EPA-450/4-84-007H
September 1985
Locating And Estimating Air Emissions
From Sources Of Manganese
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office Of Air And Radiation
Office Of Air Quality Planning And Standards
Research Triangle Park, North Carolina 27711
September 1985
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This report has been reviewed by the Office Of Air Quality Planning And Standards, U.S. Environmental Protection
Agency, and has been approved for publication as received from the contractor. Approval does not signify that the
contents necessarily reflect the views and policies of the Agency, neither does mention of trade names or commercial
products constitute endorsement or recommendation for use.
EPA-450/4-84-007h
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CONTENTS
,t *
Page
1. Purpose of Document 1-1
2. Overview of Document Contents 2-1
3. Background 3-1
3.1 Manganese Characteristics 3-1
3.2 Overview of Manganese Production 3-3
3.3 Overview of End Uses of Manganese 3-10
4. Manganese Emissions From Production and Use of Manganese 4-1
4.1 Manganese Ore Beneficiation, Transport, and Storage 4-2
4.2 Production of Manganese-Bearing Alloys 4-3
4.3 Production of Manganese Metal and Synthetic Manganese Oxide 4-14
4.4 Production of Manganese Chemicals 4-21
4.5 Iron and Steel Production 4-25
4.6 Iron and Steel Foundries 4-53
4.7 Battery Manufacturing 4-58
5. Indirect Sources of Manganese 5-1
5.1 Coal and Oil Combustion 5-1
5.2 Cement Production 5-7
5.3 Municipal Refuse and Sewage Sludge Incineration 5-12
5.4 Manganese Fuel Additives 5-20
6. Source Test Procedures 6-1
6.1 Literature Review of Sampling Methods 6-1
6.2 Literature Review of Analytical Procedures 6-1
m
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FIGURES
Number .1 v Page
3-1 End Use of Manganese and Manganese Compounds 3-11
4-1 Flow Chart of Manganese-Bearing Ferroalloys Production
by Electric Arc Furnace Process 4-5
4-2 Open Furnace 4-7
4-3 Semisealed Furnace . 4-7
4-4 Sealed Furnace 4-7
4-5 Generalized Flow Diagrams for Chemical MnCL Production 4-16
4-6 Electrolytic MnCL Production From MnOp Ores and
Rhodochrosite Ores 4-18
4-7 Production of KMnO.: Roasting and Liquid-Phase Oxidation
Processes 4-23
4-8 Cross-Sectional View of a Typical Blast Furnace 4-29
4-9 Schematic Flow Diagram of a Typical Sinter Plant 4-35
4-10 Schematic Representation of an Open Hearth Furnace 4-39
4-11 Basic Oxygen Process Furnace 4-42
4-12 Schematic of Electric Arc Furnace Process 4-48
4-13 Generalized Flow Diagram of Iron/Steel Foundry 4-54
5-1 Basic Process Flow Diagram for Wet and Dry Cement
Production 5-8
5-2 Basic Configuration of a Municipal Refuse Incinerator 5-13
5-3 Schematic of a Typical Multiple-Hearth Incinertion
System 5-15
iv
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FIGURES (continued)
Number Page
5-4 Schematic of a Fluidized-Bed Sewage Sludge Incinerator 5-16
5-5 Schematic of a Typical Municipal Rotary-Kiln Incineration
tv Facility 5-17
6-1 Schematic of Method 5 Sampling Train 6-2
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TABLES
Number * Page
3-1 Physical Properties of Metallic Manganese 3-2
3-2 Physical Properties of Selected Manganese Compounds 3-4
3-3 Common Manganese-Containing Minerals 3-7
3-4 Domestic Manganese Ore Production, Imports, and Exports 3-7
3-5 Consumption of Manganese Ores in the United States 3-12
3-6 U.S. Consumption of Manganese Ferroalloys According to End
Use in 1981 • 3-12
3-7 Primary Nonmetallurgical Uses of Manganese Oxides 3-14
3-8 Primary Uses of Manganese Compounds 3-16
3-9 Principal Uses of Potassium Permanganate 3-17
4-1 Specifications and Typical Compositions of Manganese
Ferroalloys 4-4
4-2 Manganese Emission Factors for Processing of Raw Materials
at Manganese-Bearing Ferroalloy Production Facilities 4-11
4-3 Manganese Emission Factors for Finishing Operations 4-11
4-4 Manganese Emission Factors for Submerged-Arc Electric
Furnaces Producing Ferromanganese and Silicomanganese 4-12
4-5 Characterization of Particulate Emissions from Ferroalloy
Furnaces 4-13
4-6 Domestic Producers of Manganese Ferroalloys, 1980 4-13
4-7 Derived Manganese Emissions for Synthetic Manganese
Production 4-19
4-8 Domestic Producers of Manganese Metal and Synthetic
Manganese Dioxide 4-20
(continued)
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TABLES (continued)
Number Page
4-9 Manganese Emission Factors for the Manufacture of Manganese
Chemicals 4-24
4-10 v Domestic Producers of Manganese Chemicals 4-26
4-11 Manganese Emissions from Iron Blast Furnaces 4-31
4-12 Manganese Content of Raw Materials and Byproducts of Blast
Furnace Production 4-31
4-13 Locations (By State and City) of Blast Furnaces in the
United States 4-33
4-14 Manganese Emission Factors for Sintering Operations 4-36
4-15 Locations (By State and City) of Sinter Plants in the U.S.
Integrated Steel Industry 4-38
4-16 Manganese Emissions Factors for Open-Hearth Furnace Opera-
tions 4-40
4-17 Locations (By State and City) of Steel Plants With Open-
Hearth Furnaces in the United States 4-41
4-18 Manganese Content of Raw Materials and Products of BOF
Process 4-44
4-19 Manganese Emission Factors for Basic Oxygen Furnace
Operations 4-45
4-20 Locations (By State and City) of Basic Oxygen Furnaces in
the Iron and Steel Industry in the United States 4-46
4-21 Manganese Emission Factors for Electric Arc Furnace
Operations 4-50
4-22 Alphabetical Listing (By Company Name) of Electric Arc
Furnace/Locations in the United States 4-51
4-23 Manganese Emission Factors for Iron Foundries 4-57
4-24 Manganese Emission Factors for Steel Foundries 4-57
4-25 Manganese Emission Factors for Battery Manufacture 4-60
(continued)
vn
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TABLES (continued)
Number Page
5-1 Manganese Concentrations in U.S. Coals 5-2
5-2 Manganese Concentrations in U.S. Crude Oils 5-2
5-3 .t * Particle Size Distribution of Manganese in Fly Ash From
Coal Combustion 5-3
5-4 Manganese Particulate Collection Efficiencies of Various
Types of Control Devices 5-3
5-5 Emission Factors for Manganese From Coal and Oil Combustion:
Utility Boilers (>264 GJ/h Input) 5-5
5-6 Emission Factors for Manganese from Coal and Oil Combustion:
Industrial Boilers (>26 GJ/h Input) 5-6
5-7 Emission Factors for Manganese From Coal and Oil Combustion:
Commercial/Institutional Boilers (>26 GJ/h Inpit) 5-6
5-8 Emission Factors for Manganese from Coal and Oil Combustion:
Residential Boilers (<422 MJ/h Input) 5-7
5-9 Manganese Emission Factors for Cement Plants 5-10
5-10 Location of Cement Plants in the United States 5-11
5-11 Manganese Concentrations in Municipal Refuse and Sev/age
Sludges 5-12
5-12 Emissions Factors for Manganese From Municipal Refuse and
Sewage Sludge Incinerators 5-18
5-13 Population of Municipal Refuse and Sewage Sludge Incinera-
tors in the United States, 1978 5-19
vm
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SECTION 1
t * PURPOSE OF DOCUMENT
The U.S. Environmental Protection Agency (EPA), States, and local air
pollution control agencies are becoming increasingly aware of the presence of
substances in the ambient air that may be toxic at certain concentrations.
This awareness, in turn, has led to attempts to identify scurce/receptor
relationships for these substances and to develop control programs to regulate
emissions. Unfortunately, very little information is available on the ambient
air concentrations of many of these substances or on the sources that may be
discharging them to the atmosphere.
To assist groups interested in inventorying air emissions of various
potentially toxic substances, EPA is preparing a series of documents such as
this that compiles available information on sources and emissions of these
substances. This document specifically deals with manganese and manganese
compounds. Its intended audience includes Federal, State, and local air
pollution personnel and others who are interested in locating potential emit-
ters of manganese and making gross estimates of air emissions therefrorr.
Because of the limited amounts of data available on manganese emissions,
and since the configuration of many sources will not be the same as those
described herein, this document is best used as a primer to inform air pollu-
tion personnel about (1) the types of sources that may emit manganese,
(2) process variations and release points that may be expected within these
sources, and (3) available emissions information indicating the potential for
manganese or manganese compounds to be released into the air from each opera-
tion.
The reader is strongly cautioned that the emissions information contained
in this document will not yield an exact assessment of emissions from any
particular facility. Since insufficient data are available to develop sta-
tistical estimates of the accuracy of these emission factors, no estimate can
1-1
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be made of the error that could result when these factors are used to cal-
culate emissions for any given facility. It is possible, in some extreme
cases, that orders-of-magnitude differences could result between actual and
calculated emissions, depending on differences in source configurations,
control equipment, and operating practices. Thus, in situations where an
accuratetassessment of manganese emissions is necessary, source-specific
information should be obtained to confirm the particular operations, the types
and effectiveness of control measures, and the impact of operating practices.
A source test and/or material balance should be considered as the best means
to determine air emissions directly from an operation.
1-2
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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 manganese and manganese compounds and
making gross estimates of air emissions therefrom. Because of the limited
background data available, the information summarized in this document does
not and should not be assumed to represent the source configuration or emis-
sions associated with any particular facility.
This section provides an overview of the contents of this document. It
briefly outlines the nature, extent, and format of the material presented in
the remaining sections of this report.
Section 3 of this document provides a brief summary of the physical and
chemical characteristics of manganese, its commonly occurring forms, and an
overview of its production and uses. A table summarizes the quantities of
manganese consumed in various end uses in the United States. This background
section may be useful to someone who needs to develop a general perspective on
the nature of the substance and where it is manufactured and consumed.
The fourth section of this document focuses on major industrial source
categories that may discharge manganese-containing air emissions. Sectior 4
discusses the production of manganese and manganese compounds, the use of
manganese in ferroalloys, and the discharge of manganese from industrial
sources due to its being a trace contaminant in fossil fuels. For each major
industrial source category described in Section 4, example process descrip-
tions and flow diagrams are given, potential emission points are identified,
and available emission factor estimates are presented that show the potential
for manganese emissions before and after controls employed by industry.
Individual companies are named that are reported to be involved with either
the production and/or use of manganese and manganese compounds based on indus-
try contacts and available trade publications.
2-1
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The sources of all emission factors presented in this report have been
cited, and the reader is referred to these sources for discussions concerning
the basis and limitations of these estimates. Because most of the emission
factors have been developed for materials that contain manganese, the manga-
nese emissions will depend both on the amount of material emitted and the
manganese content of the material. For example, in a foundry operation that
produces a casting that is 5 percent manganese, the manganese emissions would
amount to 5 percent of the total emissions. If the same operation with the
same total emissions were to produce a casting with 2.5 percent manganese, the
manganese emissions associated with the furnace castings would be cut in half.
Because few plants produce only one product, this is a significant considera-
tion.
The final section of this document summarizes available procedures for
source sampling and analysis of manganese. Details are not prescribed, nor is
any EPA endorsement given or implied to any of these sampling and analysis
procedures. At this time, EPA has generally not evaluated these methods.
Consequently, this document merely provides an overview of applicable source
sampling procedures and references for those interested in conducting source
tests.
This document does not contain any discussions of health or other environ-
mental effects of manganese or manganese compounds, nor does it include any
discussion of ambient air levels or ambient air monitoring techniques.
Comments on the contents or usefulness of this document are welcomed, as
is any information on process descriptions, operating practices, control
measures, and emissions that would enable EPA to improve its contents. All
comments should be sent to:
Chief, Source Analysis Section (MD-14)
Air Management Technology Branch
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
2-2
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SECTION 3
BACKGROUND
3.1 MANGANESE CHARACTERISTICS
Manganese (Mn) is a hard, brittle, grayish-white metal widely distributed
in the Earth's rocks. A transition element whose properties fall between
those of chromium and iron, manganese has an atomic number Df 25 and an atomic
weight of 54.938. Manganese-55 is the only stable isotope. Manganese can
exist in several different crystalline forms of complex structure. These
forms are stable below 1100°C and are usually brittle and unworkable. Manga-
nese constitutes 0.1 percent of the Earth's crust and ranks twelfth in abun-
dance among the elements found there. Of the most commonly known metals, only
aluminum, iron, magnesium, and titanium are more abundant. Although manganese
just precedes iron in the periodic table, it is not ferromagnetic like iron;
however, some of its alloys and compounds are. Manganese compounds can have
various valences, but manganese is divalent in the most stable salts, and
2
manganese dioxide (MnO) is the most stable oxide. Table 3-1 presents the
physical constants and properties of manganese.
Manganese is ubiquitous in the Earth's crust and water bodies. In most
soils, concentrations range from 200 to 300 ppm; in many ro:ks, concentrations
range from 800 to 1400 ppm; and in some sedimentary rocks, :oncentrations can
range from 6000 to 8000 ppm. Seawater contains a few parts psr billior, and
concentrations increase at greater depths. Manganese oxide nodules have been
found on large areas of the ocean floor; some analyzed deposits have shown an
2
average manganese content of 24.2 percent. Concentrations in fresh water can
range from a few parts per billion to several parts per million. Atmospheric
precipitation also contains manganese—around 0.012 ppm— primarily introduced
2
through air pollution.
3-1
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TABLE 3-1. PHYSICAL PROPERTIES OF METALLIC MANGANESE*
Property
Value
Atomic number
Atomic weight
Crystal structure
Valence state
Melting point, °C
Boiling point, °C
Specific Gravity
Specific heat at 25.2°C, J/g
Linea^ coefficient of thermal expansion
x 10~6 per °C at 0-100°C range
Hardness, Mohs scale
Compressibility
Solidification shrinkage, %
Standard electrode potential
Magnetic susceptibility, mVkg
Latent heat of fusion, J/g
Latent heat of vaporization, J/g
Solubility
25
54.938
Cubic or tetragonal
-3, 1, 2, 3, 4, 5, 6, and 7
1244± 3°C
1962
7.21 to 7.44 (depending
on the allotropic form)
0.48
22.8
8.4 x ID'7
1.7
1.134
1.21 x 10-7
244
4020
Decomposes in water; is
soluble in slightly di-
lute acid
Sources: References 1 and 3.
3-2
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The most important valence states of manganese are +2, +4, and +7, as
exhibited in manganese oxide (MnO), manganese dioxide (MnOpK and permanganate
(MnO^), respectively. Thus, oxide manganese ores can serve as sources of
active oxygen, the degree of activity varying with the type of ore and com-
pound. Table 3-2 presents the physical properties of selected manganese
compounds^.
Ores are generally classified according to their manganese content as
follows: ores containing more than 35 percent Mn are classed as manganese
ores; those containing 10 to 35 percent, as ferroginous manganese ores; and
those containing 5 to 10 percent Mn, as manganiferrous ores. None of the U.S.
ores contain more than 35 percent Mn; most of the high-quality ores and ferro-
alloys are imported. Because manganese is considered a strategic material,
the Government has maintained stockpiles since 1916. Table 3-3 lists the
common manganese-bearing minerals, and Table 3-4 presents production, import,
and export data.
3.2 OVERVIEW OF MANGANESE PRODUCTION
The different methods used in the production of the various manganese
products are briefly described in this subsection. More detail is presented
in Section 4.
3.2.1 Production of Ferroalloys
High-carbon ferromanganese (or standard ferromanganese), which contains
up to 7.5 percent carbon, is used in larger quantities (primarily by the steel
industry) than any other form of manganese. Until 1978, U.S. high-carbon
ferromanganese was produced primarily in blast furnaces similar to those used
to smelt iron ore. Now it is produced primarily in submerged-arc electric
furnaces. The furnace charge consists of a mixture .of Mn ores, coke, and some
flux. Recovery of Mn in the alloy ranges from 70 to 80 percent. In some
cases, the slag from this process also is used to produce silicomanganese for
use in the manufacture of low-carbon steel. The manganese content of this
slag ranges from 30 to 42 percent.
3-3
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TABLE 3-2. PHYSICAL PROPERTIES OF SELECTED MANGANESE COMPOUNDS1
oo
Compound
Dinanganese
Methylcyclopentadi-
enyliaanganese
tricarbonyl
Manganese acetate
tetrahydrate
Manganese borate
Manganese carbonate
(rhodochrosite)
Manganese chloride
Manganese hydroxide
(pyrochroite)
Manganese nitrate
hexahydrate
Manganese (II) oxide
(nanganosite)
Manganese sulfate
Manganese dihydrogen
phosphate di hydrate
Trimanganese
tetraoxide alpha
phase (Hausnannite)
Manganese (III)
acetate di hydrate
Manganese (III)
acetylacetonate
Manganese (III)
fluoride
Manganese (III)
oxide n
Formula
Hn2(CO)10
C9H7Mn(CO)n
Mn(C2H302)2.4H20
MnB407.8H20
MnC03
MnCl2
Mn(OH)2
Mn(N03)2.6H20
MnO
MnS04
Mn(H2P04)2.2H20
Mn304
Mn(C2H302)3,2H20
Hn(C5H702)3
MnF3
Hn20l
Oxidation
state
0
+1
+2
+2
+2
+2
+2
+2
+2
+2
+2
+2, +3
+3
+3
+3
+3
Appearance
Golden-yellow crystals
Light-amber liquid
Pale- red crystals
White to pale red
solid
Pink solid
Pink crystal solid
White to pink
Colorless to slightly
pink crystals
Green
Almost-white crystals
solid
Almost colorless crystal
solid; four-sided prisms
Black crystals with
metallic sheen
Cinnamon brown crystal
solid
Brown to black crystal
solid
Red crystals
Black to brown solid
Density,
9/caf
1.75
1.39
1.589
3.125
2.977
3.26
1 81
5.37
3.25
4.84
3.54
4 89
Melting
point, °C
154°-155°
1.5°
Decom
poses at
>200°
652°
Decom-
poses at
140°
25 8°
1945°
Decom
poses at
850°
H20,
100°
1560°
172
Decom-
poses
(stable
to 600°)
871° 887°
decom
poies
Boiling
point. °C
233
1190
)ecomposes
Solubility
Insoluble in H20; solufile in most
organic solvents "
Insoluble in H20; soluble in most
organic solvents
Slightly soluble in H20; soluble in
ethanol and methanol
Insoluble in H20, ethanol, and soluble
dilute acids
Soluble product H20:B.2 x 10~"; soluble
in dilute acids
Soluble in H20, soluble pyridine,
ethanol, insoluble ether
Soluble in acid; soluble base at higher
temperatures
Soluble in H20, soluble ethanol
Insoluble in H20
Soluble in 52 g/100 g H20; slightly soluble
in methanol; insoluble in ether
Soluble in H20; insoluble in ethanol;
di liquescent
Insoluble in H20
Decomposes in H20
Insoluble in M20, soluble in organic
solvent
Decomposes in H20
Insoluble in H20
(continued)
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TABLE 3-2 (continued)
Compound
Manganese (III)
oxide Y, hydra ted
Pen tananganoc tox i de
Manganese (IV) oxide
p, pyrolusite
Potassium manganate
(IV)
Barium raanganate (V)
CO
' Potassium manganate
cn (y)
Sodium manganate (V)
Barium manganate (VI)
Potassium manganate
(VI)
Cn.i4J.UK ««««&«. 4. /MT\
*rt/u > t*iH tuaitijcHia bt? \ » * f
Potassium manganate
(VI), permanganate
(Vll), double salt
Manganese heptoxide
Formula
MnO(OH)
Mns08
Hn02
K2Mn03
Ba3(MnO«)2
K3HnO«
Na3MnO«
BaMrt04
K2Mn04
Ntj_/\
a2nnu4
K3(MnO,)2 or
KMh04«K2MnOH
Mn207
Oxidation
state
+3
+2, +4
+4
+4
+5
+5
+5
+6
+6
TO
+6, +7
+7
Appearance
Black solid
Black solid
Black to gray crystal
solid
Black microscopic crystals
Emerald green crystals
Turquoise-blue micro-
scopic crystals
Jluish, dark-green
microscopic crystals
Small green to black
crystals
)ark-green to black
needles
Sraoii dark yreen needles
)ark, small hexagonal
plates
)ark-red oil
Density,
g/cm1
4.2-4 4
4.85
5.118
3.071
5.25
2.78
5.20
2 80
2.396
Melting
point, °C
Decomposes
at 250°
to gamma
Mnz03
Decomposes
at 550°
to alpha
Mn203
Decom
poses
at 500°-
600°
1100°
Decom
poses
at 960°
Decom
poses at
8000-1100'
Decom-
poses at
1250°
Decom-
poses at
1150°
Decom-
poses
at 600°
Decom-
poses
at 300°
5 9, de-
composes
at 55°
Boiling
point, °C
Solubility
Insoluble in H20; dissociates in
dilute acids
Insoluble in H20
Insoluble in H20
Decomposes in H20 dissociates
Insoluble in H20
Soluble in H20, decomposes; is hygro-
scopic; soluble in 40% KOH at -15°C
Soluble in H20, decomposes; is hygro-
scopic
Insoluble in H20; soluble product 2.46
x 10~l°
Soluble in H20; decomposes
soiuole in H2u, Decomposes
Soluble in H20; decomposes
Soluble in H20; is hygroscopic
(continued)
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TABLE 3-2 (continued)
Compound
Ammonium
Permanganate
Barium permanganate
Calcium permanganate
tetrahydrate
Cesium permanganate
Lithium permanganate
Magnesium
permanganate
hexahydrate
Potassium
permanganate
Rubidiun
permanganate
Silver permanganate
Sodium permanganate
Zinc permanganate
hexahydrate
Formula
NH4Hn04
Ba(MnOH4)2
Ca(Mn04)2.4H20
CsHn04
Li(Mn04)'3H20
Mg(Mn04)2«6H20
KMn04
RbMrvO,
AgMn04
AgHn04
Zn(Mn04)2*6H20
Oxidation
state
+7
+7
+7
+7
+7
+7
+7
+7
+7
+7
+7
Appearance
Dark purple, rhombic,
bipyramidal, needles
Dark purple crystals
Black crystals; solutions
look purple
Dark purple rhombic,
bipyramidal prisms
or needles
Long, dark purple
needles
Bluish gray crystals
Dark purple, bipyramidal,
rhombic prisms
Dark purple, rhombic,
bipyramidal, prisms
Dark purple
Dark purple crystals
Jlack crystals; solu-
tions look purple
Density,
g/cms
2.22
3.77
About
2.49
3.60
2.06
2.18
2.703
3.23
4.27
1.972
2.45
Heltinq
point, °C
Decom-
poses at
>70°
Decom-
poses at
95°-100°
Decom-
poses at
130°- 140°
Decomposes
at 250°
Decomposes
at 104°-
107°
Decom-
poses
at 130°
Decom-
poses at
200°-300°
Decom
poses at
250°
Decom-
poses at
110°
36.0
Decom-
poses at
90° 105°
Boiling
point, °C
Solubility"
8 g/100 g H20 at 15°C
(86 g/liter at 25°C)
72.4 g/100 g H20 at 25 H20
388 g/100 g H20 at 25°C; deliquescent
0.23 g/100 g H20 at 20°C
71 g/100 g H20 at 16°C
Soluble in H20, CH3OH, pyridine,
and glacial acetic acid
Soluble in H20, acetic acid, triflu-
oroacetic acid, acetic anhydride, acetone,
pyridine, benzonitrile, and sulfolane
1.1 g/100 g H20 at 19°C
0.92 g/100 g H20 at 20°C
Soluble in H20; deliquescent
Soluble in H20; deliquescent
Source: Reference 1.
Roman numerals indicate valence number.
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TABLE 3-3. COMMON MANGANESE-CONTAINING MINERALS3
Mineral
Composition
Weight
percent Mn
Bementite
Braunite
Cry p/tome lane
Franklinite
Hausmannite
Manganite
Manganoan calcite
Psilomelane
Pyrolusite
Rhodochrosite
Rhodonite
Wad
Mn8ST6015(OH)10
(Fe,Zn,Mn)0-(Fe,Mn)203
(Ca,Mn)C03
(BaMn)Mng016(OH)4b
Mn02
MnC03
MnSi03
Hydrous mixture of qxides
43.2
66.6
59.8
10-20
72.0
62.5
35.4
51.7
63.2
47.8
41.9
Variable
.Source: Reference 1.
Manganese appears in different oxidation states in these minerals'.
TABLE 3-4. DOMESTIC MANGANESE ORE PRODUCTION, IMPORTS, AND EXPORTS'
(1000 tons)
Domestic mine ore production
Imports, manganese ore
Imports, ferromanganese
Exports, manganese ore
Exports, ferromanganese
1981
0
639
671
65
15
1982
0
238
493
29
10
1983
0
368
342
19
8
1984
0
410
500
140
6
a
Source: Reference 4.
Excludes manganiferous ore containing less than 35 percent manganese,
which accounts for about 2 percent or less of apparent consumption of
manganese.
3-7
-------
Silicomanganese, a ferroalloy containing 12.5 to 18.5 percent silicon
(Si) and 65 to 68 percent Mn, is added to steel when both silicon and manga-
nese are required. The electric arc smelting process by which it is produced
is similar to that used to produce high-carbon ferromanganese, but the charge
contains large amounts of quartz and, sometimes, the high-Mn slag from the
high-carbon ferromanganese process (as mentioned earlier). The carbon content
of this alloy is 2 percent.
Ferromanganese silicon (28 to 32 percent Si and <0.06 percent carbon) is
normally made in a two-step process. Regular Silicomanganese (with 16 to 18
percent Si and 2 percent carbon) is made in the first step, and this product
is then charged (in solid form) to an electric arc furnace along with quartz
and coal or coke. In this slagless process, the quartz is reduced to Si and
displaces the carbon in the remelted Silicomanganese.
Refined ferromanganese alloys (which are not carbon-saturated and have s
carbon content of 0.1 to 1.5 percent) are usually made by the reaction of Si
with Mn ore and lime.
A process recently developed and used by the El kern Metals Company in-
volves the production of medium-carbon ferromanganese by the oxygen refining
of high-carbon ferromanganese in a special furnace. '
3.2.2 Production of Manganese Metals
Manganese is recovered from aqueous solutions by means of electrolysis.'
The manganese produced by this method is 99.5 percent pure. In this process,
manganese ores are roasted to reduce higher oxides to MnO, which is acid-sol-
uble. After the various impurities are removed, the solution is electrolyzed
in a diaphragm cell. The Mn deposited on the cathode is thin and brittle and
sulfur is the primary impurity. Hydrogen is removed by heating the Mn flakes
to 500°C. Nitrogen-bearing electrolytic Mn containing 6 to 7 percent N9 is
^ i
also produced by heating the Mn flakes up to 900°C in an atmosphere of Np.
Another process (developed and used by Chemetals Corporation) is fused-
salt electrolysis. The feed, which is a Mn ore that has been reduced, is
charged to an electrolytic cell containing molten calcium fluoride and lime.
The cell is operated at 1300°C, and the molten Mn is cast into cast iron pots.
The metal produced by this process contains 92 to 98 percent Mn, and the main
impurity is iron.
3-8
-------
3.2.3 Production of Manganese (II) Oxide
Manganese (II) oxide is an important precursor of many commercial manga-
nese compounds. It is made by reductive roasting of Mn ores. In one process,
crushed Mn ore is processed in a countercurrent reactor by us-'ng a reducing
gas (e.g., CH* and air). The MnO that is formed is cooled in an inert atmo-
^ i
sphere,* ^and then ground to -200 mesh. Other processes use a rotary kiln in
the reduction step.
3.2.4 Production of Synthetic Manganese Dioxide
Synthetic manganese dioxide is produced by both chemical and electrolytic
methods. Chemical manganese dioxide (CMD) is produced either by the chemical
reduction of permanganate (Type 1), or by thermally decomposing manganese
salts, such as MnCXU or Mn(N03)2» under oxidizing conditions, followed (if
necessary) by oxidation in the liquid phase (Type 2).
Electrolytic manganese dioxide (EMD) is produced by electrolysis of MnSO,
solution. The MnSO* is prepared from rhodochrosite and manganese dioxide
ores; and the Mn02 that deposits on the solid electrode has, to be removed from
time to time during the process. The product is a black powder with a par-
ticle size <74 pm (-200 mesh). It contains 2 to 5 percent low-Mn oxides and 3
to 5 percent chemically-bound water.
A number of continuous processes have been devised for the generation of
Mn09 as a precipitate that collects at the bottom of the cell, from which it
^ i
can be removed without interruption of the electrolysis process.
3.2.5 Production of Manganese Chemicals
This subsection describes the production of an important and widely used
chemical, potassium permanganate (KMnO»).
Permanganate can be produced by several different processes. The only
one-step process is based on the electrolytic conversion of ferromanganese.
The others begin with Mn09 ore and involve two steps: thermal synthesis of
-'»
potassium manganate followed by electrolytic oxidation of MnO; to MnO*. The
thermal synthesis can be done by roasting or by liquid-phase oxidation.
The roasting processes all involve two steps. First, the formation of
KgMnO^ is promoted by high temperatures and high-KOH and Icw-l-LO concentra-
tions. In the second step, the valence of the Mn is converted from 5 to 6 by
the use of lower temperatures and control of the moisture in the air.
3-9
-------
In the liquid-phase oxidation, maintaining the MnOp and KOH ratio at 1:5
or higher causes the mixture to be a liquid.
3.3 OVERVIEW OF END USES OF MANGANESE
Figure 3-1 presents a diagram of the end uses of manganese and manganese
compounds, and Table 3-5 shows the consumption figures by major usage. Note
from Table 3-5 that the consumption of manganese ores decreased significantly
in 1982 and has not yet grown back to 1981 levels.
3.3.1 Metallurgical Uses
Table 3-6 shows the consumption of manganese-bearing ferroalloys and
manganese metals in the manufacture of various types of steel, cast irons,
superalloys, and other products.
The principal use of manganese is in the production of iron and steel.
It is essential to the production of virtually all steels, and it is important
to the production of cast irons. When added to steel, ferromanganese reacts
with the sulfur and retains it as manganous sulfide (MnS). Manganese also
acts as a deoxidizer and imparts the alloying effects of strength, toughness,
hardness, and hardenability. Silicomanganese is used as the alloy feedstock
when both Si and Mn are desired in the steel. Ferroalloys are introduced in
the furnace or the ladle, or both.
The amount of alloy feedstock added is directly proportional to the
percentage of Mn desired in the steel end product. The most common grades of
steel contain about 0.5 to 1.0 percent manganese.
Common grades of ferromanganese contain about 80 percent Mn. The recov-
ery of Mn in the steel is also about 80 percent; the remainder is lost to
oxidation (i.e., MnO). Most of the oxides are captured in the slag layer in
the ladle, which is discarded, but some escape as emissions during the pouring
of the molten steel from the furnace into the ladle.
When ferroalloys are added to molten steel, heavy emissions occur due to
rapid oxidation. Emissions from the furnace are generally better controlled
than those from the ladle.
Various specialty steels contain higher amounts of Mn; thus, larger
amounts of ferroalloy are used. These include spring steels and high-strength,
low-alloy steels (in which the Mn content varies from 0.35 to 1.4 percent) and
heat-resisting alloys (in which the Mn content varies between 1 and 2 percent).
3-10
-------
FORM OF MANGANESE
END USE
.FERROALLOYS
Fe-Mn, Si-Mn-
•MASTER ALLOYS, BRIQUETTES, ELECTROLYTIC Mn METAL-
MANGANESE
-LOW-GRADE Mn ORES-
-Mn02 (BOTH ELECTROLYTIC AND CHEMICAL GRADE-
AND CERTAIN Mn ORES)
->-Mn02 (SYNTHETIC)-
*Mn02 ORE OR Fe-Mn
^MANGANESE SULFATE ORE-
AND Mn OXIDE ORE
-Mn ORES, Mn METAL
-MANGANESE PHOSPHATE —
METAL
—^NATIVE Mn ORES-
-ORGANOMANGANESE COMPOUNDS (MMT)
CARBON STEELS
STAINLESS STEELS, HE^T-RESISTING STEELS
Ni-FREE STAINLESS ST€EL
HADFIELD, HIGH Mn STEELS
ELECTRIC STEELS,
TOOL STEELS
CAST IRONS
SUPER ALLOYS
NONFERROUS INDUSTRIES
Mn-BRONZE
MANGANIN ELECTRICAL RESISTANCE ALLOYS
ALUMINUM ALLOYS
IRON
•BATTERIES
-^CHEMICALS
-^POTASSIUM PERMANGANATE
->SOIL CONDITIONERS
->-WELDING ROD COATINGS AND FLUXES
-^-PLATING OF FERROUS PARTS
-^Mn-Zn FERRITES IN ELECTRONIC INDUSTRY
-^-FERTILIZERS, FEED ADDITIVES
COLORANT IN BRICK AND TILE MANUFACTURE
-^-COLORANT IN GLASS MAKING AND FRIT
-*-FUEL ADDITIVES
Figure 3-1. End use of manganese and manganese compounds.
-------
TABLE 3-5. CONSUMPTION OF MANGANESE ORES3 IN THE UNITED STATESb
(short tons)
Use
Manganese alloys and metals
Pig iron and steel
DV*y cells, chemicals, and miscellaneous
Total
Consumption0
1981
744,832
147,812
183,987
1,076,631
1982
412,280
83,906
112,555
608,741
Containing 35 percent or more manganese.
Source: Reference 6.
cWeights represent total weight of ore, not just manganese content.
TABLE 3-6. U.S. CONSUMPTION OF MANGANESE
ACCORDING TO END USE IN 1981°
(short tons, gross weight)
FERROALLOYS
Ferromanganese
End use
Steel :
Carbon
Stainless and heat-
resisting
Full alloy
High-strength, low-alloy
Electric
Tool
Unspecified
Total steel
Cast irons
Superalloys
Alloys (excluding alloy
steels and superalloys)
Miscellaneous and unspeci-
fied
TOTAL CONSUMPTION
High-
carbon
270,633
7,472
36,926
29,534
16
179
302
345,062
12,543
224
1,289
3,549
362,667
Medium-
and low-
carbon
58,784
645
8,318
7,032
87
26
90
74,982
434
NAC
580
534
76,530
Silico-
manga-
nese
66,601
3,178
18,343
6,823
317
36
551
95,849
7,736
NA
1,785
275
105,645
Man-
ganese
metal
5,085
1,803
687
704
80
52
0
8,411
10
126
8,206
388
17,141
Source: Reference 6.
Virtually all electrolytic.
CNA = Not available
3-12
-------
Other metallurgical uses include the following:
0 Manganese alloys are used as hard facing materials to give abrasion
resistance to steel parts.
0 Low-grade manganese ores are directly charged to blast furnaces to
recover the contained Mn in the pig iron. (Basic oxygen furnace
slag, which contains MnO, is often recycled for Mn recovery by
** charging it into the blast furnaces or adding it to the sinter
feed.)
0 A thin coating of Mn phosphate is used to provide the initial lubri-
cation during the breaking in of parts such as bearings and gears.
The coating is applied by immersion in a hot solution of Mn-phos-
phate.
0 A small quantity of MnCL is added to resin-sand mixtures for single-
investment shell molds used in casting various alloys.
0 Manganese is used as an alloy in nonferrous metals. In manganese
bronze, for example, 0.5 to 4 percent Mn is used to impart corrosion
resistance.
0 In aluminum alloys, 0.05 to 0.5 percent Mn is added, either as an
alloy or in briquettes made of aluminum and manganese powder.
Manganese imparts strength, hardness, and stiffness to aluminum.
0 An important use of manganese is in the manufacture of electrical
resistance alloys used for electrical instruments. These are essen-
tially Cu-Mn-Ni alloys. Some grades contain 10 to 27 percent Mn.
0 Another Mn alloy, which contains 12 percent Mn, is used in the
bimetallic element of thermostats.
3.3.2 Nonmetallurgical Uses of Manganese Oxides
Table 3-7 lists the primary nonmetallurgical uses of manganese oxides.
Some of these uses are briefly addressed in the following items:
0 High-purity MnO^ is used in the production of high- quality fer-
rites. The Mn-zinc ferrites are used in items such as magnetic
recording heads, digital and video recordings, and bubble memories.
0 Low-grade Mn02 is used as a colorant in the manufacture of brick and
tile. Low-grade native ores are used as colorants in glass making
and frits.
0 Manganese oxide is used in uranium hydrometallurgy for oxidizing the
uranium dioxide (UO^) to uranimum dioxide sulfate (l^SO,).
0 Native ores containing MnO^ are used in the manufacture of welding
rod coatings and fluxes.
3-13
-------
TABLE 3-7. PRIMARY NONMETALLURGICAL USES OF MANGANESE OXIDES'
Compound
Applications
Manganese (II) oxide
Technical
High-purity
Dimanganese trioxide
Trimanganese tetroxide
Manganese dioxides
Native ores
Chemical manganese dioxide
Electrolytic manganese dioxide
Fertilizer
Feed additive
Intermediate in the manufacture
of electrolytic Mn metal, Mn (II)
salts, EMD
High-quality ferrites; ceramics
intermediate for higher-purity
Mn (II) salts such as
Mn (H2P04)2
Mn acetate
High-purity grades used in
production of ferrites,
thermistors, and in other
electronic applications
Colorant in brick and tile manu-
facturing
Colorant in glass making frits
Raw materials for most other Mn
chemicals
Hydrometallurgy of uranium
Hydrometallurgy of zinc
Welding rods and fluxes
Dry-cell batteries
Oxidant in chemical processes
Absorbent for H2S and S02
Ferrites (lower grade)
Dry-cell batteries, oxidant
in organic synthesis, high-purity
Mn02 for ferrites and thermistors,
curing agent for polysulfide rub-
bers, constituent in oxidation
catalysts
Dry-cell batteries, ferrites
Source: Reference 1
3-14
-------
0 Synthetic MnCL is used extensively in the manufacture of dry-cell
batteries.
0 Manganese ore is used as an oxidant in the production of hydroqui-
none in a process that generates byproduct manganese sulfate.
3.3.3 End Uses of Manganese Compounds
Tabfe 3-8 lists the primary uses of various manganese compounds, and
Table 3-9 presents a separate listing of the principal uses of potassium
permanganate, one of the better-known compounds. This latter compound is used
extensively in the manufacture of chemicals, in inorganic synthesis, as an
oxidizer in water purification to remove odors, in metal-surface treating, and
as a bleaching agent.
References for Section 3
1. Kirk-Othmer. Encyclopedia of Chemical Technology. 3d Ed., Vol. 14.
1981.
2. National Research Council. Medical and Biological Effects of Environ-
mental Pollutants—Manganese. National Academy of Sciences, Washington,
D.C. 1973.
3. Weast and Astle. Handbook of Chemistry and Physics. 61st Ed. CRC
Press. 1980-81.
4. -Bureau of Mines. Mineral Commodity Summary - 1985; Manganese. U.S.
Department of Interior. 1985.
5. Letter from W. R. Pioli of El kern Metals Co. to T. Lahrs of EPA, January
31, 1985.
6. Jones, T. S. Minerals Yearbook: Manganese. U.S. Department of Inte-
rior, Bureau of Mines. 1982.
3-15
-------
TABLE 3-8. PRIMARY USES OF MANGANESE COMPOUNDS
Manganese
Application
Mn Salts of inorganic acids
Carbonate
v Mn Chloride
Mn Trifluoride
Mn Hypophosphite
i.e., nylon
Mn Nitrate
Mn Phosphate (monobasic)
Mn Pyrophosphate
Mn Sulfate
Mn
Acetate
Acetylacetonate
Ethylenebisfdithio
carbanate)(Maneb)
Gluconate
Glycerophosphate
Lactate
Soaps
Mn chelates (complexes
with EDTA, lignosul-
fonates, dibasic sugar
acids, gluconic acid)
Metal organic
methylcyclopentadienyl-
manganese tricarbonyl
(MMT, CI-2)
Intermediate in the synthesis of other Mn salts,
such as phosphate, gluconate, acetate, nitrate;
for manufacture of ferrites, welding rods, also
as hydrogenation catalyst
Magnesium metallurgy; synthesis of MMT, as
brick colorant; textile dyeing, dry cell bat-
teries, chlorination catalyst
Fluorination agent
Manufacture of delustered polycondensate fibers,
Intermediate in manufacturing of high purity Mn
oxides; in production of tantalum capacitors
Rust-proofing; wear-reduction in moving metal
parts (bearings, etc.)
Textile dyeing
Intermediate in manufacture of many Mn prod-
ucts, i.e., electrolytic Mn metal, EMD, Maneb,
Mn soaps, etc.; important Mn fertilizer, feed
additive, for organic pigments, catalyst in
H~S oxidation
Salts of organic acid
Oxidation catalyst in manufacture of dibasic
acids (i.e., terephthalic, adipic acids) for
synthetic fibers; also polymerization catalyst
Catalyst
Fungicide
Feed and food additive; dietary supplement
Food additive, dietary supplement
Medicine
Driers in printing inks, paints, and varnishes
Liquid fertilizers, as feed and food additives
Antiknock additive for motor fuels, combustion
improver for heavy fuel oils
Source: Reference 1.
Borate, linoleate, naphthenate, oxalate, phthalate, resinate, stearate,
tall ate, neodecanoate, octoate.
3-16
-------
TABLE 3-9. PRINCIPAL USES OF POTASSIUM PERMANGANATE'
General category
Specific application
Chemical manufacture and
processing
Orga'nic synthesis
Inorganic manufacture
Purifying agent
Environmental
Water
Air
Metal-surface treatment
Hydrometallurgical uses
Miscellaneous
Important industrial oxidant in the manu-
facture of chemical and pharmaceutical inter-
mediates; also used as oxidation catalyst,
e.g., in fatty acid production from paraffins
Mn catalysts, Purafil
Organic compounds, mostly solvents
Potable: removal of Fe-Mn, taste and odor;
control of trihalomethanes
Industrial and waste; removal of phenol and
other organic contaminants; radioactive
decontamination; cleanup of acid mine
drainage
Industrial effluents: removal of odorous
contituents by wet scrubbing (rendering and
roofing plants; foundries; food processing
plants; sewage plants)
Indoor spaces; odor control with Purafil
(solid formulation containing KMn04)
Scale and smut removal from carbon steel
and stainless steels
Purification of zinc sulfate solution in
electrowinning of zinc; Fe-Mn removal from
ZnCl2 solns
Bleaching of beeswax, jute fibers, clays; in
fishery management for detoxification of fish
poisons; alleviation of temporary oxygen de-
pletion, control of fish parasites, etc; as
laboratory chemical in analytical and prepara-
tive organic chemistry
Source: Reference 1.
^Arranged in order .of importance.
3-17
-------
-------
SECTION 4
MANGANESE EMISSIONS FROM
PRODUCTION AND USE OF MANGANESE
In this discussion, manganese emission sources are divided into two
categories—direct and indirect sources. The direct category primarily in-
cludes sources that either produce manganese or consume manganese or a manga-
nese compound to manufacture a usable product. Direct sources of manganese
emissions include the following: '
0 Manganese ore beneficiation, transport, and storage
0 Production of manganese-bearing ferroalloys
0 Production of manganese metal and manganese oxides
0 Production of manganese chemicals
0 Iron and steel production
0 Iron and steel foundries
0 Manufacture of batteries
Indirect sources of manganese emissions are generally those that do not
produce manganese or manganese-containing products and only inadvertently
handle manganese because it is present as an impurity or additive in a feed-
stock or fuel. For example, manganese is released from the combustion of coal
or oil because it is a trace constituent in these fuels. Indirect sources
induce:
0 Coal and oil combustion
0 Production of cement
0 Incineration of municipal refuse and sewage sludge
0 Manganese fuel additives
4-1
-------
4.1 MANGANESE ORE BENEFICIATION, TRANSPORT, AND STORAGE
In 1982, no manganese ore containing 35 percent or more manganese was
either produced or shipped from domestic mines in the United States. Al-
though lower-grade manganiferous ores (5 to 10 percent manganese) were pro-
duced and/or shipped in Minnesota and South Carolina, the quantities were much
lower than in 1981. No ferruginous manganese ores or concentrates (10 to 35
percent Mn) were produced, but some were shipped (on a much curtailed basis)
from the Cuyuna Range in Minnesota. Some manganiferous schist (5 to 15
percent Mn) also was mined in Cherokee County, South Carolina, for use by
brick manufacturers to color the brick. Total shipments of all domestic
manganese ores amounted to only 31,509 tons in 1982; down from 175,000 tons in
1981; manganese content of these ores totaled only 3984 tons.
Mined from open pits, manganese ores are beneficiated by conventional
means involving crushing, washing, and concentration with jigs and Deister
tables.
Because domestic production and reserves are limited, Mn ores and Mn-bear-
ing ferroalloys are considered strategic materials and government stockpiles
are maintained. Imported ores and ferroalloys are stored at designated stock-
piles, some in open areas and others in closed areas. These imported ores
have already been beneficiated, and all contain more than 35 percent Mn. The
ores are further crushed and blended (as required) by processing plants near
the port of entry before they are dispatched to the point of final consump-
tion.
4.1.1 Emissions and Emission Factors
Fugitive emissions of manganese occur during the crushing, transfer, and
stockpiling of manganese-bearing ores, and as a result of wind erosion of the
stockpiles. Estimates of other fugitive emissions can be generated by the use
of predictive equations developed for open dust sources at iron and steel
2
mills. Data on the silt content of the ore piles, moisture content of the
ore, number of dry days in the year, duration of material storage, and han-
dling methods are required for these equations. Process-specific emission
factors for crushing and transfer of manganese ores are presented in the
appropriate sections of this document (Section 4.2.3, for example).
4-2
-------
References for Section 4.1
1. Jones, T. S. Minerals Yearbook, Vol. 1, Metals and Minerals. U.S.
Department of the Interior. 1983.
2. Cowherd, C. Iron and Steel Plant Open Source Fugitive Emission Evalua-
tion. Midwest Research Institute, Kansas City, Missouri. EPA-600/2-79-
103, 1979.
.t v
4.2 PRODUCTION OF MANGANESE-BEARING ALLOYS
In 1982, around 20 percent of the ferroalloys produced in the United
States contained manganese. The use of ferroalloys has progressively de-
creased since 1979 in proportion to the decrease in steel production. Table
4-1 indicates the specifications and typical composition of manganese ferro-
alloys. High-carbon ferromanganese constitutes more than 80 percent of the
p
total ferromanganese used. Currently, all manganese ferroalloys are produced
by electric arc furnaces, with one exception. The Chemetals Corporation plant
at Kingwood, West Virginia, produces manganese metal with low carbon content
by fused salt electrolysis. The Bureau of Mines classifies this product (also
3
known as Massive Manganese) as low-carbon ferromanganese. The production of
manganese metal is described in Subsection 4.2.3.
Figure 4-1 is a generalized flow sheet of the production of manganese-
bearing ferroalloys. Manganese ores and other raw materials are brought in by
rail or trucks and stored in stockpiles. The ore is crushed to the required
size and screened. The fines and undersize are collected and sintered in a
sintering machine. The sintered fines and sized ore are then fed to the stock
bins, from which measured quantities of the feed mix are charged into an
electric furnace.
4.2.1 Electric Arc Furnace Process
Three types of submerged-arc electric furnaces are used to make the
5
ferroalloys: open, semisealed, and sealed furnaces. These furnaces are
charged either continuously or intermittently with the manganese ores, a
reducing agent (e.g., coke or coal), and fluxes (e.g., lime). The blend of
ores is based on cost, availability, and composition to give a proper balance
of slag-forming constituents.
4-3
-------
TABLE 4-1. SPECIFICATIONS AND TYPICAL.COMPOSITIONS
OF MANGANESE FERROALLOYS, 'D
(Weight percent)
Alloy
Ferromanganese
High-carbon
Grade A
Grade B
Grade C
Typical
commodity
grade
Medium-carbon
Regular grade
• MS grade
Low-carbon
Silicomanganese
Ferromanganese-
silicon
Mn
78-82
76-78
74-76
78-80
80-85
80-85
85-90
65-68
63-66
C,
max
7.5
7.5
7.5
6.7
1.5
1.5
d
2.00
0.08
Si , max
1.2
1.2
2.2
0.7
1.5
0.35
2.0
16.0-18.5
28-32
P,
max
0.35
0.35
0.35
0.30
0.30
0.30
0.20
0.20
0.05
s,
max
0.05
0.05
'0.05
0.04
0.02
0.02
0.02
0.04
0.04
As,
max
0.30
0.30
0.30
0.25
0.10
0.15
0.10
0.10
0.15
Fe
7.8-11.8
11.8-13.8
13.8-15.8
12-14
7-12
11-16
7-12
10.5-16
1-8
Pb,
max
0.050
0.050
0.050
0.050
0.020
0.050
0.020
0.030
0.050
Reference 4.
C = carbon; P = phosphorus; S = sulfur; As = arsenic; Pb = lead.
°Machine-silicon grade.
May have any of the following percentages: 0.50, 0.30, 0.15, 0.10, and
0.070 percent C.
eAlso known as low-carbon silicomanganese.
4-4
-------
I
Ul
A A A DU
nun TDAuconDT CRUSHING SIZING
AND TRANSPORT ^nujmnu ji/.mu
A
STORAGE AND
PACKAGING
CUKb
SINTERING FLUX 1 SILIC/
1 1
SI 111
^ MCTPU-
* WLlbll
* FEED HOPPERS
S^ SLAG ^X
/^RECYCLE HIGH Mn
( SLAG FOR Si-Mn
\PRODUCTION OR DISCA
A A
«_ SIZING ,e_ ^Jc'L6,^
*^ * CRUSHING
\
RD/
A
ELECTRIC ARC
FURNACE SMELTING
.
TAPPING
A
LADLE TREATMENT
1
A
CASTING
MANGANESE EMISSION SOURCES
Figure 4-1. Flow chart of manganese-bearing ferroalloys production
by electric arc furnace process.
-------
The electric submerged-arc furnace consists of a refractory-lined hearth
and water-cooled steel shell. A taphole is provided for draining metal and
slag. Carbon electrodes are vertically suspended above the hearth in a tri-
angular formation. Normally, three electrodes, which may be prebaked or the
self-baking, Soderberg type, extend 1 to 1.5 m (3 to 5 ft) into the charge
material^. Three-phase current passes through the charge materials from
electrode to electrode, and the electrical energy smelts the charge. Coke and
other reducing materials that are added to the furnace react with the oxygen
in the metal oxides to form carbon monoxide and base metal. Furnace emissions
consist of carbon monoxide, particulate matter, and metal vapors. Molten
ferroalloy and slag are intermittently tapped into ladles. Slag from the
metal ladle overflows into a slag pot. The slag is water-cooled and processed.
If the slag has a high manganese content and is going to be used in the manu-
facture of silico-manganese, it is crushed and recycled. If the manganese
content is low and the slag is going to be discarded, it is processed and sold
for ballast or disposed of in landfills. In either case, slag processing is a
source of manganese emissions.
The furnaces and tapping stations are hooded, and the gases are ducted to
a particulate control device. The configuration of the hood and/or furnace
roof determines whether the furnace is categorized as open, semi sealed, or
closed.
The configuration of the open furnace is such that a canopy hood (through
which the electrodes extend) is located 2 to 2.7 m (6 to 8 ft) above the
furnace rim (Figure 4-2). This opening between the furnace and hood permits
large amounts of air to enter the hood and exhaust system. As the air com-
bines with the hot exhaust gases, the carbon monoxide and most of the organic
compounds are burned and the furnace emissions are diluted and cooled by the
ambient air. This type of furnace is by far the most popular in the United
States because of its product flexibility and because it can be stoked during
operation. If sufficient draft is not provided, however, the large opening
around the hood allows fumes to escape. Control equipment must be designed to
handle the large volume of gas inherent in an open furnace design.
The semisealed furnace has a water-cooled hood that fits tightly around
the top of the furnace and is vented to an air pollution control system (Fig-
ure 4-3). The electrodes extend down through the hood, and raw materials are
4-6
-------
A.
4*
TAP HOLE
V-
'C.
ELECTRODES MTY _.
EXTENDING mUJŁD
./THROUGH.^ Jr™TE
HOOD
^N
HOOD
".'DUST."-
(TYPICAL)
TO CONTROL
E DEVICE
^vHrl
•C"sfcl
-------
charged through annular gaps around the electrodes. Because the seal provided
by the raw material mixture around each electrode is not air- tight, fumes may
escape unless sufficient draft is provided by the air pollution control sys-
tem. Much less outside air is drawn into this system than into the open
furnace, and the pollutant concentrations are much higher. The resulting
gases are high in carbon monoxide. These furnaces cannot be readily stoked
t *
from the outside.
The sealed furnace has a tight-fitting, water-cooled hood on top, which
is vented to an air pollution control system (Figure 4-4). Raw materials are
fed through separate sealed chutes, and the electrodes penetrate the hood
through seals. Thus, the furnace is completely sealed and operates under a
slight positive pressure regulated by the fume exhaust system. No outside air
enters the furnace system, and high concentrations of CO (80 to 90 percent)
and particulates are emitted. No sealed furnaces are in use in the United
o
States , however, they are used for Fe-Mn production in Japan and Canada.
Regardless of the type of furnace used, the molten ferromanganese is cast
into molds or in a casting machine. The solidified product is removed from
the molds, crushed, sized, and stored for shipment. The casting, crushing,
and sizing steps produce particulate emissions containing manganese.
High-carbon ferromanganese and silicomanganese are produced in both open
and semisealed furnaces. The same furnace can be used for both, provided the
gas cleaning system has the capacity and the furnace can be operated at the
higher power rate required for silicomanganese.
4.2.2 Emissions and Emission Factors
The possible sources of manganese emissions from the production of manga-
nese ferroalloys by the electric arc furnace process are shown in Figure 4-1.
Ore handling and wind erosion of the stockpile result in emissions of Mn-bear-
ing particulates. Emissions from storage piles can be reduced by erecting
wind barriers, covering the piles with plastic, or spraying them with water.
The extent of such practices is unknown. Pretreatment of the Mn ore, includ-
ing crushing and screening, also produces emissions.
The smelting of Mn ore and other raw materials in the electric arc fur-
nace is the major source of Mn emissions. All three types of electric arc
furnaces (open, semisealed, and sealed) emit Mn-bearing particulates. Open
4-8
-------
furnaces generate the highest level of emissions because the large opening
between the furnace rim and hood allows more circulation of air and gases
through the charge material, which entrains Mn and other particulates.
Fabric filters are used to control emissions from submerged-arc furnaces
producing ferromanganese. Testing of these control systems has indicated a
total particulate removal efficiency of over 99 percent,
t v
High-pressure-drop venturi scrubbers that have been applied to sumberged-
arc furnaces producing ferromanganese alloys reportedly have particulate
collection efficiencies ranging from 94 to 98 percent. Wet scrubbers, includ-
ing both multistage centrifugal scrubbers and venturi scrubbers, have been
used on semisealed ferroalloy furnaces. A particulate removal efficiency as
high as 99 percent has been reported for centrifugal scrubbers.
Because no air enters sealed furnaces, gas volumes to the control device
are only 2 to 5 percent of those from open furnaces. This results in a much
smaller mass of particulates. Venturi scrubbers are commonly used on these
furnaces.
The tapping of molten ferroalloys from the furnace into a ladle is a
source of emissions in all three types of furnaces. Ten to 15 percent of the
furnace operating time involves tapping operations, during which fumes and
some particulates are emitted. Hood systems are sometimes installed over the
tapping hole and ladle to capture and direct the emissions to a fabric filter
or scrubber.
Additional Mn emissions occur during casting and finishing operations.
Particulates and fumes escape as the molten product is poured into molds.
Casting operations may be hooded, but emissions from casting are uncontrolled
at many ferroalloy plants. Other sources of Mn emissions include the final
crushing, sizing, and packaging of the ferroalloy products. Most plants
2
control these operations with fabric filters or scrubbers.
Manganese emission factors for ferroalloy production can be calculated
from data available in the literature. A 1974 U.S. EPA study estimated par-
ticulate emissions from raw materials handling and processing at 16 electric
2
arc furnace ferroalloy plants. The specific types of ferroalloys these
plants produced was not specified. Because the raw material handling proce-
dures for Mn-bearing ferroalloys are similar to those for the production of
4-9
-------
other ferroalloys, however, it was assumed that particulate emission factors
for general ferroalloy production also apply to the production of Mn ferro-
alloys. To derive Mn emission factors from total particulate emission factors
required the further assumption that metallurgical-grade Mn ore contains an
average of 45 percent Mn by weight. Table 4-2 presents the derived Mn emis-
sion factors for raw material processing.
Reference 2 also lists particulate emissions from handling and finishing
of ferroalloy products, including casting, crushing, and grinding. The Mn
content of particulate emissions varies with the Mn content of the ferroalloy
being produced. The composition of Mn ferroalloys can range from 75 to 90
percent in ferromanganese to 63 to 68 percent in silicomanganese. Table 4-3
presents derived Mn emission factors for these operations. The Mn emission
factors were obtained by multiplying average total particulate emissions from
finishing and handling by 80 and 65 percent for ferromanganese and ferrosili-
con, respectively.
Table 4-4 presents derived emission factors for ferromanganese-producing
furnaces. Uncontrolled emission factors are based on AP-42 data for ferro-
alloy production. The total particulate emission factors were multiplied by
the measured average percent Mn in particulate emissions. Table 4-5 presents
a chemical analysis of particulate emissions from ferromanganese and silico-
manganese furnaces. Most of the controlled Mn emission factors were based on
tests of total particulate emissions. Again, these were multiplied by the
measured typical percent Mn in particulate emissions from Mn-bearing ferroal-
loy furnaces.
4.2.3 Source Locations
In 1982, five plants manufactured ferromanganese and silico- manganese in
5
electric arc furnaces. In 1980, nine plants were producing manganese-bearing
ferroalloys, but three of these suspended production because of the low market
demand. Table 4-6 lists the plants that were actively engaged in production
of manganese-bearing ferroalloys in 1980. An upturn in the domestic steel
industry could alter the demand pattern and bring some of the domestic man-
ufacturers back on line. Imported products are economically competitive and
have obtained a significant share of the market.
4-10
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TABLE 4-2. MANGANESE EMISSION FACTORS FOR PROCESSING OF RAW
MATERIALS AT MANGANESE-BEARING FERROALLOY PRODUCTION FACILITIES3
Source
Mn emission factors,
kg/Mg (Ib/ton) of
Mn ore processed
Receipt Vnd storage of Mn ore
Crushing and sizing
Weighing and feeding
0.45 (0.90)
0.45 (0.90)
0.40 (0.80)
Based on an average Mn content of 45 percent in the manganese ore. The
emission factors are expressed in terms of elemental manganese. Manganese
is probably present as an oxide or silicate along with other metal oxides
and silicates. These factors are based on information obtained from ques-
tionnaires to the industry and predictive equations developed for the iron
and steel industry.2
TABLE 4-3. MANGANESE EMISSION FACTORS FOR FINISHING OPERATIONS3
Mn emission factors,
kg/Mg (Ib/ton) of Mn product
Source
Ladle treatment
Casting
Crushing/grinding/sizing
Ferromanganese
3.75 (7.5)
0.24 (0.48)
0.08 (0.16)
Si li co-manganese
3.0 (6.0)
0.12 (0.24)
0.065 (0.13)
Based on an average Mn content of 80 and 65 percent in FeMn and SiMn, respec-
tively. The emission factors are expressed in terms of elemental manganese.
These factors are based on information obtained from questionnaires to the
industry and predictive equations developed for the iron and steel industry.2
Some sources may employ more stringent controls than are reflected in these
factors.
4-11
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TABLE 4-4. MANGANESE EMISSION FACTORS
PRODUCING FERROMANGANESE
FOR SUBMERGED-ARC ELECTRIC FURNACES
AND SILICOMANGANESE3
(
Product
Uncontrolled sources
Ferromanganese
Ferromanganese
Ferromanganese .
Ferromanganese .
Silico-manganese
Controlled sources
Ferromanganese
Ferromanganese
Ferromanganese
Silicomanganese
Silicomanganese
Silicomanganese
Furnace type
Open
Semi sealed
Sealed
NAe
NA
Open (con-
trolled by
scrubbers)
Semi sealed
(controlled
by scrubbers)
Sealed (con-
trolled by
scrubbers)
Open (con-
trolled by
scrubbers)
Semi sealed
controlled
by scrubbers)
Sealed (con-
trolled by
scrubbers)
Manganese emission factors
kg/Mg (Ib/ton)
of product
6.60 (13.2)
2.6 (5.2)
9.6 (19.2)
5.7 (11.4)
23.2 (46.4)
0.2 (0.4)
0.04 (0.08)
NA
NA
0.016 (0.032)
NA
kg/MWhc (Ib/MWh)
2.8 (6.16)
1.06 (2.33)
4.3 (9.46)
NA
NA
0.086 (0.189)
0.017 (0.037)
0.0038 (0.008)
0.05 (0.11)
0.004 (0.009)
0.001 (0.002)
References 2,5, and 6. Some sources may employ more stringent controls
than are reflected in these factors.
Chemical form of particulate is specified in Table 4-5.
c"MWh" refers to megawatt-hours of electrical energy consumed by furnace dur-
ing operation.
Uncontrolled emissions based on AP-42 factors for ferroalloys.
eNA = not available.
4-12
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TABLE 4-5. CHARACTERIZATION OF PARTICULATE EMISSIONS
FROM FERROALLOY FURNACES3
Parameter
Furnace hood type
Particle size, ym
Maximum
Range of most particles
Chemical analysis, wt %
Si02
FeO
MgO
CaO
MnO
A1203
Loss on ignition
SiMn
Covered
0.75
0.2-0.4
15.63
6.75
1.12
NA
31.35
5.55
23.25
FeMn
Open
0.75
0.05-0.4
25.48
5.96
1.03
2.24
33.60
8.38
NA
Reference 2. Some sources may employ more stringent controls than are
reflected in these factors.
NA - Not available.
TABLE 4-6. DOMESTIC PRODUCERS OF MANGANESE FERROALLOYS, 1980C
Producer
Autlan Manganese
Chemetals Corp.
Interlake, Inc. ,
Roane Ltd.
SKW Alloys, Inc.
El kens Metal Co.
Plant location
Mobile, Ala.
Kingwood, W. Va.
Beverly, Ohio
Rockwood, Tenn.
Calvert City, Ky.
Marietta, Ohio
Products
SiMn
FeMn
SiMn
FeMn, SiMn
FeMn, SiMn
FeMn, SiMn
Type of process
Electric furnace
Fused-salt electro-
lytic
Electric furnace
Elactric furnace
El metric furnace
Electric furnace
References 7 and 8.
Note; This listing is subject to change as market conditions change, facil-
ity ownership changes, plants are closed, etc. Ths reader should
verify the existence of particular facilities by cansulting current
listings and/or the plants themselves. The level Df manganese emis-
sions from any given facility is a function of variables such as
capacity, throughput, and control measures, and should be determined
through direct contacts with plant personnel.
4-13
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References for Section 4.2
1. American Iron and Steel Institute. Annual Statistical Report. 1982.
2. Dealy, J. 0., and A. M. Kill in. Engineering and Cost Study of the Ferro-
alloy Industry. EPA-450/2-74-008, May 1974.
3. Jones, T. S. Mineral Commodity Profiles. Manganese - 1983. Bureau of
Mines, U.S. Department of the Interior. 1983.
4. Kirk-Othmer. Encyclopedia of Chemical Technology. Vol. 14. John Wiley
& Sons, Inc., New York. 1981.
5. Szabo, M. F., and R. W. Gerstle. Operation and Maintenance of Particu-
late Control Devices on Selected Steel and Ferroalloy Processes. EPA-600/
2-78-037, March 1978.
6. U.S. Environmental Protection Agency. A Review of Standard of Performance
for New Stationary Sources—Ferroalloy Production Facilities: EPA-450/3-
80-041, December 1980.
7. Bureau of Mines. Minerals Yearbook. Volume 1, Metals and Minerals.
U.S. Department of the Interior. Washington, D.C. 1980.
8. Letter from W. R. Pioli of El kern Metals Co. to T. Lahre of EPA, January
31, 1985.
4.3 PRODUCTION OF MANGANESE METAL AND SYNTHETIC MANGANESE OXIDE
4.3.1 Manganese Metal
Manganese metal is produced by one of two electrolytic processes: electro-
lysis of aqueous solution, or 2) electrolysis of fused salt.
When electrolysis of aqueous solution is used, the manganese ore is
crushed, ground, and roasted to reduce the higher oxides to Mn (II) oxide,
which is acid soluble. Elkem Metals, Marietta, Ohio, uses a process in which
Mn (II) oxide is supplied from the slag produced in the high-carbon ferromanga-
nese smelting operation. The reduced ore or slag is leached with hUSO* at pH
3 to yield Mn (II) sulfate. This solution is neutralized with ammonia to a pH
of 6 to 7 to precipitate Fe and Al, which are later removed by filtration.
"Tramp" metals are removed as sulfides by the introduction of FLS gas. Ferrous
sulfide or aluminum sulfide plus air are then introduced to remove colloidal
sulfur, colloidal metallic sulfides, and organic matter. The purified liquid
is electrolyzed in a diaphragm cell. The Mn metal deposits on the cathode are
thin and brittle and about 99.5 percent pure.
4-14
-------
In the fused salt electrolysis process (developed by Cherretals Corpora-
tion), the feed Mn ore, which is reduced to Mn (II), is charged to an electro-
lytic cell that contains molten calcium fluoride and lime. Fluorspar and lime
are added to maintain the desired fused salt composition. As the volume of
fused salt increases, excess fused electrolyte is periodically removed. The
cell is operated at about 1300°C to maintain the Mn in a molten stage. Man-
.k ^
ganese metal is tapped from the cell periodically and cast into cast-iron
pots. The metal produced is 92 to 98 percent pure, the main impurity being
p
Fe. Manganese ore that has been chemically pretreated to reirove iron is used
as cell feed'to produce 98 percent pure Mn grade metal.
4.3.2 Synthetic Manganese Oxides
The two kinds of synthetic manganese dioxides are Chemical Manganese
Dioxide (CMD) and Electrolytic Manganese Dioxide (EMD). The CMD is further
subdivided into Type 1 and Type 2. Type 1 CMD is produced by chemical reduc-
tion of permanganate, and Type 2 CMD is produced by thermal decomposition of
Mn salts, such as MnC03 or Mn (NO-Jp, under oxidizing conditions. Figure 4-5
is a generalized flow diagram for CMD, Type 1 and Type 2.
Type 1 CMD—
When potassium permanganate (KMnCL) is used in organic oxidations, such
as in the conversion of 0-toluenesulfonamide to saccharin, byproduct MnCL is
generated. To obtain battery grade synthetic oxide requires the removal of
excessive quantities of adherent and bound alkali by treating the material
with HpSO* or HC1 and then with MnSO,. Subsequent treatment with KMnCK solu-
tion converts the ion-exchanged divalent Mn into MnCL. The product is then
washed and dried at low temperature. This Type 1 hydrate (known as Manganit)
is also sold under the trade name of Permanox in Europe.
Type 2 CMD
The manufacture of Type 2 CMD by thermal decomposition of Mn(N03)2 gives
high-purity Mn02 (99 percent). The pH of an aqueous solution of impure Mn(N03)2
is adjusted to between 4 and 5.5, which causes contaminants such as aluminum
(Al) to precipitate as hydroxides. The mixture then is heated to about 90° to
100°C and filtered. The filtrate is first concentrated to 55 percent by
weight and then mixed with previously made MnCL. This mixture is heated to
4-15
-------
PERMANGANATE
AQUEOUS
REACTIONS
r
HASHING
LOW-
TEMPERATURE
DRYING
PACKAGING/
HANDLING
HC1 or H2S04
PERMANGANATE PROCESS
FILTRATE
MnO
A MANGANESE EMISSION SOURCES
Mn(N03)2[(AQUEOUS) ^ ^
t.
Mn02 ORE
THERMAL DECOMPOSITION PROCESS
Figure 4-5. Generalized flow diagrams for chemical Mn02 production/
-------
between 139° and 146°C while being vigorously agitated. The decomposition of
MnCNOOp is controlled. The NCL generated is allowed to react with water and
thereby forms nitrous and nitric acids (HNCL and HNCO. This acid mixture is
then used to convert new Mn(X, ore into MnCNOgK. The MnCL, produced by thermal
decomposition is filtered and dried before it is packaged.
Electrolytic Manganese Dioxide (EMD)--
The starting material for EMD is either rhodochrosite (MrC03) ores or
Mn02 ores. The former ores are used primarily in Japan, flfter the MnCCL ore
has been dried and ground, it is treated with 10 percent excess hLSCL. A
small amount of finely ground MnCL is added to the reaction mixture to oxidize
the divalent iron present. The pH of the slurry is adjusted to between 4 and
6 with Ca(OH)9 or CaCO,. The solids are removed by filtratior and the filtrate
L- 0
containing MnSO, is sent for further electrolysis.
When MnCL ores (minimum 75 percent MnO^ in ore) are used, the Mn00 ore is
first roasted (with a reducing agent) in rotary kilns to convert the Mn02 to
MnO. After the reduction, the solid mixture is allowed to cool to below 100°C
in an inert or reducing atmosphere. The subsequent leaching step with FUSO.
is similar to the rhodochrosite ore process just described, except that it
involves an additional step in which heavy metals are precipitated by the
addition of FUS or CaS. The Kerr-McGee Chemical Corporation uses a process in
which MnO is wet-ground with leach solution in a ball mill before it is con-
tacted with acid effluent from electrolytic cells. Figure 4-6 is a gen-
eralized flow diagram of the EMD production process.
The electrolytic cells are usually rectangular open troughs lined with
corrosion-resistant material. The electrodes are flat plates or cylindrical
rods or tubes. The anodes are generally made of hard lead and can be easily
removed for stripping of the EMD deposits. The cathodes are made from graph-
ite, soft or hard lead, or stainless steel.
The EMD is stripped from the anodes manually or by an automated system.
The lumpy fragments of raw MnCL are washed with water, dried, and ground.
After a neutralization step, they are further dried and packed.
4.3.3 Emissions and Emissions Factors
The major operations in the electrolytic process of Mm metal production
(aqueous solution electrolysis) and MnCL manufacture by both chemical and
4-17 -
-------
SPENT ELECTROLYTE
ORE-
DRYING AND
GRINDING
REDUCTION
TO MnO
Ca(OH),
ICaC03 <•
OXIDATION
NEUTRALIZATION
MnC03 ORE
OXIDATION
NEUTRALIZATION
RECOVERY OF ANODE
DEPOSIT
WASHING AND CLEANING
DRYING
GRINDING
NEUTRALIZATION
DRYING AND PACKING
A MANGANESE EMISSION SOURCES
Figure 4-6. Electrolyic Mn02 production from Mn02 ores and
rhnrlnrhrnsite nres.l
4-18
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electrolytic methods do not generate participate emissions containing Mn;
however, Mn-bearing participate emissions are likely to occur from the drying,
grinding, and roasting operations, and fugitive emissions can result from
product handling and packaging. The possible sources of Mn emissions are
shown in the flow diagrams (Figures 4-5 and 4-6) for both cherrical and elec-
trolytic Mn07.
.» v ^
Table 4-7 presents Mn emission factors for drying, grinding, roasting,
handling, and packaging operations. The emission factors are arrived at by
multiplying the particulate emission factor by the average percentage of Mn in
the materials handled.
TABLE 4-7. DERIVED MANGANESE EMISSIONS FOR SYNTHETIC MANGANESE PRODUCTION3
Source
Drying and
grinding
Roasting
Packaging/
handling
Control equipment
Uncontrolled
Fabric filters
Uncontrolled
Fabric filter
Uncontrolled
Fabric filters
Particulate
emissions factors,
kg/Mg of material
processed Ob/ton)
9.9 (19.8)b
0.0099 (0.0198)
122 (245)e
0.244 (0.49)
4.4 (8.8)b
0.0044 (0.0088)
Manganese
emission factors,
kg/Mg of material
processed (Ib/ton)
4.45(8.9)c
0.0045 (0.009)
55 (110)c
0.11 (0.22)
2.7 (5.4)
0.0027 (0.0054)
During ore processing, particulate emissions will be the sarre composition as
the ores. Manganese is present in these emissions as an oxide or silicate.
If manganese metal is the product, particulate emissions in the form of man-
ganese metal may be emitted during packaging and handling operations.
Reference 3.
c The Mn content will vary based on the starting materials (Average - 45%).1
Mn02 ores (minimum 75% Mn02) will contain 47.4% Mn. Rhodochrosite will
contain 47.8% Mn.
Many different roasting processes are used. The emission factor given
is for kiln-type roasting. (Assumed to be same as for cement manufacture.)
e Reference 4.
4.3.4 Source Locations
Table 4-8 lists the locations of manufacturers of manganese metal and
synthetic manganese oxides.
4-19
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TABLE 4-8. DOMESTIC PRODUCERS OF MANGANESE METAL
AND SYNTHETIC MANGANESE DIOXIDE3
Producer
Plant locations
Products
Type of process
Electrolytic manganese
metal
El kern. Metals Company
Foote Mineral Company
Kerr-McGee Chemical
Corporation
Chemetals Corp.
Synthetic manganese
dioxide
ESB Materials Co.
Kerr-McGee Chemical
Corp.
Union Carbide Corp.
Shepherd Chemical Co.
Chemetals Corp.
General Metallic
Oxides
Marietta, Ohio
New Johnsonville,
Tenn.
Hamilton, Miss.
Kingwood, W. Va.
Covington, Tenn.
Henderson, Nevada
Marietta, Ohio
Cincinnati, Ohio
Baltimore, Md.
Jersey City, N.J.
Mn
Mn
Mn
Mn
MnO,
MnO,
MnO,
MnO,
MnO,
MnO,
Electrolytic
Electrolytic
Electrolytic
Fused Salt
Electrolysis
Electrolytic
Electrolytic
Electrolytic
Chemical
Chemical
Chemical
References 1,5.
Note: This listing is subject to change as market conditions change, facil-
ity ownership changes, plants are closed, etc. The reader should
verify the existence of particular facilities by consulting current
listings and/or the plants themselves. The level of manganese emis-
sions from any given facility is a function of variables such as
capacity, throughput, and control measures, and should be determined
through direct contacts with plant personnel.
References for Section 4.3
1. Kirk-Othmer. Encyclopedia of Chemical Technology. Vol. 14. 3d Ed. John
Wiley & Sons, Inc., New York. 1981.
2. Walsh, J. J., and J. P. Faunce. The Production of Manganese Metal.
Presented at the 105th Annual Meeting of AIME in Las Vegas, Nevada, Feb-
ruary 1976.
4-20
-------
3. Nelson, T. P., et al. Study of Sources of Chromium, Nickel, and Manga-
nese. Prepared by Radian Corporation for the Office of Pir Qaulity Plan-
ning and Standards, U.S. Environmental Protection Agency, Research Tri-
angle Park, North Carolina. October 1983.
4. U.S. Environmental Protection Agency. Compilation of Air Pollutant Emis-
sion Factors. AP-42, Supplement 14. May 1983.
5. Jones, T. S. Mineral Commodity Profiles. Manganese. Bureau of Mines,
U.S. Department of the Interior. 1983.
4.4 PRODUCTION OF MANGANESE CHEMICALS
About 40 different manganese chemicals are manufactured in the United
States. Most are low-volume chemicals. The ones with the largest volumes and
the most significance are manganese sulfate (MnSO.), manganese oxide (MnO),
and potassium permanganate (KMnO.). Of secondary importance sre Maneb, MnCO-,
and others.
The process descriptions for manganese chemical production focus on
MnSO., MnO, and KMnO, because of their large volume of production and higher
potential for emissions.
4.4.1 Manganese Sulfate Process
Manganese sulfate is made by dissolving rhodo^chrosite ore or Mn (II)
oxide in H^SO,. It is also obtained as a byproduct of the manufacture of
hydroquinone from aniline sulfate and MnO^ (usually a Mn02 ore). The direct
production of MnS04 involves the use of Mn02 or MnC03 ores and H2SO» (to
dissolve the ores). For a high-purity product, the solution is treated with
MnOp for oxidation of Fe. The pH is adjusted to about 6.5 and the precip-
itated Fe(OH)3 and other impurities are filtered out. The MnSO, is recovered
by evaporation of the solution. Manganese sulfate is used as an intermediate
in the manufacture of many Mn Products, as an Mn fertilizer, as an animal feed
additive, etc.
4.4.2 Manganese Oxide Process
Manganese (II) oxide (MnO) is an important precursor of many commercial
manganese compounds, and it is used in fertilizer and feedstuff formulations.
It is produced by reductive roasting of Mn02 ores. The Chemetals process uses
4-21
-------
a stationary bed of crushed Mn ore (<10 mm); the ore is continuously replen-
ished from the top, and a reducing gas, CH4, and air are introduced from the
bottom. The MnO is formed in a reaction zone immediately beneath the top
layer, where the temperature is controlled to between 760° and 1040°C to avoid
sintering. The MnO moves downward and finally passes through an inert atmo-
sphere cooling zone. The Mn09 is removed and ground to 200 mesh size. Other
.t * <-
processes use rotary kilns or pile roasting for the reduction step.
4.4.3 Potassium Permanganate Process
Potassium permanganate is produced by several different processes. The
only one-step process is based on the electrolytic conversion of ferromanga-
nese to permanganate. The others begin with MnO^ ore and involve two steps:
thermal synthesis of potassium manganate followed by electrolytic oxidation of
p
Mn04 to Mn04. Figure 4-7 presents an overview of the production of KMnO^ by
roasting and liquid-phase oxidation processes.
In the liquid phase oxidation process, preconcentrated molten potassium
hydroxide (70 to 80%) is placed in a reactor together with a quantity of 78 to
80 percent Mn02 ore at a 1:5 ratio of Mn02:KOH.1 Enough air or 02 is intro-
duced below the liquid level to maintain a positive pressure of 186 to 216 kPa
(1.9 to 2.2 atm). The temperature is kept at 250° to 320°C throughout the
reaction period (4 to 6 hours). This process converts about 87 to 94 percent
of the Mn02 to ICMnO*. The ICMnO* product is then separated from the hot
caustic metal by diluting it with recycled KOH of about a 10 to 12 percent
concentration and allowing it to cool to 30° to 40°C. The ICMnO, settles and
is separated by centrifugation.
The Carus Chemical Company in LaSalle, Illinois (the only U.S. producer
of potassium permanganate) uses a liquid-phase oxidation process. The process
is similar to that described, but it is continuously operated and uses a
special filtration technique to separate the I^MnO* from the hot caustic melt
(one that does not require dilution).
4.4.4 Emission Sources and Emission Factors
Because most of the operations in the manufacture of Mn chemicals are
carried out in a wet state, emissions are not a problem; however, Mn-contain-
ing particulate emissions can occur from the drying, grinding, and roasting
operations involving ores and other chemicals containing Mn. Also, fugitive
4-22
-------
ROASTING PROCESSES
Mn02: KOH = 1: <3
LIQUID-PHASE OXIDATION
(CARUS PROCESS)
Ca(OH)
MANGANESE
EMISSION
SOURCES
Figure 4-7. Production of KMn04: roasting and liquid phase
oxidation processes.!
4-23
-------
emissions occur from materials handling and packaging. The possible emission
sources of Mn are indicated in Figure 4-7.
Table 4-9 presents Mn emission factors for drying/grinding, roasting, and
packaging/handling operations. The emission factors are calculated by multi-
plying the particulate emission factor by the average percentage of Mn in the
materials..
TABLE 4-9. MANGANESE EMISSION FACTORS FOR THE MANUFACTURE
OF MANGANESE CHEMICALS
Source
Ore drying/grind-
ing
Ore roasting0
Packaging/handling
of products
Control equipment
Uncontrolled
Fabric filters
Uncontrolled
Fabric filter
Uncontrolled
Fabric filters
Particulate
emissions factors,
kg/Mg (Ib/ton) of
material processed
9.9 (19.8)a
0.0099 (0.0198)
122 (245)d
0.244 (0.49)
4.4 (8.8)a
0.0044 (0.0088)
Manganese
emission factors,
kg/Mg (Ib/ton) of
material processed
4.45(8.9)b
0.0045 (0.009)
55 (110)b
0.11 (0.22)
e
e
Reference 2.
Mn content of ores used in chemical manufacture: 45% (Range 30-55%).l
Many different roasting processes are used; this emission factor is for
kiln-type roasting. (Assumed to be same as for cement manufacture).
Reference 3.
Extremely variable; depends on the Mn content of the product. For example,
is 34.8 percent manganese, Mn02 is 63.2 percent manganese, and
yHaO is 19.6 percent manganese. Manganese emissions would be deter-
mined by multiplying the particulate emission rate by the percent manganese
in the product divided by 100.
Note: Mn may be present as oxide in the ore and evolved as Mn-bearing par-
ticulates during drying and grinding operations. During roasting,
the Mn-bearing particulates may be in the form of oxides. Packag-
ing and handling emissions will essentially be in the same chemical
form as the material processed.
4-24
-------
4.4.5 Source Locations
Table 4-10 indicates the locations of manganese chemical producers in the
United States.
References for Section 4.4
t \
1. Ki'rk-Othmer. Encyclopedia of Chemical Technology. Vol. L4 3d Ed. John
Wiley & Sons, Inc., New York. 1981.
2. Nelson, T. P., et al. Study of Sources of Chromium, Nickel, and Manga-
nese. Prepared by Radian Corporation for the Office of Air Quality
Planning and Standards, U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina. October 1983.
3. U.S. Environmental Protection Agency. Compilation of Air Pollutant
Emission Factors. AP-42, Supplement 14. May 1983.
4. SRI International. 1982 Directory of Chemical Producers, U.S.A. Menlo
Park, California. 1982.
5. Jones, T. S. Mineral Commodity Profiles. Manganese - 1983. Bureau of
Mines, U.S. Department of Interior. 1983.
4.5 IRON AND STEEL PRODUCTION
Manganese enters the process of steel making as low-grade Mn ores charged
to the blast furnace and as ferroalloys added to the refined steel. The three
principal types of steelmaking furnaces used are open hearths (OH), basic
oxygen furnaces (BOF), and electric arc furnaces (EAF). Iron ore fines, blast
furnace flue dust, mill scale, and other iron-bearing materials generated in
an integrated steel plant are often recycled to the sinter plant for agglom-
eration. All of these materials contain some manganese; consequently, blast
furnaces, sinter plants, open hearths, basic oxygen furnaces., and electric arc
furnaces are the main source of manganese emissions.
4.5.1 Blast Furnace Operations
Molten iron (hot metal) for steel production is obtained by reducing iron
ore [Fe20, (Hematite) or Fe,04 (Magnitite)] to iron in the blast furnace.
The blast furnace is a countercurrent, refractory-lined cylinder (Figure
4-8). Preheated air is introduced through a large number of water-cooled
4-25
-------
TABLE 4-10. DOMESTIC PRODUCERS OF MANGANESE CHEMICALS
Product
Producer
Location
Manganese acetate
(manganese acetate)
Manganese acetate tetra-
hydrate
Manganese acetylacetonate
(manganic and manganous
acetylacetonate)
(bls/2,4-pentaned1onato/
manganese)
Manganese benzoate
Manganese borate
(manganous borate)
Manganese boride
Manganese carbonate
(manganous carbonate)
Manganese carbonyl
Manganese chloride
(manganous chloride)
Manganese d1fluoride
Manganese 2-ethylhexanoate
(also manganese octanoate,
manganese octoate, manganous
2-ethylhexanoate, and man-
ganous octanoate)
Manganese formate
Manganese gluconate
(manganous gluconate)
Manganese hydrate
(manganic hydroxide)
C. P. Chems., Inc.
Sulf 011 Corp.
Harshaw Chemical Co., Subsidiary
Industrial Chemicals Department
The Hall Chemical Company
Mineral Research and Development Company
The Shepherd Chemical Company
National Starch and Chemical Corp.
Proctor Chem. Co., Inc., Subsidiary
HacKenzie Chemical Works, Inc.
MacKenzle INTERVAR
The Shepherd Chemical Company
The Hall Chemical Company
General Metallic Oxides Company
Union Oil Company of California
Molycorp, Inc., Subsidiary
Chemicals and Rare Earth Division
North American Phillips Corp.
T H Agriculture and Nutrition Co., Inc.
Crop Protection Division
Leffingwell Chemical Company, Div.
Richardson-Vicks, Inc.
J. T. Baker Chemical Company, Subsidiary
The Shepherd Chemical Company
Pressure Chemicals Company
Strem Chemicals, Inc.
Allied Corp.
Allied Chemical Company
Chemetals Corp.
Mineral Research and Development Corp.
R1chardson-V1cks, Inc.
J. T. Baker Chemical Company, Subsidiary
Pennwalt Corporation
Chemical Group
Ozark-Mahoning Company, Subsidiary
Ferro Corp., Chemical Division
Interstab Chemicals, Inc.
Mooney Chemicals, Inc.
The Shepherd Chemical Company
Troy Chemical Corporation
The Shepherd Chemical Company
Beca Products, Inc.
Pfizer, Inc., Chemicals Division
General Metallic Oxides Company
Sewaren, New Jersey
Cleveland, Ohio
Arab, Alabama
MickHffe, Ohio
Concord, North Carolina
Cincinnati, Ohio
Salisbury, North Carolina
Bush, Louisiana
Cincinnati, Ohio
HIckHffe, Ohio
Jersey City, New Jersey
Washington, Pennsylvania
Brea, California
PhilUpsburg, New Jersey
Cincinnati, Ohio
Pittsburgh, Pennsylvania
Newburyport, Massachusetts
Claymont, Delaware
Curtis Bay, Maryland
Concord, North Carolina
Phillipsburg, New Jersey
Tulsa, Oklahoma
Bedford, Ohio
New Brunswick, New Jersey
Franklin, Pennsylvania
Cincinati, Ohio
Newark, New Jersey
Cincinnati, Ohio
Janesv1lie, Wisconsin
Brooklyn, New York
Jersey City, New Jersey
(continued)
4-26
-------
TABLE 4-10 (continued)
Product
Producer
Location
Manganese hypophosphite
(manganous hypophosphite)
Manjatiese isocarboxylate
Manganese naphthenate
(manganous naphthenate)
Manganese (manganous)
nitrate
Manganese oleate
(linoleate)
Manganese oxide
Manganese pentacarbonyl
bromide
Manganese pentacarbonyl
chloride
Manganese stearate
(manganous stearate)
Manganese sulfide
Manganese sulfate
Occidental Petroleum Corp.
Hooker Chemicals Corp., Subsidiary
Mooney Chemicals, Inc.
Ferro Corporation, Chemicals Division
Interstab Chemicals, Inc.
Mooney Chemicals, Inc.
Tenneco, Inc.
Tenneco Chemicals, Inc.
Troy Chemical Corporation
Witco Chemical Corporation
Organics Division
Allied Corporation
Allied Chemical Company
Ashland Oil, Inc.
Ashland Chemical Company, Subsidiary
Speciality Chemicals Division
Chemetals Corporation
C. P. Chemicals, Inc.
The Hall Chemical Company
Mineral Research and Development Corp.
The Shepherd Chemical Company
Troy Chemical Corporation
American Minerals, Inc.
Agricultural Division
Chemetals Corporation
Eagle-Pitcher Industries, Inc.
Agricultural Chemicals Division
Elkem Metals Company
Phillipp Brothers Chemicals, Inc.
The Prince Manufacturing Company
Pressure Chemical Company
Pressure Chemical Company
The Norac Company, Inc.
Mathe Division
El kern Metals Company
Eagle-Pitcher Industrial, Inc.
Agricultural Chemicals Division
Eastman Kodak Company
Eastman Chemicals Products, Inc.
Subsidiary of Tennessee Eastman
Company
Richardson Vicks, Inc.
J. T. Baker Chemical Company, sub-
sidiary
Niagara Falls, New York
Franklin, Pennsylvania
Bedford, Ohio
New Brunswick, Nev> Jersej
Franllin, Pennsylvania
Elizcbeth, New Jersey
Newark, New Jersey
Chicigo, Illinois
Claymont, Delaware
Cincinnati, Ohio
Eastern, Pennsylvania
Curtis Bay, Maryland
SumpLer, South Carolina
Arab Alabama
Concord, North Carolina
Cine nnati, Ohic
Newark, New Jersey
El Peiso, Texas
Philadelphia, Pa.
Rosidare, Illinois
Curtis Bay, Maryland
Cedar town, Georgia
Marietta, Ohio
Bowmjnstorfn, Pa.
Quincy, Illinois
Pittsburgh, Pennsylvania
Pittsburgh, Pennsylvania
Lodi New Jersey
Niagara Falls, New York
Cedartown, Georgia
Kings port, Tennessee
Phillipsbjrg, New Jersey
(continued)
4-27
-------
TABLE 4-10 (continued)
Product
Mangarese Tallate
(manganous tallate,
manganous linoresinate)
t *
Manganese trifluoride
(manganic fluoride)
Potassiurr penranganate
Producer
Interstab Chemicals, Inc.
Mooney Chemicals, Inc.
The Shepherd Chemical Company
Tenneco, Inc.
Tenneco Cheiricals, Inc.
Troy Chemicals Corp.
Pennwalt Corp.
Chemicals Group
Ozark-Mahoning Company, subsidiary
Carus Corp.
Carus Chemical Company, Division
Location
New Brunswick, New Jersey
Franklin, Pennsylvania
Cincinnati , Ohio
Elizabeth, New Jersey
Newark, New Jersey
Tulsa, Oklahoira
LaSalle, Illinois
'Reference 4.
Note: This listing is subject to change as market conditions change, facility ownership changes, plants are
closed, etc. The reader should verify the existence of particular facilities by consulting current
listings and/or the plants themselves. The level of manganese emissions from any given facility 1s
a function of variables such as capacity, throughput, and control measures, and should be determined
through direct contacts with plant personnel.
4-28
-------
LARGE BELL ROD
SMALL BELL ROD
SMALL BELL
LARGE BELL
COKE
ORE
LIMESTONE
BUSTLE
PIPE
HOT
BLAST
TUYERE
HEARTH
IRON
NOTCH
SLAG -
NOTCH
Figure 4-8. Cross-sectional view of a typical blast furnace.
4-29
-------
tuyeres at the bottom of the furnace, passes through the descending charge,
and is exhausted at the top of the furnace. It takes an average charge of 1.7
unit weights of iron-bearing material, 0.55 unit weight of coke, 0.2 unit
weight of limestone, and 1.9 unit weights of air to produce 1 unit weight of
iron. Average blast furnace byproducts consist of 0.3 unit weight of slag,
0.05 untit weight of dust, and 3.0 unit weights of gas. Molten iron and slag
accumulate in the hearth and are drained intermittently (continuously on very
large furnaces) through runners to ladle cars that transport the hot metal to
the steel making facilities. The slag is diverted to slag pots or directly to
slag pits or slag granulators, depending on the facilities provided.
Dust-laden gases from the furnace are exhausted through a cyclone (dust
catcher) and a one- or two-stage cleaning operation. The primary cleaner is
normally a wet scrubber, which removes 90 percent of the remaining particu-
lates. The secondary cleaner is normally a high-energy wet scrubber (usually
a venturi) or an electrostatic precipitator. After it is cleaned, the gas
3 3
contains less than 0.05 gr/m (0.02 gr/ft ) of particulates.
Emissions and Emission Factors--
Manganese-bearing emissions occur during the storage and transfer of iron
ore, sinter, and pellets to the blast furnace. Emissions also occur during
the tapping and transfer of metal and slag within the casthouse (casthouse
emissions). Conditions known as "slips" can cause emissions from the emer-
gency pressure-release valves on top of the furnace, but these are rare in
modern practice, occurring when the materials charged in the furnace do not
move smoothly and thus leave a gas-filled space between two portions of the
charge. When the unsettled section of the charge collapses, the sudden dis-
placement of gas causes the exhaust gases, which contain manganese-bearing
particulate, to exit from the emergency pressure-release valves. During
tapping, emissions are produced when hot metal comes into contact with air.
Dissolved gases are released and emissions emanate from both the slag and the
metal.
Many blast furnace casthouses are uncontrolled. The most common control
system comprises runner covers and pickup hoods vented to a fabric filter.
Some plants are now using new systems that involve emission suppression tech-
niques. These entail blanketing the molten iron with an inert gas to suppress
oxidation. Table 4-11 indicates the manganese emissions from blast furnaces.
4-30
-------
TABLE 4-11. MANGANESE EMISSIONS FROM IRON BLAST FURNACES
Source
Control
device
Emission factors,9'
kg/Mg (Ib/ton) of iron
Blast furnace
Slips
Casthouse emissions
None
None
Runner covers
and pickup
hoods to fab-
ric filter
_-_c
0.1185 (0.261)/slip
0.0009 (0.0018)d
0.00009 (0.00018)
Reference 1.
Most of the manganese emissions are in the form of oxides.
cMn content of flue dust = 0.3 percent.
Mn content of the slag runner fumes =0.2 percent.5 Mn content = 0.4 percent
from the hot metal. It is assumed that the Mn content from the hot metal
runners is the same as the Mn content of the dust from fabric filter control-
ling hot metal transfer.3
The manganese content of the raw materials used in ironmaking and byprod-
ucts are presented in Table 4-12.
TABLE 4-12. MANGANESE CONTENT OF RAW MATERIALS
AND BYPRODUCTS OF BLAST FURNACE PRODUCTION3
Raw material or byproduct
Manganese content, %
Iron ore pellets
Iron ores
Manganese ores
(manganiferous)
BOF slag
Blast furnace hot metal
Blast furnace slag
Blast furnace flue dust
0.06 to 0.25
0.25 to 1 (0.3 average)
<5
2.1 to 4.9 (4 average)
0.5 to 1.2 (0.75 average)
0.2 to 1.0 (0.3 average)
0.2 to 0.6 (0.3 average)
References 2,3, and 4.
4-31
-------
Source Locations—
Table 4-13 lists the blast furnace operations in the United States.
4.5.2 Sintering Operations
Iron-bearing dusts, iron ore fines, mill scale, and sludges generated in
an integrated steel plant operation are recycled to the sinter plant. Sinter
is an agglomerated product of a size and strength suitable for blast furnace
charging. Figure 4-9 presents a flow diagram of a typical sinter plant. The
charge materials, consisting of suitable proportions of iron ore fines, BF
flue dust, mill scale, return sinter fines, limestone fines, and coke breeze,
are mixed with controlled amounts of water and fed to a pug mill or to a
balling drum. The prepared burden is spread in a 12-inch layer over a con-
tinuous moving grate called the sinter strand. A burner hood above the front
third of the sinter strand ignites the coke breeze in the mixture. Natural
gas or fuel oil is used for these burners. Once ignited, the combustion is
self-supporting and provides sufficient heat, 1300° to 1480°C (2400°-2700°F),
to cause surface melting and agglomeration of the mix. On the underside of
the sinter machine are wind boxes, which draw the combusted air through the
sinter bed into a common duct to a particulate control device. The fused
sinter is discharged at the end of the sinter machine, where it is crushed and
screened; the undersized portion is recycled to the sinter mix. The sized
sinter is cooled in open air by water sprays or by mechanical fans and then
charged to the furnaces.
Emissions and Emission Factors—
In the sintering process emissions occur from the wind box exhaust, the
discharge (sinter crusher and hot screen), the cooler, and the cold screens.
Mechanical collectors are typically used for product recovery and initial
cleaning, of windbox exhaust. Secondary collectors that have been used to
control wind box exhaust emissions include wet and dry electrostatic precipi-
tators, fabric filters, scrubbers, and gravel bed filters.
Manganese emission factors are obtained by multiplying the particulate
emission factors for sintering operations by the manganese content of the
sinter. In a high-basicity sinter, the Mn content of 1.2 percent was mea-
sured. Table 4-14 presents Mn emission factors for sinter operations.
4-32
-------
TABLE 4-13.
LOCATIONS (BY STATE AND CITY) OF BLAST FURNACES
IN THE UNITED STATES3
City/State
Company
Alabama
Fairfield
Gadsden
Colorado
Pueblo
Illinois
South Chicago
Indiana
Burns Harbor
Gary
East Chicago
Kentucky
Ashland
Maryland
Sparrows Point
Michigan
Dearborn
Ecorse
Trenton
New York
Buffalo
Ohio
Cleveland
Lorai n
Middletown
New Miami
Portsmouth
Steubenville
Warren
Youngstown
U.S. Steel
Republic Steel
CF&I Steel
Interlake, Inc.
U.S. Steel
Bethlehem Steel
U.S. Steel
Inland Steel
J&L Steel
National Steel
Bethlehem Steel
Ford Motor Rouge Works
National Steel
McLouth Steel •
Republic Steel
J&L Steel
Republic Steel
J&L Steel
Armco, Inc.
Armco, Inc.
Cyclops (Empire-Detroit Steel)
Wheeling-Pittsburgh Steel
Republic Steel
Republic Steel
(continued)
4-33
-------
TABLE 4-13 (continued)
City/State
Pennsylvania
Aliquippa
Baddock
Bethlehem
v Duquesne
Fair!ess
Monessen
Nelville Island
Rankin
Sharon
Texas
Houston
Lone Star
Utah
Geneva
West Virginia
Weirton
Company
J&L Steel
U.S. Steel
Bethlehem Steel
U.S. Steel
U.S. Steel
Wheeli ng-Pi ttsburgh
Shanango, Inc.
U.S. Steel
Sharon Steel
Armco, Inc.
Lone Star Steel
U.S. Steel
National Steel
Reference 6.
Note; This listing is subject to change as market conditions change, facility
ownership changes, plants are closed, etc. The reader should verify
the existence of particular facilities by consulting current listings
and/or the plants themselves. The level of manganese emissions from
any given facility is a function of variables such as capacity,
throughput, and control measures, and should be determined through di-
rect contacts with plant personnel.
4-34
-------
oo
01
CRUSHER/\
MILL DUSTS ft SCALE
SINTER
ORE
COLD
SCREEN
U^t_l_IIHVJ L/l\<_M»ir
LJC A OTLJ 1
MILL*
AYE
SINTER COOLER
S
a.
\ HOT RETURNS
/ SURGE BIN
f
4"
HOT
SCREEN
u
SINTER MACHINE
IGNITION
FURNACE
1
YYYYYYYYY
YYYYYYYYYYYY
SINTER BREAKER
COOLING FAN
SINTER FAN \J
Figure 4-9. Schematic flow diagram of a typical sinter plant.
-------
TABLE 4-14. MANGANESE EMISSION FACTORS FOR SINTERING OPERATIONS
Source
Control Equipment
Emissions factor,3'
kg/Mg (Ib/ton)
of sinter
Sintering
Windbox emissions
Sinter discharge (breaker
and hot screen)
Windbox and discharge
Uncontrolled
After coarse particle
removal
Dry ESP
Wet ESP
Scrubber
Cyclone
Uncontrolled
Fabric filter
Orifice scrubber
Fabric filter
0.067 (0.134)C
0.052 (0.104)
0.0096 (0.0192)
0.001 (0.002)
0.0028 (0.0056)
0.006 (0.012)
0.04 (0.08)
0.0006 (0.0012)
0.0035 (0.007)
0.0018 (0.0036)
Reference 1.
Most of the manganese emissions are in the form of oxides.
cMn content of sinter =1.2 percent.
4-36
-------
Source Locations--
Sintering operations are generally part of the integrated steel plant
operations. Table 4-15 lists the locations of sinter plants in the United
States.
4.5.4 Open Hearth Furnace Operations
.1 *
In the open hearth (OH) furnace, steel is produced from a charge of scrap
and hot metal in varying proportions. The production of steel from OH fur-
naces is gradually being replaced by basic oxygen furnaces and electric arc
furnaces. Steel production from OH furnaces accounted for 8.2 percent of the
total steel production in 1982. No new OH furnaces are planned, and produc-
tion is expected to continue to decline.
The OH furnace is heated alternately by a combustion flame from either
end of the hearth. Figure 4-10 is a schematic of the OH furnace. The gas
flow is reversed at regular intervals to recover the sensible heat from the
combusted gases. This is accomplished by passing the gas thrcugh brick lat-
tice work (checkers) at either end of the furnace and then into the gas-
cleaning system. At each reversal, the sensible heat in the brick is trans-
ferred to the incoming air. Oxidation reduces impurities such as C, Mn, Si,
and P to specified levels. A slag layer is formed above the molten steel.
Oxygen lancing is used to hasten the refining process. When the desired
specifications of the steel are reached, the steel is drained through a tap
hole into a ladle. Ferroalloys are added to the furnace ard/or ladle as
required. The molten steel is poured (teemed) into ingot molds for cooling
and further processing.
Emissions and Emission Factors—
Sources of fugitive emissions from open hearth furnaces include charging,
leakage from the furnace, tapping, and slag drainage. Tapping emissions can
be controlled by ladle hoods vented to a control device. Very limited controls
for fugitive emissions have been applied in open hearth steelmaking.
Emissions from open hearth furnaces are generally controlled with ESP's
or wet scrubbers. Fabric filters have also been installed for particulate
emissions control, but they require that the gases be pre-c:ooled.
4-37
-------
TABLE 4-15. LOCATIONS (BY STATE AND CITY) OF SINTER PLANTS
IN THE U.S. INTEGRATED STEEL INDUSTRY*5
State/City
Company
Alabama
Fair-field
Gadsden
Colorado^ \
Pueblo
Illinois
Granite City
South Chicago
Indiana
Burns Harbour
East Chicago
Gary
Kentucky
Ashland
Maryland
Sparrows Point
Michigan
Ecorse
Ohio
Middletown
Youngstown
Pennsylvania
Aliquippa
Bethlehem
Fairless
Monessen
Saxonburg
Texas
Utah
Lone Star
Houston
Geneva
West Virginia
East Steubenville
Weirton
U.S. Steel
Republic Steel
•CF&I Steel
National Steel
U.S. Steel
Bethlehem Steel
Inland Steel
Jones & Laughlin Steel
U.S. Steel
ARMCO
National Steel
National Steel
ARMCO
Republic Steel
J&L Steel
Bethlehem Steel
U.S. Steel
Wheeling-Pittsburgh Steel
U.S. Steel
Lone Star Steel
ARMCO
U.S. Steel
Wheeling-Pittsburgh Steel
Weirton Steel
Reference 6.
Note: This listing is subject to change as market conditions change, facil-
ity ownership changes, plants are closed, etc. The reader should
verify the existence of particular facilities by consultilng current
listings and/or the plants themselves. The level of manganese emis-
sions from any given facility is a function of variables such as
capacity, throughput, and control measures, and should be determined
through direct contacts with plant personnel.
4-38
-------
CHARGING DOOR
I
oo
FURNACE HEARTH
BURNER
PORT
EXHAUST GAS
TO STACK
COMBUSTION AIR
Figure 4-10. Schematic representation of an open hearth furnace.
-------
Manganese emission factors are derived by multiplying the particulate
emission factors for OH operations by the Mn content of the dust collected
from an ESP. The measured Mn content of the dust is around 0.37 percent.
Table 4-16 indicates the emission factors for Mn from open hearth furnaces.
TABLE 4-16. MANGANESE EMISSIONS FACTORS FOR OPEN HEARTH FURNACE OPERATIONS
Source
Control equipment
Emission factors,3
kg/Mg (Ib/ton) of pig iron
Melting and refining
Roof monitor
Teeming
Uncontrolled
ESP
Uncontrolled
Uncontrolled
Side-draft hood to
fabric filter
0.039 (0.078)D
0.0005 (0.001)
0.0003 (0.0006)
0.00013 (0.00026)
0.000003 (0.000006)
Reference 1.
Mn content of ESP dust =0.37 percent. Most of the manganese emis-
sions are in the form of oxides.
Location of Sources—
Table 4-17 lists plants with open hearth furnaces in the United States.
4.5.5 Basic Oxygen Furnace Operations
The BOF process (Figure 4-11) converts hot metal to steel in batches in
around 45 minutes (depending on the size of the vessel). This process is
superior to the older open-hearth process used in integrated steel operations.
About 60 percent of U.S. steel was produced by this method in 1983.
A typical charge consists of 70 percent hot metal and 30 percent scrap.
Commerically pure oxygen is blown into the vessel through a lance to oxidize
the impurities and carbon. The oxidation generates the required heat to melt
all the scrap charged. Lime is added to the vessel to form a slag that con-
tains the oxidized impurities from the hot metal and scrap. The furnace is a
4-40
-------
TABLE 4-17. LOCATIONS (BY STATE AND CITY) OF STEEL PLANTS
WITH OPEN-HEARTH FURNACES IN THE UNITED STATES
State/City
Company
Indiana
East Chicago
Maryland
Sparrows Point
Ohio
Middletown
Pennsylvania
Fairless Hills
Homestead
Texas
Lone Star
Utah
Geneva
Inland Steel
Bethlehem Steel
ARMCO
U.S. Steel
U.S. Steel
Lone Star Steel
U.S. Steel
Reference 6.
Note: This listing is subject to change as market conditions change,
facility ownership changes, plants are closed, etc. The reader should
verify the existence of particular facilities by consulting current
listings and/or the plants themselves. The level of manganese emissions
from any given facility is a function of variables such as capacity,
throughput, and control measures, and should be deternr ned through
direct contacts with plant personnel.
4-41
-------
HIGH-PUR ITT
OXTGEN AT
SUPERSONIC
SPEED
RETRACTABLE
OXTGEH
LANCE
EXHAUST HOOD
REFRACTORT LINING
TAPPIKG PORT
Figure 4-11. Basic oxygen process furnace.
4-42
-------
large, open-mouthed vessel lined with basic refractories. The vessel is
mounted on trunnions, which allow it to be rotated through 360 degrees.
Recent modifications entail many new configurations of oxygen entry Into
the vessel. In the Q-BOP process, the required oxygen is blown through tuyeres
at the bottom of the vessel. A relatively new process, known as the KMS
processes used in one plant, in which oxygen is introduced both from the top
and through bottom and side nozzles.
The large quantities of carbon monoxide (CO) produced by the reactions in
the EOF can be combusted at the mouth of the vessel, cooled, and then vented
to gas-cleaning devices (open- hood system), or the combustion can be sup-
pressed at the furnace mouth (closed hood system). The volume of gases to be
handled in a gas-cleaning device for closed-hood systems is substantially
lower than that for open-hood systems.
Although most of the furnaces installed before 1975 are of the open-hood
design, new furnaces are being designed with closed hoods.
After the oxygen blowing step, the metal is tapped into a ladle, to which
deoxidizers and alloying elements are added. The slag is poured into a slag
pot or onto the ground.
Emissions and Emission Factors—
The primary emissions during oxygen blowing range from 2C to 50 Ib/ton
steel. The gas is vented to either an ESP or a venturi scrubber. In the
closed-hood configuration, high energy, variable-throat, ventiri scrubbers are
used to clean the gas. The clean gas, which contains CO, is flared at the
stack.
Emissions occur during the transfer of hot metal from the ladle cars to
the ladles, the charging of scrap and hot metal to the BOF vessel, slag dump-
ing, and tapping of the steel. Hot metal transfer is controlled by close-
fitting hoods evacuated to a fabric filter. Secondary controls used to con-
trol the charging and tapping emissions may evacuate emissions to a separate
fabric filter or to the primary emission control system. The Q-BOP furnaces
are generally completely enclosed to control emissions.
Calculations of the manganese emission factors are based on the Mn con-
tent of the particulate emissions. Analysis of BOF dust shows 1.2 percent
3
Mn. The Mn content in the raw materials entering and products exiting the
BOF process are shown in Table 4-18.
4-43
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TABLE 4-18. MANGANESE CONTENT OF RAW MATERIALS
AND PRODUCTS OF BOF PROCESS3
Raw material or byproduct
Mn content, %
t
Steel scrap
Hot metal
Reladling fabric filter dust
BOF slag
ESP dust
Variable (0.5 average)
0.5 to 1.2 (0.75 average)
0.24 to 0.28 (0.25 average)
2.1 to 4.9 (4 average)
0.8 to 1.3 (1.0 average)
Reference 3.
These figures only represent a general range; individual plant data may
be quite different.
Table 4-19 presents calculated Mn emission factors for the BOF process.
Source Locations—
Table 4-20 indicates the BOF locations in the United States.
4.5.6 Electric Arc Furnace Operations
In 1982, electric arc furnaces accounted for 31.3 percent of total steel
Q
production in the United States. This share is expected to reach 36 percent
by 1990. The electric arc furnace is a refractory-lined steel cylinder with a
bowl-shaped hearth and a dome-shaped removable roof. Many of the new furnaces
have water-cooled side panels and a water-cooled roof. Three carbon elec-
trodes extended through holes in the roof reach the charge in the furnace.
The furnace roof and electrodes can be lifted and swung aside for charging of
scrap. The furnace can be tilted for tapping the molten steel and removing
the slag. Steel scrap is charged from the top by means of a special drop
bottom bucket or a clam shell bucket. After the charge, the roof is swung
back into position and the electrodes are lowered into the furnace. Melting
of the scrap is accomplished by the heat of resistance of the metal between
the arc paths. Oxyfuel burners may be used to hasten the melting. Oxygen
lancing is done to increase the melting rate of scrap. Required fluxes (lime)
are either added along with the charge or by pneumatic injection.
4-44
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TABLE 4-19. MANGANESE EMISSION FACTORS FOR BASIC OXYGEN FURNACE OPERATIONS
Source
Control equipment
Emission factors,
a,b
kg/Mg (Ib/ton) of steel
Top-blown BOF melting
and refining -
Q-BOP melting and
refining
Charging
At source
At building monitor
Tapping
At source
At building monitor
Hot metal transfer
At source
At building monitor
BOF monitor
All sources
Uncontrolled
Controlled by open hood
vented to:
ESP
Scrubber
Controlled by closed hood
vented to scrubber
Scrubber
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
0.1425 (0.285)c
0.0065 (0.013)
0.0045 (0.009)
0.00034 (0.00068)
0.00028 (0.00056)
0.003 (0.006)
0.00071 (0.00142)
0.0046 (0.0092)
0.00145 (0.0029)
0.0002 (0.0004)d
0.00007 (0.00014)
0.0025 (0.005)
Reference 1.
Most of the manganese emissions are in the form of oxides.
°Mn content = 1.0 percent of the BOF dust and sludge. (Range 0.8 to 1.3
percent, Reference 3).
Mn content = 0.26 percent; based on Reladling Baghouse Dust Analysis in
Reference 3.
4-45
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TABLE 4-20. LOCATIONS (BY STATE AND CITY) OF BASIC OXYGEN FURNACES
IN THE IRON AND STEEL INDUSTRY IN THE UNITED STATES*
State/city
Alabama
Fairfield
Gadsden
Colorado
Pueblo
Illinois
Chicago
Granite City
South Chicago
Indiana
Burns Harbor
East Chicago
Gary
Kentucky
Ashland
Maryland
Sparrows Point
Michigan
Dearborn
Ecorse
Trenton
New York
Buffalo
Ohio
Cleveland
Lorain
Middletown
Steubenville
Warren
Pennsylvania
Aliquippa
Bethlehem
Braddock
Duquesne
Parrel!
Midland
Monessen
Natrona
West Virginia
Weirton
Company
U.S. Steel Corporation
Republic Steel Corporation
CF&I Steel Corporation
Interlake, Inc.
National Steel Corporation
Republic Steel Corporation
U.S. Steel Corporation
Bethlehem Steel Company
Inland Steel Company
Jones and Laugh!in Steel Corporation
U.S. Steel Corporation
Armco Steel Corporation
Bethlehem Steel Corporation
Ford Motor Company
National Steel Corporation
McLouth Steel Corporation
Republic Steel Corporation
Jones and Laughlin Steel Corporation
Republic Steel Corporation
U.S. Steel Corporation
Armco Steel Corporation
Wheeling-Pittsburgh Steel Corpo-
ration
Republic Steel Corporation
Jones and Laughlin Steel Corporation
Bethlehem Steel Company
U.S. Steel Corporation
U.S. Steel Corporation
Sharon Steel Corporation
Crucible, Incorporated
Wheeling-Pittsburgh Steel Corpo-
ration
Allegheny Ludlum Steel Company
Weirton Steel
Reference 6.
Note; This listing is subject to change as market conditions change, facility
ownership changes, plants are closed, etc. The reader should verify the
existence of particular facilities by consulting current listings and/or the
plants themselves. The level of manganese emissions from any given facility
is a function of variables such as capacity, throughput, and control measures,
.and should be determined through direct contacts with plant personnel.
4-46
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Ultra-high-power (UHP) furnaces use larger electrodes and allow more
power input to the charge and thus a faster melting rate.
After the proper chemistry and temperature of the bath are achieved, the
furnace is tilted and the steel is poured into a ladle. Ferroalloys are added
in the ladle. After tapping, the steel may be degasified by several means, or
other l§dle operations, such as stirring, may be performed. Continuous cast-
ers then cast the steel. Figure 4-12 is a schematic diagram of EAF opera-
tions.
In stainless steel production, the molten steel is transferred from the
electric furnace to an Argon oxygen deoxidation (ADD) vessel similar to the
BOF. Argon and oxygen and/or nitrogen are blown into the steel for prefer-
ential removal of carbon instead of oxidation of chromium ("r), the principal
alloying element in stainless steel. Because the yield of "r is high in this
process, it is more economical.
Emissions and Emission Factors—
Electric arc furnace emissions are classified as process or fugitive.
Emissions generated at the furnace during periods when the furnace roof is
closed (e.g., during melting and refining) are classified as process emis-
sions. Emissions generated during periods when the furnace roof is open
(e.g., during charging) or when the furnace is tilted (e.g., during tapping)
are classified as fugitive emissions.
Process emissions from the meltdown operation consist Df metallic and
mineral oxide particulate generated from the vaporization of iron and the
transformation of mineral additives, as well as some carbon monoxide and
hydrocarbons. Trace constituents (including manganese) are emitted in par-
ticulate form from EAF's. During the melting process, emissions escape
through electrode holes, the slag door, and other furnace openings.
Charging emissions may contain particulate, carbon monoxide, hydrocarbon
vapors, and soot. During tapping, fumes consisting of iron and other oxides
are generated from the alloys that are added to the ladle.
Fabric filters are the most widely used control devices on EAF's. Wet
scrubbers are used on less than 2 percent of the existing E^F units in the
United States, and only one shop uses an ESP unit to control EAF dust.
4-47
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I
-fa
GO
CLEANED GAS LOUVERS
GF^-
CANOPY HOOD
SCRAP
DIRECT SHELL EVACUATION
ALLOYS
LIME-
SILICA,
\
L
CHARC7ING
BUCKET
L
T-7
COMBUSTION AIR GAP
STEEL
1
BAGHOUSE
\/\/\/
COLLECTED
DUST
Figure 4-12. Schematic of electric arc furnace process.
-------
Evacuation systems of various configurations are adopted to capture both
primary and secondary emissions in EAF shops.
0 Direct-shell evacuation control system (DEC)
0 Side-draft hood
0 t v Canopy hood
0 Partial furnace enclosure (PFE)
0 Total furnace enclosure (TFE)
0 Tapping hood
0 Scavenger duct system
0 Roof monitor
0 Building evacuation
The DEC and canopy hood (shown in Figure 4-12) are the most common.
The manganese emission factors are calculated based on the Mn content of
the particulate emissions. The following are analyses of manganese content in
EAF dust generated in the production of various types of steel.
Stainless steel and
alloy - 4.92% (average of 6 samples)
Mixed products in- - 3.25% (average of 6 samples)
eluding stainless
and/or specialty
alloys
Low and medium alloy - 5.76% (1 sample)
Carbon and alloy - 4.0% (average of 7 samples)
Carbon steel - 3.48% (average of 10 samples)
Manganese content of electric arc furnace slag also varies with the type
3
of steels made. The average Mn content is around 4 percent
Table 4-21 presents manganese emission factors for electric arc furnace
operations.
Source Locations—
Table 4-22 lists the locations of EAF shops in the United States.
4-49
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TABLE 4-21. MANGANESE EMISSION FACTORS FOR ELECTRIC ARC FURNACE OPERATIONS
Source
Control equipment
Emission factors,3'
kg/Mg (Ib/ton)
of product
Melting and refining
carbon steel
Roof monitor emissions
(charging, tapping,
and slagging)
Melting, refining,
charging, tapping,
and slagging
Carbon steel
Alloy steel
Uncontrolled
Uncontrolled
Uncontrolled
DEC plus charging hood to
common fabric filter
Uncontrolled
Total building evacuation
to fabric filter
0.665 (1.33)c
0.0245 (0.049)
0.875 (1.75)
0.00075 (0.0015)
0.328 (0.656)°
0.0087 (0.0174)
a
Reference 1.
DMost of the manganese emissions are in the form of oxides.
•»
"Mn content of EAF dust—carbon steel, 3.48 percent (average of 10 samples).11
Mn content of EAF dust—low and medium alloy, 5.76 percent.11
4-50
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TABLE 4-22. ALPHABETICAL LISTING (BY COMPANY NAME) OF
ELECTRIC ARC FURNACE/LOCATIONS IN THE UNITED STATES9
Plant/location
Plant/location
Pltn1./loc»tion
AL Tech Specialty Steel Corp.,
Uatervliet, New York
Allegheny ludlum Steel Corp.,
Brackenridge, Pennsylvania
ARMCO',* Inc.
0 Baltimore Works,
Baltimore, Maryland
0 Butler Works,
Butler, Pennsylvania
0 Houston Works,
Houston, Texas
• Kansas City Works,
Kansas City, Missouri
° Marion Works,
Marion, Ohio
° Sand Springs Works
Sand Springs, Oklahoma
Atlantic Steel Company
0 Atlanta Works,
Atlanta, Georgia
0 Cartersville Works,
Cartersville, Georgia
Auburn Steel Company,
Auburn, New York
Babcock S Wilcox Company,
Beaver Falls, Pennsylvania
Bayou Steel Corporation,
New Orleans, Louisiana
Bethlehem Steel Corp.
0 Bethlehem P.lant,
Bethlehem, Pennsylvania
° Steel ton Plant,
Steelton, Pennsylvania
0 Johnstown Plant,
Johnstown, Pennsylvania
0 Los Angeles Plant,
Los Angeles, California
0 Seattle Plant,
Seattle, Washington
Border Steel Mills, Inc.
El Paso, Texas
Braeburn Alloy Steel Division
Lower Burre.11, Pennsylvania
Interlake, Inc.
Hoaganaes Corporation
Gallatin, Tennessee
ITT Harper
Morton Grove, Illinois
B.W. Steel,
Chicago Heights, Illinois
Cabot Corporation
Stellite Division,
Kokomo, Indiana
Cameron Iron Works, Inc.
Cypress, Texas
Carpenter Technology Corp.,
° Steel Division
Bridgeport, Connecticut
0 Reading Plant,
Reading, Pennsylvania
Cascade Rolling Mills
McMinnville, Oregon
The CECO Corporation
° Lemont Manufacturing Company
Lemont, Illinois
CF&I Steel Corp.
Pueblo, Colorado
Champion Steel Corp.,
Orwell, Ohio
Chaparral Steel Co.,
Midlothian, Texas
Charter Electric Melting, Inc.
Chicago Heights, Illinois
Columbia Tool Steel Company
Chicago Heights, Illinois
Connors Steel Co.,
0 Birmingham Works,
Birmingham, Alabama
0 Huntington Works
Huntington, West Virginia
Continental Steel Co.,
Kokomo, Indiana
Copperweld Steel Co.,
Warren, Ohio
Crucible, Inc.
0 Stainless Steel Division,
Midland, Pennsylvania
0 Specialty Metals Division
Syracuse, New York
National Forge Company
0 Erie Plant
Erie, Pennsylvania
0 Irvine Forge Division
Irvine, Pennsylvania
Cyclops Co'-p.
° Empire Detroit Steel Division,
Mansfieli, Ohio
e Umversa Cyclops Specialty Steel
Bridgeville, Pennsylvania
Earle M. Jjrgensen Company,
Seattle, Wishington
Eastern Stainless Steel Company,
Baltimore, Maryland
Edgewater Steel Corp.
Oakmont, Psnnsylvama
Electralloy Corp.,
Oil City, 'ennsylvania
Finkle 8 Sans Company,
Chicago, Illinois
Florida Stsel Corp.
0 Charlotte Mill
Charlott;, North Carolina
0 Baldwin 11,11,
Baldwin, Florida
0 Tampa Mill,
Tampa, Florida
Ford Motor Steel Division,
Dearborn, Michigan
Georgetown Steel Division,
Georgetown, South Carolina
Georgetown Texas Steel Corp.
Beaumont, Texas
Green River Steel,
Owensboro, Kentucky
Hawaiian Wsstern Steel Ltd.,
Eva, Hawaii
Hurricane Industries,
Sealy, Tex is
Ingersol Jjhnson Steel Company,
New Castle, Indiana
Ingersol Rind-Oil Field Prod.,
Pampa, Tex is
Inland Steel Company,
East Chicajo, Indiana
Intercoastil Steel Corp.,
Chesapeake, Virginia
Roanoke El;ctric Steel Corp.
Roanoke, Virginia
Rob!in Steul Company
Dunkirk Wo^ks,
Dunkirk, New York
(continued)
4-51
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TABLE 4-22 (continued)
Plant/location
Plant/location
Plant/location
Jackson Hill.
Jackson, Tennessee
Jessop St^el Company
Washington Works
Washington, Pennsylvania
Jones & Laughlln Steel Corp.
• Cleveland Works
Cleveland, Ohio
0 Pittsburgh Works
Pittsburgh, Pennsylvania
0 Warren Works,
Warren, Michigan
Joslyn Stainless Steels,
Fort Wayne, Indiana
Judson Steel Corp.,
Emeryville, California
Kentucky Electric Steel Company,
Ashland, Kentucky
Keystone Consolidated Industries,
Inc.
Keystone Group Steel Works
Peopria, Illinois
Knoxville Iron Company
Knoxville, Tennessee
Laclede Steel Company,
Alton, Illinois
Latrobe Steel
Latrobe, Pennsylvania
Latrobe Works
Latrobe, Pennsylvania
Lonestar Steel Company,
Lone Star, Texas
Lukens Steel,
Coatsville, Pennsylvania
MacStee1 Division
Ft. Smith, Arizona
Marathon Le Tourneau Company,
Tenpe, Arizona
HcClouth Steel Corp.,
Trenton, Michigan
Mississippi Steel Division
Flowood Works, Flowood, Mississippi
National Steel
Great Lakes Steel Division
Ecorse, Michigan
New Jersey Steel & Structure
Corp.
Sayerville, New Jersey
Newport Steel,
Newport, Kentucky
North Star Steel Company
0 St. Paul Plant,
St. Paul, Minnesota
0 Monroe Plant, Monroe, Michigan
0 Wilton Plant, Wilton, Iowa
Northwest Steel Rolling Mills,
Inc., Kent, Washington
Northwestern Steel & Wire
Sterling, Illinois
NUCOR Corp.
0 Darlington Mill,
Darlington, South Carolina
0 Jewett Mill,
Jewett, Texas
0 Norfolk Mill,
Norfolk, Nebraska
0 Plymouth Mill,
Plymouth, Utah
Owens Electric Steel Company,
Cayce, South Carolina
Phoenix Steel Corp.
0 Plate Division
Claymont, Delaware
Quantex Corp.
MacSteel Division
Jackson, Michigan
Raritan River Steel Company
Perth Amboy, New Jersey
Republic Steel Corp.
0 Central Alloy Works
Canton, Ohio
0 Republic Steel Corp.
South Chicago Works,
South Chicago. Illinois
Ross Steel Works
Ami to, Louisiana
Sharon Steel Corp.
Sharon, Pennsylvania
Simonds Steel Division,
Wallace Murray Corp.,
Lockport, New York
Soule Steel Company,
Carson Works, Carson, California
Standard Steel
Burnham, Pennsylvania
Structural Metals, Inc.,
Sequin, Texas
Teledyne Vasco,
Latrobe, Pennsylvania
Tennessee Forging Steel Corp.
0 Harriman Works,
Harriman, Tennessee
Tennessee Forgining Steel Corp.
0 Newport Works
Newport, Arkansas
Texas Steel Company,
Fort Worth, Texas
Tlmkin Company
° Steel and Tube Division
Canton, Ohio
Torrence Plant,
Torrence, California
Union Electric Steel Corp.
Burgettstown, Pennsylvania
United States Steel Corp.
° Fairless Works,
Fairless Hills, Pennsylvania
° Johnstown Works,
Johnstown, Pennsylvania
° National Duquesne Works,
Duquesne, Pennsylvania
0 South Works,
South Chicago, Illinois
° Texas Works, Baytown, Texas
Washington Steel Company,
Fitch Works, Houston, Pennsylvania
Reference 6.
Note: This listing is subject to change as market conditions change, facility ownership changes, plants are closed,
etc. The reader should verify the existence of particular facilities by consulting current listings and/or the
plants themselves. The level of manganese emissions from any given facility is a function of variables such as
capacity, throughput and control measures, and should be determined through direct contacts with plant personnel.
4-52
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References for Section 4.5
1. U.S. Environmental Protection Agency. Compilation of Air Pollutant
Emission Factors. AP-42, Supplement 14. May 1983.
2. Strassburger, J. H. (Ed.) Blast Furnace - Theory and Practice. Vol. 1.
Gordon and Breach Science Publishers, 1969.
3. CaTs'pan, et al. Assessment of Industrial Hazardous Waste Practices in
the Metal Smelting and Refining Industry. Vol. IV. U.S. Environmental
Protection Agency. 1977.
4. Fornacht, D. R. Characterization and Utilization of Steel Plant Fines.
Presented at the First Symposium on Iron and Steel Pollution Abatement
Technology, Chicago, October 1979. EPA-600/9-80-012.
5. Kelly, J. F., and A.' W. Simon. Characterization of Slag Emissions at a
Blast Furnace Casthouse. Presented at the EPA/AISI Symposium at Chicago,
Illinois, October 1983.
6. World Steel Industry Data Handbook. 33 Metal Producing. Volume 5,
U.S.A. McGraw-Hill, New York. 1982.
7. U.S. Environmental Protection Agency. Control Techniques for Particulate
Emissions From Stationary Sources. Vol. 2. EPA-450/3--81-005b, September
1982.
8. Balajee, S. R., and G. A. Walton. Investigations of the Effect of
Sintering Process Variables on Super-Fluxed Sinter Production and
Quality. In: Proceedings of Iron Making Symposium, Toronto, Ontario,
1981. Volume 40, published by the Iron and Steel Society of AIME.
9. Hogan, W. T. The Expanding Electric Furnace: A Threat to the BOF? Iron
and Steel Engineer, October 1983.
10. Lehigh University. Characterization, Recovery, and Recycling of Electric
Arc Furnace Dusts. Prepared for U.S. Department of Commerce. Bethlehem,
Pennsylvania. February 1982.
4.6 IRON AND STEEL FOUNDRIES
Figure 4-13 presents a generalized flow diagram for iron and steel four-
dries. The raw materials flow, sand preparation for the molds, and.core
preparation .are similar in both iron and steel foundries. Three major types
of furnaces are used in both: cupolas, induction furnaces, and electric arc
furnaces. About 70 percent of all iron is produced in cupolas,, A major
4-53
-------
RAW MATERIALS
UNLOADING, STORAGE,
TRANSFER
• FLUX
•METALLICS
•CARBON SOURCES
•SAND
•BINDER
SCRAP
PREPARATION
FUGITIVE •*--->
FURNACE
TAPPING,
TREATING
MOLD POURING,
COOLING
SAND
CASTING
SHAKEOUT
COOLING
CLEANING,
FINISHING
SHIPPING
A SOURCES OF MANGANESE
Figure 4-13. Generalized flow diagram of iron/steel foundry.
Source: Reference 1.
4-54
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portion of the remainder is produced in electric arc and induction furnaces.
A small percentage of melting in gray iron foundries takes place in air fur-
naces, reverberatory furnaces, pot furnaces, and indirect arc furnaces A
Steel foundries rely almost exclusively on EAF's or induction furnaces; open
hearth furnaces and induction furnaces are used infrequently.
Rawt material handling operations include receiving, unloading, storage,
and conveying all raw materials to the foundry. The raw materials, which
include pig iron, iron scrap, steel scrap, foundry returns, ferroalloys,
fluxes, additives, sand, sand additives, and binders, are stsred in both open
and enclosed areas.
4.6.1 Cupolas
The cupola furnace is the major furnace used in a gray iron foundry. It
is typically a vertical, refractory-lined, steel shell, which is charged at
the top with alternate layers of pig iron, coke, and flux. The larger cupolas
are water-cooled. Air for combustion of coke is introduced at the bottom, and
the heat generated melts the charge. Hot-blast cupolas use preheated air.
Typical melting capacities range from 0.9 to 25 Mg (1 to 27 tons) per hour,
and a few units approach 90 Mg (100 tons) per hour. Cupolas can be tapped
either continuously or intermittently from a side tap hole at the bottom of
the furnace.
4.6.2 Electric Arc Furnaces
Electric arc furnaces used in foundries are the same as those used in
integrated steel plants described in Section 4.5.6.
4.6.3 Induction Furnaces
Induction furnaces are vertical refractory-lined cylinders surrounded by
electrical coils energized with alternating current. The resulting fluctua-
ting magnetic field heats and melts the metal. Induction furnaces are kept
closed except during charging, skimming, and tapping operations. Tapping is
done by tilting the furnace and pouring the molten metal through a hole in the
side. Induction furnaces are also used to hold and superheat the charge after
melting and refining has been done in other furnaces.
The basic melting process operations are 1) furnace charging, in which
metal, scrap, alloys, carbon, and flux are added to the furnace; 2) melting;
4-55
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3) backcharging, which is the addition of more metal; 4) refining; 5) slag
removal; and 6) tapping into a ladle or directly into molds.
4.6.4 Casting and Finishing
When the melting process is complete, the molten metal is tapped and
poured into a ladle. In iron foundries the molten metal may be treated by the
additicfo of magnesium to produce ductile iron and by the addition of soda ash
or lime to remove sulfur. Sometimes graphite is added to adjust carbon levels.
In steel foundries, the molten steel may be further treated by alloy addi-
tions, degasification, and other operations. The treated molten metal is then
poured into molds and allowed to cool partially. The partially cooled cast-
ings are placed on a vibrating grid, where the mold and core sand is shaken
away from the casting.
In the cleaning and finishing process, burrs, risers, and gates are
broken off or ground off to match the contours of the castings; the castings
are then shot-blasted to remove remaining mold sand and scale.
4.6.5 Emissions and Emission Factors
Particulate emissions can occur during all of the operations just dis-
cussed. Figure 4-13 indicates the major manganese emissions sources. The
highest concentration of furnace emissions occurs during charging, backcharg-
ing, alloying, slag removal, and tapping operations., when the furnace lids and
doors are opened. Emissions generated during the melting and refining opera-
tions are vented directly to a collection and control system. Controls for
fugitive furnace emissions involve the use of roof hoods or special hoods in
proximity to the furnace doors and tapping ladles.
High-energy scrubbers and bag filters with respective efficiencies greater
than 95 percent and 98 percent are used to control particulate emissions from
cupolas and electric arc furnaces. Induction furnaces are usually uncon-
trolled.1
The calculated emission factors for manganese, which are based on the Mn
content in the particulate matter, are presented in Tables 4-23 and 4-24 for
iron and steel foundries, respectively.
4-56
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TABLE 4-23. MANGANESE EMISSION FACTORS FOR IRON FOUNDRIES
Source
Control equipment
Emission factors,9'
kg/Mg fib/ton) of iron
Cupola
Electric arc furnace
Induction furnace
Uncontrolled
Wet cap
Impingement scrubber
High energy scrubber
Fabric filter
Uncontrolled
Fabric filter (99%)
Uncontrolled
0.13 (0.25)c
Range, 0.045-0.215
(0.09 - 0.43)
0.06 (0.12)
0.0375 (0.075)
0.006 (0.012)
0.0015 (0.003)
0.075 (0.15)d
Range, 0.045 - 0.15)
(0.09 - 0.30)
0,00075 (0.0015)
0,01125 (0.0225)6
Reference 1.
Most of the manganese emissions are in the form of oxides.
cMn content in cupola dust =1.5 percent (range of 1 to 2%).3
Mn content in EAF dust =1.5 percent.2
eMn content assumed to be 1.5 percent (as in cupola and EAF dust).
TABLE 4-24. MANGANESE EMISSION FACTORS FOR STEEL FOUNDRIES
Source
Control equipment
sian factors,
kg/Mg (Ib/ton) of steel
Electric arc furnace
Induction furnace
Uncontrolled
ESP (95% efficiency)
Venturi scrubber
(97.5% efficiency)
Fabric filter
(98.5% efficiency)
Uncontrolled
0.26 (0.52)D
Range, 0.08 - 0.8
(0.16 - 1.6)
O.D13 (0.026)
O.D065 (0.013)
0.0004 (0.0008)
0.002 (0.004)c
Reference 1.
Mn content in EAF dust = 4 percent (average of seven carbDn and alloy steel
plants).^
cMn content assumed to be 4 percent (same as EAF dust).
4-57
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4.6.6 Source Locations
In 1978, a total of 2,728 foundries were producing iron and steel cast-
ings throughout the United States. A high concentration of these foundries
were located east of the Mississippi. The following is a breakdown of the
2
type of castings produced by these foundries :
4 Gray iron - 1400 foundries
Ductile iron - 590 foundries
Malleable iron - 107 foundries
Steel - 631 foundries
References for Section 4.6
1. U.S. Environmental Protection Agency. Compilation of Air Pollutant
Emission Factors. AP-42, Supplement 14. May 1983.
2. U.S. Environmental Protection Agency. Electric Arc Furnaces in Ferrous
Foundries - Background Information for Proposed Standards. EPA-450/3-
80-020a, May 1980.
3. Nelson, T. P., et al. Study of Sources of Chromium, Nickel, and Manga-
nese. Prepared by Radian Corporation for the Office of Air Quality
Planning and Standards, U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina. February 24, 1984.
4. Lehigh University. Characterization, Recovery, and Recycling of Electric
Arc Furnace Dusts. Prepared for the U.S. Department of Commerce. Beth-
lehem, Pennsylvania. February 1982.
4.7 BATTERY MANUFACTURING
In the present-day dry cells, the cathode is Mn02 with about 10 to 30
percent by weight carbon added to improve the conductivity. The collector for
the cathode is usually either a carbon rod or a metal rod coated with carbon.
The anode is usually the zinc can or zinc sheet. The electrolyte used is
generally either a saturated solution of ammonium chloride, NaOH, or KOH.
Batteries that use a saturated solution of ammonium chloride as the
*•
electrolyte are known as Leclanche, cells (after their inventor). The batter-
ies that use NaOH or KOH as the electrolytes are known as alkaline cells.
*•
Alkaline cells generally perform better than Leclanche, cells. The alkaline
s
manganese dioxide-zinc cell is essentially the same as the Leclanche, system
except for the electrolyte used. These cells have a better shelf life, good
low-temperature performance, and longer operating lives.
4-58
-------
The Mn ore or synthetic oxides used in the manufacture of dry cell bat-
teries are generally received in bags already ground to the required sizes.
The bags are stored and covered with plastic covers. The bags are manually
dumped into storage hoppers. The material handling systems are provided with
pickup hoods at all transfer points and evacuated to a fabric filter.* In the
subsequent steps, the Mn02 powder is combined with the electrolyte and densi-
fied, and the rest of the process is conducted under semiwet conditions.
4.7.1 Emissions and Emission Factors
The only emission sources during dry battery manufacture are at the
points of initial handling of the Mn-ore or MnCL powders. In the case of
natural ores, grinding and screening may be done at these points, depending on
the onsite facilities. These points are generally well controlled by the use
of hoods evacuated to fabric filters. The manganese content in the ore powder
handling area is monitored regularly, and the values are found to be lower
than the permitted limits.* Table 4-25 presents the Mn emission factors for
battery manufacturing.
4.7.2 Source Locations
.>
Some of the principal manufacturers of Leclanche and MnCL-Zn dry cells in
the United States are Bright Star Industries, Burgess Battery Company, ESB-
Polaroid, Marathon Battery Company, Ray-0-Vac Company, and Union Carbide
Corporation.2 Primary battery manufacturers, both dry and wet, are listed
under SIC Code 3692.
*
Personal communication from Union Carbide Corporation personnel at Cleveland,
Ohio.
. 4-59
-------
TABLE 4-25. MANGANESE EMISSION FACTORS IN BATTERY MANUFACTURE0
Source
Control equipment
Manganese .
emission factors,
kg/Mg (Ib/ton)
of material processed
Ore grinding
Screening
Storage and han-
dling
Uncontrolled
Fabric filter
(99.9% efficiency)
Uncontrolled
Fabric filter
(99.9% efficiency)
Uncontrolled
Fabric filter
(99% efficiency)
15.0 (30.0)
0.015 (0.03)
0.5 (1.0)
0.0005 (0.001)
2.2 (4.4)
0.0022 (0.0044)
a Reference 1.
Mn content of the ores = 50 percent (range = 48 to 53%).
ent as Mn02. Pure Mn02 is 63.2 percent manganese.
Manganese is pres-
References for Section 4.7
1. Nelson, T. P., et al. Study of Sources of Chromium, Nickel, and Manga-
nese. Prepared by Radian Corporation for the Office of Air Quality
Planning and Standards, U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina. February 24, 1984.
2. Kirk-Othmer. Encyclopedia of Chemical Technology. Vol. 14. 3d Ed.
John Wiley & Sons, New York. 1981.
4-60
-------
SECTION 5
INDIRECT SOURCES OF MANGANESE
5.1 COAL AND OIL COMBUSTION
Manganese emissions from combustion processes depend on the manganese
content of the fuel fired. The distribution of manganese between boiler fly
ash and bottom ash and the manganese content in fine fly ash are two very
important factors that influence atmospheric emissions'of manganese.
Manganese concentrations in coal range from 5 to 240 ppm and are typi-
cally around 25 ppm. Table 5-1 shows the manganese concentrations and ash
contents of several U.S. coals. Manganese concentrations in crude oil are
much lower, ranaing from 0.005 to 1.45 ppm and averaging 0,21 ppm for U.S.
2
crude oils. The manganese content in residual fuel oils in the United States
averages about 0.16 ppm. The manganese content of distillate oil is reported
3
to be lower than 0.01 ppm from some refineries. Table 5-2! shows the typical
manganese content of several U.S. crude oils.
The fate of trace elements from the combustion process can be classified
by one of three categories:
Class I. Approximately equal distribution between fly ash and bottom
ash.
Class II. Preferential distribution in the fly ash.
Class III. Discharge to the atmosphere primarily as vapors.
Many studies on coal combustion have indicated that manganese emissions
A
from this source generally fall under Class I. In a study correlating trace
element emissions from hot-side and cold-side precipitators, at coal-fired
plants, however, manganese was found to be more concentrated in the fly ash
from the cold- side station (i.e., Class II behavior). Manganese emissions
from oil combustion generally fall into Class II, primarily because little
bottom ash is formed in the oil combustion process.
5-1
-------
TABLE 5-1. MANGANESE CONCENTRATIONS IN U.S. COALS1
Coal type (source)
Manganese levels
in coal, ppm
Ash content
of coal, %
Appalachian
(Pennsylvania, Maryland, Virginia,
West Virginia, Ohio, Eastern
Kentucky, Tennessee, Alabama)
Interior Eastern
(Illinois, Indiana, Western
Kentucky)
Interior Western
(Iowa, Missouri, Kansas,
Oklahoma, Arkansas)
Northern Plains
(Montana, North Dakota, South
Dakota)
Southwestern
(Arizona, New Mexico, Colorado,
Utah)
5-55
6-181
108
88-101
6-240
6.2-18.3
3.3-17.3
25.9
11.3-15.8
6.6-13.7
Reference 4.
TABLE 5-2. MANGANESE CONCENTRATIONS IN U.S. CRUDE OILS0
Oil source
Manganese concentrations
in oil, ppm
Arkansas
California
Colorado
Kansas
Montana
New Mexico
Oklahoma
Texas
Utah
Wyoming
0.12
0.14
0.21
0.01
0.005
0.02
0.03
0.03
1.45
0.04
Reference 2.
5-2
-------
The size distribution of manganese concentrations in the fly ash is an
important consideration because this determines the efficiency of particulate
capture. Table 5-3 shows the particle size distribution of airborne fly ash
measured at a coal-fired power plant. The results reveal a slight tendency
for increased manganese concentrations in the finer fly ash fractions. Table
5-4 shows^measured overall manganese particulate collection efficiencies for
various types of air pollution control devices. As shown, fabric filters have
high manganese collection efficiencies.
TABLE 5-3. PARTICLE SIZE DISTRIBUTION OF MANGANESE
IN FLY ASH FROM COAL COMBUSTION3
Particle diameter,
vim
11.3
7.3-11.3
4.7-7.3
3.3-4.7
2.06-3.3
1.06-2.06
Manganese concentration,
ppm
150
210
230
200
240
470
Measured by X-ray fluorescence spectrometry; Reference 5.
TABLE 5-4. MANGANESE PARTICULATE COLLECTION EFFICIENCIES OF VARIOUS TYPES
OF CONTROL DEVICES
Source
Coal -fired
utility boiler
Coal -fired
utility boiler
Coal -fired
industrial
boiler
Oil-fired
industrial
.boiler
Control
device type
Electrostatic
precipitator
Fabric filter
Wet scrubber
Wet scrubber
Overall
manganese
collection
efficiency, %
94.2
99.8
98.1
83.3
Reference
6
7
8
9
5-3
-------
5.1.1 Emission Factors
Manganese emissions from boilers are, a function of the fuel type, furnace
type (or firing configuration), and type of control device used. Tables 5-5,
5-6, 5-7, and 5-8 present emission factors for manganese from coal- and oil-
fired combustion in utility, industrial, commercial/institutional, and resi-
dential boilers, respectively. These emission factors are based on an exten-
Q
sive survey of the existing literature. As with all emission factors, these
are only general guidelines, and emissions from specific sources may vary
considerably.
5.1.2 Source Locations
Information on individual source locations is available through the
American Boiler Manufacturers Association, the Electric Power Research Insti-
tute, and data bases maintained by the U.S. Environmental Protection Agency
and the U.S. Department of Energy.
References for Section 5.1
1. Edwards, L. 0., et al. Trace Metals and Stationary Conventional Combus-
tion Processes. Vol. 1 EPA-600/7-80-155a, August 1980.
2. Anderson, D. Emission Factors for Trace Substances. EPA-450/2-73-001,
December 1973.
3. Letter from E. D. Blum of Union Oil to T. Lahre of EPA, January 31, 1985.
4. Ray, S. S., and F. G. Parker. Characteristics of Ash From Coal-Fired
Power Plants. EPA-600/7-77-010, January 1977.
5. Mann, R. M., et al. Trace Elements of Fly Ash: Emissions From Coal-
Fired Steam Plants Equipped With Hot-Side and Cold-Side Electrostatic
Precipitators for Particulate Control. EPA-908/4-78-008, December 1978.
6. Ensor, D. S., et al. Evaluation of the George Neal No. 3 Electrostatic
Precipitator. EPRI FP-1145, August 1979.
7. Ensor, D. S., et al. Kramer Station Fabric Filter Evaluation. EPRI
CS-1669, January 1981.
8. Leavitt, C., et al. Environmental Assessment of Coal- and Oil-Firing in
a Controlled Industrial Boiler. Vol. II. EPA-600/7-78-164b, August
1978.
9. Krishnan, E. R., and G. V. Hellwig. Trace Emissions From Coal and Oil
Combustion. Environmental Progress. Vol. 1, No. 4. November 1982.
pp. 290-296.
5-4
-------
TABLE 5-5. EMISSION FACTORS FOR MANGANESE FROM COAL
AND OIL COMBUSTION: UTILITY BOILERS3
Fuel type
Bituminpus
coal
Anthracite
coal
Lignite
coal
Residual
oil
Furnace type
Pulverized,
dry-bottom
Pulverized,
wet-bottom
Cyclone
Stoker
Pulverized
" Stoker
Pulverized,
dry-bottom
Pulverized
wet-bottom
Cyclone
Stoker
Tangential
Wall
Control device
Electrostatic precipitator
Scrubber
None
Electrostatic precipitator
Electrostatic precipitator
Scrubber
None
Multicyclones
Electrostatic precipitator
Multicyclones
Electrostatic precipitator
Electrostatic precipitator
Electrostatic precipitator
Multicyclones
Multicyclones
Electrostatic precipitator
None
Electrostatic precipitator
None
Manganese
emission factor,
pg/JD
41.3
48.2
98.0
33.5
26.1
54.2
98.0
47.3
41.3
47.3
18.1
14.7
57.2
711
47.3
2.2 •
11.0
2.2
11.0
Reference 9.
'Picograms per joule of heat
Btu, multiply by 2.33.
input to boiler; to convert from pg/J to lb/1012
5-5
-------
TABLE 5-6. EMISSION FACTORS FOR MANGANESE FROM COAL
AND OIL COMBUSTION: INDUSTRIAL BOILERS3
Fuel type
Bituminous
coal
Residual oil
Furnace type
Pulverized
Stoker
Tangential
Wall
Control device
Multi cyclones
Scrubber
Multicyclones
Scrubber
None
Scrubber
None
Manganese
emission factor,
P9/Jb
29.4
6.3
47.3
1.3
6.5
1.3
6.5
Reference 9.
^Picograms per joule of heat input to the boiler; to convert from pg/J to
lb/1012 Btu, multiply by 2.33.
TABLE 5-7. EMISSION FACTORS FOR MANGANESE FROM COAL.
AND OIL COMBUSTION: COMMERCIAL/INSTITUTIONAL BOILERS'
Fuel type
Bituminous
coal
Residual oil
Distillate oil
Furnace type
Stoker
All
All
Control device
None
None
None
Manganese
emission factor,
pg/Jb
111
6.5
0.6
Reference 9.
Picorgrams per joule of heat input to the boiler; to convert from pg/J to
lb/1012 Btu, multiply by 2.33.
5-6
-------
TABLE 5-8. EMISSION FACTORS FOR MANGANESE FROM COAL
AND OIL COMBUSTION: RESIDENTIAL BOILERS3
Fuel type
Bitumirwus coal
Anthracite coal
Lignite coal
Distillate oil
Furnace type
All
All
All
All
Control device
None
None
None
None
Manganese
emission factor,
pg/Jb
2150
66.2
430
0.6
Reference 9.
Picograms per joule of heat input to the boiler; to convert from pg/J to
lb/1012 Btu, multiply by 2.33.
5.2 CEMENT PRODUCTION
Cement production is a potential source of manganese emissions because
manganese can be a component of the raw materials and because manganese-con-
taining fuels (e.g., coal and oil) are burned in the process kilns and dryers.
In 1981, approximately 67.6 million Mg (75.1 million tons) of cement was
produced in the United States. The manufacture of portland cement accounts
for about 98 percent of this total. Hydraulic cement, whiclh includes port-
land, natural, masonry, and pozzolan cements, is listed undsr SIC Code 3241.
Two methods are used for cement manufacture. In the dry method, feed
materials are sent to the process as dry solids. In the wet method, feed
materials are mixed with water and sent to the process as a slurry. Of the
total domestic cement output, about 42 percent or 28.4 million Mg (31.2 mil-
lion tons) is produced by the dry method and roughly 58 percent or 39.2 mil-
lion Mg (43.9 million tons) is produced by the wet method. The basic process
flow diagram for cement production by the wet and dry methods is shown in
Figure 5-1.
The raw materials used to make cement fall into four basic categories:
lime, silica, alumina, and iron. Approximately 1600 kg (3520 Ib) of dry raw
materials are required to produce 1 Mg (1.1 ton) of cement. The quarried raw
5-7
-------
QUARRYING RAW
MATERIALS
PRIMARY AND
SECONDARY
CRUSHING
RAW
MATERIALS
STORAGE
I
PR(
1
PR(
)RY
JCESS
RAW MATERIAL
PROPORTIONED
JET
DCESS
RAW MATERIAL
PROPORTIONED
_ GRINDING
HILL
^ GRINDING
f MILL
AIR
SEPARATOR
—i
WATER
tn
i
oo
GYPSUM
CEMENT
PRODUCT
A MANGANESE EMISSION SOURCE
Figure 5-1. Basic process flow diagram for wet and dry cement production.
-------
materials are crushed to a suitable size before they enter either the wet or
dry processing loop. Regardless of the type of process used, the materials
are proportioned, ground to a finer size, and blended before the primary
cement production steps are begun.
In the dry process, the moisture content of the raw material is reduced
to less than 1 percent either before or during the grinding operation. The
.t v
dried materials are ground to a powder, blended to the prescribed proportion,
and fed directly into an inclined rotary kiln. The powdered raw materials are
fed into the upper end of the kiln and travel slowly to the lower end. The
kilns are fired from the lower end, and the hot gases pass upward and through
the raw materials. Drying, decarbonating, and calcining occur as the material
travels through the heated kiln and finally fuse to form what -"s known as
clinker. The clinker is then cooled, mixed with about 5 percent gypsum by
weight, and ground to a final product size. The product is then stored for
packaging and shipment.
In the wet process, a slurry is made by adding water to the raw materials
prior to the initial proportioning and grinding. Excess water is then removed
and the slurry is blended, mixed, and adjusted to achieve the proper composi-
tion. This homogeneous mixture (which is fed to the kilns) is usually either
a slurry of 30 to 40 percent moisture or a wet filtrate of about 20 percent
moisture. Wet process kilns are usually longer than dry prccess kilns, as
water must be evaporated in the first part of the kiln. The remaining steps
(kiln burning, clinker cooling, and gypsum addition) are the same as those in
the dry process. The dry process is more fuel-efficient because less energy
is needed to evaporate the water before clinker formation. Most new plants
use the dry process.
5.2.1 Emissions and Emission Factors
Manganese emissions consist largely of manganese-containing particulate
originating from the raw materials; however, particulate and manganese emis-
sions generated by fuel combustion are also present. The major manganese
emission source is the rotary kiln. Lesser amounts are emitted from grinding
mills and the clinker cooler. In the initial grinding stage, emissions are
higher at dry-process plants than at wet-process plants.
Most plants in the cement industry use controls such as multicyclones,
ESP's, ESP's with cyclones, and fabric filters. Both fabric filters and
5-9
-------
modern ESP's have participate removal efficiencies in excess of 99 percent.
Multicyclones are about 80 percent efficient. In 1979, the New Source Per-
formance Standards based on 99 percent removal efficiency were being met by 96
percent of the new sources.
Few direct measurements of manganese emissions from cement plants have
been made; however, total particulate emissions from each stage of the process
have been reported in References 1 and 3, and the manganese content of emis-
sions (References 1 and 2) has also been measured. The Mn content of kiln
dust measured varies widely. Two reported values are 130 ppm (Reference 1)
and 900 ppm (Reference 2). All of these values were to calculate the emission
factors shown in Table 5-9.
TABLE 5-9. MANGANESE EMISSION FACTORS FOR CEMENT PLANTS0
Emission Source
Control
Mn emissions factor,
Kg/103 Mg (lb/103 tons)
of cement produced
Dry process
Kiln
Dryers and grinders
Wet process
Kilns
Dryers and grinders
Clinker cooler
Uncontrolled
ESP
Fabric filter
Uncontrolled
Uncontrolled
ESP
Fabric filter
Uncontrolled
Fabric filter
Gravel bed
Wet scrubber
61 (122)
0.0105 - 0.0625 (0.021 - 0.125)
0.0065 - 0.062 (0.013 - 0.124)
24 (48)
57 (114)
0.01 - 0.071 (0.02 - 0.142)
0.0245 - 0.066 (0.049 - 0.132)
8 (16)
0.0025 - 0.03 (0.005 - 0.061)
0.011 - 0.022 (0.023 - 0.045)
0.011 (0.022)
Manganese emission factors were obtained by multiplying particulate factors
from References 1 and 3 by 0.05 percent (the percentage of manganese in
particulate emissions). Manganese is probably present as an oxide.
5-10
-------
5.2.2 Source Locations
Table 5-10 lists the locations of cement plants in the United States.
TABLE 5-10. LOCATION OF CEMENT PLANTS IN THE UNITED STATES3
State(s)
Plants active
(as of December 31, 1980)
New York and Maine
Pennsylvania, Eastern
Pennsylvania Western
Maryland and West Virginia
Ohio
Michigan
Indiana
Illinois
Tennessee
Kentucky, North Carolina, Virginia
South Carolina
Florida
Georgia
Al abama
Louisiana and Mississippi
Nebraska and Wisconsin
South Dakota
Iowa
Missouri
Kansas
Oklahoma
Texas
Wyoming,
and Arkansas
Montana,
Colorado, Arizona
Washington
Oregon and Nevada
California, North
California, South
Hawaii
Puerto Rico
and Idaho
, Utah, New Mexico
9
11
4
4
5
7
5
4
6
3
3
6
3
7
4
5
1
5
7
5
5
19
4
8
4
3
4
8
2
2
Total
163
Reference 4.
5-11
-------
References for Section 5.2
1. Barrett, K. W. A Review of Standards of Performance for New Stationary
Sources - Portland Cement Industry. EPA-450/ 3-79-012, March 1979.
2. Anderson, D. Emission Factors for Trace Substances. EPA-450/2-73-001,
December 1973.
3. IUS. Environmental Protection Agency. Compilation of Air Pollutant
Emission Factors. AP-42, Supplement 14, May 1983.
4. U.S. Department of Interior. Minerals Yearbook. Vol. 1. Bureau of
Mines. 1980.
5.3 MUNICIPAL REFUSE AND SEWAGE SLUDGE INCINERATION
Manganese emissions can result from the incineration of municipal refuse
and sewage sludge. Table 5-11 shows typical manganese levels in such wastes.
Concentrations of manganese in municipal sewage vary widely, depending on the
sewered industrial population, the mixing of storm and sanitary sewage, and
the amount of infiltration of material other than sewage sludge.
TABLE 5-11. MANGANESE CONCENTRATIONS IN MUNICIPAL REFUSE
AND SEWAGE SLUDGES
(ppm)
Waste type
Municipal refuse
Sewage sludge
Range
50-480
100-8800
Mean
85
1190
Reference
1
2
Municipal incineration is a process that reduces the volume of solid
waste by burning. Some incinerators are best suited for incineration of a
waste with particular physical characteristics. Typical municipal refuse
incinerators consist of either refractory-lined or water-walled combustion
3
chambers with a grate upon which refuse is burned. Figure 5-2 shows the
basic configuration of a municipal refuse incinerator. The manganese-laden
exhaust gases are commonly sent to a control device before being emitted to
the atmosphere. Sewage sludges are typically combusted in multiple-hearth,
5-12
-------
en
i
CO
\
X
*
5
SUPERSTRUCTURE
1
\
X
X
CURTAIN
WALL \
/ \ X
/-*— CURTAIN \
7 WAI L \
\ j
X
\
MANGANESE-
LADEN GASES
rn rnwTDni -M.
INCLINED CHARGING AND
BURNING GRATE
DEVICE OR TO
ATMOSPHERE
CHAMBER
ASH AND CLINKER
DISCHARGE
HORIZONTAL BURNING GRATE
•v
\\\\\\\\\\\\\\\\\\\\\\\ \ \
FURNACE
ACCESS
DOOR
\\\\\\\
\\
Figure 5-2. Basic configuration of a municipal refuse incinerator.'
-------
fluidized-bed, or rotary kiln incinerators. Figures 5-3, 5-4, and 5-5 are
schematics of a multiple-hearth, a fluidized-bed, and a rotary-kiln incin-
erator system, respectively.
5.3.1 Emission Factors
Manganese emissions from municipal refuse and sewage sludge incineration
L \
are a function of 1) the manganese concentration of the refuse or sludge, 2)
the amount of manganese adsorbed on particulate or volatilized in the gas
stream, and 3) the type of air pollution controls used. The combustion
temperature of the incinerator can influence the volatilization of the manga-
nese species and increase emissions. Multiple-hearth and fluidized- bed
incinerators operate at temperatures of 1030-1370K; rotary-kiln incinerators
4
sometimes operate at even higher temperatures. In fluidized-bed units, the
velocity of the fluidizing air, which controls the rate of elutriation, also
affects atmospheric manganese emissions. Over the years, the control systems
used on municipal incinerators have evolved from systems that simply reduce
gas velocity in settling chambers to sophisticated electrostatic precipitators
that remove up to 99 percent of all particulate matter. Wet scrubbers and (to
a lesser extent) fabric filter systems are also used.
Table 5-12 presents manganese emission factors for controlled and uncon-
trolled municipal refuse and sewage sludge incinerators. This table shows
that incinerators equipped with electrostatic precipitators or scrubbers emit
only a very small fraction of the manganese typically present in the incoming
waste. The emission factors for municipal refuse incinerators are based on
two measurements, whereas those for the multiple-hearth and fluidized-bed
sewage sludge incinerators are based on four and three measurements, respec-
tively. No data were available on emission factors for manganese from rotary
kiln incinerators.
The city of Gal latin, Tennessee, burns municipal wastes in two 100-ton-
per-day rotary combustors and uses the heat to produce steam. Measured un-
controlled manganese emissions were 0.030 kilogram per megagram of waste
(0.060 pound per ton); 95 percent by weight of the manganese was found in the
particles larger than 3.9 micrometers. In contrast, appreciable fractions of
the total arsenic, cadmium, zinc, mercury, lead, antimony, and tin were found
in the
-------
en
en
MANGANESE EMISSIONS
TO ATMOSPHERE
MANGANESE EMISSIONS
TO ATMOSPHERE
VACUUM
FILTERS
SLUDGES
FILTRATE
BURNERS
(FUEL OIL, GAS, LIQUID
AND GASEOUS WASTE)
AIR
MULTIPLE-
HEARTH
INCINERATOR
INDUCED
DRAFT FAN
SCRUBBERS
WATER
AIR
BLOWER
ASH TO
DISPOSAL
ASH SLURRY TO
FILTRATION AND
ASH DISPOSAL
Figure 5-3. Schematic of a typical multiple-hearth incineration system.
-------
SLUDGE
INLET
FLUIDIZING
AIR
MANGANESE-LADEN
FLUE GASES
TO CONTROL DEVICE
FLUIDIZED MEDIA
GAS DISTRIBUTION
PLATE
SOLIDS OUTLET
i
Figure 5-4. Schematic of a fluidized-bed sewage sludge incinerator.
5-16
-------
CHARGING CHUTE
OVERFIRE AIR DUCTS
UNDERFIRE
AIR DUCTS
MANGANESE-LADEN GASES
FORCED
DRAFT FAN
RESIDUE CONVEYORS
Figure 5-5. Schematic of a typical municipal rotary-kiln
incineration facility.4
5-17
-------
TABLE 5-12. EMISSIONS FACTORS FOR MANGANESE FROM MUNICIPAL
REFUSE AND SEWAGE SLUDGE INCINERATORS9
Incinerator
type
Control
device
Manganese emission factor,
kg/Mg (lb/ton)
of waste incinerated
Municipal refuse
Municipal refuse
Sewage sludge
multiple-hearth
Sewage sludge
fluidized-bed
None
Electrostatic
precipitator
Wet scrubber
Wet scrubber
0.025 (0.05)
0.005 (0.01)
0.002 (0.004)
0.0003 (0.0006)
References 6 and 7.
5.3.2 Source Locations
Table 5-13 presents a breakdown (by state) of the number of municipal
refuse and sewage sludge incinerators in the United States. In 1978, a total
of 106 municipal refuse and 358 sewage sludge incinerators were in operation
nationwide. Information on the specific locations of these facilities can be
found in the Compliance Data System or National Emissions Data System main-
tained by the U.S. Environmental Protection Agency.
References for Section 5.3
1. Gerstle, R. W., and D. N. Albrinck, Atmospheric Emissions of Metals From
Sewage Sludge Incineration. J. of Air Pollution Control Association,
32(11):1119-1123, 1982.
2. Edwards, L. 0., et al. Trace Metals and Stationary Conventional Combus-
tion Processes. Vol. 1. EPA-600/7-80-155a, August 1980.
3. Helfand, R. M. A Review of Standards of Performance for New Stationary
Sources - Incinerators. EPA-450/3-79-009, March 1979.
4. Mason, L., and S. Unger. Hazardous Material Incinerator Design Criteria.
EPA-600/2-79-198, October 1979.
5. Liptak, B. G. Environmental Engineers' Handbook. Vol. III. Chilton
Book Company, Radnor, Pennsylvania. 1974.
5-18
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TABLE 5-13. POPULATION OF MUNICIPAL REFUSE AND SEWAGE SLUDGE
INCINERATORS IN THE UNITED STATES, 1978a
State
Alabama
Alaska •* *
Arkansas
California
Connecticut
Delaware
Florida
Georgia
Hawaii
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Missouri
Nebraska
Nevada
New Hampshire
New Jersey
New York
North Carolina
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
South Carolina
Tennessee
Texas
Utah
Virginia
Washington
West Virginia
Wisconsin
Total
Number of municipal
refuse incinerators
16
1
8
4
1
3
1
3
2
2
7
31
6
10
1
2
2
2
4
106
Number of sewage
sludge in:inerators
1
6
2
18
11
3
8
2
6
10
4
4
•4
6
1
7
15
55
11
16
2
3
5
17
32
5
27
2
1
21
5
3
9
9
15
5
3
4
358
Reference 3.
5-19
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6. Cooper Engineers. Air Emission Tests of Solid Waste Combustion in a
Rotary Combustor/Boiler System at Gal latin, Tennessee. Prepared for West
County Agency of Contra Costa County, California. July 1984.
7. Anderson, D. Emission Factors for Trace Substances. EPA-450/2-73-001,
December 1973.
5.4 MANGANESE FUEL ADDITIVES
Manganese organometallic compounds are used as fuel additives. The most
important is tricarbonylmethyl-cyclopentadienylmanganese [CH,C,-H4Mn(CO)3].
Usually known as MMT, this additive is used as an octane enhancer in leaded
gasoline. Other manganese carbonyls and substituted carbonyls are used as
smoke suppressants in diesel fuel, residual fuel oil, and jet fuel. Most of
the additives (about 99 percent) are burned along with the fuel and the manga-
1 2
nese is converted to the oxide, Mn,0A. Manganese in unburned and spilled
. i 2
fuel is rapidly converted by sunlight to manganese oxides and carbonates. *
Ethyl Corporation (the only producer of MMT) developed this additive in
1957; however, its use was limited because it is much more expensive than
tetraethyl and tetramethyl lead. When lower lead levels in gasoline were
mandated, MMT was used as a partial lead replacement. At levels of 1/8 to 1/2
gram per gallon of gasoline, MMT enhanced the octane improvement achieved by
3 4
lead compounds. Subsequently, studies at General Motors * found that MMT
contributed to the plugging of catalytic converters, and studies at Ford
concluded that MMT had an adverse effect on the control of hydrocarbon emis-
sions. In another study, the investigator concluded that MMT did not have
adverse effects at levels of 1/4 gram per gallon of gasoline.
An EPA statistical evaluation of all published reports led to the fol-
lowing conclusions, which have a confidence level of at least 98 percent:
0 MMT was strongly suspected of having an adverse effect on the
oxygen sensors used in catalytic converters.
0 Some increased potential for catalyst plugging was evident with
increased use of MMT.
0 MMT caused or contributed to the failure of motor vehicles to
comply with hydrocarbon emission levels.
5-20
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Because the case for the benefits of using MMT, such as catalyst enhance-
ment and fuel economy, could not be established, EPA has prohibited the use of
MMT in unleaded gasoline. The EPA is also requiring the phase-out of the use
o
of MMT in leaded gasoline.
5.4.1 Processing Procedures
t1
It was not clear which of the number of procedures for making MMT de-
scribed in Ethyl Corporation's patents is used in the manufacturing process.
9 10
Information from published work ' make it apparent high carbon monoxide
pressures (300 atmospheres typical), elevated temperatures (200°C typical),
and strongly reducing conditions are common to all procedurss. The following
are examples:
0 Manganese chloride, methyl cyclopentadiene, carbon monoxide, and
magnesium metal are reacted at 200°C and 300 atmospheres in dimethyl -
formamide solution to which amines have been added. The yield is 70
percent.
0 The pyridine complex of manganese chloride, magnesium metal, methyl-
cyclopentadiene, and carbon monoxide are reacted under heat and
pressure (conditions not specified) in dimethylformamide solution
and in the presence of hydrogen gas. The yield is; 80 percent.
0 Manganese chloride is reacted with the molten magnesium methylcyclo-
pentadiene salt and carbon monoxide under heat and pressure. The
yield is 37 percent.
0 Manganese carbonyl, MN2(CO)xo (also a fuel additive), is prepared by
reacting manganese acetate, triethyl-aluminum, and carbon monoxide
under pressure in diisopropyl ether solution. The yeld is 50 to 60
percent.
These reactions take place in closed reactors, and the reactor must be
carefully depressurized and cooled to ambient or near-ambiert temperatures to
prevent the volatilization of noxious, toxic, and expensive solvents and the
escape of carbon monoxide.
5.4.2 Emissions
Combustion Emissions—
A publication fron
that indicated hydrocarbon emissions increased linearly with MMT levels in
A publication from Ethyl Corporation described a mathematical model
5-21
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fuel and that MMT enhanced catalytic converter efficiency. The finding regard-
12
ing increased emissions supported EPA's position. A 1983 patent indicated
that hydrocarbon emissions from vehicles fueled with MMT-containing gasoline
were reduced by 27 percent by the addition of 1,3 dioxolane. The patent did
not indicate whether the inventor had any corporate affiliation. Such an
additivtev could extend the use of MMT.
Approximately 500 tons of manganese-containing fuel additives were used
in 1974.13 Peak U.S. production was 3750 tons in the 12 months prior to MMT's
ban in September 1978. Based on a manganese content of 24.7 percent in the
MMT, and conservatively assuming that all manganese is exhausted to the atmos-
phere, this corresponds to annual manganese emissions of 930 tons from fuel
combustion. Data are not available on the actual percentage of manganese from
MMT that is exhausted. Only about 0.1 percent of MMT is emitted unburned from
the tail pipe. Most of the manganese is converted to Mn,0/,. Current
O T"
emissions due to manganese-containing fuel additives are lower and decreasing.
Evaporation—
The evaporation of MMT and other manganese carbonyls is probably not a
source of significant manganese air emissions. Commercial MMT is a dark
orange liquid that solidifies at -2CC (28°F) and has a boiling point of 233°C
(451°F).1 The flash point is above 110°C (230°F), and the density is 1.38
grams per milliliter or 11.5 pounds per gallon. Typically, gasoline is 90
percent distilled at 167°C (333°F), and the dry point is 209°C (408°F).15
Hence, MMT is appreciably less volatile than gasoline. Other manganese car-
bonyls have similar volatilities. Therefore, evaporative losses from fuel
tanks are not a significant source of manganese emissions.
Process Losses--
The manufacture of MMT (because of its low volatility) and other manga-
nese-containing fuel additives is not a source of significant manganese air
emissions. Process yields, however, are substantially less than 100 percent,
and there may be significant amounts of manganese-containing hazardous wastes
that would require careful disposal to avoid ground-water contamination.
5-22
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References for Section 5.4
1. Unzelman, G. H. Manganese Gains Stature as Octane Improves for Unleaded
Gasoline. The Oil and Gas Journal, 73(46):49-57, 1975.
2. Ter Haar, G. L., et al. Methylcyclopentadienyl Manganese Tricarbonyl As
An Antiknock. Composition and Fate of Manganese Exhaust Products.
J. Air Pollution Control Association, 25(8):858-60, 1975.
.t *
3. Furey, R. L., and J. C. Summers. How MMT Causes Plugging of Monolithic
Converters. Available from the Society of Automotive Engineers. Report
CONF-780208-46, 1978.
4. Berson, J. D. Manganese Fuel Additive (MMT) Can Cause Vehicle Problems.
SAE Technical Paper 770655, 1977.
5. Holiday, E. P., and M. C. Parkinson. Another Look at the Effects of
Manganese Fuel Additive (MMT) on Automotive Emissions. In: Proceedings
of Annual Meeting of Air Pollution Control Association. 71st Volume 4,
Paper No. 54.2, 1978.
6. Lenane, D. L. Effect of MMT on Emissions From Production Cars. Avail-
able from the Society of Automotive Engineers. Report CONF-780208-44,
1978.
7. Wallace, J. S., and R. J. Garbe. Effect of MMT on Exhaust Emissions.
Available from Society of Automotive Engineers. Report 790707, 1979.
8. Federal Register Citations 43 FR4 1414 (September 18, 1978) and 46 Fr
58360 (December 1, 1981) relating to denial of waivers to use manganese
additives as requested by Ethyl Corporation.
9. King, R. B. Transition Metal Organometallic Chemistry. Academic Press,
New York. 1961. pp. 93-104.
10. Dub, M. Organometallic Compounds. Volume 1, Second Edition, First
Supplement. Springer-Verlas, New York. 1963. pp. 255-257.
11. Hughmark, G. A., and B. A. Sobel. A Statistical Analysis of the Effect
of MMT Concentrations on Hydrocarbon Emissions. SAE Technical Paper
800393, 1980.
12. Somorjai, G. A. Fuel Compositions and Additive Mixtures for Reducing
Hydrocarbon Emissions. U.S. 4,390,345, June 28, 1983.
13. U.S. Environmental Protection Agency. Scientific and Technical Report
on Manganese. EPA-600/6-74-002, April 1975.
14. U.S. Environmental Protection Agency. Health Assessment Document for
Manganese. EPA 600/8-83-013F, May 1984.
15. Lane, J. C. Gasoline and Other Motor Fuels. Kirk-Othmer Encyclopedia
of Chemical Technology, 3rd. Edition, Volume 11. John Wiley-Intersci-
ence, New York. 1981. pp. 652-694.
5-23
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SECTION 6
.* ' SOURCE TEST PROCEDURES
6.1 LITERATURE REVIEW OF SAMPLING METHODS I
Sampling stationary source emissions for manganese requires a procedure
that provides representative samples; therefore, sampling must be done iso-
kinetically with a sampling train that has a high efficiency for removing
manganese. The EPA Method 5 source sampling train, Figure 6-1, is the basic
sampling system used to obtain representative particulate emission samples
from stationary sources. A heated glass-fiber filter with a collection
efficiency of 99.95 percent for particles 0.3 mm in diameter provides the main
particulate sample collection surface. Large particles are also caught in the
probe and nozzle. Particulate matter recovered from the probe, nozzle, fil-
ter, and front-half of the filter holder are defined as the particulate sample
used to calculate emissions from sources subject to New Source Performance
Standards. The impinger section of the Method 5 sampling train is efficient
for collecting particles that penetrate the filter media and aerosols. If
necessary, the impinger contents can be recovered and analyzed.
6.2 LITERATURE REVIEW OF ANALYTICAL PROCEDURES
6.2.1 Wet Chemical Method
The Periodate Method is the classic wet-chemical method of analyzing air
p
samples for manganese. The nature of this method is such that it can be used
in almost any chemical laboratory with relatively simple equipment. If neces-
sary, the final colorimetric estimation can be made satisfactorily with Nes-
sler tubes. During analysis of very low concentrations, it is difficult to
get and maintain complete oxidation of the manganese to permanganate. Also,
the sensitivity of this method is rather poor compared with that of other
methods.
6-1
-------
I
NJ
THERMOMETER
HEATED AREAv V /FILTER HOLDER
STACK WALL
— v_
Mr—
^n==
TUBE
1
s\\i
^
1
TEMPERATURE
SENSOR
lui ,
^^Hj,
PITOT
MANOMETER
3
-
— f
— 1
)
:
i
1
-n— '
/THERMOMETER
/
THERMOMETER
ORIFICE
ICE WATER BATH
BY-PASS
VALVE
VACUUM GAUGE
Q .
VACUUM LINE
MAIN VALVE
VACUUM PUMP
Figure 6-1. Schematic of Method 5 sampling train.
-------
6.2.2 Spectrographic Method
The spectrographic method has been used for some time to determine trace
metals, including manganese, in air samples. Cholak and Hubbard described a
spectrochemical method in which the manganese is isolated from interferences
and concentrated in a small volume by complexing it with sodium diethyl-dithio-
carbonate and extracting it with chloroform before analysis with the spectro-
graph. Tabor and Warren briefly discuss a semiquantitative method suitable
for estimating trace metals, including manganese, in samples collected on
glass-fiber filters such as those used in air sampling. The advantages of
spectroscopy are that it can be made specific (or nearly so) fcr almost any
element, its sensitivity is adequate for most types of air samples, and it can
be used for concurrent determination of a number of elements in the same
sample.
6.2.3 Atomic Absorption
Salvin described the use of atomic absorption analysis for trace metals,
including manganese, in the atmosphere. The advantages of this method over
the others are that it is relatively simple to use and it is highly specific
for a given element. Also, its sensitivity is as good or, in many cases,
better than that of other methods. When glass-fiber filters are used, silica
extracted from the fibers can interfere with the determination of manganese,
zinc, iron, and other elements unless they are removed by the presence or
addition of calcium to the solution before analysis.
6.2.4 Neutron-Activation Analysis
Neutron-activation analysis is most suitable for the analysis of very low
concentrations (nanogram range) of manganese. The use of this method for air
samples is described by NiFong, et al., and Dams, et al. * The principal
disadvantage of this method is that it is necessary to have access to a suit-
able neutron source.
6-3
-------
References for Section 6
1. Standards of Performance for New Stationary Sources. Federal Register,
42 (160), August 18, 1977.
2. American Conference of Governmental Industrial Hygienists. Manual of
Analytical Methods Recommended for Sampling and Analysis of Atmospheric
Contaminants. 1958.
3. Chrflak, J., and D. M. Hubbard. Determination of Manganese in Air and
Biological Material. Amer. Ind. Hyg. Assoc. J., 21:356-360, 1960.
4. Tabor, E. C., and W. V. Warren-. Distribution of Certain Metals in the
Atmosphere of Some American Cities. A.M.A. Arch. Ind. Health, 17:145-
151, 1958.
5. Salvin, W. Atomic Absorption Spectroscopy. Interscience Publications,
New York. 1968.
6. Nifong, G. D., E. A. Boettnee, and J. W. Winchester. Particle Size
Distributions of Trace Elements in Air Pollution Aerosols. Amer. Ind.
Hyg. Assoc. J.
7. Dams, R., et al. Nondestructive Neutron Activation Analysis of Air
Pollution Particulates. Anal. Chem., 42:861-867, 1970.
6-4
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO.
EPA-450/4-85-007h
3. RECIPIENT'S ACCESS ON NO.
4. TITLE AND SUBTITLE
Locating And Estimating Air Emissions From Sources Of
Manganese
5. REPORT DATE
September 1985
S. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
Office Of Air Ouality Planning And Standards (MD 14)
U. S. Environmental Protection Agency
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
EPA Project Officer:Thomas F. Lahre
16. ABSTRACT
To assist groups interested in inventorying air emissions of various
potentially toxic substances, EPA is preparing a series of documents such as this
to compile available information on sources and emissions of these substances.
This document deals specifically with manganese. Its intended audience includes
Federal, State and local air pollution personnel and others interested in
locating potential emitters of manganese and in making gross estimates of air
emissions therefrom.
This document presents information on 1) the types of sources that may emit
manganese, 2) process variations and release points that may be expected within
these sources, and 3) available emissions information indicating the potential
for manganese release into the air from each operation.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDE-.D TERMS C. COSATI Field/Group
Manganese
Emissions Sources
Locating Air Emission Sources
Toxic Substances
18. D STRIBUTION STATEMENT
EPA Form 2220—1 (Rev. 4—77) PREVIOUS eo TION s OBSOLETE
19. SECURITY CLASS (ThisReport;
21. NO. OF PAGES
118
20. SECURITY CLASS (This page)
22. PRICE
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