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

-------
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

-------
                                    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

-------

-------
                                    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

-------
                             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

-------
                                    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)

-------
                              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

-------
                             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

-------

-------
                                  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

-------
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

-------
                                  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

-------
     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

-------
                                  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

-------
           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

-------
     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

-------
                     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)

-------
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)

-------
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.

-------
        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

-------
        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

-------
 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

-------
           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

-------
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

-------
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

-------
            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

-------
               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

-------
 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

-------
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

-------
     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

-------
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

-------
  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

-------
            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

-------
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

-------
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

-------
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

-------
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

-------
          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

-------
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

-------
       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

-------
 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

-------
     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

-------
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

-------
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

-------

-------
                                 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

-------

-------