APTD-1509
   NATIONAL INVENTORY
               OK soi |{< i:s
           AND EMISSIONS:
        MANGANESE - 1968
I .S. ENVIRONMENTAL PROTECTION AGENCY
    Office of Air and Water Programs
 Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711

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                                    APTD-1509


  NATIONAL INVENTORY


                OF


SOURCES AND EMISSIONS:


     MANGANESE - 1968



                 by

         W. E. Davis § Associates
           9726 Sagamore Road
            Leawood,  Kansas
         Contract No.  CPA-70-128
     EPA Project Officer:  C. V. Spangler
             Prepared for


       ENVIRONMENTAL PROTECTION AGENCY

       Office of Air and Water Programs
   Office of Air Quality Planning and Standards

      Research Triangle Park, N.C. 27711


             August  1971

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The APTD (Air Pollution Technical Data) series of reports is issued by
the Office of Air Quality Planning and Standards, Office of Air and
Water Programs, Environmental Protection Agency, to report technical
data of interest to a limited number of readers.  Copies of APTD reports
are available free of charge to Federal employees, current contractors
and grantees, and non-profit organizations - as supplies permit - from
the Air Pollution Technical Information Center, Environmental Protection
Agency, Research Triangle Park, North Carolina 27711 or may be obtained,
for a nominal cost, from the National Technical Information Service,
5285 Port Royal Road, Springfield, Virginia 22151.
This report was furnished to the Environmental Protection Agency
in fulfillment of Contract No. CPA-70-128.  The contents of this report
are reproduced herein as received from the contractor.  The opinions,
findings and conclusions expressed are those of the author and not
necessarily those of the Environmental Protection Agency.  The report
contains some information such as estimates of emission factors and
emission inventories which by no means are representative of a high
degree of accuracy.  References to this report should acknowledge the
fact that these values are estimates only.
                       Publication No. APTD-1509
                                   11

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                        PREFACE







This report was prepared by W.  E. Davis & Associates pursu-





ant to Contract No. CPA 70-128  with the Environmental Pro-





tection Agency,  Office of Air Programs.







The inventory of atmospheric emissions has been prepared to




provide reliable information regarding the nature, magnitude,




and extent of the emissions of manganese in the  United States




for the year 1968.







Background information concerning the  basic characteristics




of the manganese industry has been assembled and included.





Process descriptions are given,  but they are brief, and are





limited  to the areas that are closely related to existing or po-





tential atmospheric losses of the pollutant.







Due to the limitation of time and funds allotted for the study,




the plan was to personally contact about fifteen percent of the





companies in each major emission source group to obtain the




required information.  It was known that published data con-




cerning emissions of the pollutant was virtually nonexistent,




and contacts with industry ascertained that atmospheric emis-




sions  were not a matter  of record.
                             ill

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The manganese emissions and emission factors presented are





based on the  summation of information obtained from manufactur-




ing companies that represent  approximately eighty percent of the





total production,  and reprocessing companies that handle about





thirty percent of the manganese used in consumer products.  Air





pollution control equipment is in use at many of the manganese





reprocessing facilities, but its use at processing plants is limited.







Manganese emissions and emission factors are considered to be





reasonably accurate.
                                   IV

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                  ACKNOWLEDGEMENTS







This was an industry oriented study and the authors express





their appreciation to the many companies and individuals in





the manganese industry for their contributions.







We wish to express  our gratitude for the assistance of the




various societies and associations,  and to the many branches





of the Federal and State Governments.







Our express thanks  to Mr. C. V. Spangler,  Project Officer,




Office of Air Programs, for his helpful guidance.

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                     CONTENTS
SUMMARY	     1

      Emissions by Source.	     2
      Emission Factors	     3

SOURCES OF MANGANESE	     4

MATERIAL FLOW

      Material Flow Chart	     6
      Mining	     7
      Imports and  Exports	     8
      Manganese Stocks	     8
      Processing	     9
      Reprocessing 	    10
           Carbon Steel	    10
           Other Steel	    11
           Cast Iron	    11
           Welding Rods	    12
           Nonferrous Alloys	    12
           Batteries	    13
           Chemicals   	    14

EMISSIONS

      Mining	    15
      Processing	    17
           Manganese Metal   	    17
           Manganese Alloys	    20
      Reprocessing 	    26
           Carbon Steel	    26
           Other Steel	    35
           Cast Iron	    37
           Welding Rods	    38
           Nonferrous Alloys	,  .  . .  .    40
           Batteries	    42
           Chemicals and Other Uses	    44
                               vn

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      Consumptive Uses	     48
           Coal	     48
           Oil	     51
      Incineration and Other Disposal	     55
           Sewage and Sludge	     55
APPENDIX A
      Companies Dealing in Manganese and
       Manganese Compounds	     56
TABLES

Table I
      Uses of Manganese Ore	      9
Table II
      Properties of Particulate Matter from a
       Ferromanganese Blast Furnace	     22
Table III
      Spectrographic Analyses of Particulate Discharge
       from an Open-Hearth Furnace	     30
Table IV
      Particle Size Distribution of Fume from a
       Basic Oxygen Furnace	     32
Table V
      Composition of Fume and Dust from Basic
       Oxygen Furnaces 	     32
Table VI
      Electric Arc Steel Furnace Fume
       Particle Size	/	     34
Table VII
      Typical Emissions from an Electric
       Arc Furnace	     36
Table VIII
      Typical Analysis of Welding Rod Coatings ....     39
Table IX
      Average Manganese Content in Ash of Coal   ...     49
Table X
      Manganese Content of Domestic Crude Oils  ...     52
                            Vlll

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                           -1-
                        SUMMARY







The flow of manganese in the  United States has been traced and




charted for the year 1968.  The consumption was  1, 150,000





tons while  domestic production was only 48, 000 tons.  Imports




principally from Brazil, Gabon,  Republic of South Africa,




Congo,  Guyana, India, Angola, and Australia totaled 1, 053, 000




tons.







Emissions to the atmosphere  during the year were 18,992 tons.





About 47 percent of the emissions resulted from the production




of ferroalloys and about 37 percent from the production of iron





and steel.  The combustion of coal was also a significant source





of manganese  emissions.







Emission estimates for mining, production of manganese metal,





and reprocessing operations are  based on data obtained by per-




sonal contact with processing  and reprocessing companies.

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                          -2-
Source Category


Mining


Processing
                 EMISSIONS BY  SOURCE
                           1968
Source Group
Reprocessing
Consumptive Uses
                      Manganese Metal

                      Manganese Alloys
                      Carbon Steel

                      Cast Iron

                      Welding Rods

                      Nonferrous Alloys

                      Batteries

                      Chemicals
                      Coal
                      Oil
Incineration and Other
  Disposal
                      Sewage and Sludge
Short Tons
                         325

                       8,946
                       4,340

                       2,770

                          24

                          60

                          90

                         300
                       1,950

                           7
                                 9,271
                                7, 584
                                 1,957
                                  175
                         175
          TOTAL
                                18,992

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                          -3-
                  EMISSION FACTORS
Mining
 0. 2 Ib/ton of manganese mined
Processing

   Manganese Metal
   Ferromanganese
     Blast Furnace
     Electric Furnace
   Silicomanganese
     Electric Furnace
 25. 0 Ib/ton of manganese processed

  4. 1 Ib/ton of ferromanganese produced
 23. 9 Ib/ton of ferromanganese produced

 69.4 Ib/ton of Silicomanganese produced
Reprocessing

   Carbon Steel
     Blast Furnace
     Open-Hearth Furnace
     Basic Oxygen Furnace
     Electric Furnace
   Cast Iron
   Welding Rods
   Nonferrous Alloys
   Batteries
   Chemicals
 22.5 lb/1,000
 51   lb/1,000
 44   lb/1,000
 78   lb/1,000
330   lb/1,000
 16   Ib/ton of
 12   Ib/ton of
 10   Ib/ton of
 10   Ib/ton of
tons of pig iron produced
tons of steel produced
tons of steel produced
tons of steel produced
tons of cast iron
manganese processed
manganese processed
manganese processed
manganese processed
Consumptive  Uses

   Coal
  7. 7 lb/ 1, 000 tons of coal burned

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                           -4-
                SOURCES OF MANGANESE







Manganese is a hard and very brittle metal that melts at 1, 260 C.




Its atomic weight is 54.93 and its specific gravity is 7.4.  It is a





relatively abundant element present in varying  quantities in about




ninety-five percent of the earth's crust.  Ore deposits of commer-





cial importance are found throughout the world.  The most import-




ant manganese-producing countries are Australia, Brazil, China,





Gabon,  Ghana, India,   the Republic of South Africa, and the





U.S.S.R..







The most common manganese minerals are pyrolusite, psilomela.ne,





braunite,  hausmannite,  rhodonite, and rhodochrosite.  They range in





color from red to brown and black, containing from forty to seventy




percent manganese.







In the United States ores containing manganese are found in Arizona,





Arkansas, Colorado, Maine,  Montana, Minnesota,  New Mexico,  and




South Dakota.  Most of the ore mined  in these states is manganiferous




ore (5 to 35 percent Mn content).  The United States is largely self-





sufficient with respect  to its use of manganiferous ore, but is almost




entirely dependent on other countries  for manganese ore (35 percent




or more Mn content).

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                           -5-
Manganese is also commonly found associated with iron ores,




usually in concentrations too low to make its commercial re-




covery economically feasible.

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SOURCES
         MANGANESE




MATERIAL  FLOW  CHART  -  1968




    Short Tons - Mn Content







                    USES

48,000
DOMESTIC
PRODUCTION
1,053.000
IMPORTS
15.000
^ EXPORTS
73.000 ^
GOVERNMENT
STOCK
^ Q nnn
INDUSTRY
STOCK




1. 160. 000 ,




850.000
FERRO-
MANGANESE
120,000
SILICO-
MANGANESE
10,000
SPIEGELEISEN
18. POO
BATTERIES
60. 000 >
CHEMICALS
26.000
ELECTROLYTIC
METAL
66. 000 jr
MISCELLANEOUS
149.000



1.001.000 ^




744.000 ^
CARBON STEEL"
150,000
ALL OTHER
STEEL
16.000
CAST IRON r\
WELDING RODS" > ^UNSUMER
10.000
NONFERROUS
ALLOYS
18.000 J
BATTERIES
60. 000 ^i
CHEMICALS '
                              PROCESS LOSSES
                                            Figure  I

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                           -7-


                 MATERIAL  FLOW

                        MINING


Manganese produced in the United States during 1968 was approxi-

mately 4 percent of the manganese consumed.  Manganese ore (35

percent or more Mn) was produced and shipped from Montana and

New Mexico.  Manganiferous ore (5 to 35 percent Mn) was produced

and shipped from Colorado,  Minnesota,  Montana, and New Mexico.


       MANGANESE PRODUCTION IN UNITED STATES l_l
                           1968

                                       Manganese  Content
	Short Tons	

Manganese Ore                                6,000

Manganiferous Ore                            42, 000

                               Total          48, 000
]- Personal Communication;.  U. S.  Department of Interior;
   Bureau of Mines:  August,  1970.

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                           -8-
                IMPORTS  AND EXPORTS


During 1968 imports of manganese ore were principally from

Brazil,  the Congo,  Gabon,  Ghana, India,  and  the Republic of

South Africa.  The  imports of manganese ore  totaled 1,83J,210

short tons (gross weight),  silicomanganese  imports for consump-

tion were 25, 142 short tons (gross weight),  and ferroma.nga.nese

imports were 207,677  short tons (gross weight)  /.  The man-

ganese content of the imports  was 1, 053, 000 short tons  /.


Exports of all forms of manganese during 1968 were 15, 000

short tons (Mn content)  /  including ferromanganese, manga-

nese and manganese alloys, waste and scrap,  ore, and concen-

trates containing more than 10 percent manganese.



                   MANGANESE STOCKS


During 1968 industry stocks of manganese in all. forms in-

creased 9, 000 short, tons (.Mn  content),  while  government.

stocks decreased 73,000 short tons (Mn content.)  /.
1- Minerals Yearbook;  Bureau of Mines;  1968.

2- Personal communication;  U. S. Department of Interior;
   Bureau of Mines; August,  1970.

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                           -9-
                     PROCESSING

The chief use of manganese ore (35 percent or more Mn) in the

United States is in the production of manganese metal,  ferro-

manganese, silicomanganese, and  spiegeleisen.  These prod-

ucts are used principally in the iron and steel industry.

Other important uses of smaller quantities of the  ore include its

use in the manufacture of chemicals, batteries, welding rods and

nonferrous alloys.

During  1968, manganese ore was used in the manner shown in

Table I.

                        TABLE I

            USES OF MANGANESE  ORE 1J
                           1968

                                            Short, Tons
          Use
	Mn  Content	

Manganese Metal (electrolytic)                 26, 000
Ferromanganese                              850, 000
Silicomanganese                               120,000
Spiegeleisen                                  10,000
Chemical Manufacture                         60, 000
Battery Manufacture                           18,000
Miscellaneous                                 66, 000
1- Personal communication;  U. S. Department of Interior;
   Bureau of Mines; August,  1970.

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                            -10-
                      REPROCESSING


In the United States the principal use of manga.nese is in the pro-

duction of carbon and alloy steels.  Metallurgical.ly, it is used

chief.ly as ferromanganese and to a lesser extent in the forms of

silicomanganese,  spiegeleisen and manganese metal.  For battery

manufacture,  it is used in the form of manganese dioxide.


In the chemical industry, manganese is used as  an oxidizing agent

in the manufacture of hydroquinone and  for-the production of

various chemicals including manganous oxide, manganous chloride,

potassium permanganate,  and manganese su.lfate.


The consumption of manganese in the United  States during 1968

has been reported at 1, 101, 000 short tons V.


CARBON STEEL

Manganese is  used in steelmaking, chiefly, to counteract, the

effects of sulfur; however, it also has other advantages. It has

some deoxidizing power and, when added in  certain proportions,

it can. act to harden and reduce the plasticity of  steel.


Steels that  contain too much sulfur tend to crack during rolling

operations;  a condition, known as  "hot shortness".  Excess sulfur
1- Personal communication;  U.  S.  Department of Interior:
   Bureau of Mines;  October, 1970.

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                           -11-
also tends to create surface imperfections during fabrication.

The use of manganese in steelmaking effectively prevents these

difficulties.  Most of the unwanted sulfur combines with the man-

ganese and is carried into the slag.


In the United States the use of manganese in carbon steel during

1968 was  744, 000 short tons _/.


OTHER STEEL

In addition to its  functions in the production  of carbon steel,

manganese is used as an alloying agent in special steels to

produce harder and tougher metals for special applications.  In

plain carbon steel the manganese content is  less than one percent,

but in one group of extremely hard and tough alloy stee.ls the man-

ganese content is from 10 to 14 percent.


During 1968, the  use of manganese in other  steels was 150, 000

short tons  /.


CAST IRON

The principal use of manganese-in^the~produclion of cast iron is
1- Personal communication;  U. ~S.. Department of Interior;
   Bureau of Mines;  October, 1970.

2- Personal communication;  U.  S. Department of .Interior;
   Bureau of Mines:  August,  1970.

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                           -12-
t;o nullify the effects of sulfur.
During 1968 the use of manganese in cast iron totaled 16, 000

short tons  /.
WELDING RODS

Manganese, in the dioxide form, has important uses in the man-

ufacture of welding rods and welding rod coatings.  Its principal

use is as an oxidizing agent.  The MnC^ content of typical weld-

ing rod  coatings is in the order of 1J percent.


During  1968 about 3, 000 short tons of manganese  were used in

the manufacture of welding rods  /.


NONFERROUS ALLOYS

Manganese is  important in many miscellaneous metallurgical

applications.  It is used in the production of aluminum and mag-

nesium  and it  is alloyed with copper to make manganese bronze.

It impa.rts stiffness and ha. rdness to aluminum and magnesium;

manganese also increases the corrosion resistance of magnesium.


The alloy,  manganese bronze, is a. complex b:r.ass.   It: has hot
1- Personal communication;  U.  S. Department of Interior;
   Bureau of Mines;  October, 1970.

2- Personal communication;  U.  S. Department of Interior;
   Bureau of Mines:  August,  1970.

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                            -13-
working properties, high strength,  and abrasion resistance.  It

is used extensively for ship propellers, boat shafting and other

similar applications.


In the United States, the use of manganese in nonferrous alloys

during 1968 was  10, 000 short tons _/.


BATTERIES

Synthetic ore is a term used chiefly to identify manganese di-

oxide that is produced chemically or electrolytically for use in

dry cell batteries. The Bureau of Mines define synthetic ore

as a material that is the equivalent of, or better than, natural.

ore, which can be put  to the same uses, a.nd is produced by

means other than ordinary concentrations, calcining,  sintering,

or nodulizing.


In batteries, manganese dioxide acts as a depola.rizmg agent.

Hydrogen released from the electrolyte of the cell tends to form

around the carbon electrode and slow down the cell a.ction.  Oxy-

gen provided by the manganese dioxide corrects this condition

by its reaction with the hydrogen.
1- Personal communication;  U. S. Department of Interior;
   Bureau  of Mines;  October,  19?0.

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                            -14-
During 1968 manganese used in batteries totaled 18,000 short

tons  ./.
CHEMICALS

Manganese dioxide ores are important in the manufacture of

manganese chemicals,  ma.ny of which are used as oxidizing

agents.  Manganese sulfate is used in fertilizers, fertilizer

additives, as a constituent of animaJ and poultry  feeds, as a

paint drier, as a coloring a.gent for ceramics and textiles, and

as a ba.se for other chemicals.  Manganous chloride is used  in

dyeing textiles,  and as  a ve.hic.le for alloying manganese with

ma.gnesium.  Manganous oxide is also used in a.nima] and poul-

try feeds, fertilizers, and welding applications.


Manganese used in the manufacture of chemicals du.rin.g  1968

totaled 60,000 short tons  ./.
1- Persona] communication;  U. S.  Department of Interior;
   Bureau of Mines:  August, 1970.

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                            -15-





                      EMISSIONS







                         MINING







Because of the marked differences in the manner in which man-




ganese deposits occur, a wide variety of mining methods are used.





In the United States,  in recent years, high grade manganese ore





has come from underground mines.  On the other hand,  manganif-




erous ores are usually mined in the same manner as iron ores




from the same district and,  in the United States, this has meant




open pit mines.







Before 1950, very few of the world's  manganese ore producers had





milling plants other than simple crushing,  screening and washing





installations.  This wa.s also the situation in the United States, ex-





cept in the State of Montana  where concentrating equipment was





used for  battery grade ores.  Due to the recent high rate of indus-





trial growth more producers have installed various k.inds of con--





ceint,rating  equipment, many  times including sintering a.nd  nodu.hz-




ing equipment to agglomerate fines and remove deleterious




impurities.







While this  study was  in progress, mining  companies were con.i.a.cted




concerning the quantity of ore mined,  its manganese content, and




the manganese emissions occuring during mining and concentration.




It was found that records of  manganese emissions  to the atmosphere




are not maintained.   Mosi of those contacted indicated losses >,o the

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                           -16-
atmosphere are slight,  occuring principally during ore handling




or crushing and due to wind loss from tailings.







Based on information obtained and observations made during




visits to mining locations,  the manganese emissions  to the at-




mosphere from  sources of mining are estimated at 0. 2 pounds




per ton  of manganese mined.  Manganese emissions to  the atmos-




phere during 1968 were 4.8 tons.

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                           -17-
                      PROCESSING







In the United States the principal use of manganese ore (35 percent




or more Mn) is in the production of manganese alloys and pure




manga.nese metal.







MANGANESE METAL




The process  currently used to produce pure manganese metal is




an electrolytic process consisting of four principal steps: roasting




of the ore, leaching,  purification of the leach liquor, and electro-





deposition Of the  manganese.   During roasting the primary object:





is to convert all manganese to the oxide form and at the  same





time leave as much iron as possible as Fe^O.;  however, most





ores treated  by this process are relatively low in iron and roasting




is at a high temperature to achieve  maximum recovery of manga-





nese without  regard to iron content.  When the iron content is




low it can be controlled by pH adjustment of the lea.ching  acid.







After grinding a.nd roa.sting,  the ore is leached with  anoJyte from




the electrolytic cell.   The concentration of the leach is adjusted




by addition of ammonium sulphate to maintain a concentra.tion of




about 140 grams/litre, and sulphuric acid to give a pH of about




2. 5.   After solution,  the leach liquor is neutralized to pH 6. 5




by adding ammonia,  milk of lime,  or calcined ore.  On neutrali-




zation of the  leach liquor,  iron and aluminum hydroxides are

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                            -18-
precipitated.  Overall ex.trac.t.ion of manganese f:rom the ore is





about 98 percent.







The neutral leach liquor contains small quantities of numerous





elements,  such as arsenic,  cobalt, copper, iron, lead,  molybde-





num,  and zinc which must be removed prior to electrolysis.   The





removal is accomplished by first treating the liquor with hydrogen




sulphide or ammonium sulphide,  then fi.l.?:e.ring to remove the





sulphides.  At this point most of the impurities have been removed




except colloidal sulphur a.nd small quantities of arsenic and molyb-





denum.  These are removed by the addition of iron in the form of




copperas.  The iron is oxidized at room temperature at a  pH of





6. 5 to 7. 0  and ferric hydroxide is precipitated;   the arsenic,




molybdenum,  and colloids are absorbed.  At. this stage the solu-





tion has been  purified a.nd is ready for feeding to the el.ec.trolyr.ic





cell.







The cell, consists  of an anode compartment and a. cathode com-




partment separated by a diaphragm.  The purified solution first




enters the  cathode compartment,  then flows through a. canvas





diaphragm into the a.node compartment and is discharged to a




storage tank for reuse.  The manganese is deposited at the





cathode of  the cell.

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                           -19-
The principal manganese emissions to the atmosphere that




occur are due to handling,  grinding, and roasting of the ore.




The data obtained regarding two electrolytic plants indicate




overall emissions average 25 pounds per  ton of manganese pro-




cessed.  In the year 1968 the atmospheric emissions of manga-




nese resulting from the production, of manganese metal totaled




.325 tons.

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                           -20-
MANGANESE ALLOYS





About 85 percent of the manganese ore consumed in the United




States during 1968 was used  to produce manganese alloys,  the





greater part of which was in the form of high, medium and low





carbon ferromanganese.  These and other alloys, including





silicomanganese and spiegeleisen,  are used principally by the




steel industry.







Air pollution controls  have not been satisfactory in the ferroalloy




industry;  thus a more intensive effort will be required in order




to provide adequate control of process emissions.  There a.re




numerous technical problems that must be  solved and the addition




of proper fume collection equipment is not  the only requirement




for  a satisfactory long-range solution. There a.re many  dust and




fume producing operations.  The dust (larger than 2 micron size)




that results from raw  material handline,  as we 1.1. a.s that  from




crushing and sizing of the product, can be handled by  conventional




techniques;  the major pollution problem  is associated with, the





ferroalloy furnaces and the collection of fume that is less than




2 microns in size.








About 65 percent of the ferromanganese is  made in blast furnaces




and the  remaining 35 percent in electric furnaces.  The blast




furnaces used in making ferromanganese  are the same type as




those used in making pig iron;  quite  often the same furnace is

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                           -21-
used to produce both products.  Ferromanganese is  often pro-

duced by operating a pig iron furnace on manganese  alloy pro-

duction long enough to obtain a supply of the alloy, after which

the blast furnace is returned to its normal operation of producing

pig iron.


The effluent from a ferromanganese blast furnace is reported to

be a greater air pollution problem than  that from an iron blast

furnace _/.  It is said to be the most, prolific pollution producer

of any  of the metallurgical processes _/.   One investigator has

reported that emissions from ferromanganese blast  furnaces, if

uncontrolled, are nearly ] 50 tons of dust per 1, 000  tons of metal.

produced _/.   Another invest-.i gator has reported the properties

of ferromanganese blast furna.ce fume as shown i.r. Tab.le II.


Electric furnaces used for making manganese ferroalloys are the

same type  as those used in making other ferroalloys a.nd, again,

the furnace used  is not always devoted, exclusively to making one

particula.r  product.  Jr. fact,  there is  often some inter change-

ability in scheduling production of the various ferroalloys.
1- Thring, N.  W. and Sarjant,  R.  J. ;  "Dust Problems of the
   Iron and Steel Industry";  Iron and Coal Traders Rev. ;
   Vol. 174:  Mar. 29, 1957.

2- Wurts,  T.  C. ;  "Industrial Sources of Air Pollution  -
   Metallurgical"; PHS Publ. 654;  1959.

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                            -22-
                         TABLE II
       PROPERTIES  OF  PART1CULATE MATTER
   FROM A  FERROMANGANESE BLAST FURNACE  J/
            Component
Content %
Manganese

Iron
Total alkali (as Na2O and
Silicon dioxide

Aluminum oxide

Calcium oxide (CaO)

Ma.gnesium oxide  (MgO)

Total, sulfur (as SO4)

Carbon


    Pa.rticle Size (a.verage)

    Appa.rent  Density
 15 to 25

0. 3 to 0.5

  8 to 15

  9 to 19

  3 to 11

  8 to 15

  4 to 6

  5 to 7

  .1. to 2
                                    0. 3 micron

                                    ]2 J.b/cu.  ft.
1- Bishop, C. A.  et al;  "Cleaning Ferromanganese B.la.st
   Furna.ce Gas";  Iron Steel Engine ei;  28;  -Aug.  1951.

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                            -23-
When using the conventional submerged arc electric furnace to





produce  manganese alloys, large quan.titi.es of carbon monoxide





a.re generated as a result of carbon, redxiction of metallic oxides.





This gas, along with other primary gas due to moisture in the





charge,  reducing agent volatile matter, and various products





of thermal decomposition, rises from the top of the furna.ce




carrying furr.e and  entrained micron-size particles of the  charge.




In an open furnace  all of the carbon monoxide burns with induced




air at the top of the charge,  resulting in a, large volume of high.




tempera.ture gas.   In a closed furnace most of the carbon  monox-





ide is removed without combustion with air.   Due to the steady





state operation of the  submerged arc  furnace,  gas generation is





continuous.







Additional fume is  generated at the  furnace ta.ph.oles, principally





the result of air flow induced by heat  transfer from the molten





metal or sl.a.g.  After  the taphole, there are other sources of





fume tha.t occur in.  handling the metal.  Because most furnaces




are tapped intermittently, these fumes occur  o.nly part of  the





operating time.







As mentioned above, the  fume size  is generally below 2 microns;




fume chemical analysis from the typical open-type furnace pro-




ducing ferromanganese shows the manganese  oxide content to be

-------
                           -24-
about: 33 percent.


In addition to the numerous intermittent and continuous gas

flows described,  other factors also contribute to the problem

of air pollution control.  Manganese ores contain volatile mat-

ter  and moisture that disturb the smooth operation of the fur-

nace.  Sudden release of gas results in substantial charge

ejection from  the furnace.


Normal gas flow from the typical closed furnace producing

ferromanganese is approximately  160  to 170 scfm per mega-

watt and peak  flows may be 40 percent higher.  From an open

furnace with, a low hood the gas flow rate may be in the order

of 3,.000 to 5, 000 scfm per megawatt.


Atmospheric emissions resulting from the production of ferro-

manganese in  blast furnaces a.verage 4. 1 pounds of manganese

per ton based  on 95 percent control, 20 percent manganese in

the  particulate (Table II), and 410 pounds of particulate per ton

of ferromanganese (uncontrolled) _/.   During 1968 the manga-

nese emissions totaled 1, 113 tons.


Emissions to the atmosphere from electric furnaces producing
1- Office of Air Programs; Emissions report in progress;
   1971.

-------
                           -25-
ferromanganese a.verage 23. 9 pounds of manganese per ton of

ferromanganese produced including a 10 pound per- ton loss dur-

ing handling, mixing, and other non-melting operations _/.   .In

the United States the manganese emissions from electric fur-

na.ces during 1968 totaled 3, 669 tons.


Atmospheric emissions due to  the production of silicomanganese

in electric furnaces averaged. 69.4 pounds of manganese per ton

including a 10 pound per ton loss during handling, mixing, and

other non-melting operations   ./.   During 1968 manganese emis-

sions resulting from the production of silicomanga.n.ese totaled

4, 164 tons.
]•• Office of Air Programs; Reactive metals report in
   progress;  J9?l.

-------
                            -26-
                      REPROCESS1NG







More than ninety percent of the manganese used in the United





States during 1968 was consumed by the steel industry in the





production of carbon steel, stainless steel,  and special steel





alloys,  The remainder was used in ma.king cast iron, nonfer-





rous alloys,  batteries, chemicals,  and numerous  other products.







CARBON STEEL





From  the standpoint of air pollution, steel mills are very im-





portant sources of manganese emissions.   The basic steps in





the production of steel include the partial  removal of impurities





when iron ore is reduced to pig iron in the blast furnace.  Fur-





ther purification takes place when pig iron and scrap are con-




verted to steel in an open-hearth, a ba.sic oxygen, or an elec-





tiic furnace.  Other associated opera.tions include ore crushing,





materials handling, sintering, palletizing a.nd scarfing.







Blast  Furnace •- Commencing with i;he production of pig iron,





ma.nganese is part of each principal ingredient charged into the





blast furnace.  It is in the iron and  ma..ngajuferous ore, in the




scrap, and in the slag recycled from the steel converter.  More




manganese enters the iron blast furnace through the sma.ll con-




tent of manganese in some iron ores than  through  the deliberate

-------
                           -27-
addition of manganese.  The pig iron emerging from the blast

furnace contains about 70 percent of the manganese from the

charge, and the other 30 percent is in the slag and ga.ses that

are byproducts of the reaction.


As the gas leaves  the blast furnace, it contains large quantities

of particulates a.veraging about 150 pounds per ton of pig iron  /;

however,  it is  subsequently cleaned and used as fuel.  The gas

cleaning is accomplished in two or. three sta.ges and the annual

overall efficiency  is a.n estimated 97 percent.


During 1968,  140 million tons of net oies and agglomerates

were consumed in producing 89 million tons of pig iron  /.   The

estimated manganese content of the particula.te was 0. 5 percent.

Emissions to the atmosphere totaled ], 000 tons, based on. 22.5

pounds of manganese per 1, 000 tons of pig iron.


Open-Hearth Furna.ce -  The nex:t  step in  steelmak.mg  is to  pro-

duce steel using pig iron,  home scrap, and purchased  scrap.

Three types of furnaces  are  commonly used; the open-hearth,

the basic oxygen, and the electric  furnace.  Rega.rdless of the
1- "Air Pollutant Emission Fa.cr.or s "; Environmental Protection
   Agency;  Preliminary Document;  Apr. 1971.

2- Minerals Yearbook;  Bureau, of Mi.ties;  1968.

-------
                           -28-
kind of furnace, the primary object of the operation is to reduce





the impurities present in the charge to the limits specified for





the melt.







In the open-hearth furnace, steel is produced from a mixture





of scrap (about 45 percent) and pig iron (about 55 percent) using





oil,  coke-oven gas,  natural gas, tar,  or producer gas to provide





the required heat.  The melting begins when the first scrap is





charged and continues as solid material is added.  After all the





scrap has melted, molten pig iron  is delivered and poured into





the furnace.  This step is followed by the ore and lime boil.




Next the working period is employed to:  (1) lower the phos-





phorus and sulfur content; (2) eliminate  carbon as rapidly as




possible;  and,   (3) increase the  heat for final  deoxidation.  It




is during this process that the greatest loss of manganese oc-




curs.  About 80 to 90 percent emerges in the fume and slag.




It oxidizes readily and tends to pass into the slag,  rather  than




remaining with the product.







The overall operating cycle of the open-hearth furnace is  about





10 hours; fumes are discharged continuously at varying rates.





In spite of the varying actions, average emission factors have





been established for operation both  with and without oxygen

-------
                           -29-
lancing.  With oxygen lancing,  the factor for uncontrolled

emissions is 21 pounds of particulate per ton of steel.   With-

out lancing, the factor is 8 pounds per ton.   The degree of

emission control is estimated at 40 percent, and the average

emission factor (controlled) for all open-hearth furnace opera-

tions is 10. 2 pounds of particulate per ton of steel produced  /.


The mean particle size of the dust is generally considered to

be 0. 5 micron _/  and a  typical chemical analysis  is shown in

Table III.


During 1968 the steel produced in open-hearth furnaces was

65 million short tons _/, and the manganese content of the

particulate matter emitted was about 0. 5 percent.   Manganese

emissions to the atmosphere totaled 1, 660 tons based on 51

pounds per 1,000 tons of steel produced.


Basic Oxygen Farnace  - The basic oxygen furnace is a re-

fractory-lined,  cylindrical vessel that is mounted  on trunions

so that it can be rotated  and placed in a horizontal or vertical
1- "Emissions,  Effluents and Control Practices";  Environ-
   mental Protection Agency;  Study in progress (unpublished);
   1970.

2- Aberlow,  E.  B. ;   "Modification to  the Fontana Open-Hearth
   Precipitators";  JAPCA;  7_; May,  1957.

3- Minerals Yearbook;  Bureau of Mines;  1968.

-------
                           -30-
                        TABLE III

   SPECTROGRAPHIC ANALYSIS OF PARTICULATE
 DISCHARGE FROM AN OPEN-HEARTH  FURNACE  1/
  „,                           Approximate Amount
  Element                      ^   _
                                     Percent
Fe
Zn
Na
K
Al
Ca
Cr
Ni
Pb
Si
Sn
Cu
Mn
Mg
Li
Ba
Sr
Ag
Mo
Ti
V
Remaining amount
10 to 15
1 to 2
1 to 2
5
5
2
2
5
5
1
0. 5
0. 5
0. 1
Trace
Trace
Trace
0.05
Trace
Trace
0.05
 These data are qualitative only and require supplementary
 quantitative analysis for actual amounts.
1- Air Pollution Engineering Manual;  Public Health Service
   Publication No. 999-AP-40;  p.  243;  1968.

-------
                           -31-
position as required during operation.  When charged and in

the vertical position, a stream of oxygen is supplied from

overhead downward into the converter.  The oxygen impinges

on the liquid metal surface causing violent agitation and inti-

mate mixing with the pig iron. During the operating cycle of

about one hour,  large quantities of gas and particulate are dis-

charged from the furnace.


The emission factor for the basic oxygen furnace has  been es-

timated at 46 pounds  of particulate per ton of steel _/ and the

degree of emission control at 97 percent.  The mean particle

size of the dust is 0. 7 micron (Table IV).


During  1968 the  steel produced in basic oxygen furnaces was

48 million short tons _/ and the estimated manganese content

of the particulate emissions was 3.2 percent  (Mn,O.  4.4 per-

cent ao  shown in Table  V).  Manganese emissions to the atmos-

phere totaled 1, 060 tons during the yea.r, based on 44 pounds

per 1, 000 tons of steel  produced.
1- "Air Pollutant Emission Factors";  Environmental Protection
   Agency;  Preliminary Document: Apr.  1971.

2- Minerals Yearbook;  Bureau of Mines;  1968.

-------
                          -32-
                      TABLE IV

      PARTICLE SIZE DISTRIBUTION OF FUME
        FROM  A BASIC OXYGEN FURNACE  ]/
  Microns                             Percent

  0-0.5                             20.0

 0.5 -  1.0                             65.0

 1.0 -  15.0                            15.0
                      TABLE V
      COMPOSITION OF FUME AND DUST FROM
            BASIC OXYGEN  FURNACES  1 /
  Material                             Percent

   Fe2O3                               90.0

   Mn3O4                                4.4

   FeO                                  1. 5

   SiO-,                                  1.3
   CaO2                                  0.4

   P205                                  0. 3

   A12O3                                 0. 2
1- Gaw, R. G. ;  "Symposium on Basic Oxygen Furnaces,
   Gas Cleaning";  Iron Steel Engr. ;  37;  Oct.  I960.

-------
                           -33-
Electric Furnace  - Electric arc furnaces are well suited to

the production of alloy steels and are used extensively for

that purpose.  They are  refractory-lined, cylindrical vessels

with large carbon  electrodes passing through the furnace roof.


Emissions generated during steelmaking consist of fume and

dust emitted from  the furnace during charging and refining.

While charging the furnace, the top is open to receive the cold

metal and the exposure of the1 cold  charge to the high tempera-

ture inside the furnace results in the generation of large quan-

tities of fume.  In  general, the rate of fume release increases

throughout the operation.


Particulate  emissions from electric arc furnaces have been

estimated at 11 pounds per ton of steel with oxygen lancing,

and 7 pounds per ton without _/.    The particle size is shown

in Table VI.  The  degree of control is estimated at 78 per-

cent,  and the average emission factor (controlled) at 2. 5

pounds per ton of steel produced.


During  1968 the  steel produced in electric arc furnaces was

16 million short tons  /.   The manganese content of the
1- Air Pollutant Emission Factors;  Environmental Protection
   Agency;  Preliminary Document; Apr. 1971.

2- Minerals Yearbook;  Bureau of Mines;  1968.

-------
                           -34-
                        TABLE  VI

            ELECTRIC  ARC  STEEL  FURNACE
                 FUME PARTICLE SIZE
  •..,.                                  Percent
  Microns                 	
                                                     B
    0-5                  71. 9                    67.9

    5-10                  8.3                     6.8

   10 - 20                  6.0                     9.8

   20 and larger           13.8                    15.5
A  -   Los Angeles County Air Pollution Control District,
      unpublished data, Los Angeles,  California,  1950-51.

B  -   Erickson, E. O. ;  "Dust Control of Electric Foundries
      in Los Angeles  Area";  Electric Furnace Steel Process;
      American Institute of Mining and Metallurgical Engi-
      neers;  11;  1953.

-------
                           -35-
particulate emissions is estimated at 3. 1 percent (4 percent





MnO as shown in Table VII).  Manganese emissions  to the





atmosphere totaled 620 tons,  based on  78 pounds per 1, 000





tons of steel produced.







OTHER STEEL




Even though there is more manganese in certain alloy steels





than in carbon steel, the production steps are essentially the





same.   The principal difference is that more of the alloying





elements are added near the end of the cycle.







Stainless steels are usually produced in an electric arc or





high-frequency induction furnace.  The largest tonnages are




processed in an electric arc furnace of the  Heroult type.  This





furnace is refractory-lined and the steel may be poured by




tilting the entire furnace.  After the working period  the slag'





is removed and  a finishing slag is placed on the bath prior  to




the addition of manganese and other alloying elements.







Manganese steels are made by any of the conventional steel-




making processes with  the exception that an acid-lined furnace





may not be used.  Only a base iron charge is melted in the




acid-lined furnace.  The ferromanganese or other manganese





alloy is melted separately  in a basic-Lined furnace and added

-------
                           -36-
                       TABLE VII

           TYPICAL EMISSIONS FROM AN
             ELECTRIC ARC  FURNACE l/
        Component                        Weight  %


Zinc Oxide (ZnO)                             37

Iron Oxides                                  25

Lime (CaO)                                   6

Manganese Oxide (MnO)                        4

Alumina (A12O )                               3

Sulfur Trioxide (SOJ                          3

Silica (SiO2)                                   2

Magnesium Oxide (MgO)                        2

Copper  Oxide  (CuO)                            0. 2

Phosphorus Pentoxide  (P^Cv)                  0. 2
1- Coulter,  R.  S. ;  "Smoke,  Dust,  Fumes Closely Controlled
   in Electrode Furnaces";  Iron Age; 173;  Jan.  14,  1954.

-------
                           -37-
to the base iron in the ladle.  Hadfield's method consists of




adding molten ferromanganese to carbon-free blown iron.  This





is the most widely used method for producing manganese steel





castings.







Manganese emissions resulting from the production of alloy




steels have been included with the emissions estimated for




carbon steel.







CAST IRON




The principal use of manganese in cast iron is to nullify the





effects of sulfur.  In  spite of recent advancements in the tech-





nology of melting with electric arc and induction furnaces, the




cupola is still the most widely used  method for producing  cast





iron.  The charge into the cupola furnace includes coke, scrap,





and pig iron, each-containing  some manganese.  As air is in-





troduced,  the coke burns  and  causes the metallic charge in the




furnace to melt.  Part of  the manganese oxidizes and part com-




bines with sulfur to form  manganese sulfide which is discharged




in the slag.







The rate of particulate emissions from gray  iron cupolas has




been reported as 4 to 26 pounds per ton of process weight not




including emissions from handling,  charging, or other non-




melting operations.

-------
                           -38-
Based on information obtained from industry the pa.rticulate





emission factor is estimated at  22 pounds per ton of process





weight,  including melting and non-melting operations.  The





manganese content of the particulate is 2 percent  /  and the





degree of emission control approximately 25 percent.








During 1968 the pig iron and scrap used by  iron foundries





totaled 16,788,000 short tons _/.   Manganese emissions to





the atmosphere due to the production of cast iron were 2, 770





tons.







WELDING  RODS




Some welding rods and welding rod coatings contain manganese.




In the coatings there is approximately 10 percent manganese




dioxide as shown in Table VIII,  and  in aluminum welding rods




there is as much as  1. 5 percent manganese.







During the  production  of aluminum welding  rods  the manganese




is added as a general purpose alloy  for applications requiring





moderate strength and good workability.  An aluminum-rich




alloy  ingot  containing the manganese is added to  a charge of
1- Private communication with industrual source.





2- Minerals Yearbook;  Bureau of Mines;  1968.

-------
                       -39-
                   TABLE VIII




TYPICAL ANALYSIS  OF WELDING ROD COATINGS
Material
SiO2
TiO2
MnO-,
Fe2°3
MgO
CaO
co2
Moisture, organic
volatile matter
Other
TOTAL
Percent
20.5
41.5
10.9
8.8
5.9
2.5
1.4
6.9
1.6
100. 0

-------
                           -40-
virgin aluminum and alloy scrap in a reverberatory furnace





fired to a temperature of about  1,400 F.  During the melting





process the metal flows from the main furnace hearth to the





holding hearth through a trough outside the furnace enclosure.





The  metal is then  tapped and poured into ingots and cooled.







Next, the ingots are heated and rolled in the blooming mill




prior to milling in the rod mill.  The product is finished by





forging,  swaging,  or drawbenching.







Based on  information obtained from three  industrial sources,




manganese emissions to the atmosphere are estimated at 16





pounds per ton of manganese processed.  During 1968 the man-





ganese emissions  resulting from the manufacture of welding




rods totaled 24 tons.







NONFERROUS ALLOYS




In aluminum alloy production, manganese  is dissolved in the





molten aluminum to provide superior hardness, tensile





strength,  and corrosion resistance.  Such alloys contain man-





ganese at a level of less than  25 percent;   one  master alloy





uses 4 or 5 percent.







Magnesium producers use manganese chloride as a flux to im-





part qualities of stiffness, hardness, and corrosion resistance.

-------
                           -41-
Also, magnesium can be melted and alloyed in steel pots when





manganese is used  since it inhibits alloying of the magnesium




with the steel.







When alloyed with copper and zinc, manganese bronze is





formed.  These bronzes,  containing up to 3. 5 percent manga-




nese, possess good tensile strength and are well known for





their resistance to  the corrosive effects of sea water.







Manganese-copper-nickel alloys have a high affinity for carbon




and rapidly'attack acid refractories.   Therefore,  melting





should be conducted in a basic-lined high-frequency furnace.




The  basis of the furnace charge consists  of ordinary carbon-





free metallic manganese, ingot copper,  nickel pellets, and




returned scrap from previous melts, if available.  Satisfac-




tory results have been obtained by melting the copper and




nickel under an oxidizing slag of manganese ore.







Producers of nonferrous alloys contacted during this study




stated their atmospheric emissions average about 12 pounds




per ton of manganese processed.  During 1968 manganese




emissions to the atmosphere were 60 tons.

-------
                           -42-
BATTERIES





An important use of manganese dioxide is as a depolarizing





agent in the ordinary dry cell battery.  Hydrogen released





from the electrolyte of the cell tends to form around the car-





bon electrode,  slowing the action of the cell.  This condition





is corrected as the hydrogen combines with the oxygen that is





provided by manganese dioxide contained in the cell mix.







The  main steps in a dry cell battery-making process are dia-





gramed in Figure  II.







Emissions to the atmosphere are principally during the early




stages of  production.  Manganese dioxide, calcined manganese,




and other dry ingredients are emptied from vats and containers




into  a dry mixer.  These mixed ingredients then travel in buc-




ket elevators to the hopper where they are dumped and enter




the wet mixer.







Information obtained from manufa.cturers of dry  cell batteries





shows that their manganese emissions to the atmosphere aver-





age 10 pounds per  ton of manganese processed.   During 1968





the atmospheric emissions were 90 tons.

-------
                            -43-
                     FLOW DIAGRAM

              BATTERY MANUFACTURING
Manganese dioxide, calcined
manganese, graphite carbon
black, ammonium chloride,
and vita film
Zinc chloride and ammonium
chloride solution
Battery cases
Zinc and ammonium chloride
solution
Carbon rod added by machine
Wet  Mixer
                                               Pulverizer
                                                 Paste
                                                Filling
                                               Machine
 Solution
  Filling
 Machine
                                              Combining
                                               Machine
                        Figure  II

-------
                           -44-
CHEMICALS AND  OTHER USES





Manganese ore, mainly in dioxide form,  is used in the chemical





industry as an oxidizing agent in the manufacture of hydroqui-




none and for the production of various manganese chemicals,





including potassium permanganate,  manganese sulfate, manga-





nous chloride,  and manganous oxide.  It is used in  the lea.ching





of uranium and zinc ores,  in fertilizers as a trace  element,  in





animal and poultry feed as a supplement,  in pharmaceuticals,




frits, glass,  ceramics, and to give a variety of coloring effects




to face brick.   For certain of these applications the ore is used




directly;  for others, it may be  processed into compounds or




salts of manganese prior  to use in the final product.







Hydroquinone is important as a  photographic developer.   Per-





manganates have many uses in a wide variety  of applications.




They are used in the chemical industry in air  pollution control





for  sulfides and mercaptans,  in water treatment, as bacteri-




cides and pesticides, and for  odor control in barnyards.   Potas-





sium permanganate is a powerful oxidant.







Manganese sulfate  is used in a multitude of commercial prod-




ucts;  one of the largest areas is as a fertilizer or  fertilizer





additive.  It is  also important as a constituent of animal  and

-------
                           -45-
poultry feeds, fungicides,  paint driers,  coloring agents for the





textile and ceramic industries,  and is bften used as a base for





the production of other manganese chemicals.  Approximately





10, 000 tons of manganese are used annually in the production




of fertilizers.







Manganous oxide is also found in fertilizers and in animal and





poultry feeds.  In addition it is used in certain welding applica-





tions.  In dyeing textiles,  making welding rod fluxes, and in





alloying manganese with magnesium, manufacturers use man-





ganous chloride.







Another area of interest is the molybdenum-manganese process of




joining ceramics to metal, better known as the  moly-manganese





process.  It is one of the most widely employed methods in elec-





tronic  applications.  A thin coating (0. 005 to 0. 002 inch) of a




fine suspension  of molybdenum and manganese is  fired on the




ceramic in a reducing atmosphere at temperatures approaching




3, 000  F.  Then  a coating of nickel and copper is electroplated




over the molybdenum and manganese, and is wetted by a brazing




alloy.  The resulting metal-ceramic  bonds ha.ve a better high-




temperature strength than those formed by any  other method.





Tensile strength of 20, 000 pounds per square inch has been re-





ported.

-------
                           -46-
Fuel additives of organic manganese compounds have been





patented and tested.  The most successful antiknock compound





is methylcyclopentadienyl manganese tricarbonyl,  which is





mixed with tetraethyl lead to increase the  octane rating of gas-





oline.  A typical mixture is composed of the following ingredi-





ents:  57.5 percent tetraethy] lead;  7.0 percent methylcyclo-





pentadienyl  manganese tricarbonyl;  16. 7 percent ethylene di-





bromide; 17.6 percent ethylene dichloride;  and 1.2 percent





other additives such as dye  and inert materials.







Various  methods of using manganese to remove air pollutants





ha.ve been suggested.  Manganese nodules  from the ocean floor





can be loosely packed in  a column through  which a  gas passes,




causing a reaction with the  sulfur dioxide in the gas to produce




manganese sulfate.  One-third of  the manga.nese can be re-





covered  from  the sulfated nodules by ]eaching with weak su.l-




furic acid.







There is no reliable information  regarding the average  manga-




nese emissions  that occur during  the production, of compounds





and the  subsequent manufacture of products that contain man-





ganese.  However,  a few rough estimates  of atmospheric emis-





sions have been obtained from people in industry.  In this report

-------
                          -47-
manganese emissions to the atmosphere are 10 pounds per ton




of manganese processed.







During 1968 the manganese in chemicals and other miscellaneous




uses was 60, 000 tons, and atmospheric emissions were an esti-




mated 300 tons.

-------
                           -48-
                   CONSUMFTIVE USES







The largest manganese emissions to the atmosphere during





consumptive use are those due to the combustion of coal and




oil.  Others that occur are usually of such a nature that atmos-




pheric emissions are negligible.







COAL





The manganese content of various samples of coal has been re-





ported as shown in Table IX, and the average  concentration in





domestic coal is about 26.4 ppm.  Coal consumed in the United




States during 1968 was 508,990, 000 tons (bituminous and anthra-





cite)   /;  therefore,  the manganese in coal was about 1.3,400




tons.   Since fly ash is about 65 percent of total ash and approxi-




mately 75 percent of fly ash is collected,  the manganese emis-




sions  to the atmosphere should be 16 percent  of the manganese




contained in the coal, or 2, 150 tons.







A study has been  made regarding emissions from coal fired




power plants and  the emissions of manganese  have been recorded.




Six power boilers were  tested, each a  different type,  and each




value  reported was the average of at least two tests.  Two of
1- Minerals Yearbook;  Bureau of Mines; 1968.

-------
                                     TABLE  IX

              AVERAGE MANGANESE  CONTENT IN  ASH QF COAL
Region Frequency of Mn Content Ash Content
Detection - % of Ash - % of Coal - %
Eastern Province 100 0. 026 9. 3
Interior Province 100 0.0325 10.5
Western States 100 0.0212 9.8
Average Manganese Content of Coal
Mn Content
of Coal -%
0. 0024
0. 0034
0.0021
0. 00264
NOTE  -  The above table based on "Spectrochemical Analyses of Coal Ash for Trace
         Elements"  Table 1;  Bureau of Mines RI7281;  July, 1969.

-------
                           -50-
the boilers were fired with Illinois coal;  two burned Pennsyl-

vania coal;  one used some coal from Ohio and some from West

Virginia;  one burned part Kentucky and part West Virginia coal.


Manganese concentrations in the fly ash samples taken before fly

                                                         A
ash collection ranged from 4. 2 to 17. 0 grains per scf x 10   .

                                         A
The average was  8.47 grains per scf x 10'  . In the  samples

taken after fly ash collection, the manganese concentration

ranged from 0. 26 to 1. 6 grains  per  scf x 10   and the average

was 0. 92 grains per scf x 10"4  _/.   Based  on 508, 990, 000 tons

of coal consumed in the United States during 1968, 90 percent

application of control, 160 scf of flue gas per pound of coal and

the average concentration in fly ash stated above, the manganese

emissions for 1968 due to the combustion of  coal are calculated

at 1, 950 tons.
In this report the figure of 1,950 tons is used as manganese emis

sions to the atmosphere due to the combustion of coal.
1- Cuffe,  Stanley T. and Gerstle, Richard W. ;  "Emissions from
   Coal Fired Power Plants";  Public Health Service Publication
   No. 999-AP-35;  1967.

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                           -51-
OIL




In order to estimate manganese emissions to the atmosphere





resulting from the combustion of fuel oil,  it was necessary to





determine the manganese content as  well as the quantity of oil





received from numerous foreign and domestic sources.  Analy-





ses of more than 400 samples of crude and residual oils were




obtained from the major oil companies and the utilities along




the east coast of the United States.







The data show that nearly all crude oil contains some manga-





nese; the concentrations ranging from nearly zero to more





than 2,000 ppm.  It also shows that residual oil contains a





higher percentage of manganese than the crude.  When oil is





refined  the manganese and other trace  metals tend to concen-




trate  in the heavy fractions;  the residual oil,  the road oil,  and





the asphalt.   According to  the information obtained from oil




companies,  the  residua] fuel oils may be expected to contain




4 to 6 times as much manganese as the crude oils.







Unfortunately,  most of the analyses available weve of crude




oil.  They show oil from California,  Colorado, and Utah con-




tains  more manganese than that from Kansas, Oklahoma, and




Texas (Table X). Residual fuel oil from the United States con-





tains  about 158 ppb manganese, while that from the Middle East

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                           -52-
                        TABLE X

  MANGANESE CONTENT OF  DOMESTIC CRUDE  Oi:LS
Source
Arkansas
California
Colorado
Kansas
Montana
New Mexico
Oklahoma
Texas
Utah
Wyoming
Manganese
Content - ppb
120
138
208
13
5
21
30
29
1,445
44
NOTE  -  The above table is based on private communication
         with industrial sources.

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                           -53-
averages about 120 ppb.  Analyses of eight residual fuel oils

from South America show that manganese is below the limit

of detection.


During 1968 the demand for residual fuel oil in the United States

was 668, 239, 000 barrels.  Imports were 409, 928, 000 barrels,

and the remainder were principally from domestic production V.

Imports were about 92 percent from South America and the West

Indies;  8 percent from the Middle East, Canada,  and other

countries   /.
              MANGANESE IN RESIDUAL OIL,
       CONSUMED IN  THE  UNITED  STATES -  1968
      g                    Quantity    Mn Content    Mn Content
                           Barrels        ppb          Tons
United States
South America
Middle East and Other
TOTAL
258, 311,
376,000,
33,928,
668,239,
000 158
000
000 120
000
7
-
1
8
1- "Crude Petroleum, Petroleum Products,  and Natural-Gas-
   Liquids:  1968";  Petroleum Statement, Annual;  Mineral
   Industry  Surveys;  Bureau of Mines;  Washington,  D. C.

2- Based on import data from the Office of Air Programs;
   Durham,  N. C.

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                            -54-
In the past power boilers designed to burn fuel oil were not us-





usually equipped with air pollution control apparatus.   It  was only





the coal fired or the combination coal-oil units that included





mechanical collectors and/or electrostatic precipitators.  When





these combination units burn oil, only a  small part of the particu-





late matter becomes an atmospheric emission.







The records show that 669 million barrels of residual oil were





consumed in the United States during 1968.   The electric utili-





ties used 28 percent of the total,  or  185  million barrels,  and




were the only users with  any significant  degree  of air pollution




control. A survey was conducted and it  was determined that





the electric utility percent of control when burning fuel oil was




about 32 percent.







Based  on 10 percent overall control, the manganese emissions





to the atmosphere during 1968 due to the combustion  of fuel oil





totaled  7 tons.

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                           -55-
         INCINERATION AND OTHER  DISPOSAL


Information concerning sewage and sludge was the only data

available during this  study regarding atmospheric emissions

of manganese that result from incineration or disposal.


SEWAGE AND SLUDGE

A recent report concerning the burning of sewage and sludge

indicates the present burning rate in the United States  is about

Z, 000 tons  per day  /.   Based on a manganese content of 240

ppm (dry weight)  /  the atmospheric emissions currently

total 175 tons of manganese per year.
1.- Private communication from the Federal Water Pollution
   Control Authority.

2- Clark, L. J. and Hill,  W.  L. ;  "Occurrence of Manganese,
   Copper,  Zinc, Molybdenum,  and Cobalt in Phosphate
   Fertilizers and Sewa.ge Sludge";  J.  Assoc. Official Agr.
   Chemists;  4];  pp. 63.1-637; 195*T

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                           -56-


                    APPENDIX  A

        COMPANIES DEALING IN  MANGANESE
            AND MANGANESE  COMPOUNDS
ALABAMA
   Woodward Company
LOCATION
Woodward
CALIFORNIA

   American Potash and Chemical Corp.
   Capco Alloy Steel Company
   Electronic Space Products, Inc.
   Metal Organics,  Inc.
   Wilson and  George Meyer ;& Company
   Mountain Copper Company, Ltd.
Los AngeJ.es
Los Angeles
Los Angeles
San Carlos
So. San Francisco
Martinez
CONNECTICUT

   Anaconda American Brass Company      Waterbury
   Michael Schiavone & Sons, Inc.          New Haven
D. C.
   Hercules, Inc.
Wa shington
GEORGIA

   Frank Smith
   Tennessee Corporation
Carre rsville
Atlanta
ILLINOIS

   Amsco Division of Abex Corp.
   Atlantic Chemicals and Metals Co.
   Carus Chemical Company
   Ben J. Harris and Company
   Hickma.n,  Williams and Company
   Kraft Chemical Company
Chicago Heights
Chicago
LaSalle
Chicago Heights
Chicago
Chicago

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                           -57-
   R. Lavin and Sons,  Inc.
   Miller and Company
   Stresen-Reuter International
   Wilson Labs
Chicago
Chicago
Bensonville
Chicago
IOWA

   Bonewitz Laboratories, Inc.
Burlington
MARYLAND

   Ansam Metals Corporation              Baltimore
   Chemetals Division, Diamond Shamrock
    Chemical Company                    Baltimore
   Glidden Metals Group                   Baltimore
   Manganese Chemical Corporation        Baltimore
MICHIGAN

   Frankel Company, Inc.
   Haviland Products Company
Detroit
Grand Rapids
MINNESOTA
   Manganese Chemical Corporation
Minneapolis
MISSOURI
   Mallinckrodt Chemical Works
St.  Louis
NEW  JERSEY

   Advance Division,  Carlisle'Chemical
    Works,  Inc.
   A and S Corporation
   J.  T. Baker Chemical Compa.ny
   Leonard J. Buck, Inc.
   Eastern Chemical Corporation
New Brunswick
Verona
Phillips burg
Jersey City
Pequannock

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                           -58-
   General Metallic Oxides Company
   Hummel Chemical Company,  Inc.
   Import Chemical Company
   Metallurgical International Inc.
   Nitine, Inc.
   Octagon Process, Inc..
   Shieldalloy Corporation
   Taylor-Wharton Company
   Tenneco Chemicals,  Inc.
   Troy Chemical Corporation
   Var-Lac-Oid Chemical Company
   Max Zuckerman and  Sons,  Inc.
Jersey City
Newark
Jersey City
New Shrewsbury
Whippany
Edgewater
Newfield
High Bridge
Piscataway
Newark
Elizabeth
Owings Mills
NEW  YORK

   Airco Alloys and Carbide Division
   Air Reduction  Company, Inc.
   Allied Chemical Corporation
   Alloys Unlimited, Inc.
   American Smelting and Refining Co,
   Anchor Metal Company, Inc.
   Anglo-American Metal & Fe.rro Alloy
    Corporation
   Associated Metals and Minerals Corp.
   Atomergic  Chemetals Company
   H.  J.  Baker Brothers, Inc.
   Be]mont Smelting & Refining Works,  Inc.
   Berkshire Chemicals, Inc.
   Charles  B. Chrystal Company, Inc.
   City Chemical Corporation
   Cometals,  Inc.
   Continental Ore Corporation
   Debevoise-Anderson Company, In.c.
   Faesy and Besthoff, Inc.
   Fallek Products Company, Inc.
   Galla rd-Schlesinger  Chemi ca.l
    Manufacturing Corporation.
   M. Golodetz and Company
   W. R. Grace and Company
   Herzog Metal Corporation
   Hooker Chemical Corporation
   Industrial Chemical and Dye Corp.
   A.  Johnson and Company,  Inc.
   Kingston Chemical  Company, Inc.
Niagara Falls
New York
New York
Melville
New York
Brooklyn

New York
New York
Carle Place, L.I.
New York
Brooklyn
New York
New York
New York
New York
New York
New York
New York
New York
Carle Place,
New York
New York
New York
Niagara Falls
New York
New York
New York
L.I.

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                           -59-
   Kolon Trading Company,  Inc.
   Mackenzie Chemical Works
   McKesson Chemical Company
   Messina, Inc.
   Metallurg Alloy Corporation
   Milwaukee Tool and Equipment Co.
   Wm. H. Muller and Company,  Inc.
   Naftone,  Inc.
   The New Jersey  Zinc Company
   Ore and Ferro Corporation
   Pancoast International Corporation
   Charles Pfizer and  Company,  Inc.
   Philipp Brothers
   Primary Industries  Corporation
   Progressive Alloys  Corporation
   The Selney Company, Inc.
   Semi Alloys,  Inc.
   E. M. Sergeant Pulp and Chemical
    Company, Inc.
   Smith Chemical and Color Co.  , Inc.
   Sterwin  Chemicals,  Inc.
   C. Tennant Sons and Company
   The Titan Industrial Corporation
   Union Carbide Corporation,  Ferro-
    alloys  Division
   Union Carbide Corporation,  Mining
    and Metals Division
   United Mineral and  Chemical Corp.
   Winth.rop Laboratories
   Witco Chemical Corporation
New York
Central Islip
New York
Bedford Hills
New York
New York
New York
New York
New York
New York
New York
New York
New York
New York
Brooklyn
New York
Mount Vernon

New York
Brooklyn
New York
New York
New York

New York

New York
New Yor k
New York
New York
NORTH CAROLINA
   Mineral Research and Development Corp.  Concord
OHIO
   Barium and Chemicals,  Inc.             Steubenville
   Chemetron Corporation                  Cleveland
   Chemical. Division Ferro Corporation    Bedford
   Glidden-Du.r.kee Division                Cleveland
   Globe Metallurgical Division,
    Interlake Steel Corporation             Cleveland

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                           -60-
   Haley Smelting,  Inc.
   Hall Chemical Company
   Harshaw Chemical Company
   McGean Chemical Company
   Mooney Chemicals, Inc,
   Oglebay-Norton Company
   Ohio Ferro-Alloy Corporation
   Pickards Mather  and Company
   I. Schumann and Company
   S. C. M. Corporation
   Shepherd Chemical Company
   C.  L. Zimmerman Company
Parma
Wickliffe
Cleveland
Cleveland
Cleveland
Cleveland
Canton
Cleveland
Bedford
Cleveland
Cincinnati
Cincinnati
PENNSYLVANIA

   Bethlehem Steel Corporation
   Bram Metallurgical Chemical Co.
   Brass and Copper Sales, Inc.
   C. E. Minerals
   Ceramic Color and Chemical
    Manufacturing Company
   Chase Chemical Corporation
   Chemalloy Company, Inc.
   Chromium Mining and Smelting Corp.
   Colonial Metals Company
   Damascus Steel Casting
   Fisher Scientific Company
   Foote Mineral Company
   Gano Moore Company,  Inc.
   O. Hommel  Company
   Lavino Division, International
    Minerals and Chemicals Corp.
   Mercer  Alloys
   Metallurgical Products Company
   J.  Meyer and Sons,  Inc.
   Prince Manufacturing Company
   Reading Alloys,  Inc.
   Fra.nk Samuel and Company,  Inc.
   Shenango, Inc.
   Taylor • Wha.rton Company,  Division
    of Harsco Corporation
   Charles A.  Wagner Company, Inc.
   Welding Wholesale Company
Bethlehem
Philadelphia
Philadelphia
King of Prussia

New Brighton
Pittsburgh
Bryn Mawr
Pittsburgh
Columbia
New Brighton
Pittsburgh
Exton
Wynnewood
Pittsburgh

Philadelphia
Greenville
Philadelphia.
Philadelphia
Bowmanstown
Robesonia.
King of Prussia
Pittsburgh

Easton
Philadelphia
Philadelphia

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                           -61-
TENNESSEE

   Eastman Chemical. Products, Inc.        Kingsport
   Foote Mineral Company                 Knoxville
(American Meta] Market,  Aug.  10,  1970;   Thorny s  Register,
Dec. 1968 Ed. )

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 BIBLIOGRAPHIC DATA
 SHEET
1. lU-port No.
 APTD-1509
                                                                      3. Recipient's Accession No.
4. Title and Subtitle
  National  Inventory of Sources and  Emissions: Manganese - 1968
                                                 5- Report Date
                                                   August  1971
                                                                      6.
7. Author(s)
                                                 8- Performing Organization Kept.
                                                   No.
9. Performing Organization Name and Address
  W.  E. Davis  & Associates
  9726 Sagamore Road
  Leawood,  Kansas
                                                 10. Project/Task/Work Unit No.
                                                 11. Contract/Grant No.

                                                    CPA 70-128
12. Sponsoring Organization Name and Address
  ENVIRONMENTAL PROTECTION  AGENCY
  Office of  Air Programs
  Durham, North Carolina
                                                 13. Type of Report & Period
                                                    Covered
                                                 14.
15. Supplementary Notes
16. Abstracts
  The inventory of atmospheric emissions  has been  prepared to  determine the  nature,
  magnitude,  and extent of the emissions  of manganese in the United States for the year
  1968.   The  flow of manganese in the  U.  S. for that  .year has  been traced and charted.
  The consumption was 1,150,000 tons while domestic  production  was only 48,000 tons.
  Imports principally from Brazil, Gabon, Republic of South Africa, Congo, Guyana, India
  Angola, and Australia totaled 1,053,000 tons.  Emissions to  the atmosphere during the
  year were  18,992 tons.   About 47% of the emissions  resulted  from the production of
  ferroalloys and about 37% from the production of iron and steel.  The combustion of
  coal was also a significant source of manganese  emissions.
 17. Key Words and Document Analysis.  17a. Descriptors
  Air pollution
  Emission
  Inventories
  Sources
  Manganese
  Consumption
  Production
  International  trade
  Industries
  Reprocessing
17b. Identificrs/Open-Ended Terms
  Year 1968
  United States
     Utilization
     Metallurgical  furnaces
17c. COSATI Field/Group
 13B
18. Availability Statement
FORM NTIS-35 (REV. 3-721
                     Unlimited
                                     19..Security Class (Tliis
                                        Report)
                                          UNCLASSIFIED
                                                          20. Security Class (This
                                                             Page
                                                               UNC1.ASS1FIFD
21. No. of Pages
     68
                                                           22. Price
                                                                                USCOMM-DC I4Q52-P72

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FORM NTIS-3S IREV. 3-721                                                  .                                USCOMM-OC 14
                                                t G. P. O. 1973 — 746-77O / 4182

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