen cyanide emissions, kg (Ib)
Nonpoint
Point
Total
Dupont
Orange, TX
Dupont
Victoria, TX
Total
12
(26)
0
(0)
12
(26)
1.4
(3)
0
(0)
1.4
(3)
13.4
(29)
0
(0)
3.4
(29)
1,002
(2,210)
1,038
(2,290)
2,040
(4,500)
30,970
(68,288)
2,531
(5,580)
33,501
(73,868)
31,972
(70,498)
3,569
(7,870)
35,541
(78,368)
Source: Reference 11.
3 These facilities produce multiple derivatives of HCN. Therefore, it is not clear as to what the
specific sources are that emit cyanide compounds and/or HCN.
5.2 ACETONE CYANOHYDRIN
Acetone cyanohydrin is an intermediate in the manufacture
of methyl methacrylate. Most of the acetone cyanohydrin
produced is used to produce methyl methacrylate, and it
accounts for 6 percent of HCN use.9 Acetone cyanohydrin is
produced by directly reacting acetone with HCN. The four
facilities which produce acetone cyanohydrin in the U.S. are
presented in Table 5-3.18 Three of these facilities use the
acetone cyanohydrin in a captive process to produce methyl
methocrylate. The production capacity of the fourth producer,
BP America, Inc., is not available. A description of the
process used to manufacture acetone cyanohydrin and a
discussion of the emissions resulting from the various
operations are presented below.
5-5
-------
TABLE 5-3. DOMESTIC ACETONE CYANOHYDRIN PRODUCERS
Source: Reference 14.
N/A = Not available
1991 Production capacity. Ma
Facility
BP American, Inc.
GYRO Industries
DuPont
Rohm & Haas Company
Location
Green Lake, TX
New Orleans, LA
Memphis, TN
Deer Park, TX
(tons)
N/A
N/A
N/A
N/A
5.2.1
Process Description1
Figure 5-2 presents a process flow diagram for the process
of manufacturing acetone cyanohydrin by the catalytic reaction
of acetone with HCN. Acetone and HCN are fed continuously
along with sodium hydroxide catalyst into the reactor where
the following reaction takes place:
(CH3)2 CO
Acetone
HCN - (CH3)2C(OH)CN + heat
Acetone
Cyanohydrin
Because the reaction is exothermic, the reaction mixture
is chilled. The crude product stream is transferred to an
intermediate holding tank to force the equilibrium towards
acetone cyanohydrin production. The mixture is then sent to a
neutralization tank where it is neutralized with sulfuric acid
to a pH between 1 and 2 to prevent decomposition of the
cyanohydrin. As a result of the neutralization, the sodium
catalyst that is carried over precipitates as sodium sulfate.
The neutralized product stream is routed through a filter
where the sodium sulfate is separated. The crude acetone
cyanohydrin mixture is fed to a distillation column where the
5-6
-------
Cn
I
Pigura 5-2, Proc&ss flow diagram for production of acetone cyanohvdrin
-------
light ends are separated. The bottoms from the distillation
column, containing concentrated acetone cyanohydrin and water,
is then fed to a dehydration column where water is removed and
anhydrous acetone cyanohydrin is recovered.
Three facilities--CYRO Industries, (New Orleans,
Louisiana) DuPont (Memphis, Tennessee), and Rohm & Haas
Company (Deer Park, Texas)--use the acetone cyanohydrin
directly for the production of methyl methacrylate.14 The
production of methyl methacrylate does not involve the use of
HCN.19 Therefore, it is believed that the process steps
starting with acetone cyanohydrin, leading to the production
of methyl methacrylate, do not result in HCN emissions.
5.2.2 Emission Control Measures
Information pertaining to HCN emission control during the
production of acetone cyanohydrin is not available.
5.2.3 Emissions
Sources of HCN emissions are shown in Figure 5-3 by solid
circles. Emissions of HCN can potentially result from the
reactor, holding tank, neutralization tank, filter, and light
ends distillation column. However, approximately 99 percent
or more of the HCN fed to the reactor is converted to acetone
cyanohydrin. Therefore, very little HCN is present in the
process streams. Emissions of HCN may also result from
sources of fugitive emissions such as storage, wastewater
treatment operations, joints, valves and other fittings. Data
reported in the TRI show that the nonpoint emissions are only
about one percent of the total emissions.
Test data pertaining to cyanide emissions from individual
sources at acetone cyanohydrin manufacturing facilities are
not available. However, three of the four facilities
5-1
-------
manufacturing acetone cyanohydrin have reported cyanide
compound emissions in the TRI for the year 1991. The TRI data
are presented in Table 5-4." All of these facilities produce
multiple derivatives of HCN. Therefore, it is not clear which
specific sources emit cyanide compounds and/or HCN.
TABLE 5-4. ACETONE CYANOHYDRIN PRODUCERS REPORTING CYANIDE COMPOUNDS OR
HYDROGEN CYANIDE EMISSIONS IN THE 1991 TOXICS RELEASE INVENTORYa
Cyanide compound emissions, kg (Ib) Hydrogen cyanide emissions, kg (Ib)
Facility
Dupont
Memphis, TN
Rohm & Haas
Deer Park, TX
BP Chemicals, Inc
Green Lake, TX
Total
Nonpoint
205
(451)
1,224
(2,700)
0
(0)
1,429
(3,151)
Point
1,180
(2,602)
426
(940)
0
(0)
1,606
(3,542)
Total
1,385
(3,053)
1,650
(3,640)
0
(0)
3,035
(6,693)
Nonpoint
459
(1,012)
254
(560)
3,810
(8,400)
4,523
(9,972)
Point
13,224
(29,159)
49,887
(110,000)
11,791
(26,000)
74,902
(165,159)
Total
3,683
(30,171)
50,141
(110,560)
15,601
(34,400)
79,425
(175,131)
Source: Reference 11.
3These facilities produce multiple derivatives of HCN. Therefore, it is not clear as to what the
specific sources are that emit cyanide compounds and/or HCN.
5.3 CYANURIC CHLORIDE
Cyanuric chloride, which is used to produce pesticides,
accounts for 6 percent of HCN used in the United States.
Cyanuric chloride is produced in two steps. In the first
step, chlorine is reacted with HCN to produce cyanogen
chloride. In the second step, cyanogen chloride is trimerized
to form cyanuric chloride. Two facilities, Degussa Corp. in
Theodore, Alabama, and Ciba-Giegy in St. Gabriel, Louisiana,
are reported to produce cyanuric chloride.4 Information
pertaining to cyanide chloride production capacity at both
plants is not available. A description of the process used to
manufacture cyanuric chloride and a discussion of the
emissions resulting from the various operations are presented
below.
5-9
-------
5.3.1 Process Description
Figure 5-3 presents a process flow diagram for the
manufacture of cyanuric chloride by the reaction of chlorine
with HCN. Chlorine and HCN are added to the reactor
(chlorinator) where the reaction to form cyanogen chloride
(CNC1) takes place at a temperature between 20° and 40°C (68°
and 104°F). The cyanogen chloride formed in the chlorinator
is washed with water in a scrubber. The wash water dissolves
the excess HCN and HC1 from the reactor. The water containing
HCN and HC1 goes to a stripper that recycles any dissolved
cyanogen chloride and HCN and releases HC1. Cyanogen
chloride, which is devoid of HC1, is passed through a drying
unit to remove traces of water. After exiting the dryer,
chlorine is added to the cyanogen chloride and the mixture
sent to the trimerizer where the CNC1 is trimerized on
activated charcoal at temperatures above 300°C (572°F) to form
cyanuric chloride. Cyanuric chloride vapors from the
trimerizer are condensed to molten or solid product, which is
dissolved in a solvent for captive use or filled from a hopper
into containers. Tail gases (containing CNC1 and C12) are
scrubbed. The CNC1 yield in this process exceeds 95 percent
and the (CNC1)3 yield exceeds 90 percent.
5.3.2 Emission Control Measures4'20
As described above, HCN, cyanogen chloride and cyanuric
chloride emissions may occur as a result of the manufacture of
cyanuric chloride. The HCN and cyanogen chloride emissions
from the reactor are controlled by a water scrubber.
Emissions of cyanogen chloride resulting from the cyanuric
chloride condenser (following the trimerizer) are controlled
by a water scrubber followed by a caustic scrubber. The
control efficiency of these scrubbers for cyanogen chloride
are unknown but it could be anticipated to be an efficient
method because of the solubility of the compound in water.
However, the ultimate control depends upon the specific
5-10
-------
Cn
I
and aolwml
Trasrtmwnt
5-3- Process fJaw diagram for pradyctlon of cyariuric chlarids.
-------
wastewater treatment practices, which are unknown.
5.3.3 Emissions
Sources of HCN, cyanogen chloride, and cyanuric chloride
emissions are shown in Figure 5-3 by solid circles. Test data
pertaining to cyanide emissions from individual sources during
the manufacture of cyanuric chloride are not available.
Degussa Corp. and Ciba-Geigy have reported hydrogen cyanide
emissions of 1,116 kg (2,460 Ib) and 121 kg (267 Ib),
respectively, to the TRI, for the year 1991." Of the total
emissions from the Degussa facility, 31 percent were from
nonpoint sources; for the Ciba-Geigy facility, 24 percent were
from nonpoint sources.
5.4 CHELATING AGENTS PRODUCTION
Chelating agents are a minor use of HCN, consuming 5
percent of the HCN produced in the United States.9 The
primary chelating agents using HCN as a raw material are
ethylenediaminetetraacetic acids (EDTA), aliphatic
hydroxycarboxylic acids, and nitrilotriacetic acids (NTA).
Table 5-5 lists the U.S. producers of these agents.14
5.4.1 Process Descriptions
Ethylenediaminetetraacetic acids--21
The two-step Singer synthesis is the only commercial
process currently used to manufacture EDTA that uses HCN as a
raw material. The Singer synthesis has two separate steps,
the cyanomethylation step and hydrolysis. In
cyanomethylation, hydrogen cyanide and formaldehyde react with
ethylenediamine to form insoluble (ethylenedinitrilo)tetra-
acetonitrile (EDTN). The intermediate nitrile is then
5-12
-------
TABLE 5-5. U.S. PRODUCERS OF HCN-USING CHELATING AGENTS
Chelating agent
Company
Location
Ethylenediaminetetraacetic acids3
-Citric acidb
-Lactic acid
CIBA-GEIGY Corp.
Dow Chemical
Eastman Kodak Co.
Emkay Chemical Co.
GFS Chemicals, Inc.
Hart Products Corp.
Hickson DanChem Corp.
Mayo Chemical Co.
Vinings Industries, Inc.
Vinings Industries, Inc.
W.R. Grace & Co.
Mclntosh, AL
Freeport, TX
Rochester, NY
Elizabeth, NJ
Columbus, OH
Jersey City, NJ
Danville, VA
Dalton, GA
Marietta, GA
Washougal, WA
Nashua, NH
Hydroxycarboxylic acids
-Butyrolactone
BASF Corp.
GAF Corp.
GAF Corp.
Geismar, LA
Calvert City, KY
Texas City, TX
Archer Daniels Midland Co.
Bayer USA, Inc.
Bayer USA, Inc.
Cargill, Inc.
Pfizer, Inc.
Sterling Chemicals, Inc.
Pfanstiehl Laboratories, Inc.
Southport, NC
Dayton, OH
Elkhart, IN
Eddyville, IA
Groton, CT
Texas City, TX
Waukegan, IL
Nitrilotriacetic acids
Dow Chemical, Inc.
W.R. Grace & Co.
Mayo Chemical Co.
Monsanto Co.
Freeport, TX
Nashua, NH
Dalton, GA
Alvin, TX
Source: Reference 14.
a It could not be verified whether all U.S. producers of EDTA use the Singer process.
b Production capacity data are available only for citric acid, as below:
Archer Daniels Midland Co., Southport, NC
Bayer USA, Inc., Dayton, OH
Bayer USA, Inc., Elkhart, IN
Cargill, Inc., Eddyville, IA
Pfizer, Inc., Groton, CT
110 million pounds
65 million pounds
86 million pounds
55 million pounds
70 million pounds
5-13
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separated, washed, and hydrolyzed with sodium hydroxide to
tetrasodium EDTA. Ammonia is liberated as a byproduct.
Aliphatic Hydroxycarboxylic Acids 22--
Aliphatic hydroxycarboxylic acids are manufactured in many
different ways. Two processes utilize HCN in their syntheses.
a-Hydroxycarboxylic acids (e.g., (R,S)-lactic acid) are
produced by cyanohydrin synthesis. 15-Hydroxcarboxylic acids
can be prepared by treating epoxides with HCN and then
hydrolyzing the intermediate nitriles. No information is
available regarding what percentage of hydroxycarboxylic acids
are prepared by either of these two methods. It is not known
which of the plants listed in Table 5-5 uses the HCN-based
process for the manufacture of aliphatic hydroxycarborylic
acids.
Nitrilotriacetic Acids 23--
Nitrilotriacetic acids (Na3 NTA) are produced by two
processes. The older process, the alkaline process, utilizes
NaCN, not HCN, and is not discussed here. A newer, two-stage
process (the acid process) uses HCN as a raw material and was
developed due to the significant yield of byproducts produced
by the alkaline process. In the first stage of the acid
process, ammonia reacts with formaldehyde to produce
hexamethylene-tetramine, which then reacts with HCN in
sulfuric acid solution to yield triscyanomethylamine. The
solid triscyanomethylamine is filtered off, washed, and
saponified with NaOH to produce Na3 NTA. It is not known
which of the two nitrilotriacetic acid manufacturing processes
is used predominantly in the United States.
5.4.2 Emission Control Measures
Information pertaining to controlling cyanide emissions
resulting from the production of chelating agents is not
available.
5-14
-------
5.4.3 Emissions
Test data pertaining to cyanide emissions from individual
sources at chelating agent manufacturing facilities are not
available. Additionally, based on the limited process data
available, it is not possible to identify the potential
emission sources of HCN or cyanide compounds during the
manufacture of chelating agents. However, seven facilities
manufacturing chelating agents have reported facilitywide
cyanide compounds or HCN emissions to the TRI for the year
1991. The TRI data are presented in Table 5-6."
TABLE 5-6. PRODUCERS OF CHELATING AGENTS REPORTING CYANIDE COMPOUND OR
HYDROGEN CYANIDE EMISSIONS IN THE 1991 TOXICS RELEASE INVENTORY3
Cyanide compound emissions,
kg (Ib)
Hydrogen cyanide emissions,
kg (Ib)
Facility
Ciba-Geigy
Mclntosh, AL
Dow Chemical
Freeport, TX
W.R. Grace
Nashua, NH
Pfizer, Inc.
Groton, CT
Sterling Chemicals
Texas City, TX
Pfanstiehl Labs
Waukegan, IL
Monsanto
Alvin, TX
Total
Nonpoint
N/R
0(0)
0(0)
0(0)
0(0)
0(0)
N/R
0(0)
Point
N/R
0(0)
0(0)
2.3
(5)
0(0)
0(0)
N/R
2.3
(5)
Total
N/R
0(0)
0(0)
2.3
(5)
0(0)
0(0)
N/R
2.3
(5)
Nonpoint
113
(250)
2
(4)
812
(1 J90)
N/R
3,936
(8,680)
N/R
680
(1 ,500)
5,543
(12,224)
Point
113
(250)
0(0)
216
(477)
N/R
17,451
(38,480)
N/R
635
(1 ,400)
18,415
(40,607)
Total
226
(500
2
(4)
1,028
(2,267)
N/R
21,387
(47,160)
N/R
1,315
(2,900)
23,958
(52,831)
Source: Reference 11.
N/R = not reported in 1991 TRI.
a These facilities produce multiple derivatives of HCN. Therefore, it is not clear as to what the
specific sources are that emit cyanide compounds and/or HCN.
5-15
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5.5 CYANIDE ELECTROPLATING
Cyanide compounds are used in a number of electroplating
solutions. Cyanide compounds are used in copper, brass,
cadmium, gold, indium, silver, and zinc plating baths. The
primary cyanide compounds used in electroplating solutions are
sodium or potassium cyanide and the metal cyanide, such as
gold and silver cyanide. In some cases, cyanide plating baths
are being replaced with baths composed of less toxic
compounds. However, there are specific applications and
plating operations that require the use of cyanide-based
plating solutions.
Table 5-7 presents the number of metal finishing job shops
that perform the types of plating operations listed above.24
Some duplication of shops will be presented because most metal
finishing operations perform more than one type of
electroplating operation. Copper and zinc plating baths are
the most common plating solutions that use cyanide compounds.
The demand for precious metal deposits is not as high as that
for functional deposits, such as copper and zinc. In
addition, not all of the job shops accounted for in Table 5-7
will use the cyanide version of the plating bath. Some
operations may use substitute baths that have been developed
to replace the cyanide plating baths, such as acid copper
plating baths.
Metal finishing shops are typically located at or near
industries they serve. Therefore, the geographical
distribution of the metal finishing shops closely follows that
of the U.S. manufacturing base.
5.5.1 Process Description
A flow diagram for a typical cyanide electroplating
process is presented in Figure 5-4. Prior to plating, the
parts undergo a series of pretreatment steps to smooth the
5-16
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TABLE 5-7. ESTIMATED NUMBER OF METAL FINISHING JOB SHOPS
PERFORMING SELECTED PLATING OPERATIONS
Type of plating operation
Copper plating
Zinc plating
Cadmium plating
Silver plating
Gold plating
Brass plating
Percent of total job shops, %
41
35
29
22
18
17
Estimated number of job shops
1,649
1,408
1,166
885
724
684
Source: Reference 24.
surface of the part and to remove any surface soil, grease, or
oil. Pretreatment steps include polishing, grinding, and/or
degreasing of the part to prepare for plating. The part being
plated is rinsed after each process step to prevent carry-over
of solution that may contaminate the baths used in successive
process steps.
Polishing and grinding are performed to smooth the surface
of the part. Degreasing is performed either by dipping the
part in organic solvents or by vapor degreasing the part using
organic solvents. Vapor degreasing is typically used when the
surface loading of oil or grease is excessive. The two
organic solvents most commonly used for cleaning applications
are trichloroethylene and perchloroethylene.
Alkaline cleaning is sometimes used to dislodge surface
soil and prevent it from settling back onto the metal. These
cleaning solutions are typically made up of compounds, such as
sodium carbonate, sodium phosphate, and sodium hydroxide; they
usually contain a surfactant. Alkaline cleaning techniques
include soaking and cathodic and anodic cleaning.
Acid dips may be used to remove any tarnish or oxide films
formed in the alkaline cleaning step and to neutralize the
5-17
-------
SUBSTRATE TO BE
PLATED
PRETREAJMENT
STEP (POLISHING,
DECREASING)
i
CLEANING
RINSE
ACID DIP
FURTHER
ELECTROPLATING
RINSE
CYANIDE
ELECTROPLATING
RINSE
ELECTROPLATED
PRODUCT
POTENTIAL CYANIDE
EMISSIONS
5-18
-------
alkaline film. Acid dip solutions typically contain from 10
to 30 percent by volume hydrochloric or sulfuric acid in
water.
The exact pretreatment steps depend upon the amount of
soil, grease, or oil on the parts and the type of plate being
used. Following pretreatment, the parts are transferred to
the plating tank.
Tables 5-8 through 5-14 present the plating bath
formulations that use cyanide compounds as a integral part of
the plating bath.25 In these plating operations, the part(s)
is placed in a tank and connected into the electrical circuit
as the cathode. If small parts are to be plated, the parts
are first placed in a plating barrel or on a plating rack.
The barrel or plating rack is then placed in the tank and
connected to the electrical circuit. The efficiency of the
plating bath is based on the amount of current that is
consumed in the deposition reaction versus the amount of
current that is consumed by other side reactions. Cyanide
plating baths range from very efficient baths (90 to
99 percent) to less efficient baths (50 to 75 percent). For
the less efficient baths, the temperature of the plating bath
plays an important role in determining how efficient the bath
will operate.
Following cyanide plating, the parts can be sent to
another series of plating tanks to add further layers of metal
or may be rinsed and sold as final end products. Some of the
cyanide plating baths, such as copper, are used as an
underplate for other metals. For example, a plate of copper,
nickel, and chromium is used in the decorative chromium
plating process for parts, such as automotive trim. Other
plates, such as gold or silver, may not undergo any further
treatment other than rinsing prior to their use as a final end
product.
5-19
-------
Component
TABLE 5-8. COMPOSITION AND OPERATING PARAMETERS OF
A TYPICAL COPPER CYANIDE PLATING BATH
Operating range
Composition of bath, g/L (oz/qaD
Copper cyanide
Potassium or sodium cyanide
Potassium carbonate or sodium carbonate
Potassium hydroxide or sodium hydroxide
Rochelle salt (if potassium bath is used)
60 to 75 (8 to 10)
102 or 97.5 (13.6 or 13.0)
15(2)
15(2)
45(6)
Operating Parameters
Temperature, °C (°F)
Current density, A/m2 (A/ft2)
Cathode efficiency, %
60 to 71 (140 to 160)
up to 860 (up to 80)
90 to 99
Source: Reference 25.
Component
TABLE 5-9. COMPOSITION AND OPERATING PARAMETERS OF
A TYPICAL ZINC CYANIDE PLATING BATH
Operating range
Composition of bath, q/L (oz/qal)
Zinc oxide or zinc cyanide
Sodium hydroxide
Sodium cyanide
Low cyanide
7.5- 11.2
(1.0-1.5)
75 to 90
(10-12)
11.2- 18.7
(1.5-2.5)
Mid cyanide
13.5- 18.7
(1.8-2.5)
75 to 90
(10-12)
26-45
(3.5-6.0)
Hiqh cyanide
26-34
(3.5-4.5)
75 to 90
(10-12)
82- 105
(11-14)
Operating Parameters
Temperature, °C (°F)
Bath efficiency, %
15 to 38 (60 to 100)
65 to 80
Source: Reference 25.
5-20
-------
TABLE 5-10. COMPOSITION AND OPERATING PARAMETERS OF
A TYPICAL CADMIUM CYANIDE PLATING BATH
Component Operating range
Composition of bath, g/L (oz/gal)
Cadmium 20 (2.7)
Cadmium oxide 22 (3.0)
Sodium carbonate 30-60 (4.0-8.0)
Sodium cyanide 101(13.5)
Sodium hydroxide 14(1.9)
Operating Parameters
Temperature, °C (°F) 15 to 38 (60 to 100)
Current density, A/m2 (A/ft2) 54 to 970 (5-90)
Cathode efficiency, % 90 to 95
Source: Reference 25.
TABLE 5-11. COMPOSITION AND OPERATING PARAMETERS OF
A TYPICAL SILVER CYANIDE PLATING BATH
Component Operating range
Composition of bath, g/L (oz/gal)
Silver as KAg(CN2 ) 5 to 40 (0.7 to 6)
Potassium cyanide 12 to 120 (1.6 to 16)
Potassium carbonate 15(2)
Operating Parameters
Temperature, °C (°F) 20 to 30 (70 to 85)
Current density, A/m2 (A/ft2 ) 10 - 430 (1 - 40)
Source: Reference 25.
5-21
-------
TABLE 5-12. COMPOSITION AND OPERATING PARAMETERS OF
A TYPICAL GOLD ALKALINE CYANIDE PLATING BATH
Component Operating range
Composition of bath, g/L (oz/gal)
Gold as potassium gold cyanide 8-20 (1.1-2.7)
Dipotassium phosphate 22-45 (2.9-6.0)
Potassium cyanide 15-30 (2.0-4.0)
Operating Parameters
Temperature, °C (°F) 49 to 70 (120 to 160)
Current density, A/m2 (A/ft2 ) 33 to 54 (3 to 5)
Cathode efficiency, % 90 to 95
Source: Reference 25.
TABLE 5-13. COMPOSITION AND OPERATING PARAMETERS OF
A TYPICAL BRASS CYANIDE PLATING BATH
Component Operating range
Composition of bath, g/L (oz/gal)
Copper cyanide 32(4.2)
Zinc cyanide 10(1.3)
Sodium cyanide 50 (6.5)
Sodium carbonate 7.5 (1)
Ammonia 2.5 to 5 ml/L
(1 to 2 qts/gal)
Sodium bicarbonate 10(1.5)
Operating Parameters
Temperature, °C (°F) 25 to 35 (75 to 95)
Source: Reference 25.
5-22
-------
Component
TABLE 5-14. COMPOSITION AND OPERATING PARAMETERS OF
A TYPICAL INDIUM CYANIDE PLATING BATH
Operating range
Composition of bath, g/L (oz/gal)
Indium as metal
Dextrose
Potassium cyanide
Potassium hydroxide
33(4)
33(4)
96(12.8)
64 (8.5)
Operating Parameters
Temperature, °C (°F)
Cathode efficiency, %
Current Density, A/m2 (A/ft2)
room temperature
50 to 75
162-216(15-20)
Source: Reference 25.
5.5.2 Emission Control Measures
No data were available on the use of air pollution control
measures on cyanide plating tanks. However, most cyanide
plating tanks are ventilated as a precautionary measure
against worker exposure.
5.5.3 Emissions
No emission test data were available for the cyanide
plating operations listed above. Based on emission estimates
reported in the 1991 TRI, a total of 123 facilities reported
cyanide emissions under SIC 3471, Plating and Polishing.
Cyanide emission estimates for these facilities totaled 10,117
kg (22,309 Ib).
5-23
-------
SECTION 6
CYANIDE COMPOUND EMISSIONS FROM MISCELLANEOUS SOURCES
Cyanide emissions have been reported from miscellaneous
sources, including production of iron and steel, carbon black,
carbon fiber, and mobile sources. It is not known whether
cyanide emissions occur as a result of the chemical changes
that take place during the different manufacturing steps or as
a result of volatilization of cyanide compounds present in the
raw materials processed during the production process. This
section presents process information, air pollution control
measures, and estimates of cyanide emissions from these
sources.
6.1 IRON AND STEEL PRODUCTION 26~28
Two types of iron and steel plants will be discussed in
this section: integrated and nonintegrated. Integrated iron
and steel plants are those iron and steelmaking facilities
that are capable of starting with iron ore as a raw material
feed and producing finished steel products. At a minimum,
these facilities have blast furnace facilities for pig iron
production; steelmaking furnaces (generally one or more basic
oxygen furnaces), and steel finishing operations. Many
facilities also have coke making operations, sinter plants,
and electric arc furnace shops for melting scrap. In its
simplest form, the integrated iron and steel process begins
with pig iron production from iron ore or pellets in the blast
furnace. The molten iron is transferred from the blast
furnace to the basic oxygen furnace, where the hot pig iron
and scrap metal are heated and transformed metallurgically to
carbon steel. This carbon steel is then cast and rolled into
a final project.
6-1
-------
Nonintegrated plants consist of "minimills" or specialty
mills that produce carbon steel, stainless steel and other
steel alloys from scrap. Typical operations at these
facilities include electric arc furnaces for steelmaking and
steel casting and finishing operations, as well as alloying
operations. Table B-l lists those facilities that use
electric arc furnaces. Total steel (carbon and alloy)
production for 1991 was 79.7 x 106 Megagrams (Mg)(87.8 x 106
tons).
The principal components of the process are iron
production, steelmaking, and steel finishing. However, two
important ancillary components are coke making and sinter
production. The process steps discussed below apply to an
integrated plant. Process differences will be noted for
nonintegrated plants.
Frequently, the first step in the process for an
integrated plant is to produce metallurgical coke (elemental
carbon) for the blast furnace. Coke is used to: (1) provide
a substrate for raw materials in the blast furnace, (2)
function as fuel for the hot blast air, and (3) remove iron
ore oxides. Nonintegrated plants do not use blast furnaces
and, therefore, do not need coke. The coke is made from coal
that is pulverized and then heated in a coke oven without
oxygen at 1050°C (1925°F) for 12 to 20 hours. Volatiles are
driven off, and elemental carbon (coke) and ash are formed.
No information is available for cyanide emissions from coke
production.
A second ancillary process found at many integrated plants
is the sintering operation. The sintering process is a
materials-recovery process, which converts fine-sized raw
materials, including iron ore, coke breeze (undersized coke),
limestone, mill scale, and flue dust, into an agglomerated
product called "sinter."
6-2
-------
The initial process common to all integrated plants is the
blast furnace, which is used to produce molten iron ("pig
iron"). Iron ore, coke, limestone flux and sinter are
introduced ("charged") into the top of the furnace. Heated
air is injected through the bottom of the furnace. This blast
air combusts the coke contained in the breeze to melt the
sinter, and flux with the iron oxides in the ore and form
molten iron, slag, and carbon monoxide (CO). The molten iron
and the slag collect in the hearth at the base of the furnace
and are periodically tapped. The molten iron from the blast
furnace undergoes desulfurization, after which it is
introduced to a basic oxygen furnace (EOF) or open hearth
furnace to make steel. There are two types of BOF's:
conventional BOF's and the newer Quelle Basic Oxygen process
(Q-BOP) furnaces. The open-hearth furnace (OHF) is a shallow,
refractory-lined basin in which scrap and molten iron are
melted together and then refined into steel. Nonintegrated
plants use electrical arc furnaces (EAF's) to produce carbon
and alloy steels. The raw material for an EAF is typically
100 percent scrap.
Molten steel from the furnace is cast into molds or is
continuously cast to form a finished product. This final
product consists of shapes called blooms, slags, and billets.
If steel parts are produced at the iron and steel
production facilities, the parts thus produced are subjected
to a "carburizing" step to provide wear resistance. Two
processes are used for carburizing. In the first process,
steel parts are immersed in a molten-salt bath containing
about 30 percent sodium cyanide (NaCN) at an approximate
temperature of 870°C (1600°F) for a period range between 1/2
to 1-hour to obtain a light (shallow) (0.01 inch) hard case
for wear resistance. In the second process, carburizing is
carried out in activated baths which employ a floating slag of
calcium cyanide as the active agent and which produce deeper
cases which are lower in nitrogen and higher in carbon than
6-3
-------
those obtained with just the NaCN bath. A typical composition
of an activated bath used in the second process is as given
below:
Calcium cyanamide (CaCN2 ) 2-5%
Calcium cyanide (Ca(CN)2 ) 43-48%
Sodium chloride (NaCl) 30-35%
Calcium oxide (CaO) 14-16%
Carbon (C) 4-5%
It is not known which carburizing process is more popularly
used.
Based on the limited information available, it is assumed
that the carburizing step is the only source of emissions of
cyanide compounds. The cyanide compounds emitted as a result
of carburizing may include NaCN, CaCN2 , and Ca(CN2, depending
on which of the two carburizing processes is used.
6.1.1 Emission Control Measures
No information is available pertaining to control of
cyanide compound emissions resulting from the carburizing step
in iron and steel production facilities.
6.1.2 Emissions
No test data are available pertaining to cyanide emissions
resulting from carburizing step during iron and steel
production. However, 21 facilities have reported emissions of
cyanide compounds in the 1991 Toxic Release Inventory (TRI).
The TRI data are presented in Table 6-1."
6.2 CARBON BLACK PRODUCTION
Carbon black is produced by partial combustion of
hydrocarbons. The most predominantly used process (which
6-4
-------
TABLE 6-1. IRON/STEEL AND COKE PRODUCTION FACILITIES REPORTING
CYANIDE COMPOUND EMISSIONS IN THE 1991 TOXIC RELEASE INVENTORY
Emission, kg (Ib)
Facility
New Boston Coke Corp.
New Boston, OH
Acme Steel Co.
Chicago, IL
ARMCO Steel Co.
Middletown, OH
ARMCO Steel Co.
Ashland, KY
Bethlehem Steel
Chesterton, IN
Bethlehem Steel
Sparrows Point, MD
Carpenter Technology
Reading, PA
Detroit Coke Corp.
Detroit, Ml
Granite City Steel
Granite City, IL
Gulf States Steel
Gadsden, AL
Inland Steel Co. 2
East Chicago, IN
LTV Steel Co.
East Chicago, IN
LTV Steel Co.
Aliquippa, PA
Sharon Steel Corp.
Monessen, PA
USS Clairton Works 4,
Clairton, PA
USS Gary Works 4,
Gary, IN
USS Mon Valley Works
Braddock, PA
USS Fair-field Works
Fairfield, AL
Wheeling-Pittsburgh SteeS,
Follansbee, WV
Wheeling-Pittsburgh Steel
Mingo Junction, OH
Wheeling-Pittsburgh Steel
Steubenville, OH
TOTAL 17
Nonpoint
0.5(1)
190(420)
45(100)
100(220)
0(0)
50(110)
26 (58)
0(0)
2.3 (5)
0(0)
,222 (4,900)
0(0)
0(0)
0(0)
535(10,000)
989 (1 1 ,000)
0(0)
0(0)
442(12,000)
0(0)
0(0)
,602(38,814)
Point
2,132(4,700)
63,492(140,000)
45(100)
116(255)
0(0)
45,351 (100,000)
0(0)
23 (51)
2,086 (4,600)
0(0)
0(0)
363 (800)
363 (800)
0(0)
17,687(39,000)
14,059(31,000)
0(0)
0(0)
16,780(37,000)
0(0)
0(0)
162,497(358,306)
Total
2,132(4,701)
63,682(140,420)
90 (200)
216(475)
0(0)
45,401 (100,110)
26 (58)
23 (51)
2,088 (4,605)
0(0)
2,222 (4,900)
363 (800)
363 (800)
0(0)
22,222 (49,000)
19,048(42,000)
0(0)
0(0)
22,222 (49,000)
0(0)
0(0)
180,098(397,120)
Source: Reference 1 1 .
6-5
-------
accounts for more than 98 percent of carbon black produced) is
based on a feedstock consisting of a highly aromatic petro-
chemical or carbochemical heavy oil. Cyanide compounds can be
expected to be present in the feedstock. However, data
pertaining to the content of cyanide compounds in
petrochemical or carbochemical heavy oil are not available. A
compilation of facilities, locations, type of process, and
annual capacity is presented in Table 6-2.14 A description of
the process used to manufacture carbon black and the emissions
resulting from the various operations are presented below.
6.2.1 Process Description29
Figure 6-1 contains a flow diagram for the carbon black
production process. Three primary raw materials used in this
process are: preheated feedstock (either the petrochemical
oil or carbochemical oil), which is preheated to a temperature
between 150° and 250°C (302° and 482°F); preheated air; and an
auxiliary fuel, such as natural gas. A turbulent, high-
temperature zone is created in the reactor by combusting the
auxiliary fuel, and the preheated oil feedstock introduced in
this zone as an atomized spray. In this zone of the reactor,
most of the oxygen would be used to burn the auxiliary fuel
resulting in insufficient oxygen to combust the oil feedstock.
Thus, pyrolysis (partial combustion) of the feedstock is
achieved, and carbon black is produced. Any cyanide compounds
that may be present in the feedstock will be
emitted in the hot exhaust gas from the reactor.
The product stream from the reactor is quenched with
water, and any residual heat in the product stream is used to
preheat the oil feedstock and combustion air before recovering
the carbon in a fabric filter. Carbon recovered in the fabric
filter is in a fluffy form. The fluffy carbon black may be
ground in a grinder, if desired. Depending on the end use,
6-6
-------
TABLE 6-2. CARBON BLACK PRODUCTION FACILITIES
Annual capacity13
Type of
Company
Cabot Corporation
North American Rubber Black Division
Chevron Corporation
Chevron Chemical Company, subsidiary
Olevins and Derivatives Division
Degussa Corporation
Ebonex Corporation
General Carbon Company
Hoover Color Corporation
J.M. Huber Corporation
Phelps Dodge Corporation
Colombian Chemical Company, subsidiary
Sir Richardson Carbon & Gasoline Company
Witco Corporation
Continental Carbon Company, subsidiary
Location process3
Franklin, Louisiana
Pampa, Texas
Villa Platte, Louisiana
Waverly, West Virginia
Cedar Bayou, Texas
Arkansas Pass, Texas
Belpre, Ohio
Louisa, Louisiana
Melvindale, Michigan
Los Angeles, California
Hiwassee, Virginia
Baytown, Texas
Borger, Texas
Orange, Texas
El Dorado, Arkansas
Moundsville, West Virginia
North Bend, Louisiana
Ulysses, Kansas
Addis, Louisiana
Big Spring, Texas
Borger, Texas
Phenix City, Alabama
Ponca City, Oklahoma
Sunray, Texas
F
F
F
F
A
F
F
F
C
C
C
F
FandT
F
F
F
F
F
F
F
F
F
F
F
103Mg
141
32
127
82
9
57
59
91
4
0.5
0.5
102
79
61
50
77
109
36
66
52
98
27
66
45
106lbs
310
70
280
180
20
125
130
200
8
1
1
225
175
135
110
170
240
80
145
115
215
60
145
100
TOTAL 1,471
Source: Reference 14.
3 A = acetylene decomposition
C = combustion
F = furnace
T = thermal
b Capacities are variable and based on SRI estimates as of January 1, 1991
3,240
6-7
-------
ATH09FHERIC EiMSMNS
I
CO
- FEEOSTOCiCHanNS
(8P10NM. ffljOHBLOCP RHJTCtE)
*• P»H=HMM£
-------
carbon black may be shipped in a fluffy form or in the form of
pellets. Pelletizing is done by a wet process in which carbon
black is mixed with water along with a binder and fed into a
pelletizer. The pellets are subsequently dried and bagged
prior to shipping.
6.2.2 Emission Control Measures29
High-performance fabric filters are reported to be used to
control PM emissions from main process streams during the
manufacture of carbon black. It is reported that the fabric
filters can reduce PM emissions to levels as low as 6 mg/m3
(normal m3 ) . If the cyanide emissions from the reactor are
primarily in the vapor phase (and not as particulate), these
emissions will proceed through the main process streams to the
fabric filters. If the cyanide remains in the vapor phase,
the cyanide control efficiency by the fabric filters is
expected to be low. If the product gas stream is cooled to
below 170°C (325°F), the fabric filter may capture a
significant fraction of the condensed cyanide compounds, thus
providing a high degree of emission control.
6.2.3 Emissions
The processing unit with the greatest potential to emit
cyanide emissions is the reactor. Cyanide emission sources
are indicated in Figure 6-1 by solid circles. Cyanide
compounds, which may be present in the oil feedstock, can
potentially be emitted during the pyrolysis step. Test data
pertaining to cyanide emissions from carbon black production
are not available. However, only six of 24 facilities have
reported facilitywide emissions of cyanide compounds in the
1991 TRI. The TRI data are presented in Table 6-3."
6-9
-------
TABLE 6-3. CARBON BLACK PRODUCERS REPORTING CYANIDE COMPOUND
EMISSIONS IN THE 1991 TOXIC RELEASE INVENTORY
Emissions, kg (Ib)
Facility
Cabot Corp.
Franklin, LA
Cabot Corp.
Waverly, WV
Cabot Corp.
Pampa, TX
Degussa Corp.
Louisa, LA
Degussa Corp.
Arkansas Pass, TX
Degussa Corp.
Belpre, OH
TOTAL
Nonpoint
0(0)
2.3 (5)
113(250)
0(0)
0(0)
0(0)
115(255)
Point
231,610(510,700)
22 (48)
53,297(117,520)
81,633(180,000)
15,420(34,000)
30,385 (67,000)
412,367(909,268)
Total
231,610(510,700)
24 (53)
53,410(117,770)
81,633(180,000)
15,420(34,000)
30,385 (67,000)
412,482(909,523)
Source: Reference 11.
6.3 CARBON FIBER PRODUCTION
Carbon fibers are black fibers used as yarns, felt, or
powderlike short monofilaments with diameters smaller than 10
micrometers (um). They are primarily applied to reinforce
polymers, much like glass fibers are used in fiber glass.
Carbon fibers are important because of their superior
stiffness, high strength, and low density.30 Table 6-4
presents a list of domestic carbon fiber manufacturing
facilities .14
This section presents a description of the carbon fiber
production process, emission control measures, and emissions
occurring as a result of the production process.
6-10
-------
TABLE 6-4. DOMESTIC PRODUCERS OF HIGH PERFORMANCE CARBON FIBERS
Company/location Annual capacity, (thousands of pounds)
Fortafil Fibers, Inc., Rockwood, TN 1,000
Amoco Corporation, Piedmont, SC 2,500
BASF Corporation, Rock Hill, SC 1,000
BP America, Inc., Gardena, CA 50
Grafil, Inc., Sacramento, CA 900
Hercules, Inc., Magna (Bacchus), UT 3,100
Textron, Inc., Lowell, MA 100
Zoltek Corporation, Lowell, MA 250
TOTAL 8,900
Source: References 4 and 14.
The most common carbon fiber production process uses
polyacrylonitrile (PAN) as the raw material. Therefore, only
the PAN-based process will be described in this section.
6.3.1 Process Description30
All commercial production processes for carbon fibers are
based on carbonization of polymer fiber precursors. For PAN-
based carbon fibers, the simplified process involves spinning
the polymer fibers by a wet-spinning process, stretching the
precursor before or during stabilization, stabilizing the
thermoplastic precursor, and carbonizing the fibers. The most
important step in this process in terms of carbon fiber
quality and process economy is the stabilization step when
oxidation occurs. The carbonization step, which can be
carried out much faster than the stabilization step, produce
volatile byproducts such as water, HCN, carbon dioxide, and
nitrogen.
The quality of the final carbon fiber product is
determined by the precursor fiber, the stabilization
treatment, oxygen content, and the carbonization schedule.
6-11
-------
6.3.2 Emission Control Measures
No information is available pertaining to the control of
emissions resulting from carbon fiber production.
6.3.3 Emissions
Test data pertaining to cyanide emissions resulting from
the carbonization step during carbon fiber production are not
available. However, five of the eight facilities have
reported facilitywide emissions of hydrogen cyanide in the
1991 TRI. The TRI data are presented in Table 6-5."
6.4 PETROLEUM REFINING
Petroleum refining involves the conversion of crude
petroleum oil into refined products, including liquified
petroleum gas, gasoline, kerosene, aviation fuel, diesel fuel,
fuel oils, lubricating oils, and feedstocks for the petroleum
industry.
As of January 1992, there were 32 oil companies in the
United States with operable atmospheric crude oil distillation
capacities in excess of 100,000 barrels per calendar day.
These oil companies operated refiners at a total of 110
different locations. In addition, there were 72 companies
with distillation capacities of less than 100,000 barrels per
calendar day. A listing of all companies, specific refinery
locations, and distillation capacities is presented in Table
B-2 of Appendix B.31
6.4.1 Process Description12'32
The operations at petroleum refineries are classified into
five general categories, as listed below:
6-12
-------
TABLE 6-5. CARBON FIBER PRODUCERS REPORTING HYDROGEN CYANIDE
EMISSIONS IN THE 1991 TOXICS RELEASE INVENTORY
Emissions, kg (Ib)
Facility
Fortafil Fibers, Inc.
Rockwood, TN
Amoco Corp.
Piedmont, SC
BASF Corp.
Rock Hill, SC
Grafil, Inc.
Sacramento, CA
Hercules, Inc.
Magnar, UT
TOTAL
Nonpoint
113(250)
5,533(12,200)
113(250)
1.4(3)
0(0)
5,760(12,703)
Point
1,950(4,300)
1,361 (3,000)
38,549 (85,000)
9,289 (20,482)
17,343(38,242)
68,492(151,024)
Total
2,063 (4,550)
6,894(15,200)
38,662 (85,250)
9,290 (20,485)
17,343(38,242)
74,252(163,727)
Source: Reference 11.
6-13
-------
1. Separation processes,
2. Petroleum conversion processes,
3. Petroleum treating processes,
4. Feedstock and product handling, and
5. Auxiliary facilities.
Separation processes--
Constituents of crude oil include a large number of
paraffinic, naphthenic, and aromatic hydrocarbon compounds, as
well as numerous impurities which may include sulfur,
nitrogen, and metals. The processes used to separate these
constituents include: atmospheric distillation, vacuum
distillation, and recovery of light ends (gas processing).
Conversion processes--
Conversion processes include cracking, coking, and
visbreaking, which break large molecules into smaller
molecules; isomerization and reforming processes to rearrange
the structures of molecules; and polymerization and alkylation
to combine small molecules into large ones.
Equipment commonly used during conversion includes process
heaters and reformers. Process heaters are used to raise the
temperature of petroleum feedstocks to a maximum of 510°C
(950°F). Fuels burned include refinery gas, natural gas,
residual fuel oils, or combinations. Reformers are reactors
where the heat for the reaction is supplied by burning fuel.
Treatment processes--
Petroleum treatment processes include
hydrodesulfurization, hydrotreating, chemical sweetening, acid
gas removal, and deasphalting. These treatment methods are
used to stabilize and upgrade petroleum products. Removal of
undesirable elements, such as sulfur, nitrogen, and oxygen, is
accomplished by hydrodesulfurization, hydrotreating, chemical
sweetening, and acid gas removal. Deasphalting is carried out
6-14
-------
to separate asphaltic and resinous materials from petroleum
products. Hydrotreating is a process in which the oil feed is
treated by mixing with hydrogen in a fixed-bed catalyst
reactor. Removal of acid gas involves controlling emissions
of sulfur dioxide (S02 ). Elemental sulfur is recovered as a
byproduct.
Feedstock and product handling--
This includes storage, blending, loading, and unloading of
petroleum crude and products. No cyanide emissions are
expected during these steps.
Auxiliary facilities--
Auxiliary facilities include boilers, gas turbines,
wastewater treatment facilities, hydrogen plants, cooling
towers, and sulfur recovery units. Boilers and gas turbines
cogeneration units within petroleum refineries may burn
refinery gas.
Two petroleum refineries have reported facilitywide HCN
emissions. It is not known which source operations result in
HCN emissions because details pertaining to the mechanism of
HCN formation are not available. It is assumed that processes
in which petroleum fractions come into contact with air at
high temperature will result in HCN emissions. Based on this
assumption, process heaters and reformers are the potential
sources of HCN emissions.
6.4.2 Emission Control Measures
No information is available pertaining to control of HCN
emissions at petroleum refineries.
6-15
-------
6.4.3 Emissions
Test data pertaining to HCN emissions from individual
sources at petroleum refineries are not available. Three
facilities, Ultramar, Inc., in Wilmington, CA, Koch Refining
Co. in Rosemount, MN, and Murphy Oil, USA in Superior, WI,
have reported facilitywide HCN emissions totalling 48,613 kg
(107,192 Ib) in the 1991 TRI. Because HCN emission factors
are not available for petroleum refineries, it is not possible
to estimate HCN emissions from other refineries.
6.5 MOBILE SOURCES
Historically, the major emissions measured and regulated
under Title II of the Clean Air Act from mobile sources are
CO, NOx , and hydrocarbons (HC). Emission factors for these
specific pollutants among the different motor vehicle classes
are compiled in AP-42, Volume II.33 Gasoline-powered motor,
on-road, light-duty vehicles comprise the most significant
mobile emission sources because of their large numbers.
According to the 1990 Statistical Abstract, 1988 nationwide
registrations were estimated to be 183.5 million cars, trucks,
and buses. Of that number, 140.7 million were passenger cars
and 42.8 million were trucks and buses.34 In 1990, the total
vehicle miles traveled (VMT) in the United States were
3,457,478 million kilometers (2,147,501 million miles).35
Small amounts of HCN (levels around 1.0 mg/mile) have been
measured in gasoline-fueled vehicle exhaust under normal
operating conditions. In the Federal Test Procedure (FTP)
driving schedule, these emission rates can increase to as high
as 112 mg/km, or 179 mg/mile, under malfunction conditions
(rich idle, misfire, high oil consumption, etc.). (All
reported emissions include HCN and cyanogen emissions since
attempts to isolate the two separately have been
unsuccessful.)
6-16
-------
Table 6-6 lists calculated fleet average emission factors
These values are obtained by multiplying each vehicle class
VMT fraction by the corresponding emission factor for that
class, giving a fraction quantity of pollutant emitted from
that particular vehicle category. These are totaled and then
averaged to obtain a total fleet average of 11.4 mg/mile for
HCN. 36
TABLE 6-6. FLEET AVERAGE EMISSION FACTORS FOR HYDROGEN CYANIDE
Vehicle class Fraction, VMT
Light-duty diesel vehicles
Light-duty diesel trucks
Heavy-duty diesel trucks
Light-duty gasoline vehicles
Noncatalyst; no air pump
Noncatalyst; air pump
Ox. catalyst; no air pump
Ox. catalyst; air pump
3-way catalyst; no air pump
3-way plus ox. catalyst; air pump
Light-duty gasoline trucks
Noncatalyst
Catalyst
Heavy-duty gasoline trucks
Total fleet average
0.015
0.002
0.027
0.147
0.098
0.289
0.261
0.012
0.008
0.096
0.010
0.035
Emission factor,
mg/mile
3.2
3.2
22.4
4.5
4.5
2.4
0.9
16.0
24.7
4.5
2.4
224.0
EF x VMT
fraction
0.048
0.006
0.605
0.662
0.441
0.694
0.235
0.192
0.198
0.432
0.024
7.840
11.4
Mg/mile
Source: Reference 36.
6-17
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SECTION 7
SOURCE TEST PROCEDURES
7 . 1 INTRODUCTION
A number of sampling methods exist to determine cyanide
compound (cyanide) emissions from stationary sources. Several
EPA offices and some State agencies, and some other Federal
agencies have developed source-specific or dedicated sampling
methods for cyanide. Other industry sampling methods do
exist, but none of these methods have been validated and are
not discussed in this section.
Subsequent parts of this section discuss EPA reference or
equivalent sampling methods for cyanide. To be a reference
method, a sampling method must undergo a validation process
and be published. Sampling methods fall into one of two
categories: (1) methods for stationary source emissions or
(2) ambient air sampling methods. Methods from both
categories will be described in this section; differences
among the methods are pointed out, and a citation is provided
for additional detailed information about the methods. Table
7-1 presents a summary of cyanide sampling methods. In
addition to the methods summarized in the table, other
analytical methods for several matrixes are described, and
citations are provided. Depending upon the specific source,
these methods may be used to augment the sampling methods in
Table 7-1.
7-1
-------
TABLE 7-1. CYANIDE SAMPLING METHODS
Method
GARB 426
NIOSH 7904
Type
Stationary
source
Ambient
Capture device
Glass fiber filter,
sodium hydroxide
impinger
Cellulose ester filter,
potassium hydroxide
impinger
Analysis
Titration with
silver nitrate
Ion-specific
electrode
Method range
>1 mg CN- /L
0.02-1 mg CN- /L
0.05-2 mg CN- /L
7.2 STATIONARY SOURCE SAMPLING METHODS
7.2.1 GARB Method 426, "Determination of Cyanide Emissions
from Stationary Sources"37
Method 426 is used to determine cyanides in aerosol and
gas emissions from stationary sources. In this sampling and
analysis method, particulate and gaseous emissions are
extracted isokinetically from a stack and passed through an
impinger-fliter train where the cyanide is collected on a
glass-fiber filter and in a solution of sodium hydroxide
(NaOH). The combined filter extract and impinger solution are
analyzed for cyanide by titration with silver nitrate or a
colorimetric procedure (see EMSLC, 335.1
on p. 7-4). A diagram of the Method 426 sampling train is
presented in Figure 7-1.
7.3 AMBIENT AIR SAMPLING METHODS
7.3.1 NIOSH Method 7904, "Determination of Cyanide
Concentrations in Workplace Atmosphere"38
Method 7904 is used to determine cyanide in aerosols and
gases in a workplace atmosphere. In this sampling and
analysis method, airborne cyanides are collected on a
cellulose ester membrane filter and in a potassium hydroxide
(KOH) bubbler. Cyanide concentration is determined with an
ion-specific electrode. A diagram of the Method 7904 sampling
7-2
-------
i
co
/ ^
PROBE
RE VERSE I WE
FJTOTTUBE
PITOT MANOMETER
DfllFICE
THiRMOMETiRS
VACUUM
GAUGE
CHICK
VALVE
VACUUM
LINE
PUMP
Figure l-\, Schemstic o< CARB Mmhod 428 gampling trsb.
-------
train is presented in Figure 7-2.
7.4 ANALYTICAL METHODS
7.4.1 EMSLC, 335.1, "Cyanides, Amenable to Chlorination
(Titrimetric and Spectrophotometric)"
A portion of the sample is chlorinated at a pH greater
than 11 to decompose the cyanide. Cyanide levels in
chlorinated and unchlorinated aliquots are determined by the
method for Cyanide, Total (Method 335.2) . Cyanides amenable
to chlorination are then calculated by difference.
The titration procedure is used for measuring
concentrations of cyanide exceeding 1 milligram per liter
(mg/L) after removal of cyanides amenable to chlorination.
Below this level, the colorimetric determination is used.
7.4.2 EMSLC, 335.2, "Cyanide, Total (Titrimetric and
Spectrophotometric)"
The cyanide as hydrocyanic acid (HCN) is released from
cyanide complexes by means of reflux-distillation and absorbed
in a scrubber containing sodium hydroxide solution. The
cyanide ion in the absorbed solution is then determined by
volumetric titration or colorimetrically.
In the colorimetric measurement, the cyanide is converted
to cyanogen chloride, CNC1, by reaction with chloramine-T at a
pH less than 8 without hydrolyzing to the cyanate. After the
reaction is complete, color is formed on the addition of
pyridine- pyrazolone or pyridine-barbituric acid reagent. The
absorbance is read at 620 nanometers (nm) when using pyridine-
pyrazolone or 578 nm for pyridine-barbituric acid. To obtain
7-4
-------
I
Cn
Cellulose ester
membrane filter
JjnpingerR cocotaiMng
15 ml of 0,1JST KOH each
Personal sampling
pump
7-2. Sehamati& af NiOSH Method 7904 sampling train.
-------
colors of comparable intensity, it is essential to have the
same salt content in both the sample and the standards.
The titrimetric measurement uses a standard solution of
silver nitrate to titrate cyanide in the presence of a silver
sensitive indicator.
7.4.3 EMSLC, 335.3, "Cyanide, Total (Colorimetric, Automated
UV) "
Cyanide as hydrocyanic acid (HCN) is released from cyanide
complexes by means of ultraviolet (UV) digestion and
distillation. Cyanides are converted to cyanogen chloride by
reactions with chloramine-T, which subsequently reacts with
pyridine and barbituric acid to give a red-colored complex.
The cyanide is then determined by automated UV colorimetry.
7.4.4 OSW, 9010A, "Method 9010A, Total and Amenable Cyanide"
The cyanide, as hydrocyanic acid (HCN), is released from
samples containing cyanide by means of a reflux-distillation
operation under acidic conditions and absorbed in a scrubber
containing sodium hydroxide solution. The cyanide in the
absorbing solution is then determined colorimetrically or
titrametrically.
In the colorimetric measurement, the cyanide is converted
to cyanogen chloride (CNC1) by reaction of cyanide with
chloramine-T at a pH less than 8. After the reaction is
complete, color is formed on the addition of pyridine-
barbituric acid reagent and CNC1. To obtain colors of
comparable intensity, it is essential to have the same salt
content in both the sample and the standards.
7-6
-------
The titration measurement uses a standard solution of
silver nitrate to titrate cyanide in the presence of a silver
sensitive indicator.
7.4.5 OSW, 9012A, "Method 9012A, Total and Amenable Cyanide
(Colorimetric, Automated UV)"
The OSW Method 9012A is identical to the OSW Method 9010A
except that an automated ultraviolet spectrophotometer is used
for analysis.
7.5 COMBINED SAMPLING/ANALYTICAL METHODS
7.5.1 Fourier Transform Infrared Spectroscopy (FTIR)
The FTIR is a spectrophotometer that scans and records the
infrared (IR) range of absorbance from an IR beam transmitted
through a sample. The sample's absorbance record is converted
to absorbance plots via fast fourier transform calculations.
The resulting plots are then compared to a spectra library of
known compounds for identification. The FTIR can be operated
as a closed-cell for extractive stationary-source testing or
as an open-cell for ambient testing.
No approved method of sampling and analysis for cyanide
using FTIR exists. Many problems must be resolved before
extractive, stationary-source FTIR testing for cyanide can be
performed. The use of FTIR in this application is currently
under development by EPA.
7-7
-------
7.5.2 ASTM, D4490, "Standard Practice for Measuring the
Concentration of Toxic Gasesor Vapors Using Detector
Tubes"
Detector tubes may be used for either short-term sampling
(grab sampling; 1 to 10 minute) or long-term sampling
(dosimeter sampling 1 to 8 hours) of atmospheres containing
toxic gases or vapors. A given volume of air is pulled
through the tube by a mechanical pump (grab sampling) or is
pulled through the detector tube at a slow, constant flow rate
by an electrical pump (dosimeter sampling).
If the substance for which the detector tube was designed
is present, the indicator chemical in the tube will change
color. The concentration of the gas or vapor may be estimated
by either (a) the length-of-stain compared to a calibration
chart, or (b) the intensity of the color change compared to a
set of standards.
7.6 SUMMARY
All of the sampling methods described in this section
collect a sample for analysis of cyanide. Significant
criteria of each method were presented previously in Table 7-
1. The major differences in the methods include: (1) type of
impinger solution, (2) volume of sample required, and (3)
isokinetic or nonisokinetic sampling.
Two EPA sampling methods are commonly modified and used to
perform cyanide sampling. Method 5 is the EPA reference
method to determine particulate emissions from stationary
sources, and Method 6 is the EPA reference method to determine
sulfur dioxide emissions from stationary sources.39'40 The
driving considerations in choosing which of these two sampling
methods to use for cyanide sampling are the temperature and
-------
moisture content of the emission source. Those sources with
moisture-laden (saturated) gas streams must be sampled using
isokinetic methods, such as a modified version of EPA Method
5, in order to collect cyanides emitted as aerosols. Drier
gas steams in which cyanide exists as a gas can be sampled
using a modified version of EPA Method 6. Both Methods 5 and
6 are modified by charging the impingers with solutions of
0.IN potassium hydroxide (KOH) or sodium hydroxide (NaOH) as
called for in the analytical method used.
In assessing cyanide emissions from test reports, the age
or revision number of the method indicates the level of
precision and accuracy of a method. Older methods are
sometimes less precise or accurate than those that have
undergone more extensive validation. Currently, EPA Method
301 from 40 CFR Part 63, Appendix A can be used to validate or
prove the equivalency of new methods.
7-9
-------
SECTION 8
REFERENCES
1. Toxic Chemical Release Reporting: Community Right-To-Know.
Federal Register 52(107): 21152-21208. June 4, 1987.
2. Jenks, W. Cyanides (HCN). (In) Kirk-Othmer Encyclopedia of
Chemical Technology, 3rd ed. Volume 7. R. E. Kirk, et al.,
eds. John Wiley and Sons, New York, NY. 1978.
3. Dowel1, A. M., Ill, et al. Hydrogen Cyanide (In)
Encyclopedia of Chemical Processing and Design, Volume 27.
J. J. McKetta and W. A. Cunningham, eds. Marcel Dekker,
Inc., New York, NY. 1984.
4. U. S. Environmental Protection Agency. Preliminary Source
Assessment for Cyanide Chemical Manufacturing. Draft
Report. Office of Air and Radiation. Office of Air Quality
Planning and Standards. Industrial Studies Branch, Research
Triangle Park, NC. September 1992.
5. Klenk, H., et al. Cyano Compounds, Inorganic. (In)
Ullmann's Encyclopedia of Industrial Chemistry, 5th ed.,
Volume A8. W. Gerbartz, et al. eds. VCH Publishers, New
York, NY. 1978.
6. Jenks, W. Cyanides (Alkai Metal). (In) Kirk-Othmer
Encyclopedia of Chemical Technology, 3rd ed., Volume 7. R.
E. Kirk, et al., eds. John Wiley and Sons, New York, NY.
1978.
7. U. S. Environmental Protection Agency. Hazardous Substances
Databank (HSDB). Sodium Cyanide. Downloaded December 13,
1991.
8. Windholz, M., et al. eds. The Merck Index, 10th ed. Merck
and Company, Inc. Rahway, NJ. 1983.
9. Chemical Profile: Hydrogen Cyanide. Chemical Marketing
Reporter. June 18, 1990.
10. Jenks, W. Cyanides (Alkali Metal). (In) Kirk-Othmer
Encyclopedia of Chemical Technology, 4th ed., Volume 7. R.
E. Kirk, et al., eds. John Wiley and Sons, New York, NY.
1993.
8-1
-------
11. U. S. Environmental Protection Agency. 1991 Toxic Release
Inventory, Office of Toxic Substances. Washington, DC.
June 1993.
12. U. S. Environmental Protection Agency. Compilation of Air
Pollution Emission Factors, AP-42, Fourth Edition, U. S.
Environmental Protection Agency, Research Triangle Park, NC.
October 1992.
13. XATEF. Crosswalk/Air Toxic Emission Factor Data Base.
Version 1.2 for October 1991 update. Office of Air Quality
Planning and Standards, U. S. Environmental Protection
Agency, Research Triangle Park, NC. October 1991.
14. SRI International. 1991 Directory of Chemical Producers:
United States of America. SRI International, Menlo Park,
CA. 1991.
15. Jenk, W. R., Potassium Cyanide. (In) Kirk-Othmer
Encyclopedia of Chemical Technology, 3rd ed., Volume 7. R.
E. Kirk, et al., eds., John Wiley and Sons, New York, NY.
1985.
16. Luedeke, V. D. Adiponitrile. (In) Encyclopedia of Chemical
Producing and Design, Volume 2. J. J. McKetta and W. A.
Cunningham, eds. Marcel Dekker, Inc., New York, NY. 1984.
17. Buchanan, S.K. Radian Corporation. Locating and Estimating
Air Emissions for Sources of 1,3-Butadiene. EPA-450/2-89-
021. U. S. Environmental Protection Agency. Research
Triangle Park, NC. December 1989.
18. Cholod, M. S. Cyanohydrin. (In) Kirk-Othmer Encyclopedia of
Chemical Technology, 3rd ed., Volume 7. R. E. Kirk, et al.,
eds., John Wiley and Sons, New York, NY. 1985.
19. Methyl Methacrylate. Chemical Products Synopsis.
Mannerville Chemical Products Corp. Asbury Park, NJ.
September 1990.
20. Knebitzsch, N. Cyanuric Acid and Cyanuric Chloride. (In)
Ullmann's Encyclopedia of Industrial Chemistry, 5th ed.,
Volume A8. W. Gerhertz, et al., eds., VCH Publishers, New
York, NY. 1987.
5-2
-------
21. Hart, J. R. Ethylenediaminetetraacetic Acid and Related
Chelating Agents. (In) Ullmann's Encyclopedia of Industrial
Chemistry, 5th ed., Volume A10. W. Gerbertz, et al., eds.,
VCH Publishers, New York, NY. 1987.
22. Miltenberger, K. Hydroxycarboxylic Acids, Aliphatic. (In)
Ullmann's Encyclopedia of Industrial Chemistry, 5th ed.,
Volume A13. B. Elvers, et al., eds., VCH Publishers, New
York, NY. 1987.
23. Gousetis, C., and H. J. Opgenorth. Nitrilotriacetic Acid.
(In) Ullmann's Encyclopedia of Industrial Chemistry, 5th
ed., Volume A17. B. Elvers, et al., eds., VCH Publishers,
New York, NY. 1987.
24. Finishers' Management Media/Market Bulletin. Metal Finishing
Job Shop Industry Profile.... 1985/86. Glenview, IL. 1986.
25. Metal Finishing. 61st Guidebook and Directory Issue.
Elsevier Science Publishing Company. Hackensack, NJ.
January 1993. Volume 91. Number 1A.
26. Houck, G.W. Iron and Steel. Annual Report: 1991. Bureau
of Mines, U.S. Department of the Interior. Washington, D.C.
December 1992.
27. Trenholm, A.R. Midwest Research Institute. DRAFT
Preliminary Description of the Integrated Iron and Steel
Industry and of Blast Furnace Basic Oxygen Furnace and
Sintering Operations. Emissions Standards Division, Office
of Air Quality Planning and Standards, U. S. Environmental
Protection Agency, Research Triangle Park, NC. October
1991.
28. The Making, Shaping and Treating of Steel. Harold E.
McGannon (ed.). United States Steel. Ninth Edition.
Herbick and Held, Pittsburgh, PA. 1971.
29. Taylor, B. R., Section 12. Carbon Black. Air Pollution
Engineering Manual. Air and Waste Management Association,
Pittsburgh, PA.
30. Fitzer, E., and M. Heine. Fibers, 5. Synthetic Inorganic.
(In) Ullman's Encyclopedia of Industrial Chemistry, 5th Ed.,
Volume All. W. Gerhartz, et al., eds. VCH Publishers, New
York, NY. 1987.
8-3
-------
31. Unites States Refining Capacity. National Petroleum
Refiners Association. Washington, B.C. January 1, 1992.
32. Rucker, J.E., and R.P. Streiter, Section 17. The Petroleum
Industry. Air Pollution Engineering Manual. Air and Waste
Management Association, Pittsburgh, PA.
33. U. S. Environmental Protection Agency. Compilation of Air
Pollutant Emission Factors-4th ed., Volume II, Mobile
Sources. AP-42. Motor Vehicle Emission Laboratory, Office
of Mobile Sources, U. S. Environmental Protection Agency,
Ann Arbor, MI. 1985.
34. U. S. Bureau of the Census. Statistical Abstract of the
United States: 1990 (110th ed.). Washington, B.C. 1990.
35. Motor Vehicle Manufacturers Association (MVMA). MVMA Motor
Vehicle Facts and Figures '92. Motor Vehicle Manufacturers
Association, Betroit, MI.
36. Be Meyer, C. L. and R. J. Garbe. The Betermination of a
Range of Concern for Mobile Source Emissions of Hydrogen
Cyanide. EPA/AA/CTAB/PA 81-13. U. S. Environmental
Protection Agency, Ann Arbor, MI. August 1981.
37. California Air Resources Board Method 426, Betermination of
Cyanide Emissions from Stationary Sources, State of
California Air Resources Board, Sacramento, CA.
38. National Institute of Occupational Safety and Health Method
7904, Betermination of Cyanide Concentrations in Workplace
Atmosphere, NIOSH Manual for Analytical Methods, U.S.
Bepartment of Health and Human Services, Public Health
Service, Centers for Bisease Control, NIOSH, 3rd Edition,
Cincinnati, OH. 1984.
39. EPA Method 5, Betermination of Particulate Emissions from
Stationary Sources. 40 Code of Federal Regulations, Part
61, Appendix A. Washington, BC. U.S. Government Printing
Office. 1992.
40. EPA Method 6, Betermination of Sulfur Bioxide Emissions from
Stationary Sources. 40 Code of Federal Regulations, Part
61, Appendix A. Washington, BC. U.S. Government Printing
Office. 1992.
5-4
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APPENDIX A
NATIONWIDE EMISSION ESTIMATES
-------
EMISSIONS OF HYDROGEN CYANIDE FROM HCN AND NaCN PRODUCTION
Hydrogen Cyanide Production
Basis of estimate: Toxic Release Inventory (TRI) data and EPA
data.
A list of domestic HCN producing facilities is given in
Section 4, Table 4-1. Fifteen facilities currently produce
HCN.
Emission factors for HCN emissions from individual sources are
not available. The only emission data available are the HCN
emission data reported by 12 facilities in the 1991 TRI and
HCN emissions estimated by U.S. Environmental Protection
Agency, Industrial Studies Branch (ISB) .l'2 Because the 1991
TRI data for the 12 facilities constitute the most recent
data, the EPA estimates were not used for these 12 facilities.
However, for two facilities, American Cyanide and BP Chemicals
(Green Lake, TX facility), HCN emission estimates reported by
EPA were used. The HCN emission data for these fourteen
facilities are summarized in Table A-l.
Emission estimates for HCN emissions at Cyanco Co. are not
available either in the 1991 TRI or in Reference 2.
Therefore, HCN emissions at this facility were extrapolated
based on facilitywide HCN emissions reported in Table A-l and
production capacity data given in Section 4, Table 4-1. Based
on HCN production capacity data given in Table 4-1 and HCN
emission estimates given in Table A-l, the ratio of HCN
emissions to individual HCN production capacity (for the
fourteen facilities in Table A-l) ranges between 6.6 x 10~4
and 1.5 Ib/ton of HCN produced. Based on a conservative
assumption that the HCN emission to production ratio at Cyanco
is 1.5 Ib/ton of HCN produced, HCN emissions at Cyanco for the
year 1991 are estimated to be 12,000 kg (26,400 Ib).
Thus the nationwide HCN emissions resulting from HCN
production is estimated to be 166,050 kg (365,969 Ib). This
is the sum total of HCN emissions estimated for Cyanco and the
HCN emission reported for the other fourteen facilities in
Table A-l.
A-l
-------
TABLE A-1. HYDROGEN CYANIDE PRODUCERS REPORTING HYDROGEN
CYANIDE EMISSIONS IN THE 1991 TOXICS RELEASE INVENTORY
Emissions, kg (Ib)
Facility
BP Chemicals
Lima, OH
Ciba-Geigy
St. Gabriel, LA
Degussa Corp.
Theodore, AL
Dow Chemical
Freeport, TX
DuPont
Beaumont, TX
DuPont
Memphis, TN
DuPont
Orange, TX
DuPont
Victoria, TX
FMC Corp.
Green River, WY
Monsanto
Alvin, TX
Rohm & Haas
Deer Park, TX
Nonpoint
998 (2,200)
29 (63)
345 (760)
2(4)
1,360(3,000)
459(1,012)
1,002(2,210)
1 ,038 (2,290)
0(0)
680 (1 ,500)
254 (560)
Point
4,308 (9,500)
93 (204)
771 (1,700)
0(0)
1 ,496 (3,300)
13,224(29,159)
30,970 (68,288)
2,531 (5,580)
36 (79)
635 (1 ,400)
49,887(110,000)
Total
5,306(11,700)
122(267)
1,116(2,460)
2(4)
2,856 (6,300)
13,683(30,171)
31,972(70,498)
3,569 (7,870)
36 (79)
1,315(2,900)
50,141 (110,560)
Sterling Chemicals
Texas City, TX
American Cyanamid3
Avondale, LA
BP Chemicals3
Green Lake, TX
3,936 (8,680)
727 (1,600)
5,909(13,000)
17,451(38,480) 21,387(47,160)
909 (2,000) 1,636 (3,600)
15,000(33,000) 20,909(46,000)
TOTAL 16,739(36,879)
Source: References 1 and 2.
137,311 (302,690) 154,050 (339,569)
' The emission estimates in Reference 2 were used for American Cyanamid and
BP Chemicals (Green Lake, TX). For all other facilities, emissions reported in
Reference 1 were used.
A-2
-------
Sodium Cyanide Production
Basis of estimate: Toxic Release Inventory (TRI) data.
A list of domestic NaCN producing facilities is given in
Section 4, Table 4-3. Seven facilities currently produce
NaCN.
Six of these seven facilities that produce NaCN also produce
HCN. Facilitywide emissions of HCN estimated for these
facilities are reported in Table A-l. Therefore HCN emissions
from these six facilities are not duplicated for this
production process. No emission data were available for the
Du Pont, TX facility, which was the only facility that
produces NaCN but did not report cyanide emissions in the TRI
or the EPA report.
A-3
-------
EMISSIONS OF HCN AND CYANIDE COMPOUNDS FROM MAJOR USES OF
HYDROGEN CYANIDE
Adiponitrile Production
Basis: TRI data
A list of domestic adiponitrile producing facilities is given
in Section 5, Table 5-1. Three facilities currently produce
adiponitrile.
Emission factors for HCN and cyanide compound emissions from
individual sources are not available. The only emission data
available are the HCN and cyanide compounds emission data
reported by individual facilities in the 1991 TRI. Two
facilities have reported HCN and/or cyanide compound emissions
in the 1991 TRI. These data are presented in Section 5, Table
5-2, and are once again summarized in Table A-2. Emissions of
HCN reported in Table A-2 are already included in Table A-l,
therefore, they should not be included in the estimation of
nationwide emission estimates. However, emissions of cyanide
compounds given in Table A-2 should be included. A total of
13.4 kg (29 Ib) of cyanide compound emissions have been
reported in the 1991 TRI.
Acetone Cyanohydrin Production
Basis: TRI data
Four facilities produce acetone cyanohydrin. Facility data
are presented in Section 5, Table 5-3.
Emission factors for HCN and cyanide compound emissions from
individual sources are not available. The only emission data
available are the HCN and cyanide compounds emission data
reported by individual facilities in the 1991 TRI. Three
facilities have reported HCN and/or cyanide compound emissions
in the 1991 TRI. These data are presented in Section 5, Table
5-4, and are once again summarized in Table A-3. Emissions of
HCN reported in Table A-3 are already included in Table A-l;
therefore, they should not be included in the estimation of
nationwide emission estimates. However, emissions of cyanide
compounds given in Table A-3 should be included. A total of
3,035 kg (6,693 Ib) of cyanide compound emissions have been
reported in the 1991 TRI. One facility, CYRO Industries, New
Orleans, LA, has not reported cyanide compound emissions in
the 1991 TRI. The limited data given in Table A-4 for cyanide
compounds are not sufficient to extrapolate for the estimation
of cyanide compound emissions from the other facility.
A-4
-------
TABLE A-2. ADIPONITRILE PRODUCERS REPORTING CYANIDE COMPOUND OR HYDROGEN
CYANIDE EMISSIONS IN THE 1991 TOXICS RELEASE INVENTORY3
Cyanide compound emissions,
kg (Ib)
Hydrogen cyanide emissions,
kg (Ib)
Facility
Dupont
Orange, TX
Dupont
Victoria, TX
Total
Nonpoint
12(26)
0(0)
12(26)
Point
1.4(3)
0(0)
1.4(3)
Total
13.4
(29)
0(0)
13.4
(29)
Nonpoint
1,002
(2,210)
1,038
(2,290)
2,040
(4,500)
Point
30,970
(68,288)
2,531
(5,580)
33,501
(73,868)
Total
31,972
(70,498)
3,569
(7,870)
35,541
(78,368)
a These facilities produce multiple derivatives of HCN. Therefore, it is not clear as to what the
specific sources are that emit cyanide compounds and/or HCN.
Source: Reference 1.
TABLE A-3. ACETONE CYANOHYDRIN PRODUCERS REPORTING CYANIDE COMPOUNDS OR
HYDROGEN CYANIDE EMISSIONS IN THE 1991 TOXICS RELEASE INVENTORY3
Cyanide compound emissions, kg (Ib)
Hydrogen cyanide emissions, kg (Ib)
Facility
Dupont
Memphis, TN
Rohm & Haas
Deer Park, TX
BP Chemicals, Inc.
Green Lake, TX
Total
Nonpoint
205
(451)
1,224
(2,700)
0(0)
1,429
(3,151)
Point
1,180
(2,602
426
(940)
0(0)
1,606
(3,542)
Total
1,285
(3,053)
1,650
(3,640)
0(0)
3,035
(6,693)
Nonpoint
459
(1,012)
254
(560)
3,810
(8,400)
713
(1 ,572)
Point Total
13,224 13,683
(29,159) (30,171)
49,887 50,141
(110,000) (110,560)
11,791 15,601
(26,000) (34,400)
63,111 63,824
(139,159) (140,731)
aThese facilities produce multiple derivatives of HCN. Therefore, it is not clear as to what the
specific sources are that emit cyanide compounds and/or HCN.
Source: Reference 1.
A-5
-------
Cyanuric Chloride Production
Basis: TRI data
Only two facilities, Degussa Corp in Theodore, AL, and Ciba-
Geigy in St. Gabriel, LA, produce cyanuric chloride. Both
facilities have reported facilitywide HCN emissions in the
1991 RTI. However, it is not clear as to how the facilitywide
HCN emissions are distributed, i.e., how much of them occur
due to HCN production as opposed to other derivatives of HCN.
Therefore, only the HCN emissions reported in Table A-l should
be used to estimate nationwide emissions.
Production of Chelating Agents
Basis: TRI data
Twenty-two facilities produce chelating agents. Facility
information is given in Section 5, Table 5-5.
Emission factors for HCN and cyanide compound emissions from
individual sources are not available. The only emission data
available are the HCN and cyanide compound emission data
reported by individual facilities in the 1991 TRI. Seven
facilities have reported HCN and/or cyanide compound emissions
in the 1991 TRI. These data are presented in Section 5, Table
5-6. Emissions of HCN reported by three facilities in
Table 5-6, Dow Chemical, Sterling Chemicals, and Monsanto, are
already included in Table A-l; therefore, they should not be
included in the estimation of nationwide emission estimates.
However, HCN emissions reported by Ciba-Geigy, Mclntosh, AL,
and W. R. Grace, Nashua, NH, need to be included in the
estimation of nationwide HCN emission rates. These two
facilities have jointly reported HCN emissions totalling
1,254 kg (2,767 Ib).
Emissions of cyanide compounds given in Table 5-6 should also
be included. A total of 2.3 kg (5 Ib) of cyanide compound
emissions was reported in the 1991 TRI by five facilities.
The remaining 17 facilities did not report any emissions in
the TRI.
Electroplating
Basis: TRI data
A total of 123 facilities have reported emissions of cyanide
compounds in the 1991 TRI. Cyanide compound emission
estimates for these facilities totaled 10,117 kg (22,309 Ib).
It is assumed that these also represent nationwide emissions
resulting from electroplating.
A-6
-------
EMISSIONS FROM MISCELLANEOUS SOURCES
Iron and Steel Production
Basis: TRI data
A list of domestic iron and steel producing facilities
(integrated) is given in Section 6, Table 6-1. Twenty-nine
facilities currently produce iron and steel.
Emission factors for cyanide emissions from individual sources
are not available. The only emission data available are the
cyanide compound emission data reported by individual
facilities in the 1991 TRI. Twenty-one facilities have
reported cyanide compound emissions in the TRI. These data
are presented in Section 6, Table 6-3. Cyanide compound
emission estimates for the 21 facilities totaled 180,098 kg
(397,120 Ib).
Carbon Black Production
Basis: TRI data
A list of domestic carbon black producing facilities is given
in Section 6, Table 6-4. Twenty-four facilities currently
produce carbon black.
Emission factors for cyanide compound emissions from
individual sources are not available. The only emission data
available are the cyanide compound emission data reported by
individual facilities in the 1991 TRI. Six facilities have
reported cyanide compound emissions to the TRI. These data
are presented in Section 6, Table 6-5. There are no cyanide
compound emission factors available to estimate the emission
rates from the remaining 18 facilities.
Carbon Fiber Production
Basis: TRI data
A list of domestic carbon fiber producing facilities is given
in Section 6, Table 6-6. Eight facilities currently produce
carbon fiber.
Emission factors for cyanide compound emissions from
individual sources are not available. The only emission data
available are the cyanide compound emission data reported by
individual facilities in the 1991 TRI. Five facilities have
reported cyanide compound emissions to the TRI. These data
are presented in Section 6, Table 6-7. There are no cyanide
compound emission factors available to estimate the emission
rates from the remaining three facilities.
A-7
-------
Petroleum Refining
Basis: TRI data
Only three facilities have reported emissions of HCN totalling
48,613 kg (107,192 Ib) in the 1991 TRI. Because HCN emission
factors are not available for petroleum refineries, it is not
possible to estimate HCN emissions at other refineries.
Mobile Sources (Nonpoint source category)
Basis: Cyanide emission factor of 11.4 mg/mile (Section 6,
Page 6-21)
Total vehicular miles travelled in 1990 - 2,147,501
million miles (Section 6, Page 6-21).
Nationwide cyanide emissions resulting from automobiles are
estimated to be:
(11.4 mg/mile) x (2,147,501 x 106 miles/yr)
= 24,481,512 kg (53,972,430 Ib)
REFERENCES FOR APPENDIX A
1. U. S. Environmental Protection Agency. 1991 Toxics
Release Inventory. Office of Toxic Substances.
Washington, DC. June, 1993.
2. U. S. Environmental Protection Agency. Preliminary Source
Assessment for Cyanide Chemical Manufacturing. Draft
Report. Office of Air and Radiation. Office of Air
Quality Planning and Standards. Industrial Studies
Branch. Research Triangle Park, NC. September 1992.
A-i
-------
APPENDIX B
ELECTRIC ARC FURNACES IN IRON AND STEEL PRODUCTION CRUDE OIL
DISTILLATION CAPACITY
-------
TABLE B-1. COMPANIES USING ELECTRIC ARC FURNACES IN IRON AND STEEL PRODUCTION3
Company/location
No. of furnaces
Shell diameter, ft
Allegheny Ludlum Corp.
Brakenridge Works, Brackenridge, PA
Special Materials Div., Lockport, NY
18
17
12
AL Tech Specialty Steel
Waterviet Plant, Waterveit, NY
13.6
Arkansas Steel Associates
Newport AR
12
12.5
Armco, Inc.
Baltimore Specialty Steel Corp., Baltimore, MD
15
Butler Works, Butler, PA
Kansas City Works, Kansas City, MO
Northern Automatic Electric Foundry, (NAEF),
Ishpeming, Ml
Atlantic Steel
Cartersville Works, Cartersville, GA
Auburn Steel
Auburn, NY
Bayou Steel
La Place, LA
Bethlehem Steel
Bethlehem Plant, Bethlehem, PA
Johnstown Plant, Johnstown, PA
Steelton Plant, Steelton, PA
Birmingham Steel
Illinois Steel Div., Birmingham, AL
Mississippi Steel Div., Jackson, MS
Salmon Bay Street, Kent, WAb
Southern United Steel Div., Birmingham, AL
Border Steel Mills
El Paso, TX
Braeburn Alloy Steel
Div., of CCX, Inc., Lower Burrell, PA
Calumet Steel
Chicago Heights, IL
Carpenter Technology
Reading Plant, Reading, PA
Cascade Steel Pulling Mills
McMinville, OR
CF&I Steel
Pueblo, CO
Champion Steel
Orwell, OH
Chaparral Steel
Midlothian, TX
3 total (No. 2,
3, and 4)
No. 5(1)
No. 6(1)
1 (melting)
1 (holding)
9
1
1
2
1
1
1
3
2
1
1
2
1
1
1
2
2
A
B
C
D
E
F
2
1
1
1
1
1
1
22 ea
22
22
9
22
16
18
15
18
18
22
24
18
14
12.5
15
12
12
11
12.5
11
11
11
11
11
13.5
12
1 9 (egg shaped)
22
22
8.5
19
22
Charter Electric Melting
Chicago, IL
13.5
5-1
-------
TABLE B-1. (Continued)
Company/Location
Citisteel USA, Inc.
Claymont, DE
CMC Steel Group
SMI Steel, Inc., Birmingham, AL
SMI-Texas, Seguin, TX
Columbia Tool Steel
Chicago Heights, IL
Copperweld Steel
Warren, OH
Crucible Materials Corp.
Crucibile Specialty Metals Div., Syracuse, NY
Cyclops Corp.
Bridgeville Works, Bridgeville, PA
Empire-Detroit Steel Div., Mansfield, OH
Eastern Stainless Steel
Baltimore Works, Baltimore, MD
Edgerwater Steel, Oakmont, PA
Electralloy Corp.
Oil City, PA
Ellwood Uddeholm Steel
New Castle, PA
A. Finkl & Sons
Chicago, IL
Florida
Charlotte Mill, Charlotte, NC
Jacksonville Mill, Baldwin, FL
Knoxville Div., Knoxville, TN
Tampa Mill, Tampa, FL
Tennessee Mill, Jackson, TN
Georgetown Steel
Georgetown, SC
Hawaiian Western Steel
Ewa, HI
Haynes International
Kokomo Works, Kokomo, IN
Inco Alloys International, Inc.
Huntington Works, Huntington, WV
Inland Steel Bar Company
Indiana Harbor Works, East Chicago, IN
IRI International
Specialty Steel Div., Pampa, TX
Jessop Steel
Athlone Industries, Inc., Washington, PA
No. of furnaces
1
2
1
1
No. 5
No. 6
No. 8
No. 9
1
1
D
C
G
No. 8
No. 9
1
1
1
1
1
1
1
1
1
1
1
1
1
2EF
2LF
1
1
1
2
2
1
1
1
1
Shell diameter, ft
22
14
18
11
18
18
18
18
15
11.5
12
12
15
20
22
16
17
15
12.5
13.5
Oval/1 5x1 7
15
17
18
12
12.5
17
20
18.5
11
9
11
14
22
11
11
12
11
-------
TABLE B-1. (Continued)
Company/Location
J&L Specialty Steel Products
Midland Plant, Midland, PA
Jorgensen Forge
Seattle, WA
Keystone Consolidated Industries
Keystone Steel and Wire Div., Peoria, IL
Laciede Steel
Alton, IL
Latrobe Steel
Latrobe, PA
Lone Star Steel
Texas Specialty Flatroll, Inc., Lone Star, TX
LTV Steel
Cleveland Works, Cleveland, OH
Lukens Steel
Coatsville, PA
MacSteel
Jackson, Ml
Ft. Smith, AR
Marathon LeTourneau
Longview Div., Longview, TX
Marion Steel
Marion, OH
McLouth Steel Products
Trenton Works, Trenton, Ml
National Forge
Irvine Forge Div., Irvine, PA
New Jersey Steel
Sayreville, NJ
North Star Steel
Milton Plant, Milton, PAC
Monroe Plant, Monroe, Ml
St. Paul, Div., St. Paul, MN
Texas Div., Beaumont, TX
Wilton Plant, Wilton, IA
Youngstown Div., Youngstown, OH
Northwestern Steel and Wire
Sterling Works, Sterling, IL
NS Group, Inc.
Kentucky Electric Steel Corp., Ashland, KY
Koppel Steel Corp., Koppel, PA
Newport Steel Corp., Wilder, KY
No. of furnaces
4
2
2
1
1
2
A
B
2
2
1
1
2
2
D
E
A
B
2
1
1
3
1
2
2
1
2
1
1
1
2
1
1
1
1
1
1
1
1
1
Shell diameter, ft
24
24
22
22
24
12
13.5
16
22
22
22
14
15
13
13
13.5
13.5
24.5
15
19
12
19
16
22
16.5
18
38
32
38
15
20
20
20
18
16
19
19
19
19
5-3
-------
TABLE B-1. (Continued)
Company/Location
Nucor Corp.
Crawfordsville, IN
Darlington Mill, Darlington, SC
Jewell Mill, Jewell, TX
Norfolk Mill, Norfolk, NE
Plymouth Mill, Plymouth, UT
Nucor-Yamato Steel Company
Nucor-Yamato Works, Blytheville, AR
Ocean State Steel, Inc.
E. Providence, Rl
Oregon Steel Mills, Inc.
Oregon Steel Mills, Portland, OR
Owen Electric Steel Company of South Carolina, Columbia, SC
Raritan River Steel
Perth Amboy, NJ
Republic Engineered Stees, Inc.,
No. 4 Melt Shop, Carlton, OH
No. 3 Melt Shop, Carlton, OH
Roanoke Electric Steel
Roanoke, VA
Rouge Steel
Rouge Works, Dearborn, Ml
Seattle Steel Inc."
Seattle, WA
Sharon Steel
Steel Div., Farrell, PA
Sheffield Steel
Sand Springs, OK
Slater Steels
Ft. Wayne Specialty Alloy Div.,
Ft. Wayne, IN
Standard Steel
Burnham Plant, Burnham, PA
Latrobe, PA
Steel of West Virginia
Huntington, WV
Tamco
Etiwanda, CA
No. of furnaces
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
1
1
1
1
1
3
2
1
1
2
2
2
2ea
1
1
1
1
1
1
3
1
Shell diameter, ft
22
12.5
12.5
12.5
14
14
13.5
13.5
13.5
13.5
13.5
13.5
13.5
13.5
13.5
12.5
15
15
24
114
(1 ,366")
18
10
11
12
20
26
20
14
18
24
20
20 ea
18ea
11
12
14
15
17
13
15ea
20
B-4
-------
TABLE B-1. (Continued)
Company/Location
Teledyne Vasco
Latrobe Plant, Latrobe, PA
Thomas Steel
Lemont Works, Lemont, IL
Timken Company Steel Business
Harrison Plant, Canton, OH
Faircrest Mill, Canton, OH
Union Electric Steel
Hamon Creek Plant, Burgettstown, PA
USS Div. of USX Corp.
South Works, Chicago, IL
Washington Steel
Fitch Works, Houston, PA
No. of furnaces
1
2
1
1
1
1
1
1
1
2
1d
2
1
1
Shell diameter, ft
10
13'5"
12'5"
22
20
22
22
24
14
24
20
14,16
14
16
1 Source: Huskonen, W. W. Adding the Final Touches. 33 Metal Producing. 29:28-131.
May 1991.
b Birmingham Steel is proceeding with a plan to close the Salmon Bay Steel melt shop and will merge the operation with the Seattle Steel,
Inc., facilities it is acquiring.
0 Presently idle.
d On standby.
B-5
-------
TABLE B-2. REFINER'S OPERABLE ATMOSPHERIC CRUDE OIL DISTILLATION CAPACITY AS OF
JANUARY 1, 1992
Refiner
Barrels per
Calendar Day
Companies with Capacity
Over 100,000 bbl/cd
Refiner
Toledo, Ohio
Tulsa. Oklahoma
Barrels per
Calendar Day
125,000
85.000
Chevron U.S.A. Inc 1,503,700
Port Authur, Texas 315,900
Pascagoula, Mississippi 295,000
El Segundo, California 254,000
Richmond, California 220,000
Philadelphia, Pennsylvania 175,000
Perth Amboy, New Jersey 80,000
El Paso, Texas 66,000
Honolulu, Hawaii 52,800
Salt Lake City, Utah 45,000
Exxon Co. U.S.A 1,157,000
Baton Rouge, Louisiana 421,000
Baytown, Texas 396,000
Linden (Bayway), New Jersey 170,000
Benicia, California 128,000
Billings, Montana 42,000
Amoco Oil Co 982,000
Texas City, Texas 433,000
Whiting, Indiana 370,000
Mandan, North Dakota 58,000
Yorktown, Virginia 53,000
Salt Lake City, Utah 40,000
Savannah, Georgia 28,000
Shell Oil Co 966,900
Wood River, Illinois 274,000
Deer Park, Texas 215,900
Norco, Louisiana 215,000
Martinez, California 144,100
Anacortes, Washington 89,300
Odessa, Texas 28,600
Mobil Oil Corp 838,000
Beaumont, Texas 275,000
Joliet, Illinois 180,000
Chalmette, Louisiana 160,000
Torrence, California 123,000
Paulsboro, New Jersey 100,000
BP America Inc 741,400
BP Oil Corp.
Belle Chasse (Alliance), Louisiana 218,000
Marcus Hook, Pennsylvania 168,000
Lima, Ohio 145,000
Toledo, Ohio 126,100
Ferndale, Washington 84,300
USX Corp.a 620,000
Marathon Oil Co.
Garyville, Louisiana 255,000
Robinson, Illinois 175,000
Detroit, Michigan 70,000
Texas City, Texas 70,000
Indianapolis, Indianab 50,000
Star Enterprise 615,000
Port Arthur/Neches, Texas 250,000
Convent, Louisiana 225,000
Delaware City, Delaware 140,000
Sun Co. Inc 515,000
Marcus Hook, Pennsylvania 175,000
Sun Refining & Marketing
Philadelphia, Pennsylvania
130,000
Petroleos De Venezuela 479,000
Citgo Petroleum Corp.
Lake Charles, Louisiana 305,000
Champion Refining & Chemical Inc.
Corpus Christi, Texas 130,000
Seaview Oil Co.c
Paulsboro, New Jersey 44,400
Atlantic Richfield Co 424,500
Arco Products Co.
Los Angeles, California 223,000
Ferndale (Cherry Point), Washington 174,500
Arco Alaska Inc.
Prudhoe Bay, Alaska 15,000
Anchorage, Alaska 12,000
E.I. DuPont De Nemours & Co 412,000
Conoco Inc.
Westlake, Louisiana 165,000
Ponca City, Oklahoma 140,000
Billings, Montana 49,500
Commerce City, Colorado 48,000
Santa Maria, California 9,500
Ashland Oil Inc 346,500
Catlettsburg, Kentucky 213,400
St. Paul, Minnesota 67,100
Canton, Ohio 66,000
Unocal Corp 341,100
Wilmington (Los Angeles), California 228,000
Rodeo (San Francisco), California 73,100
Arroyo Grande (Santa Maria), California 40,000
Koch Industries Inc 325,000
St. Paul (Pine Bend), Minnesota 200,000
Corpus Christi, Texas 125,000
Texaco Refining & Marketing Inc 324,000
Anacortes (Puget Sound), Washington 132,000
El Dorado, Kansas 80,000
Wilmington (Los Angeles), California 64,000
Bakersfield, California 48,000
Phillips Petroleum Co 305,000
Phillips 66 Co.
Sweeny, Texas 175,000
Borger, Texas 105,000
Woods Cross, Utah 25,000
Trans-America Natural Gas Corp.
Trans-American Refining Co.
Norco (Good Hope), Louisiana .
300,000
Solomon Inc 290,500
Phibro Refining Inc.d
Texas City, Texas 119,600
Houston, Texas 70,900
Krotz Springs, Louisiana 60,000
Saint Rose, Louisiana 40,000
B-6
-------
TABLE B-2. (Continued)
Refiner
Barrels per
Calendar Day
Coastal Corp., The 275,300
Coastal Refining & Marketing Inc.
Corpus Christi, Texas 85,000
El Dorado, Kansase 30,400
Wichita, Kansase 28,800
Coastal Eagle Point Oil Co.
Westville, New Jersey 104,500
Coastal Mobile Refining Co.
Chickasaw, Alabama 26,600
Lyondell Petrochemical Co.
Houston, Texas
265,000
Fina Oil & Chemical Co 199,000
Port Arthur, Texas 144,000
Big Spring, Texas 55,000
Total Petroleum Inc 197,600
Ardmore, Oklahoma 68,000
Arkansas City, Kansas 56,000
Alma, Michigan 45,600
Colorado Refining Co.
Commerce City, Colorado 28,000
Mapco Petroleum Inc 192,500
North Pole, Alaska 116,500
Memphis, Tennessee 76,000
Diamond Shamrock Refining & Marketing Co. . 165,000
Sunray (McKee), Texas 112,000
Three Rivers, Texas 53,000
Kerr-McGee Corp 156,800
Southwestern Refining Co. Inc.
Corpus Christi, Texas 104,000
Kerr-McGee Refining Corp.
Wynnewood, Oklahoma 45,000
Cotton Valley, Louisiana 7,800
Crown Central Petroleum Corp 155,000
Pasadena, Texas 100,000
La Glona Oil & Gas Co 55,000
Tyler, Texas
Uno-Ven Co.
Lemont (Chicago), Illinois
Tosco Corp.
Tosco Refining Co.
Martinez (Avon), California
147,000
131,900
Sinclair Oil Corp 128,500
Sinclair, Wyoming 54,000
Tulsa, Oklahoma 50,000
Little America Refining Co.
Evansville (Casper), Wyoming 24,500
Murphy Oil U.S.A. Inc 128,200
Meraux, Louisiana 95,000
Superior, Wisconsin 33,200
Refiner
Barrels per
Calendar Day
Horsham Corp 121,600
Clark Oil & Refining Corp
Blue Island, Illinois 64,600
Hartford, Illinois 57,000
Total 13,750,400
Companies with Capacity
30,001 to 100,000 bbl/cd
Pacific Resources Inc.
Hawaiian Independent Refinery Inc.
Ewa Beach, Hawaii
. 93,500
Farmland Industries Inc 82,900
Coffeyville, Kansas 56,600
Phillipsburg, Kansas 26,400
LL&E Petroleum Marking
Saraland (Mobile), Alabama
. 80,000
National Cooperative Refinery Association
McPherson, Kansas 75,600
Tesoro Petroleum Corp.
Kenai, Alaska
. 72,000
Pennzoil Co. Inc 69,900
Pennzoil Producting Co.
Shreveport, Louisiana 46,200
Rouseville, Pennsylvania 15,700
Roosevelt, Utah 8,000
American Ultramar Ltd
Ultramar Refining
Wilmington, California .
. 68,000
Holly Corp 63,700
Navajo Refining Co.
Artesia, New Mexico 57,000
Montana Refining Co.
Great Falls, Montana 6,700
United Refining Co.
Warren, Pennsylvania .
Castle Energy Corp.
Indiana Refining
Lawrenceville, Illinois
. 60,000
. 55,000
The Coastal Corp/Sinochem
Pacific Refining Co.
Hercules, California
. 55,000
El Paso Refinery, L.P.
El Paso, Texas
. 50,000
Placid Refining Co.
Port Allen, Louisiana
Lion Oil Co.
El Dorado, Arkansas
. 48,500
. 48,000
B-7
-------
TABLE B-2. (Continued)
Refiner
Barrels per
Calendar Day
Refiner
Thrifty Oil Co.
Golden West Refining Co.
Santa Fe Springs, California 47,000
Paramount Acquisiton Corp.
Paramount Petroleum Corp.
Paramount, California . . .
46,500
Powenne Oil Co.
Santa Fe Springs, California 45,000
Cirillo Brothers Oil Co.
Cibro Petroleum Products Inc.
Albany, New York 41,850
Cenex
Laurel, Montana 41,450
Frontier Refining Co.
Cheyenne, Wyoming
Hunt Consolidated Inc.
Hunt Refining Co.
Tuscaloosa, Alabama
38,670
33,500
Time Oil Co.
U.S. Oil & Refining Co.
Tacoma, Washington 32,400
Total 1,291,220
Companies with Capacity
10,001 to 30,000 bbd/cd
Amerada Hess Corp.
Purvis, Mississippi .
Honda Co.
Fletcher Oil & Refining Co.
Carson, California
Gold Line Refining Ltdf
Lake Charles, Louisiana
Petroserve Ltd.
Triffinery
Corpus Christ!, Texas .
Valero Refining Co.
Corpus Christ!, Texas . .
30,000
29,675
27,600
27,000
25,000
Crysen Corp 24,400
Crysen Refining Inc.
Woods Cross, Utah 12,500
Sound Refining Inc.
Tacoma, Washington 11,900
Barrels per
Calendar Day
San Joaquin Refining Co. Inc.
Bakersfield, California 24,300
Huntway Refining Co 24,100
Benicia, California 8,600
Wilmington, California 5,500
Sunbelt Refining Co.
Coolidge, Arizona 10,000
Flying J. Petroleum Inc.
Big West Oil Co.
North Salt Lake, Utah
Kern Oil & Refining Co.
Bakersfield, California .
Countrymark Cooperative Inc.g
Mount Vernon, Indiana
United Refining of Phoenix
Texas United Refining Corp.h
Nixon, Texas
Ergon Inc.
Vicksburg, Mississippi
Giant Industries of Arizona Inc.
Giant Refining Co.
Gallup, New Mexico
24,000
21,400
21,200
20,900
20,600
20,000
Barrett Refining Corp 17,500
Thomas (Custer), Okalahoma 10,500
Vicksburg, Mississippi! 7,000
Gary Williams Co.
Bloomfield Refining Co.
Bloomfield, New Mexico
16,800
VGSCorp 16,800
Southland Oil Co.
Sandersville, Mississippi 11,000
Lumberton, Mississippi 5,800
Endevco Inc 16,000
Dubach Gas Co.
Dubach, Louisiana 8,500
Lisbon, Louisianaj 7,500
Chemoil Refining Corp.
Long Beach, California 14,200
CAS Refining Co.
Jennings (Mementau), Louisiana 13,500
Longview Refining Associates
Longview, Texas 13,300
B-i
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TABLE B-2. (Continued)
Refiner
Barrels per
Calendar Day
Refiner
Wyoming Refining Co.
Newcastle, Wyoming 12,555
Barrels per
Calendar Day
Transworld Oil U.S.A. Inc.
Calcassieu Refining Co.
Lake Charles, Louisiana
12,000
Sabine Resources Group
Stonewall, Louisiana* 12,000
World Oil Co.
Sunland Refining Corp.
Bakersfield, California 12,000
Bechtel Investment Inc 11,500
Petra Source Refining Partners
Eagle Springs, Nevada* 7,000
Tonopah, Nevada 4,500
Quaker State Corp.
Newell, West Virginia 11,500
Grant Trading Co.
Eco Asphalt Inc.
Long Beach, California 10,550
Total 530,000
Companies with Capacity
10,000 bbl/cd or Less
Landmark Petroleum Inc.
Fruita, Colorado 10,000
Witco Corp.
Bradford, Pennsylvania 9,915
Asphalt Materials
Laketon Refining Corp.
Laketon, Indiana 8,700
Lunday Thagard Co.
South Gate, California 8,100
Anchor Gasoline Corp.
Canal Refining Co.
Church Point, Louisiana 8,000
Three B Oil Co.
Rattlesnake Refining Corp.
Wickett, Texas 8,000
Cross Oil & Refining Co. Inc.
Smackover, Arkansas 7,000
WSGP Partners L.P.
Petrowax Pennsylvania, Inc.
Farmer's Valley (Smethport), Pennsylvania . . . 6,700
Primary Corp.
Richmond, Virginia 6,100
Calumet Lubricants Co. LP
Princeton, Louisiana 6,000
Martin Gas Sales Inc.
Berry Petroleum Co.
Stephens, Arkansas 5,700
Young Refining Corp.
Douglasville, Georgia 5,540
Somerset Refinery Inc.
Somerset, Kentucky 5,500
Phoenix Refining Co.
Saint Mary's, West Virginia* 4,500
Oil Holdings Inc.
Tenby Inc.
Oxnard, California 4,000
Thriftway Co.
Bloomfield, New Mexico 4,000
Crystal Refining Co.
Carson City, Michigan 3,000
GNC Energy Corp.
Greensboro, North Carolina 3,000
Howell Corp.
Howell Hydrocarbons & Chemical Inc.k
San Antonio, Texas 1,900
Petrolite Corp.
Kilgroe, Texas 1,000
Total 123,655
U.S. TOTAL 15,696,155
Petro Star Inc.
North Pole, Alaska
7,000
a Formerly U.S. Steel Corp.
b Formerly Rock Island Refining.
0 Formerly Seaview Petroleum Co., L.P.
d Formerly Hill Petroleum Co.
e Formerly Coastal Derby Refining Co.
f Formerly American International Refinery Inc.
9 Formerly Indiana Farm Bureau Coop. Assn.
h Formerly Lead Petroluem Corp.
' Formerly Petro Source Resources Inc.
J Formerly Claborne Gasoline Co.
k Formerly Howell Hydrocarbons Corp.
* Refinery was reactivated on January 1, 1992.
bbl/cd = Barrels per calendar day.
Source: United States Refining Capacity, January 1,1990,
National Petroleum Refineries Association, Washington, D.C.
5-9
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