EPA-450/2-74-008
MAY 1974
                  ENGINEERING
                  AND COST STUDY
                  OF THE
                  FERROALLOY  INDUSTRY
                  U.S. ENVIRONMENTAL PROTECTION AGENCY
                  Office of Air and Waste Management
                  Office of Air Quality Planning and Standards
                  Hfcgearch Tr^ngle Park, North Carolina 27711

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                                EPA-450/2 -74-008
        ENGINEERING

     AND COST  STUDY

            OF THE

FERROALLOY  INDUSTRY
      James O. Dealy and Arthur M. Killin
    ENVIRONMENTAL PROTECTION AGENCY
      Office of Air and Waste Management
   Office of Air Quality Planning and Standards
  Research Triangle Park, North Carolina  27711

              May 1974

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This report is issued by the Environmental Protection Agency to report
technical data of interest to a limited number of readers.  Copies are
available free of charge to Federal employees,  current contractors and
grantees, and nonprofit organizations  - as supplies permit - from the
Air Pollution Technical Information Center, Environmental Protection
Agency, Research Triangle Park, North Carolina  27711;  or, for a fee,
from the National Technical Information Service,  5285 Port Royal Road,
Springfield, Virginia 22151.
                    Publication No.  EPA-450/2-74-008
                                    11

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                                 PREFACE
     To provide reliable information on the air pollution aspects of the
ferroalloy industry, the Office Of Air Quality Planning and Standards
of the United States Environmental Protection Agency and the Manufacturing
Chemists Association, Inc. (MCA) entered into an agreement on March 2, 1970.
On December 21, 1971, the Manufacturing Chemists Association withdrew and
the study was completed with the cooperation of the newly formed The Ferro-
alloy Association (TFA).  The cooperative program was established to study
atmospheric emissions from selected ferroalloy processes (primarily sub-
merged-arc electric furnaces) and publish information helpful to air
pollution control and planning agencies and industry management. Information
in the report describes the range of atmospheric emissions during normal
operating conditions and the performance of established devices and methods
employed to limit and control these emissions.
     Direction of this study was vested in a TFA-EPA Steering Committee,
presently constituted as follows:
                Representing EPA              Representing TFA
                Stanley T. Cuffe*             Rolph A.  Person*
                Reid E. Iversen               Fritz E.  Brosien
                John L. McGinnity             Leroy C.  Wintersteen
                John R. O'Connor              Harry U.  Gilmer
     Two study team members of the TFA-EPA Steering Committee, Arthur M. Kill in,
consulting engineer for The Ferroalloy Association, and James 0. Dealy,  U.  S.
''Principal representatives.

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Environmental Protection Agency, were the principal authors of this report.
Also contributing as a study team member was the late Carl V. Spangler of
the U.S. Environmental Protection Agency.  Kenneth R. Durkee, U.S.
Environmental Protection Agency, contributed to this study particularly
in providing information on control technology of foreign industry in
Japan.
     Chapter IX of this report, covering economics of emission control, was
authored by Paul Boys, Richard Jenkins and Francis Bunyard of the Economic
Analysis Branch, Strategies and Air Standards Division, Office of Air
Quality Planning and Standards, Environmental Protection Agency.

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                            ACKNOWLEDGMENTS

     Many companies and individuals in the ferroalloy industry have
been helpful in promoting this study.   For their contributions, the
project sponsors extend their gratitude to:  George Fegan, Chromium
Mining and Smelting Corporation; A. J. Primosic, Foote Mineral Company;
H. U. Gilmer, Woodward Company; Otis D. Jordan, Ohio Ferroalloys Corpo-
ration; Dr. Rolph A. Person and Dr. C. R. Allenbach, both of Union
Carbide Corporation.
     Special thanks are due the following operating companies for their
participation in a program of stack sampling specifically for this
study:
                       Airco Alloys and Carbide
                       Chromium Mining and Smelting Corporation
                       Foote Mineral Company
                       Union Carbide Corporation
     The sponsors also wish to acknowledge the source testing personnel
of the Emission Standards and Engineering Division, Office of Air Quality
Planning and Standards, Environmental  Protection Agency,  and Resources
Research, Inc.  for their contribution  made by stack sampling.

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                           TABLE OF CONTENTS

                                                                     Page

LIST OF TABLES	  xi

LIST OF FIGURES	  xvi

   I.  INTRODUCTION	1-1

  II.  SUMMARY OF STUDY	II-l

       A.  Ferroalloy Production  	  II-1
       B.  Manufacturing Processes	II-l
       C.  Typical Emissions	11-2
       D.  Control of Particulate Emissions 	  II-5
       E.  Guidelines for Emission Control  	  II-8
       F.  Research Areas	  11-9
       G.  Economic Impact of Emission Control  	  11-10

 III.  FERROALLOYS	III-l

       A.  Historical Background	III-l
           1.  Manganese and Manganese Alloys	111-4
           2.  Silicon and Silicon Alloys 	  III-5
           3.  Chromium and Chromium Alloys 	  III-6
           4,  Other Metals	III-6
       B.  Current Uses and Production	111-6
       C.  Future Trends  	  111-10

  IV.  FERROALLOY PLANTS IN THE UNITED STATES 	  IV-1

   V.  FERROALLOY MANUFACTURE 	  V-l

       A.  Description of Processes	V-l
           1.   Submerged-Arc  Furnace  Process	V-l
           2.  Exothermic Process	V-4
              «a.  Silicon Reduction  	  V-6
               b.  Aluminum Reduction 	  V-8
           3.  Electrolytic Process 	  V-8
           4.  Vacuum and Induction Furnace Process  	  V-9
       B.  Metallurgy of the Process	V-9
       C.  Sources, Preparation and Handling of Raw Materials  ...  V-l3
       D.  Product Sizing and Handling  	  V-l8

  VI.  ATMOSPHERIC EMISSIONS  	  VI-1

       A.  Sources and Characteristics of Emissions  	  VI-1
           1.  Sources of Emissions	VI-1
           2.  Sources and Characteristics  of Emissions from
                 Raw Materials Handling and Preparation 	  VI-1
                                 VI

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               3.  Sources and Characteristics of Emissions
                     from Submerged-Arc Furnace Process	VI-3
               4.  Characteristics of Emissions from Other
                     Ferroalloy Processes 	  VI-5
                   a.  The Exothermic Process	VI-5
                   b.  The Electrolytic Process	VI-7
                   c.  Vacuum and Induction Furnace Process 	  VI-7
               5.  Characteristics of Emissions from Product
                     Sizing	VI-7

           B.  Quantities of Emissions	VI-8
               1.  Variability of Furnace Emission Rates During
                     Normal Operations  	  VI-8
               2.  Variability of Furnace Emission Rates During
                     Shutdowns and Startups 	  VI-11
               3.  Data from Questionnaires	VI-12
                   a.  Quantities of Emissions from Electric
                         Furnaces Reported  	  VI-12
                   b.  Reported Estimated Quantities of Emissions from
                         Material Handling  	  VI-27
               4.  Data from EPA Source Measurements	VI-32
                   a.  Quantities of Emissions from Electric
                         Furnaces	VI-32
                   b.  Particle Size Determinations	VI-43
                   c.  Chemical Analysis  	  VI-48
               5.  Data from Other Sources	VI-50
                   a.  Quantities of Emissions from European
                         Furnaces	VI-50
                   b.  Reported Quantities of Emissions from
                         Japanese Furnaces  	  VI-52

 VII.  DESCRIPTION OF CONTROL SYSTEMS 	  VII-1

       A.   Scrubbers Serving Open Furnaces  	  VII-1
       B.   Cloth Filters Serving Open Furnaces  	  VII-5
       C.   Scrubbers Serving Covered Furnaces	••	VII-10
       D.   Electrostatic Precipitators Serving Open
             Furnaces 	  VI1-17
       E.   Waste-Water Treatment  	  VI1-20
       F.   Solid Waste Disposal 	  VII-25

VIII.  EMISSION CONTROL GUIDELINES  	  VIII-1

       A.   Field Surveillance 	  VIII-1
           1.  Typical Emission Control  Regulations
                 Pertaining to the Ferroalloy Industry  	  VIII-1
           2.  Process Description and Sources of Emissions 	  VIII-5
           3.  Emission Control Systems 	  VIII-7
           4.  Maintenance and Operating Problems	VI11-8
           5.  Monitoring Instruments 	  VIII-10

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                                                                       Page

         B.   Procedures for Reducing Emissions During
               Emergency Air Pollution Episodes 	   VIII-11

IX.   ECONOMICS OF EMISSION CONTROL  	   IX-1

     A.   Introduction	IX-1
     B.   Economic Profile 	   IX-2
         1.   Introduction	IX-2
         2.   Industry Structure 	   IX-2
             a.  Ferromanganese-Silicomanganese ....  	   IX-4
             b.  Calcium Carbide	IX-7
             c.  Ferrochromium	IX-11
             d.  Ferrosilicon	IX-20
         3.   New Units	IX-24
     C.   Control  Costs	IX-26
         1.   Introduction	IX-26
         2.   Model  Plants	IX-27
         3.   Open Furnace Control  Costs	IX-29
             a.   Fabric Filter Control  Costs	IX-29
             b.   Wet  Scrubber Control  Costs  	   IX-33
         4.   Totally  Enclosed Furnace  Control  Costs  	   IX-35
             a.   Wet  Scrubber Control  Costs  for Furnace
                   Gas Cleaning	IX-38
             b.   Fabric Filter Control  Cost	   IX-39
             c.   Tapping Fume Control  Cost	IX-39
         5.   Semi-enclosed Furnace Control Costs  	   IX-41
         6.   Case Study of a Totally Enclosed  Furnace	IX-42

     D.   Economic Impact	    IX-46
         1.   Introduction	IX-46
         2.   Model  Income Statements 	    IX-46
         3.   Economic Impact on Model  Plants  	    IX-50
         4.   Economic Impact on the Domestic Ferroalloy  Industry .  .    IX-50

 X.   RECOMMENDED RESEARCH AND DEVELOPMENT PROGRAMS 	    X-l

     A.   Introduction	X-l
     B.   Recommendations	    X-2
         1.   Process  Modifications 	    X-2
         2.   Application of Control Techniques 	    X-2
         3.   Waste Utilization 	    X-3
         4.   Waste Heat Utilization	     X-4
         5.   Emission Measurements 	    X-4
                                  vm

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                                                                      Page

APPENDIX A	A-1
Description of EPA Source Tests	'	A-1

   Furnace A	A-2
   Furnace B	A-4
   Furnace C	A-5
   Furnace D	A-9
   Furnace E	A-12
   Furnace F	A-15
   Furnace G	A-19
   Furnace H	A-21
   Furnace J	A-23
   Furnace K	A-25
   Furnace L	A-27

APPENDIX B	B-l

   Sampling and Analytical Techniques  	  B-l
      Method 1-Sampling and Velocity Traverse  	  B-2
      Method 2-Determination of Stack Gas Velocity 	  B-3
      Method 3-Gas Analysis for Carbon Monoxide,
                 Excess Air, and Dry Molecular Weight	B-5
      Method 5-Determination of Particulate Emissions
                 from Stationary Sources  	  B-6
      Method 6-Determination of Sulfur Dioxide Emissions
                 from Stationary Sources  	  B-9

APPENDIX C	C-l

   Visible Emissions Reported from EPA Tests and
     Questionnaire Data	C-l

APPENDIX D	D-l

   Particle Size Analysis	D-l

APPENDIX E	E-l

   Chemical Analysis of Particulate Emissions from
     Ferroalloy Smelting Operations  	  E-l
      I.   Introduction	E-l
     II.   Chemical  Analysis  of Emissions  from a Ferrochrome-
            silicon Furnace  (A)  and a Chrome ore/lime Melt
            Furnace (b)  	 .......   E-3
    III.   Chemical  Analyses  of Emissions  from a
            Silicomanganese  Furnace (c)  	   E-19
     IV.   Chemical  Analyses  of Emissions  from a
            Ferrochromesilicon Furnace  (D) 	  E-30
                                  IX

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      V.  Chemical Analyses of Emissions from a
            HC Ferrochrome Furnace (E)	    E-43
     VI.  Chemical Analysis of Emissions from a Silicon
            Furnace (F)	   E-48
    VII.  Chemical Analysis of Emissions from a
            50 percent Ferrosilicon Furnace (H) 	   E-55
   VIII.  Chemical Analysis of Emissions from a
            Ferromanganese Furnace (K)  	    E-64
     IX.  Chemical Analysis of Emissions from a
            SiMn Furnace	    E-69

APPENDIX F	    F-l
   United States Imports of Reactive Metals and Alloys  	    F-l

APPENDIX G	    G-l
   Glossary	    G-l
   Abbreviations 	    G-6

REFERENCES

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                               LIST OF TABLES
                                                                   Page
Table III-l      Composition of ferroalloys                       III- 2
Table III-2      World steel production vs ferroalloy turnover    III- 8
Table III-3      Ferroalloy production in the United States       III- 9
                   (short tons)
Table III-4      Imports of selected ferroalloys (excluding       111-11,12
                   imports to government stockpile) as
                   related to domestic ferroalloy consumption
Table III-5      Imports of selected ferroalloys for U.  S.        111-13
                   Government stockpile
Table III-6      Pounds of element consumed per ton of steel      111-14
                   production
Table III-7      Production of stainless steel in free world      111-14
Table III-8      Production of raw steel in the United States     111-16
                   by type of furnace and projections of
                   production to 1980
Table IV-1       Types, sizes, and locations of ferroalloy         IV- 2
                   plants in the United States, August 1971
Table IV-2       Ferroalloy plants and number of electric          IV- 3
                   furnaces by states (1971)
Table  V-l       Chemical composition of ores (percent)              V-15
Table  V-2       Principal chemical constituents of imported        V-16
                   chromium and manganese ores
Table VI-1       Typical furnace fume characteristics              VI- 6
Table VI-2       Types of control systems used on ferroalloy       VI-13
                   furnaces in the United States
Table VI-3       Production and emission factors for uncon-        VI-15
                   trolled open furnaces
Table VI-4       Potential particulate emissions (1971)             VI-19
Table VI-5       Ranges of uncontrolled particulate emissions      VI-20
                   from open furnaces
Table VI-6       Ranges of controlled particulate emissions        VI-21
                   reported for control  devices serving  open
                   furnaces
Table VI-7       Ranges of particulate emissions reported for      VI-23
                   semi-covered furnaces with mix seals
Table VI-8       Average exhaust-system gas volumes from           VI-25
                   semi-enclosed furnaces
Table VI-9       Average exhaust-system gas volumes from           VI-26
                   open furnaces
Table VI-10   ,.  Number of emission control systems reported       VI-28
                   in use in 1970 by type and product

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Table VI-11

Table VI-12

Table VI-13
Table VI-14

Table VI-15

Table VI-16
Table VI-17
Table VI-18
Table VI-19

Table VIII-1

Table VIII-2

Table IX-1

Table IX-2

Table IX-3
Table IX-4
Table IX-5
Table IX-6
Table IX-7
Table IX-8
Table IX-9
Table IX-10
Table IX-11
Table IX-12

Table IX-13
Estimates of particulate emission losses from     VI-29
  raw material handling reported from 16
  ferroalloy plants
Reported estimates of particulate emission        VI-31
  losses from product handling in ferro-
  alloy plants
Summary of production data during EPA tests       VI-39
Summary of EPA ferroalloy furnace emission        VI-40
  tests
Comparison of EPA test results and question-      VI-44
  naire data
Particle size samples                             VI-46
Particle size data from EPA tests                 VI-47
                                                    •
Chemical analysis of samples (percent)            VI-49
Reported emission data and related                VI-53
  information for well-controlled Japanese
  submerged-arc furnaces
State regulations of allowable emissions        VIII- 2
  from general process sources
Factors for process weights and ferroalloy      VIII- 4
  production related to furnace kilowatt
  capaci ty
Sources and values of ores containing 35 or       IX- 5
  more percent manganese, 1962-1971
Annual production of ferromanganese and           IX- 8
  silicomanganese (short tons]
Sources and values of ferromanganese              IX- 9
Sources and values of silicomanganese             IX-10
Sources and values of calcium carbide             IX-12
Selected statistics on chromite ore               IX-13
Price movements of chromite ore                   IX-15
Chromite imports, 46% or more Cr^CL content       IX-16
Selected statistics on ferrochromium              IX-18
Selected statistics on ferrosilicon               IX-23
Model furnace parameters                          IX-28
Control costs for fabric filters on
  open furnaces                                   IX-30
Control costs for fabric filters on
open furnaces (reported by industry)              IX-34
                                   XII

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Table IX-14      Control  costs for wet scrubbers on
                   open furnaces                                   IX-36

Table IX-15      Control  costs for a separate tapping fume
                   collection system                               IX-40

Table IX-16      Comparison of capital and annual costs
                   for an open and a totally enclosed
                   HC FeMn and SiMn furnace producing
                   HC FeMn or SiMn                                 IX-44

Table IX-17      Aggregate operating results for three
                   representative ferroalloy firms
                   1963-1971                                       IX-47

Table IX-18      Model plant income statements                     IX-48

Table IX-19      Model plant income statements                     IX-49

Table IX-20      Percentage of production and control
                   costs                                           IX-52

Table A-l        Typical dust and fume analysis  for furnace E     A-14

Table A-2        Key  to sample  numbers for  tables A-3  through     A-28 - A-34
                   A-12

Table A-3        Particulate emission concentrations and rates    A-35
                   from uncontrplled  test points

Table A-4        Particulate emission concentrations and rates    A-36
                   to atmosphere from controlled  test  points

Table A-5        Particulate losses from the fugitive  fume hood   A-37

Table A-6        Particulate emission concentrations and rates    A-38
                   to atmosphere from tapping

Table A-7        Collection efficiency (impinger  section only)of  A-39
                   scrubber serving furnace C

Table A-8        Collection efficiency (impinger  section only) of A-40
                   baghouse serving furnace D

Table A-9        Collection efficiency (impinger  section only)    A-41
                   of precipitator serving furnace E
Table A-10      Collection efficiency (impinger section only)    A-42
                   of baghouse  serving furnace  F

Table A-ll       Collection efficiency (impinqer  section only) of A-43
                   scrubber serving furnace G

Table A-12      Particulate emissions  (impinger section  only)    A-44
                   from  furnace H

Table A-l3      Furnace  gas  volumes                              A-45

Table 1-1        Location  of  traverse points  in  circular stacks   B-3

Table C-l        Opacity  of emissions reported  from  EPA tests     C-3

Table C-2        Opacity  of emissions reported  from  questionnaire C-4
                 data

Table D-l        Particle  size  vs  collection  efficiency of EPA-   D-9
                 tested  control  equipment  (percent)
                                   xiii

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Table D-2        Particulate emissions by particle size from      D-10
                   uncontrolled FeCrSi furnace (Ib/hr)

Table D-3        Particulate emissions by particle size from      D-ll
                   the scrubber inlet of a SiMn furnace (Ib/hr)

Table D-4        Particulate emissions by particle size from      D-12
                   scrubber outlet of a SiMn furnace   (Ib/hr)

Table D-5        Particulate emissions by particle size from      D-13
                   uncontrolled tapping of a SiMn furnace
                   (Ib/tap)

Table D-6        Particulate emissions by particle size from a    D-14
                   FeCrSi furnace at inlet to baghouse

Table D-7        Particulate emissions by particle size from      D-15
                   baghouse exhaust on FeCrSi furnace  (Ib/hr)

Table. D-8        Particulate emissions by particle size from      D-16
                    HC  FeCr furnace at precipitator inlet
                   (Ib/hr)
Table D-9        Particulate emissions by particle size from      D-17
                    HC  FeCr furnace at precipitator outlet
                   (Ib/hr)
Table D-10       Particulate emissions by particle size from      D-18
                   SiMn furnace at Aeronetics scrubbing inlet
                   (Ib/hr)

Table D-ll       Particulate emissions by particle size from      D-19
                   SiMn furnace at Aeronetics scrubber outlet
                   (Ib/hr)

Table E-l        Number and types of analysis made of  ten         ,£_2
                   furnaces sampled

Table E-2        X-ray diffractometer settings (furnaces A&B)     E-fi
Table E-3        Metals analysis of particulates  (furnaces A&B)   E-ll

Table E-4        Instrumental parameters (furnaces A&B)           E-12
Table E-5        Electron beam X-ray microanalysis results from   E-l6
                   qualitative analyses  (furnaces A&B)
Table E-6        Optical emission analysis (wt %) (furnaces A&B)  E-18

Table E-7        Qualitative electron beam X-ray microanalysis    E-23
                   (furnace C)

Table E-8        Instrumental parameters (furnace C)              E-25

Table E-9        Atomic absorption analysis  results elemental     £_26
                   concentration (wt %)  (furnace  C)

Table E-10       Optical emission spectrography  (furnace C)       E-28

Table E-ll       Metal analysis of ore and slag samples           E-29
                   (furnace C)

Table E-12       Qualitative electron beam X-ray microanalysis    E-33
                   (furnace D)
                                     xiv

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Table E-13       Elemental analysis of particulate matter          E-36
                   collected at outlet and inlet of a
                   baghouse serving a ferrochromesilicon
                   furnace (atomic absorption) (furnace D)

Table E-14       Optical emission spectrography (furnace D)        E-38

Table E-15       Metal and other analyses of collected             E-41
                   particulates from furnace D
Table E-16       Qualitative electron beam X-ray microanalysis     ^"45
                   arid atmoic absorption results from sample
                   collected at precipitator inlet duct (furnace E)

Table E-17       Analysis of particulates collected in a           £-47
                   precipitator (furnace E)

Table E-18       Analysis of filters and residues (furnace F)      E-5
Table E-19       Analysis of filter and residue samples            E-54
                   (furnace G)

Table E-20       Chemical analysis of particulates from            E-57
                   furnace H

Table E-21       Chemical analysis of particulates from            £.59
                   furnace H

Table E-22       Chemical analysis of particulates from            E-61
                   furnace H

Table E-23       Chemical analysis of particulates from            E-63
                   furnace H

Table E-24       Chemical analysis of particulates from            £.55
                   furnace K

Table E-25       Chemical analysis of particulates from            E-68
                   furnace K

Table E-26       Chemical analysis of particulate emissions        E-71
                   from furnace L

Table E-27       Chemical analysis of particulate emissions        £.73
                   from furnace L
Table E-28       Chemical analysis  of particulate emissions       £.75
                   from furnace L
Table F-l        United States imports of ferroalloys and          F-l - F-5
                   metals
                                     xv

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                                LIST OF FIGURES
Figure IV-1
Figure V-l
Figure V-2
Figure V-3
Figure V-4
Figure V-5
Figure VI-1

Figure VI1-1

Figure VI1-2
Figure VII-3
Figure VII-4

Figure VI1-5
Figure VII-6
Figure VII-7
Figure VI1-8
Figure VII-9

Figure V1I-10

Figure VII-11

Figure IX-1

Figure IX-2

Figure A-l
Figure A-2
Figure A-3
Figure A-4
Figure A-5
Figure A-6
                                                         Page
Ferroalloy producers,  1971                               . IV-4
Submerged-arc furnace  for ferroalloy production          Vr2
Cross section of open  furnace                            V-5
Typical flow sheet for LC ferrochrome                    V-7
Simplex vacuum furnace for ferroalloy production         V-10
Induction melting furnace                                V-ll
Ferroalloy production  flow diagram showing               VI-2
  potential emission points
High energy fume scrubbing system for submerged-         VI1-2
  arc furnace
Steam-hot water scrubber system                          VII-4
Typical baghouse                                         VII-7
Baghouse system with cooling train for submerged-        VII-9
  arc furnace
Covered furnace with mix seals                           VII-11
Covered furnace with fixed.seals                         VII-11
Shaft kiln on HC ferromanganese furnace                  VI1-14
Rotary scrubber used on covered furnaces                 VII-15
Cutaway view of flat surface-type electrostatic          VII-18
  precipitator
Spray tower in conjunction with electrostatic            VII-21
  precipitator
Flow diagram of typical waste-water treatment            VI1-24
  facility
Capital costs of open furnace control with fabric        IX-31
  fi1ters
Capital costs of open furnace control with wet           IX-37
  scrubber

Uncontrolled ferrochrome silicon furnace                 A-2
Uncontrolled chrome ore/lime melt furnace                A-4
Scrubber system serving silicomanganese furnace          A-5
Scrubber efficiency as function of pressure drop         A-8
Baghouse serving ferrochrome silicon furnace             A-9
Electrostatic precipitator serving HC ferrochrome        A-l2
  furnace
                                      xvi

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                                                                           Page
 Figure A-7        Plan view of baghouse system on silicon furnace          A-15
 Figure A-8        Eight-compartment,  open-type baghouse  showing            A-18
                     sampling points
 Figure A-9       Aeronetics    scrubbing system                            A-19
 Figure A-10       Covered  ferrosilicon  furnace with  scrubbers               A-21

 Figure A-ll       Covered  calcium carbide furnace with scrubber            A-23
 Figure A-12       Covered  ferromanganese furnace with sealed electrodes    A-25
                     served by  three Venturis in series
 Figure A-13       Covered  silicomanganese furnace with sealed electrodes   A-27
                     served by  two-stage venturi scrubber
 Figure  1-1        Minimum  number of traverse points                         B-2
 Figure 1-2        Cross section of circular stack showing  location of       B-2
                     traverse points on  perpendicular diameters
 Figure  1-3        Cross section of rectangular stack divided into 12        B-2
                     equal  areas, with traverse points at  centroid of
                     each area
 Figure 2-1        Pi tot tube manometer assembly                             B~3
 Figure 2-2        Velocity traverse data sheet                             B-4
Figure 3-1        Grab sampling train                                      B-5
Figure 3-2        Integrated gas-sampling train                            B-5
Figure 5-1        Particulate sampling train                               R-6
 Figure 5-2        Particulate  field data sheet                            B-7
 Figure 5-3        Analytical data sheet                                    B-7
 Figure 6-1        S02  sampling train                                        B-9
 Figure C-l        Emission points where visible emissions were read        C-5
                     during EPA tests on open and covered  furnaces
 Figure C-2        Visible  emissions recording  sheet                        C-6,7
 Figure  D-l        Andersen sampler showing assembled and  disassembled       D-3
                     sections
 Figure  D-2        Brink sampler showing assembled and disassembled         D-5
                     sections
 Figure  D-3        Particle sizing train                                    D-6
 Figure  D-4        Particle size distribution of uncontrolled fumes         D-20
                     from a FeCrSi furnace
 Figure D-5        Particle size distribution of SiMn fumes entering        D-21
                     a  scrubber serving  an open furnace
 Figure D-6        Particle size distribution of SiMn fumes from a          D-22
                     scrubber serving an open furnace
                                     xvi i

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                                                                           Page
 Figure D-7        Particle size distribution of uncontrolled tapping        D-23
                     fumes from SiMn furnace

 Figure 0-8        Particle size distribution of FeCrSi fumes entering      D-24
                     a baghouse

 Figure D-9        Particle size distribution of FeCrSi fumes from a        D-25
                     baghouse serving an open furnace
 Figure D-10       Particle  size  distribution  of (HC)  FeCr  fumes entering   D-26
                     a  precipitator  serving  an open furnace

Figure D-ll       Particle size distribution of  (HC)  FeCr fumes  from a     D-27
                    precipitator serving an  open furnace
Figure D-12       Particle size distribution of  SiMn  fumes  entering a       D-28
                    scrubber serving an open furnace
Figure D-13       Particle size distribution of  SiMn  fumes  from a           D-29
                    scrubber serving an open furnace
Figure E-l        Drawing of condensate from ferrochrome operation         E-5
                    areas analyzed
Figure E-2        Crystal!ographic d-spacing - Angstrom units              E-8
                                       xvi i i

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              AIR POLLUTION CONTROL ENGINEERING AND COST STUDY
                         OF THE FERROALLOY INDUSTRY

                            I.   INTRODUCTION

     In early 1970, a cooperative study on control  of atmospheric emissions
from the ferroalloy industry was initiated.  The study was to be performed
jointly by the United States Environmental  Protection Agency (then known
as the National Air Pollution Control  Administration) and the Manufac-
turing Chemists Association (since replaced by The  Ferroalloy Association).
The purpose of the study was to prepare guidelines  for control  agencies and
plant management to use in controlling air pollution from the industry  and
to set priorities for research projects that would  result in improved
control methods.
     The Clean Air Amendments of 1970  were enacted  into law after the study
was started.  Consequently, the report has been supplemented with data  to
assist industry and government in the  implementation of the new law.
     The study is culminated in this report, which  provides information on
the following aspects of the ferroalloy industry:
     1.  The significance of the industry in the American industrial  complex.
     2.  Industry characteristics such as growth rate, raw materials,
         processes (other than the manufacture of ferroalloys in a blast
         furnace), consumer products,  and number and location of producers.
     3.  Atmospheric emissions from production of ferroalloys and calcium
         carbide.
     4.  Methods and equipment used to limit these  emissions.
     5.  The cost and economic impact  of air pollution control.
                                  1-1

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    6.  A brief discussion of water pollution and solid waste disposal
         problems.
    The primary manufacturing process used in the ferroalloy industry is
based on the submerged-arc furnace, which is the focus of discussion in
this report.  The two main sources of data used in this report were
(1) questionnaire responses from approximately 80 percent of the United
States ferroalloy industry, and (2) measurements of emissions from ferro-
alloy plant electric furnaces.  (The measurements were performed by a con-
tractor of the Environmental Protection Agency and arranged and scheduled
with the assistance of The Ferroalloy Association.)
    This report has been prepared for air pollution control officials,
ferroalloy plant operators and their technical staffs, and others con-
cerned and interested in air pollution emanating from the ferroalloy
industry.
     Ferroalloys are made from ores in which the metallic constituent has
a relatively high affinity for oxygen and for other non-metals, and con-
sequently require substantial quantities of electrical energy in the
winning of them from their ores.  Ferroalloys include products made by
submerged-arc smelting, alumino/silico thermic process, vacuum furnaces,
or the electrolytic production of relatively pure metal.  The primary
products are manganese, chromium,and silicon alloys.
                                   1-2

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                          II.  SUMMARY OF STUDY

A.  FERROALLOY PRODUCTION
    The United States is the world's largest producer and user of
ferroalloys.  In 1971 about 2,000,000 tons of ferroalloys were pro-
duced by the ferroalloy industry in the United States.   In addition, about
400,000 tons of high-carbon ferromanganese were manufactured by the iron
and steel industry in blast furnaces.
    Ferroalloy consumption in the United States for 1971  was 2.3 million
tons exclusive of blast furnace production.   Consumption  of ferroalloys
showed an average annual increase of 2 percent during the 10 years  prior to
1972, while production grew at an average rate of 1.5 percent per year.   The
difference between domestic production and consumption was m&de up  by foreign
imports.  For the year 1971 imports averaged 380,000 tons or 19 percent of
domestic production and had a total value of $116,000,000.
B.  MANUFACTURING PROCESSES
    The ferroalloys considered in this study are produced primarily in
electric submerged-arc furnaces and to a limited extent in electric open-
arc furnaces.  Although calcium carbide is not a ferroalloy, it is
included in the study because it too is made by the ferroalloy industry 1n
submerged-arc furnaces.  Also included are certain ferroalloys produced
by the alumino-silico thermic process, vacuum furnace,  and electrolytic
process.  Ferrophosphorus is a ferroalloy produced in submerged-arc
furnaces, but because it is made as a byproduct outside of the ferroalloy
industry, it is not included in this study.
                                  II-l

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     The submerged-arc furnace consists  of a  high-temperature refrac-
tory-lined crucible with a taphole or arrangement  of tapholes at the
hearth surface level from which the product is  intermittently withdrawn.
Over the hearth are vertically suspended carbon electrodes,  usually three,
arranged in a delta formation.  The carbon electrodes,  through  a system of
contact plates, electrode holders  for providing vertical movement, and bus
bars connected to furnace transformers,  convert electrical energy to heat
energy within the furnace charge.   In the United States there are about
160 submerged-arc ferroalloy furnaces ranging in electrical  capacity from
7,500 to 60,000 kilovolt-amperes.
     The conventional submerged-arc furnace uses carbon to reduce metallic
oxides in the charge and continuously produces  large quantities of carbon
monoxide along with other gases from volatile matter and moisture in the
charge materials.  The hot reaction gases rising through the furnace charge
carry emissions from the extremely high-temperature interior regions of the
furnace and entrain fine particles of charge materials. •
C.  TYPICAL EMISSIONS
     Total particulate emissions to the atmosphere from electric furnaces
in the ferroalloy industry during 1968 were estimated at 150,000 ton?.  This
figure is based on an overall control efficiency of about 40 percent.
     Most of the concentrations and mass emission  rates shown  in this  report
are based on EPA standard test methods as published in the  Federal  Register,
Volume 36, Number 159, Part II, August 17, 1971, or by that  specified  by  ASME
power test code No. 17.  Other reported emission rates are  based on methods
that may not be equivalent to the EPA or ASME methods.
     Fume emissions from submerged-arc furnaces are for the  most part,
directly associated with the evolution of gases (primarily  carbon
                                 II-2

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monoxide) from the reduction process.   Carbon monoxide emissions from the
furnace are substantial  and in some cases constitute a larger amount by
weight than the metallic product.   The amount of fumes and dust from an
uncontrolled furnace may vary from about 150 to 2,000 pounds per hour.
The amount varies according to the product being made, furnace size,
furnace design, charge material  preparation, and operating conditions.
     Dust and fume concentrations  in the untreated furnace gas from covered
and open furnaces differ considerably.  Concentrations of particulates
in the untreated gas from a covered furnace range from 5 to 30 grains per
standard cubic foot (gr/scf), whereas  particulate concentrations in the
untreated gas from an open furnace vary from 0.2 to 2.2 gr/scf.   The
difference is primarily due to the much lower gas volume from a covered
furnace.
     Use of an open submerged-arc  furnace requires treatment of large volumes
of hot gas, up to 500,000 acfm and at  temperatures up to 1200°F.  These large
volumes of gas and fumes formed from the smelting process, consisting of
carbon monoxide and evaporated metallic oxides, rises through the charge bed
to the surface of the charge.  At  the  surface, the gas is burned with oxygen
from the air and very small particles  of oxide fumes are formed.  The burned
reaction gas is immediately diluted with enormous quantities of induced air,
making gas cleaning difficult and  expensive.
     Much smaller volumes of gas (from 3,000 to 7,000 scfm) come from a
covered electric furnace.  In a covered furnace, unburned carbon monoxide
gas is collected under the roof of the cover and withdrawn from the furnace
without combustion, resulting in a gas volume which may be as low as 2
                                 II-3

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percent of that from an open furnace.
     The average size (by microscopic count) of fume particles from open
furnaces is reported to be less than 0.5 micron.  Except for the larger
dust particles of feed mix carried from the furnace, the particle fume
size is generally below 2 microns and ranges from 0.1  to 1.0 micron with
a geometric mean of 0.3 to 0.6 micron, depending upon the ferroalloy
prpduced.  In some cases, agglomeration does occur and the effective
particle size may be much larger.  The bulk density of the dry collected
particulates varies (depending upon the product made) from 4 to 30 pounds
per cubic foot.
     There are two types of covered furnaces.  The type used in the United
States ferroalloy industry is referred to in this report as a covered
furnace with mix seals, but it has also been called a semi-covered or semi-
enclosed furnace.  This is a furnace with a water-cooled cover where mix
materials are charged through openings around the electrodes.  The degree of
fume escaping the mix seals depends upon the product being made and furnace
operating conditions.  The other type of covered furnace is referred to in
th^s, report as a covered furnace with fixed seals but has also been called a
totally enclosed furnace or a sealed furnace.  This type of furnace is used
to some extent in Europe and Japan.  The mix is added through spouts attached
to the cover so that the mix columns and control gates provides a gas seal
for the furnace.  The electrodes are provided with mechanical seals.  Visual
observations indicate that very little fume escapes from a sealed furnace.
     The melting operation in open-arc furnaces, unlike smelting in sub-
merged-arc furnaces, produces less reaction gas.  Occasionally large
quantities of particulates can be emitted.  The open-arc furnace is used to
produce an intermediate product for subsequently making low-carbon (LC)
                                     II-4

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and medium-carbon (MC) ferromanganese and LC ferrochrome.
     Emissions from the tapping of ferroalloy furnaces are comparatively
low.  During the tapping interval  these emissions are 2 to 4 percent of those
from the uncontrolled furnace.   Usually the emissions result from the hot gases
rising from the molten metal  or slag, but in some cases additional  gas also
issues from the taphole.  Most furnaces are tapped periodically;  consequently,
taphole emissions occur about 10 to 20 percent of the furnace operating time.
     The dust emissions from raw material handling and preparation normally
are less than 0.25 percent of the material processed.  Dust emissions from
product sizing and handling are less than 0.05 percent of the material
processed.
D.  CONTROL OF PARTICULATE EMISSIONS
     Several methods are used to control emissions from electric  submerged-
arc furnaces.  Emissions from open furnaces in the United States  industry
are controlled by wet scrubbers, cloth filters, and electrostatic precipi-
tators.  Emissions from domestic covered furnaces, however, are controlled
only by wet scrubbers, primarily because of the high gas temperature
and safety hazard of handling carbon monoxide.  A few covered furnaces in
Japan are reported to use baghouses and electrostatic precipitators.  A
ceramic filter collector is reported to be operating in Europe on a covered
furnace producing calcium carbide.
     High-energy wet scrubbers on open furnaces producing silicomanganese,
HC ferrochromium, and ferrochrome-silicon have been demonstrated  to achieve
96 to 99 percent efficiency when the outlet mass emission rates varied from
11 to 64 pounds per hour depending upon the products and furnace  size.
Because of the large volumes of gas from an open furnace and high pressure drop

                                       II-5

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across the scrubber, the electrical  power requirements  of the scrubber
system are from 1000 to 3000 horsepower (hp)  depending  on the product and
size of the furnace.  In some cases  scrubber  power needs may be as  high
as 10 percent of the total  power to  the furnace.
     High-energy venturi scrubber systems used on covered furnaces  producing
ferromanganese, silicomanganese and  50 percent ferrosilicon was found to
remove up to 99.9 percent of the particulates from the  collected reaction
gases.  Because it was unsuitable to make tests at the  venturi inlet,
calculation of the efficiency was based on uncontrolled emission factors.
Depending upon the furnace size and  the product,  the outlet measured mass
emission rate from the venturi scrubber varies from 0.2 to 4.3 pounds per hour
and the power requirement for the control system ranges from 200 to 600 hp.
     The overall collection efficiencies (excluding tapping emissions) of
the two types of covered furnaces differ because of losses from the electrodes
on the semi-covered type.  The overall collecting efficiency of controls on
totally enclosed furnaces has been reported to be better than 99 percent.
Covered furnaces with mix seals are operating with overall collecting effi-
ciencies of 75 to 98 percent.  Questionnaire data reported particulate
losses from mix seals varied from 14 to 462 Ib/hr.  These losses are
dependent upon the  product, furnace size and operating conditions.   Large
totally enclosed furnaces are used in Europe and Japan to produce ferro-
manganese, silicomanganese and calcium carbide.  In Japan, totally
enclosed furnaces are used to produce 50-percent ferrosilicon  (using  iron
ore rather than scrap steel), HC ferrochrome  (using pretreated feed
material), and ferrochrome-silicon  (with close metallurgical  control).
A 12  mw totally enclosed furnace in Japan  is  producing 75 percent
ferrosilicon.  The  United States ferroalloy  industry has not  adopted
totally enclosed furnaces for the production  of  these alloys  because  of

                                  II-6

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safety, flexibility and economics.   Covered furnaces with mix seals,
used in the United States, produce  ferromanganese,  50 percent ferro-
silicon, 75 percent ferrosilicon, HC ferrochrome and calcium carbide.
The only totally enclosed furnace in the United States produces  silico-
manganese.
   •  Cloth filters on open ferroalloy furnaces producing silicomanganese,
ferrochrome-silicon, and silicon metal  have shown collecting efficiencies
of about 99 percent.  Depending upon the furnace size and the product,  the
outlet mass emission rate varies from 10 to 17 pounds per hour.   The  amount
of gas flow a cloth filter can handle without blinding when operating on
silica fume varies from about 1.5 to 2 cubic feet per minute per square
foot of filter area making it necessary to have several  thousand bags.
The amount of power required for fans on baghouse control systems serving
open furnaces in the United States  industry varies  from 1000 to  4500  hp,
depending on the product and size of the furnace.  The gas temperature
limitation (500°F for treated fiberglass) usually requires provisions  for
cooling the gas from the furnace.  On silica fumes  unequal bag life requires
frequent bag replacement as the bag life lasts from 18 months to 2 years.
The dust collected in the dry state must be handled with care to prevent
atmospheric emissions when it is moved to the disposal area; some success
has been reported with wetting the  dust before disposal.
     Electrostatic precipitators have been used in  the United States  on
two large open furnaces producing ferrochromium and ferrochrome-silicon.
The overall collecting efficiency (including tapping emissions)  on the
high-carbon (HC) ferrochrome furnace was more than  98 percent with an
average mass emission rate of 21 Ib/hr when operated at 33 mw.   To enhance

                                  II-7

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the collecting ability of the precipitator, it is necessary to pre-
condition the gases in a preconditioning chamber.  Part of the dust is
collected in the preconditioning spray chamber, and part is collected in
the electrostatic precipitator.  Fan horsepower requirements are low,
usually about 300 hp for a large furnace.
E.  GUIDELINES FOR EMISSION CONTROL
     The present state of knowledge and experience concerning air pol-
lution control equipment limits various types of such devices to specific
ferroalloys.  A baghouse, scrubber or electrostatic precipitator has not
been found to be universally suitable for use on every type of ferroalloy
furnace, and on every product, i.e., an electrostatic precipitator can
adequately control the emissions from an open furnace producing HC ferro-
chrome but would not be feasible on an open furnace producing silicon.
     A properly designed and operated air pollution control system on
an open furnace, which may include an electrostatic precipitator, fabric
filter, or scrubber, may be expected to remove 98 percent or greater of
the total particulate emissions from the furnace.  Four out of five EPA tests
show mass emission rates below 1 pound per mw-hr can be achieved for open
furnaces.  Although the fifth test showed it was slightly over the 1 pound
per mw-hr emission rate, the control device has some compensation advantages
1n energy conservation.  These rates vary depending upon the product and
control device used.
     Wet scrubbers are generally used to clean the collected gases from
covered furnaces.  The particulate concentation in the clean gas ranges
from 0.01 to 0.07 gr/scf, depending upon the product.  The scrubbers are
expected to have an efficiency of over 99 percent.  EPA tests show mass
emission rates from these scrubbers are less than 0.10 Ib/mw-hr.

                                   II-8

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     The clean gas from a covered furnace is either flared without visible
emissions or used as fuel.  In some cases covered furnaces with mix seals
require additional control equipment to control the fugitive fumes
escaping from the mix seals.  On the other hand, covered furnaces with fixed
seals do not require additional control equipment because the fugitive fume
losses from the electrode seals are held to a minimum and can be expected to
meet visual criteria.
     Tapping fumes from a covered furnace cannot be controlled by the
primary control system serving the furnace.  They require a separate
control system.  The air pollution control system serving an open furnace
can be designed to Include the control of emissions from the tapping
station.
     Higher than normal gaseous emissions from ferroalloy furnaces will
generally occur during periods of startup and prior to shutdown, periods
of poor tapping and excessive blowing caused by metallurgical problems,
and periods, of mechanical failure of furnace equipment and the emission
control device.
     Based on EPA test data, the mass emission rates from control systems
serving open furnaces were less than 0.50 Ib/mw-hr for slUcomanganese
and ferrochrome silicon production; less than 0.70 Ib/mw-hr for HC ferro-
chrome production; and less than 1.0 Ib/mw-hr for silicon production.
F.  RESEARCH AREAS
     Research and development may find new and better uses for totally
enclosed furnaces (covered furnaces with fixed seals) 1n the United States.
A worldwide evaluation could be made of totally enclosed furnace designs,
                                   II-9

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operating techniques, and manufacturing limitations and capabilities.   The
goal of such an evaluation would be to determine the extent to which these
furnaces can be used in manufacturing various alloys other than those for
which they are already used.
     Several other means by which research and development may help reduce
particulate emissions or lower the cost of production are:
     (1)  Examine raw materials and material  pretreatment that could
          result in a lower quantity of particulate emissions;
     (2)  Determine to what extent collected  particulates may be recycled;
     (3)  Search for new uses of collected particulates that may be sold
          to other industries;
     (4)  Investigate techniques of agglomeration by sonic, electrostatic,
          or other means;
     (5)  Investigate other uses for waste heat recovery of furnace reaction
          gas;
     (6)  Determine the extent and method of control of ladle fumes.
G.  ECONOMIC IMPACT OF EMISSION CONTROL
     Estimated industry profits ranged from 0 to 5 percent of sales in
recent years.  Prices are anticipated to remain weak in the foreseeable
future due to overcapacity and strong competition from foreign manufac-
turers.
     In 1970 about 50 percent of the existing furnace capacity operating
in the United States was equipped with particulate emission control systems
with efficiencies ranging from about 75 to 99 percent.  The estimated
cost of installing new control equipment on the remaining uncontrolled
furnaces is expected to be over $120 million.
                                  11-10

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                             III.  FERROALLOYS
A.  HISTORICAL BACKGROUND
     The beneficial influence of metals on the progress of modern
civilization is widely evident; no other material  has so many economical
applications.  Versatility, the keystone of success for metals,  is
dependent in large measure on the alloying materials that provide the
special properties needed for specific applications.
     More than 50 different alloys and metals, in  hundreds of various
compositions and sizes, are produced by the ferroalloy industry  for use
in the manufacture of steel, iron, and nonferrous  metals.
          The term "ferroalloys" is defined by Webster's New
          International Dictionary of the English  Language (1961)
          as "a crude alloy of iron with some other metal, used  for
          deoxidizing molten steel and making alloy steels."  In
          practice, however, the term is used loosely to include
          alloys or compounds containing little or no iron, and
          even relatively pure metals, employed to introduce
          additive or alloying elements in the production of
          steel.  "Addition agent" is perhaps a more correct
          terminology . . . although not as freely employed.  In
          using the term "ferroalloys" in the treatment of its
          statistics, the Bureau of Mines goes beyond the strict
          definition, following the sense of the general Webster
          definition of the prefix "ferro-" as denoting the
          "presence of, or connection with, iron."!
Ferroalloys include products made by submerged-arc smelting, the electric
furnace alumino/silico thermic process, vacuum furnaces, and the electrolytic
production of some relatively pure metals.  These  do not include aluminum,
magnesium, iron and steel, cadmium, copper, nickel, lead, zinc,  products
of the chloral kali industry or products such as beryllium and uranium made
by the metallurgical extraction process.  Table III-l shows a list of
                                   III-l

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                                                        Table III-l   COMPOSITION OF FERROALLOYS

Ferroalloy
1 Ferromanrtnese
Spiegel 'sen
Ferr^anganese silicon
Mec'um-carbon (MC) ferromanganese
L*-carbon (LC) ferromanganese
Electrolytic manganese
Standard LC ferrochrome
Simplex ferrochrome
Ferrochrome
Charge Cr
9» C Cr
US Cr 50
Chromsol Fe Cr
Blocking C Reg.
High-carbor (HC) FeCr
Ferrochrome-s1 1 icon
36/40
40/43
LC grade
Silicon metal
Ferromolybdenum
Vanadium metal
Chromium metal
gi C metal
BOX Ferrosilicon
65* Ferrosilicon
High porlty
75% Ferrosilicon
0.5! Ca
Low Al
85! Ferrosilicon
0.5! Ca
Low Al
0.5 to 1.5! Ca
SMZ alloy
Magnesium ferrosilicon
51 Hg
9! Mg
Silvery pig iron
Ferrot1tan1um
Ferrocolumbium
Alslfer
Ferrotungsten
High porlty
Low moly
High moly
Ferrovanadlum
Sill co manganese
3! C grade
2! C grade
1 . 5! C grade
Low C
High Mn
Calcium silicon
Chemicals
Mn
78
16 to ig
19 to 21
21 to 23
63 to 66
80 to 85

99.9












5 to 7







65 to 68
65 to 68
65 to 68
65 to 68
73

Fe










0.35
0.50
1.00
1.50











35




1.50 to 3.0
C



1.25 to
1.50
0.10
max.
0.30
0.75

0.05
0.020
0.010
0.020
9
5.5 to 6
5.5 to 6
5
4.5 to 6




Si


28 to 22
1.50
max.





40
43



9
|50
65
65
75
75
75




0.10
max.




3
2
1.5

85
85
85
85
60 to 65
50
50
14
16
22


40


12 to 14.5
15 to 17.5
18 to 20
60 to 65
S


























Al












0.40
max.
0.10








20




Cr






67 to 73
67 to 73
68 to 72
68 to 72
64 to 67
52 to 55
65 to 68
65 mm.
65 mln.
60 to 67
67 to 70
36
40


Ca











99.8 i














0.5
0.5
0.5 to
1.5







Ho










50 to 60















0 to 33

V











90












52 to
57
Ig to


T1



















70






W
























77 to 83
76 to 84
76 to 84



Zr


















5 to 7









Cb






















5 to 60





"American Metal Market, February 3, 1972.
                                                                         III-2

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ferroalloy products with general  specifications.   The  industry  also
produces materials used in the manufacture  of chemicals,  welding  rod
coatings, and catalysts.
     The demand for ferroalloys is  governed to a  large extent by  the
requirements of the iron and steel  industry for steels of greater
strength and corrosion resistance,  qualities that are  affected  both by
internal composition and external coatings.  Basic to  both higher strength
and greater corrosion resistance in steel  is the  deliberate adjustment
of the iron and carbon content of the steel and the addition of other
metal.  These other metals are precisely classified as ferro additives,
but are more commonly known as ferroalloys—the products  of the ferroalloy
industry.
     Before 1890, ferroalloys were  made in  the blast furnace and  to a
limited extent in the open-hearth furnace.   These ferroalloys were
high-carbon (HC) ferromanganese, low-percentage-manganese alloys  such as
spiegeleisen and silicon-spiegel, and 15-percent  ferrosilicon.  The blast
furnace method is still used to make about  70 percent  of  the HC
ferromanganese today.  Temperatures are not high  enough in the  blast
furnace or open-hearth furnace for  the reduction  of most  of the other
refractory oxides of the alloying metals; also, low-carbon (LC) alloys
cannot be produced in these furnaces.
     The introduction of the electric submerged-arc furnace resulted
from the invention of the electric  dynamo in 1867 and  from the  experimental
work on the electric-arc furnace by Sir W.  Siemens in  1878. The  calcium
carbide industry began in 1892 with the use of the electric submerged-arc
                                   III-3

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furnace.  The ferroalloy Industry actually began about 6 years  later
when the industry found it had an overcapacity of calcium carbide production
equipment and was forced to find other products that could be made in  their
furnaces.  About this time, the technique was first perfected for making  HC
ferrochromium and ferrosilicon alloys in the electric furnace.   In 1898,
the Spanish American War created a relatively large demand for  ferrochrome
to produce stronger steel for use in armor plate and projectiles.  Also,
ferrosilicon was in demand as a deoxidizer in producing steel of a
higher grade.  Further refinements in the furnace design allowed the
industry to produce newer and higher-grade ferroalloys.
     The discovery and development of the principal alloying elements  of
manganese, silicon, chromium, calcium, vanadium, tungsten, molybdenum,
zirconium, columbium, titanium, and boron are of historical interest.
All of these metals were first made during a relatively short period of
about 35 years beginning in 1774; however, the full metallurgical benefits
from the use of these alloying metals were not known until the  twentieth
century.
1.  Manganese and Manganese Alloys
     Manganese is used in the production of every grade of steel.  The
function of manganese in steel is threefold:
     (1)  It acts as a deoxidizer and cleanser of the molten steel.
     (2)  It combines with sulfur, thereby greatly improving the
          hot-working properties of the steel.
     (3)  It acts as an alloying element to improve the strength,
          toughness, and response to heat treatment of a wide
          variety of structural and engineering steels.
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     Metallic manganese was first produced by the Swedish  mineralogist,
Johan Gottlieb Gahn, in 1774.   There were no important" developments
concerning the use of manganese in the manufacture of steel  until  about
1839, when manganese carbide was used in the manufacture of  crucible  steel.
In 1856 Robert Musket used manganese in the form of spiegeleisen to
make the Bessemer process a success.  About the same time, William Siemens
patented the use of ferromanganese as an addition to molten  steel  to
counteract the adverse effects of sulfur.  In 1888 Robert  Hadfield announced
the discovery of the high-manganese steel generally known  as Hadfield
manganese steel.
     Because standard ferromanganese is relatively high in carbon, it
has some disadvantages for use in steels that must have a  high manganese
content and a low carbon content.  The advent of commercial  electric
furnaces made it possible to control carbon content in ferromanganese,
however, and ferromanganese with a low carbon content was  soon manufactured.
2.  Silicon and Silicon Alloys
     Silicon is used in the iron, steel, and nonferrous metal industries.
Various grades of ferrosilicon are used by the iron and steel industries
as deoxidizers and alloying elements.  Silicon metal  is used in the
aluminum industry as an alloying agent and in the chemical industry for
producing silicones.  Silicon  is used in manufacturing steel sheets for
electrical apparatus such as transformers, motors, generators, and
electromagnets.  The silicon content in the iron is important because
it decreases the electrical energy loss from magnetization.
                                 III-5

-------
     In the year 1810 the Swedish scientist Berzelius produced the
world's first ferrosilicon.  Fourteen years later he succeeded in
producing the first silicon metal.  Ferrosilicon with as much as 22
percent silicon was produced in 1870 by Volten.   Since then, the
advantages of ferrosilicon in manufacturing steel have become recognized.
3.  Chromium and Chromium Alloys
     Chromium is one of the most important alloying metals in modern iron
and steel metallurgy.  The well-known "stainless" and "heat resistant"
steels resist corrosion and oxidation at high temperatures because
substantial percentages of chromium are present.  Improved mechanical
properties and increased susceptibility to heat  treatment are imparted
to engineering steels by adding 1.0 to 3.5 percent chromium.
     Chromium was discovered in 1797 by the French chemist Vauguelin.
The first chromium alloy was made in 1821 by Berthier, who was the first
to produce chromium steels and to recognize the  improved properties that
chromium imparted to steel.
4.  Other Metals
     Other alloying metals such as vanadium, columbium, and molybdenum
add important beneficial properties to iron and  steel, even though
small percentages may be used.
B.  CURRENT USES AND PRODUCTION
     The joint effort of the steel and ferroalloy industry to manufacture
improved products for today's requirements has resulted in exceedingly
high-strength steelsJ  These steels provide yield and tensile strengths
                                    III-6

-------
(1n excess of 100,000 pounds  per square inch)  that  are about twice those
of high-strength, low-alloy steels,  and three  times as great as  those
of carbon steels.  Improvements  of similar magnitude have been accomplished
in manufacturing corrosion-resistant steals and  high-temperature alloys.
The improvements apply equally for the  nonferrous metals, such as aluminum,
copper, magnesium, and nickel.
     The principal ferro additives used as deoxidizers and cleansers of
molten steel are manganese and silicon, and to a lesser  extent calcium,
titanium, and zirconium.  Those  used for imparting  special properties to
steel and nonferrous metals or to the formation  of  alloy steels  are
manganese, silicon, chromium, columbium, vanadium,  tungsten, molybdenum,
zirconium, and other minor tonnage materials.
     The United States ferroalloy industry is  still  the  largest  in the world
but foreign production has increased at a rapid  rate particularly in Japan,
South Africa, and Norway (Tables III-2  and III-3).   During the 1950's and
1960's, the high level of steel  production and U. S. government  purchases
for stockpiling resulted in an increased demand  for ferroalloys.  This
increased demand, however, gave  foreign ferroalloy  producers greater incentive
to compete for the United States market.
     From 1950 to 1965, the United States increased production of specialty
ferroalloys, excluding ferromanganese and ferrosilicon,  from 196,856 to
                        2
1,020,000 tons per year.
                                   III-7

-------
Table III-2.  WORLD STEEL PRODUCTION VS  FERROALLOY  TURNOVER*

Country
USA
USSR
Japan
Germany (W)
United Kingdom
France
Belgium-
Luxembourg
Italy
Poland
Canada
Czechoslovakia
India
Australia
Sweden
Germany (E)
Spain
Austria
Netherlands
Brazil
S. Africa
Yugoslavia
Norway
Turkey
Bulgaria
Others
Total
Steel production,
net tons3
131,000,000
100,000,000
45,100,000
40,600,000
30,000,000
21,600,000

15,200,000
13,900,000
10,000,000
9,800,000
9,500,000
6,900,000
5,500,000
5,200,000
4,400,000
3,800,000
3,600,000
3,400,000
3,300,000
3,000,000
1,900,000
800,000
700,000
600,000
200,000
501,000,000
Ferroalloy turnover,
net tons9
2,820,000
2,120,000,
860,000b
740,000
471,000
658,000°
j
180,000d
300,000,
120,000d
200,000
90,000
150,000
100,000
185,000
23,000
71,500
50,000e
68,000.
35,000f
365,000
54,000
440,000
10, 5009
8,000d
3,000d
10,020,000
a!965 figures (latest available information)  except where  otherwise
 indicated.
 1964 figure, including estimated imports of  30,000 tons.
C1965 figures, includes 285,000 export tons.
Estimate.
eNearly all Austrian ferroalloys are imported.
Statistics available from ILAFA 1962 date, when Brazil's  steel
 production was 2,800,000.
Slncludes 5,000 tons of imports.
                                 III-8

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     Ferroalloy imports also increased for every product during  the  years
from 1960 through 1972.  United States imports of selected ferroalloys
for domestic consumption during this period are shown in Table  III-4,
along with the amount of United States consumption and the percentage of
imported ferroalloys.  Table III-5 shows the amount of ferroalloys  imported
for the United States Government stockpile.
C.  FUTURE TRENDS
     The continuing increase in the use of ferroalloys as additives  per
ton of steel is the result of the demand for more service per pound  of
steel used.  As various materials compete in the market place,  steels
will need to be tougher and longer lasting.  To achieve these qualities,
steelmakers will need to continue improving steel production technology
and the capabilities of steel products.  This means new uses and greater
amounts of ferro additives.
     Table III-6 shows the trend of ferroalloys being used by the steel
industry.  Ferroalloys used in the production of stainless steels are
anticipated to show a modest increase in the United States.  Table III-7
shows the production of stainless steel in the United States and the
free world.  The table shows that United States production of stainless
steel changed very little from 1965 to 1970.  Stainless steel production
in Europe and Japan, on the other hand, increased significantly during
this time.
     Electric furnaces are now 10 times larger than those of 20 years
ago.  Units of 40,000 kilovolt-amperes (kv-a) and higher are becoming
                                    111-10

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-------
Table III-6.   POUNDS  OF  ELEMENT.CONSUMED
    PER TON OF STEEL  PRODUCTION0
Element
Manganese
Silicon
Chromium
Year
1950
14.5
5.8
1.7
1970
14.5
6.0
3.6
1980
(projected)
14.5
6.1
3.5
  Table III-7.   PRODUCTION OE. STAINLESS STEEL
               IN  FREE WORLD'
                (net  tons)
Year
1965
1966
1967
1968
1969
EST.1970
EST.1975
EST.1980
U.S.A.
1,490,000
1,645,000
1,450,000
1,430,000
1,565,000
1,330,000
1,595,000
1,790,000
West Europe
1,520,000
1,660,000
1,800,000
1,990,000
2,050,000
2,080,000
2,810,000
3,440,000
Japan
635,000
730,000
1,040,000
1,150,000
1,490,000
1,595,000
2,200,000
2,750,000
Total
3,645,000
4,035,000
4,290,000
4,570,000
5,105,000
5,005,000
6,605,000
7,980,000
                    in-14

-------
common.  A number of furnaces  of about  60,000  kv-a  are operating and new
units of 72,000 kv-a are being planned.   It will  be increasingly difficult
for ferroalloy plants that are not installing  larger furnaces and material
handling facilities to maintain competitive positions.
     The demand for ferroalloys should  continue to  grow  at  a faster rate
than its major customer, the steel industry, because the growth rate of
materials requiring alloy additives is  two  to  three times that of plain-carbon
steels.  Pressure by steel's users for  higher-performance steels should
accelerate this demand for alloys.
     The growth of steel production in  the  United States has been projected
by BatteHe Memorial Institute for the  United  States Government in a
                                       Q
technological report (see Table III-8).
                                  111-15

-------
          Table II1-8.   PRODUCTION  OF  RAW  STEEL
         IN THE UNITED  STATES  BY  TYPE  OF FURNACE
         AND PROJECTIONS OF PRODUCTION TO  1980^
                    (1000 net  tons)
Year
1960
1967
1975
1980
Type of furnace
Open
hearth
86,368
70,690
44,000
36,000
Bessemer
1,189
a
-
-
Basic
oxygen
3,346
41 ,434
80,000
99,000
Electric
8,379
15,089
33,000
45,000

Total
99,282
127,213
157,000
180,000
Included with open-hearth  production;  278,000  tons  of Bessemer
steel  were reported in 1966.
                              111-16

-------
               IV.  FERROALLOY PLANTS IN THE UNITED STATES

     Table IV-1, entitled "Types, Sizes, and Locations of Ferroalloy
Producing Plants in the United States," tabulates the 44 known producing
plants in the United States through 1971.  The listing is given on the
basis of ownership and the geographic locations of the plants.  Also
listed are known products produced at each plant, general run of
products made, type of furnaces, and numbers of those producing ferro-
alloys and those producing calcium carbide.  This tabulation is representative
of 1971 status and it should be recognized that the companies may fre-
quently change their product lines, take furnaces out of service, and
start up idle capacity according to product demand or operating require-
ments.  The list does not reflect furnaces under construction or those
out of service.  A total of 145 furnaces are listed as producing ferro-
alloys, and 13 produce calcium carbide.
     A map of the United States, Figure IV-1, shows the number and approx-
imate geographical location of ferroalloy plants in each state.  Table
IV-2 shows a list of ferroalloy plants and electric furnaces by states.
Ohio leads with eight plants that have a total  of 58 electric furnaces.
West Virginia has the second highest number of furnaces, 25 in three
plants.
                                  IV-1

-------
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                                                              IV-2

-------
Table IV-2.  FERROALLOY PLANTS AND NUMBER OF
             ELECTRIC FURNACES BY STATES (1971)
State
Ohio
Alabama
Pennsylvania
Tennessee
Oregon
West Virginia
New York
Kentucky
Iowa
Washington
Texas
South Carolina
Okl ahoma
Mississippi
New Jersey
Totals
Plants
8
6
5
4
4
3
3
2
2
2
1
1
1
1
1 "
44
No. furnaces
Ferroalloy
52
12
0
14
8
25
6
11
5
6
3
2
0
0
1
145
Carbide
5
0
0
0
2
0
0
4
1
0
0
0
1
0
0
13
                      IV- 3

-------
Figure IV-1.  Ferroalloy producers, 1971.
               IV-4

-------
                       V.  FERROALLOY MANUFACTURE


A.  DESCRIPTION OF PROCESSES9'10'11

     Ferroalloy manufacturing processes are described in this section.

Listed below are the processes and the product groups manufactured by

each process.

     Submerged-arc furnace process - Silvery iron  (15-22% FeSi)
                                     50% Ferrosilicon
                                     65-75% Ferrosilicon
                                     Silicon metal
                                     Calcium silicon
                                     Silicon-manganese-zirconium (SMZ)
                                     High-carbon (HC) ferromanganese
                                     Silicomanganese
                                     Ferromanganese silicon
                                     Charge chrome and  HC  ferrochrome
                                     Ferrochrome-silicon
                                     Calcium carbide
     Exothermic process -
     Electrolytic process -
                                     Low-carbon (LC) ferrochrome
                                     LC ferromanganese
                                     Medium-carbon (MC) ferromanganese
                                     Chromium metal, FeTi, FeV and FeCb

                                     Chromium metal
                                     Manganese metal
                                     LC ferrochrome

                                     Ferrotitanium
1
     Vacuum furnace process -

     Induction furnace process -

    Submerged-Arc Furnace Process

     The general design of submerged-arc furnaces is basically the same

throughout the industry.  A schematic diagram of a submerged-arc furnace

is shown in Figure V-l.  The steel furnace shell is normally cylindrical

with a flat bottom and is supported on an open foundation that permits
                                   V-l

-------
                                          REFRACTORY
                                             LINING
                                        SHELL
                                          CRUCIBLE
                                           TAP HOLE
Figure V-1.  Submerged-arc furnace for ferroalloy production.
                     V-2

-------
air cooling and heat dissipation.   The bottom interior of the steel  shell
is lined with two or more layers of carbon blocks sealed with mortar.
The furnace shell's interior walls are lined with refractory or carbon
brick.  One or more tapholes for removing slag and metal are provided
through the furnace shell at the hearth level.  In some cases, the furnace
is designed to rotate.
     The furnace process is continuous.  Power is continuously applied to
the electrodes, and feed materials that consist mostly of reducing
material (coal or coke) and ores may be charged to the furnace on either
a continuous or an intermittent basis.  Normally three electrodes are
used and are suspended over the furnace hearth in a delta formation.
They protrude into the furnace charge to a depth of 3 to 5 feet and their
vertical movement is controlled by mechanical or hydraulic means.  This
electrode depth is continually varied as required to maintain a near-uniform
electrical  load.  The trend is to use self-baking electrodes for new large
furnaces.  The major smelting occurs in the "reaction zones" surrounding
the electrodes.  This smelting utilizes carbon reduction of metallic
oxides and continuously produces large quantities of carbon monoxide,  in
many cases in larger amounts than the metallic product.  Other sources of
primary gas are moisture in the charge materials, reducing agent volatile
matter, thermal decomposition products of the raw ore, and intermediate
products of reaction.  The gas rising out the top of the furnace carries
fume from the high-temperature regions of the furnace and also entrains
the finer size constituents of the charge.
     Submerged-arc furnaces have been generally built with open tops and
the reaction gases burn on the surface of the charge.  The combusted gases
                                  V-3

-------
are vented to the atmosphere through roof monitors,  or collected  by a
hood over the furnace crucible and directed by duct  work to dust  removal
equipment or vented by stacks to the atmosphere.   The furnace parts over
the crucible, such as the electrode holders, the  hangers, the current  con-
ductors, the contact plates, and the charging chutes, are exposed to the
radiant heat of the furnace and hot furnace gases.   These components must
receive effective heat protection through the use of cooling water flowing
through interior passages in the metal  parts.  Figure V-2 shows a cross
section of a typical open furnace and some accessory equipment.  Some
ferroalloys, such as high silicons, require regular  stoking and directed
mix placement, which can only be performed in an  open furnace.
     Submerged-arc furnaces producing certain ferroalloys have water-cooled
covers.  The collected uncombusted gases are cleaned by venturi or centri-
fugal scrubbers, and the gases may be flared or used as fuel.  In such
furnaces, the raw materials required to produce the  low-energy products do
not tend to bridge excessively, and regular stoking  of the charge is not
necessary.
     Submerged-arc furnaces generally operate continuously except for
periods of power interruption or mechanical breakdown of components.
Operating time averages 90 to 95 percent on an annual basis.
2.  Exothermic Process
     Several metals and low-carbon ferroalloys are produced by the
exothermic process.  However, it is used to a lesser extent than  the sub-
merged-arc furnace process.  Most of the charge material used in  the
exothermic process may be first produced by the submerged-arc or  open-arc
furnaces.  Silicon or aluminum, or a combination of the two, is the
                                  V-4

-------
                                                o
    CRANE FOR PASTE
  AND CASING HANDLING
                                                   ELECTRODE CASING
                                                       PLATFORM

                                                        GAS OFFTAKE
TAPPING
 FLOOR
    LADLE
                                                      I TRANSFORMER
                                                         OPERATING
                                                           FLOOR
              Figure V-2.  Cross section of open furnace.
                                V-5

-------
reducing agent.  This agent reacts with the charge to remove oxygen,
thus generating considerable heat; temperatures may reach several
thousand degrees.  Since the process is exothermic, the reduction  can
take place outside a furnace -- usually in ladles.  The techniques
employed are described in the following text.
a.  Silicon Reduction - Two principal products, LC ferrochrome and LC or
MC ferromanganese, are produced by silicon reduction.  A flow diagram of
a typical silicon reduction process for manufacturing LC ferrochrome
is shown in Figure V-3.  First, chromium ore and lime are fused together
in a furnace to form a chrome ore/lime melt.  Second, a known amount
of the melt is poured into the No. 1 reaction ladle followed by a  known
quantity of molten ferrochrome-silicon previously produced in a No.  2
ladle.  Ladle reaction results in a rapid reduction of the chrome  from
its oxide and the formation of LC ferrochrome and a calcium silicate
slag.
     Since the slag still contains recoverable chromium oxide, a second
silicon reduction is made, in the No. 2 ladle, with molten ferrochrome-
silicon from the submerged-arc furnace.  Reaction in the No. 2 ladle
produces the ferrochrome-silicon used in the No. 1 ladle for the next heat,
and a throw-away slag with low chromium content.  LC and MC ferromanganese
are produced by a similar practice using a silicon-bearing manganese  alloy
for reduction.
     The silicon reduction results in strong agitation of the molten  bath
and a rise in temperature.  For about 5 minutes per heat the elevated
temperature and agitation produce emissions whose characteristics  are
similar to those from submerged-arc furnaces.
                                  V-6

-------
                                                    ELECTRODES
     FeCrSi
 SUBMERGED-ARC
    FURNACE
THROW-AWAY
   SLAG
 Cr ORE/LIME MELT
    OPEN-ARC
    FURNACE
                      SECONDARY
                      THROW-AWAY
                        SLAG
 PRODUCT
 LC FeCr
± 70% Cr
           Figure V-3. Typical flow sheet for LC ferrochrome.
                                V-7

-------
b.  Aluminum Reduction - Aluminum reduction is  used to  produce  chromium
metal, ferrotitanium, ferrovanadium,  and ferrocolumbium.   Although  aluminum
is a more expensive reductant than carbon or silicon, the products  are
purer.  Mixed aluminothermal-silicothermal  processing is  used for the
production of ferromolybdenum and ferrotungsten.   Usually such  alloys are
produced by exothermic reactions initiated by an  external  heat  source and
carried out in open vessels.   Aluminothermal  manganese  is being replaced
by electrolytic manganese.   The high-temperature  reaction of aluminum
reduction produces emissions for a limited time similar to those produced
by silicon reduction.
3.  Electrolytic Process
     The pure metals of manganese and chromium  are now  generally produced
electrolytically.  In this  process, simple ions of the  metal contained in
an electrolyte of modest concentration are plated on cathodes by a  low-
voltage direct current.  The pure metal, collected as a film about  1/8
inch thick on the cathode,  is removed and prepared for  shipment.
Metal deposition usually occurs in a number of  cells with multiple  plates
connected in a series of parallel electrical  circuits;  all are  contained
in a ventilated building.
     Because electrolyte preparation is complex,  feed materials require
some chemical preprocessing.  For example, manganese ores are calcined
and leached (usually to form manganese sulfate),  mixed  with ammonium
salts, and delivered in solution to the bath.  The sources of the feed
materials are ores, high-metal-oxide slags, and ferroalloys produced in
submerged-arc furnaces.
                                  V-8

-------
     The electrolytic process does not generate participate emissions,  but
it does result in some minor emissions of ammonia or sulfur oxides.   These
emissions have not been quantified.
4.  Vacuum and Induction Furnace Process
     The vacuum furnace process for producing LC ferrochrome was developed
commercially in the early 1950's.  In this process, carbon is removed from
HC ferrochrome in a solid state within vacuum furnaces (see Figure V-4)
carefully controlled at a temperature near the melting point of the alloy.
The process is based on the oxidation of HC ferrochrome by the oxygen in
silica or chrome oxide.  Carbon monoxide gas resulting from the reaction
is pumped out of the furnace to maintain a high vacuum and to facilitate
decarburization of the ferrochrome.  Heat is supplied to the furnaces by
electric resistance elements.  The vacuum furnace process causes no  par-
ticulate emissions.  The small  quantities of carbon monoxide gas that
evolve from the reaction are withdrawn by a steam jet ejector.
     Induction furnaces, either low-frequency or high-frequency, are used
to produce small tonnages of a  few specialty alloys through remelting of
the required constituents (see  Figure V-5).
B.  METALLURGY OF THE PROCESSES9'10'12'13
     Ferroalloys are usually produced by carbothermal  smelting in electric
submerged-arc furnaces.  Depending on the product made, the raw materials
used most often are quartz, manganese ore, chrome ore, scrap iron, and
reducing agent.  Sometimes wood chips are required for porosity within the
furnace charge.  The purpose of the reducing agent is  to remove oxygen
from the metallic oxide ore so  that droplets of the metal fall  to the
hearth and form a metal pool.  The reducing agent is usually in the  form
of lumpy or pea-size by-product coke and low-volatile  coal.   In the  pro-
                                   V-9

-------
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             V-10

-------
V-11

-------
duction of certain types of products, however,  silicon  or aluminum is
used as the reducing agent.
     Iron content in the ferroalloy charge materials  greatly facilitates
the ferroalloy smelting operation.   In the presence of  iron, some  of the
nonferrous elements can be reduced  by carbon at lower temperatures.   Iron
also serves as a collector for the  alloying element and makes it easier
to reduce.
     Before smelting can take place in the submerged-arc furnace,  the
electrical energy must be changed to heat at extremely  high temperatures.
The conversion is due to the current flow through the resistance path  of
the charge materials between the electrode tips.   Alternating current  is
used as the energy because of convenience and availability.  With  the
use of such current, the tip of each electrode continually changes its
polarity and an alternating current flows between the tips.  The current
path in the furnace establishes the reaction zone. The possible maximum
internal temperature can be estimated by the fact that  carbon vaporizes at
                          Q
6620° to 6820° Fahrenheit.   Temperatures near this level are necessary for
final reduction of the ores in the lower region of the  furnace.
     The upper portion of the furnace charge may be considered similar
to a packed tower or bed, with a portion of. the heat from  the rising not gases
                                                  q
being transferred to the descending raw materials.   The area above
the electrode tips contains unreacted and partially reacted raw materials.
The lower parts of the vertically positioned electrodes are submerged
into the mix to a depth of 3 to 5 feet and are within 3 to 6 feet  of
the hearth.  If the electrodes are not submerged deeply enough,
excessive fumes and poor operation will result.  Molten alloy accumulates
at the base of the electrodes in the furnace and is periodically  removed
through a taphole.
                                   V-12

-------
     Simplified equations illustrating the manufacture of ferroalloys
are as follows:
Ore Reducing
constituents agent Heat
Cr203 + 3C — >
MnO + c — -»
S1.02 + 2C — »
Fe203 + 3C 	 *
CaO
CaO
MgO
Si02
+ 3C 	 ^
X
r

Molten
alloy
2 Cr
Mn
Si
2 Fe
CaC.
Furnace
gas
+ 3 CO
+ CO
+ 2 CO
+ 3 CO
+ CO
                                                Slag
     Reduction reactions require high temperatures, up to 2000°C.   As
shown in the equations, carbon monoxide gas is evolved from the smelting
reaction.  In the case of silicon metal, about 2 pounds of carbon  monoxide
are produced for each pound of metal; significant amounts of silicon
monoxide are also produced as an intermediate.
C.  SOURCES, PREPARATION AND HANDLING OF RAW MATERIALS
     The evaluation and selection of individual  ores is highly technical
and specialized.  The ores must be analyzed not only for the primary
chemical constituents but also for undesirable elements.   Cost of  various
ores, including government tariffs and freight charges, is an essential  con-
sideration.  Other considerations in the purchase of ores are their physical
characteristics, ease of reduction, and analytical  specifications  necessary
to meet customer requirements.
                                   V-13

-------
     Most ores come to the market in the dressed"state and are  sold
based on their content of the desired metal  oxide,  i.e.,  manganese  oxide,
chromium oxide, etc.  In general, ores containing high percentages  of
metal oxides are easier to process and result in lower production costs
than ores with lower percentages of metal  oxides.
     The United States is dependent almost entirely upon  foreign sources
of manganese and chromium ores.  These ores are imported  mainly from
South America, Africa, Turkey, India, and Russia.   Since  the time interval
between mining the ores and their receipt at ferroalloy plants  is
usually months, or even as long as a year, a substantial  stock  of man-
ganese and chromium ores must be maintained.  The general practice  is to
procure ores from familiar sources because the fundamental chemical com-
position and physical properties of known manganese and chromium ore
deposits are reasonably well defined.  Such ores have already demon-
strated their suitability for the intended smelting process.
     Chromium ores imported for ferroalloy production in  the United
States contain about 45 to 53 percent Cr20,.  The Mn content of the
manganese ores ranges from 43 to 54 percent.  Table V-l shows typical
chemical compositions of the three most widely used ores.
     In addition to chromium and manganese ores, columbiurn-bearing
ores or slags, titanium oxides, and zirconium oxides are  also imported.
The United States Bureau of Mines publishes information on ores
imported for ferroalloy production (see Table V-2).
     Commercial sources of vanadium- and tungsten-bearing ores  exist
in the United States.  High-purity quartzes or quartzites with low
alumina, and in some cases low iron oxide, are found in selected areas
                                  V-14

-------
Table V-l.   CHEMICAL COMPOSITION OF ORES
                  (percent)
Chemical
constituent
Mn
Si02
Cr2°3
Fe
A1203
MgO
BaO
CaO
P
H2°
Manganese
ore1^
43 to 54
4.15

1 to 2
1 to 3
0.1 to 2
1 to 3
1 to 3
0.18
5 to 16
Silicon
ore14

98.5








Chromium
ore
*
1.2
45 to 53
11
9.8
16.6




                 V-15

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of this country.  A few high-quality limestone deposits are also avail-
able domestically.
     Shipments of ore, plus .the required quartzes'or quartzites, lime,
scrap steel turnings, reducing agents, etc., are generally transported
to plants by railway or river barge.  Ores are unloaded by traveling
cranes or railroad-car dumpers and moved with belt conveyors to storage
areas. Ores are stockpiled in large quantities depending  on the furnace
capacity, marketing situation, and storage capacity of the plant.   A
large inventory of stockpiles may be required for economic reasons.   For
example, a low-grade and a high-grade chromium ore may be blended to  form
the desired charge materials rather than use only the more expensive
high-grade ore.
     The furnace charge must be carefully prepared to manufacture a
specific ferroalloy.  Free moisture in the raw materials ranges from  10
to 20 percent.  In some plants, raw materials are dried before  they are
fed to the furnaces.
     Size of the ore is important; it should be neither too large nor
too small.  Oversize ores must be crushed to a suitable size.   Fine ores,
such as flotation concentrates, cannot be charged directly into a sub-
merged-arc furnace because they lack porosity and do not allow  the
release of reaction gasas.  Dust losses from fine ores may be as high
as 15 percent of the ore charged.  However, when fine ores are  charged
into an open-arc furnace (melt furnace), the dust loss has been found
to be much less.  Uhile work has been done to increase production by
briquetting fine ores, the I). S. industry has had difficulty justifying
the cost.
                                  V-17

-------
     After preparation, the raw materials are conveyed to a  mix house
where they are weighed and blended.   The weighed mix is then moved by
conveyors, buckets, skip hoists, or  cars to the hoppers above the furnaces,
from where it may periodically be charged to the furnaces by gravity flow
through chutes.
D.  PRODUCT SIZING AND HANDLING
     Ferroalloys are marketed in a broad rancje of sizes depending on
final usage, from pieces weighing 75 pounds to granules of 100 mesh or
finer.  Ferroalloys are intermediate products, and are usually melted
and blended with molten metal.  For  this reason, the ferroalloy product
size is important.
     Molten ferroalloys from the submerged-arc furnaces are  generally
tapped into refractory-lined ladles  or into molds or chills  for cooling.
The chills are low, flat, iron or steel  pans that allow heat to dissipate
rapidly from the molten metal.  Calcium carbide is tapped into chills on
either a continuous or an intermittent basis.  After the ferroalloy has
cooled to a workable temperature, it is cleaned of adhering  slag and
sized to market specifications.
     Sizing consists of breaking the large ingots by drop weights or ham-
mers, followed by crushing (with large jaw crushers, roll mills, or
grinders) and screening.  Conveyors  and elevators move the product
between the crushing and screening operations.  Storage bins hold the
finished or intermediate products.
     Because acetylene gas can be formed with airborne moisture during
sizing and handling of calcium carbide, proper ventilation is essential
to prevent small pockets of acetylene gas from forming inside the
equipment.
                                   V-18

-------
                       VI.  ATMOSPHERIC EMISSIONS
A.  SOURCES AND CHARACTERISTICS OF EMISSIONS
1.  Sources of Emissions
    Emissions occur from several areas of the production facility.   Dust
emissions result from handling of raw materials and from crushing,
screening, drying, weighing, and mixing operations.  Particulates mostly
as fume, carbon monoxide (CO), and dust are emitted from the furnace.   Fumes
are also emitted during furnace tapping and ladle transfer operations.
Figure VI-T is a flow diagram of a ferroalloy production facility showing
points of potential dust and fume emissions.
2.  Sources and Characteristics of Emissions from Raw Materials Handling
and Preparation
    Raw materials are delivered to ferroalloy plants by ship, railroad  cars,
or trucks.  Materials such as ores, quartz or quartzite, limestone, fine
scrap steel, coke, coal, and wood chips are normally stored in separate
storage piles.  Materials range in size from 5 inches to 1/4 inch or finer and
may include fines generated by handling and processing operations.   To  minimize
dust entrainment by wind, raw material storage piles  may be sheltered  by block
walls, snow fences, or plastic covers, or may possibly be sprayed with  water.
    Fugitive dust may be generated at the plant site by heavy vehicles  used
for loading, unloading and transferring material.   These emissions  may  be
minimized by using a wetting agent or paving the plant yard.  Emissions also
occur when raw materials are loaded from storage piles into trucks  or gondola
cars with cranes or ship loaders.  Moisture in the raw materials, which may
be as high as 20 percent, tends to minimize these emissions.
                                  VI-1

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     The properties of participates emitted into the atmosphere from raw
material handling are similar to the natural properties of the ores.  Dusts
range in particle size from 3 to 100 microns.  Bulk density of this  dust
when collected ranges from 35 to 100 pounds per cubic foot.
     In a questionnaire survey, over 60 percent of the plants reported that
some raw materials are pretreated before conveyance to the furnaces.  Emission
controls for preparation equipment are reported to be 90 to 99 percent effective
for particulate removal.   (Scrubbers, cyclones, or baghouse collectors  are
used.)
     Use of dry materials results in smoother furnace operation and  reduced
offgas volumes.  Raw material moisture, as high as 20 percent, is  sometimes
reduced by the use of rotary or other type dryers.  Unless adequate  control
equipment is installed, however these dryers may cause heavy particulate emissions,
Raw materials charged to calcium carbide and chrome ore/lime melt  furnaces
are generally required to be dried.
3.   Sources and Characteristics of Emissions from Submerged-Arc Furnace Process
     By far the major pollution source in the ferroalloy production  process
is the furnace.  Large quantities of CO aas and particulates are continuously
produced by conventional submerged-arc furnaces.  The CO gas, venting from
the top of the furnace, carries fume from high-temperature regions of the
furnace and entrains finer sized constituents of the mix.   In many cases,
the weight of carbon monoxide produced can exceed that of the metallic product.
Additional gas evolution is caused by moisture in the charge materials,  volatile
matter in the reducing agents, and thermal decomposition products  of the raw ores.
                                     VI-3

-------
Normally, these latter sources account for less  than  30 percent  of the
CO production.
     In an open furnace, CO and other combustibles  in the  furnace  offgas
burn with induced air at the  charge surface,  resulting in a  large volume
of high-temperature gas.  In a covered furnace,  most  or all of the CO and
other gases are withdrawn from the furnace without  combustion.
     Additional fumes occur at the furnace taphole.   In some  cases,  gases
issue from the taphole, but usually the emissions result from the  molten
alloy or slag.  Most furnaces are tapped at 1  to 5-hour intervals  with
tapping periods lasting from 10 to 15 minutes  or more.   Taphole  emissions
occur 10 to 20 percent of the furnace operating  time.
     Additional reactions may be conducted in  the ladle, such as chlorination,
oxidation, slag-metal reactions, and stirring  of molten metal with gas.   In
these cases, there may be fume generation in addition to the  treatment  gas,
and possibly ejection of a portion of the molten contents  in  the ladle.
Ladle treatment reactions have periodic emissions that have not  been
quantified.
     Another source of pollution from furnaces equipped with  self-baking
electrodes is the fumes from the electrode paste during heating  and baking.
These fumes are minor and are usually vented directly to the  atmosphere.
     Water that leaks from electrode suspension  equipment  and other components
above the furnace can result in some increased gas  flow as steam or hydrogen.
     Properties and quantities of emitted particulates depend upon the  alloy
being produced.  Except for the larger dust particles of feed mix  carried
from the furnace, the particle fume size is generally below 2 microns  (y  )
                                 vi-4

-------
and ranges from 0.1 to 1.0 y with a geometric mean of 0.3 to 0.6 y  ,  depending
                             17 18
upon the ferroalloy produced.  »' In some cases, agglomeration does  occur,
and the effective particle size may be much largar.  Grain loadings  and
flowrates depend on furnace type and hooding.  Uncontrolled open furnaces have
high flowrates with moderate grain loadings, while the gases from covered
furnaces have,flowrates as low as 1/50 that of open furnaces with high grain
loadings.    In the dry state, the collected particulates are very light, and
bulk density varies from 4 to 30 pounds per cubic foot.
     Silicon alloys produce a gray fume containing a high percentage  of amorphous
silicon dioxide (SiOp ).  '    Some tars and carbon evolve, particularly from
covered furnaces, from the coal, coke, or wood chips used in the furnace charge.
These carbonaceous materials are burned at the charge surface in the  case of
the open furnace and in the case of the covered furnace  are burned either by
flaring or using as a waste heat fuel.  Ferrochrome-silicon furnaces  produce a
Si02  emission similar to a ferrosilicon operation with  some additional
chromium oxides.  Manganese operations produce a brown fume, which analysis
indicates is largely a mixture of Si^ and manganese oxides.    Chemical
analysis thus indicates fume composition is similar to oxides of the  product
being produced.  An additional component of the fume is  carbon from the reducing
agents.  Typical chemical analyses are given in Table VI-1.
4.   Characteristics of Emissions from Other Ferroalloy  Processes
a.   The Exothermic Process - Metallic silicon, which is usually combined with
other ferroalloys, and aluminum are intense deoxidizers  and are used  as  the
reducing agents in the exothermic process for making LC  ferrochromium,  MC
and LC ferromanganese, ferromolybdenum, ferrovanadium, ferrotitanium,  and
                                   VI-5

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other alloys that are produced in minor quantities.
    Oxide fumes, similar in physical  characteristics to those from the sub-
merged-arc furnace, are emitted from the reaction ladle or furnace while the
reducing agent is being charged.  These emissions are caused by the strong
agitation and rapid temperature rise of the molten bath during the initial
reaction which lasts from 5 to 15 minutes.   The entire heat cycle is about
1-1/2 to 2 hours.  Therefore, atmospheric emissions  from the exothermic
reactions take place during about 10 percent of the  cycle time.
    The quantity of emissions from the exothermic reaction ranges from 20
to 40 pounds of particulates per ton of ferroalloy produced.  The total
tonnage of ferroalloys made by the exothermic process amounts to 200,000
to 300,000 tons per year or 10 to 15 percent of the  total ferroalloy pro-
duction in the United States.
b.  The Electrolytic Process - Chromium, manganese,  and manganese dioxide are
products of the electrolytic process as used in the  ferroalloy industry.  Only
six such electrolytic operations exist in the United States.  Essentially
no particulate or gaseous emissions result from the  ambient-temperature
electrolysis of the aqueous sulfate solutions used in these installations.
c.  Vacuum and Induction Furnace  - Although it does not appear that any
significant -emissions to atmosphere occur from the vacuum furnace or induction
furnace processes, such emissions have not been quantified.  Ferroalloys
are made by these processes in fewer than 5 locations in the United States.
5.  Characteristics of Emissions from Product Sizing
    Ferroalloys are marketed in sizes ranging from 75-pound pieces to
fine powders.  Because ferroalloys have various degrees of hardness,
                                 VI-7

-------
several types of crushers and screens are employed for breaking the
ferroalloys into smaller pieces and separating the broken pieces into
different product sizes.  The breaking process generates some  undersize
pieces and airborne dust as well.   Most of the metallic dust generated
                                                                19
from breaking and screening is in  the range of 3 to 100 microns.
The amount of dust emitted to the  atmosphere from these casting, breaking,
and screening operations has not been quantified, but is substantially  less
than that of furnace emissions. About half of the ferroalloy  plants  have
dust-abatement equipment for these operations.
B.   QUANTITIES OF EMISSIONS
1.  Variability of Furnace Emission Rate During Normal Operations
    Emission rates will vary with  (1) type of alloy produced,  (2) process
(i.e., continuous or batch), (3) choice and size of raw materials, (4)
operating techniques, (5) furnace  size, and (6) maintenance practices.
    Silicon alloys provide a good  example of emissions varying with  product.
The emission of Si02  fumes increases directly with increasing silicon
content of the product.  Therefore, a silicon-metal furnace emits substan-
tially more SiO»  fumes than an equivalent-size 50-percent-ferrosilicon
furnace.  In addition, the higher  ferrosilicon operations (75  percent Si
and above) are known as "hot" operations; i.e., the gas is emitted at a
high temperature and the furnace is subject to increased blows compared to
lower silicon alloys.  Blows are jets of extremely hot gas that issue from
the high-temperature reaction zone and flow upward around the  electrodes
at high velocity.  Higher silicon  operations are also subject  to hearth
buildups of silicon carbide; more  emissions occur under these  conditions
because the electrodes are operated at higher positions.
                                  VI-8

-------
     Manganese ores may contain significant amounts of water and higher
manganese oxides that dissociate to lower oxides and oxygen at temperatures
below 1000°C.  A manganese furnace can thus be subject to "rough" operation.
Sudden releases of gas can cause substantial ejection of mix from the
furnaces.  Silicomanganese furnaces are also subject to "slag boils," in
which slag rises up to cover the top surface of the charge, impeding mix
delivery and the uniform passage of gas through the charge.    These adverse
furnace conditions can be minimized by careful furnace operation.
     In furnaces with self-baking electrodes, the oxidizing atmosphere can
result in "fluting" or grooving of the electrodes along the metal fins,
forming direct gas passages through which fumes may escape from the high-
temperature zone of the furnace.
     Emissions from batch-operated open-arc furnaces vary during the melt  cycle.
Following sudden addition of mix containing volatile or reactive constituents
(coal, moisture, aluminum, etc.) to a hot furnace crucible, violent gas
eruptions can occur.  This is best exemplified by the manganese ore/lime
melt furnace from which momentary gas flow following mix addition can be five
times the average flow.  Under these conditions, temperature, dust loading,
and gas flow all peak simultaneously.  In contrast, chromium ore/lime melt
furnaces, to which few or no gas-releasing materials are fed, are not
subject to this violent behavior.
     The size of raw materials has some bearing on emission rate variability.
A significant contributor to rough furnace operation may be the presence of
fines or dense material in the feed.  Such materials promote bridging and
nonuniform descent of the charge, which may cause gas channels to develop.
                                  VI-9

-------
The collapse of a bridge causes a momentary burst of gases.   A porous  charge
promotes uniform gas distribution and decreases bridging.   For some products,
economics dictates the use of raw materials with more fines  or with more
volatile matter than desirable.  Each of these factors has an adverse  effect
on the smooth operation of the furnace, and consequently emissions may
increase if the raw materials are not pretreated.
     Differences in operating techniques can have a significant effect on
emissions.  The average rate of furnace gas production is directly propor-
tional to electrical energy input, so that a higher load on a given furnace
                                                     20
normally causes a proportional increase in emissions.    In some cases,
emissions increase at a rate greater than the load increase due to rough
operation and inadequate gas withdrawal.
     Operating with insufficient electrode immersion increases the furnace
gas temperature and fume content and may be above the capacity of an improp-
                                           Q
erly designed air pollution control system.   Higher voltage operation
for a  given furnace promotes higher electrode positions and can promote
increased fume emissions.
     For some operations, especially silicon metal production, the charge
must be stoked to break up crusts, cover areas of gas blows, and permit
the flow of reaction gases.  Therefore, emissions can be a function of
how well and how often the furnace is stoked.
     Semi-enclosed furnaces are designed to collect most of the furnace
gases.  Poor mix placement or  insufficient mix delivery can, however,  cause
the release of heavy fumes around the electrodes.
                                  VI-10

-------
     Design and maintenance practices may significantly affect emissions
from covered furnaces because materials may accumulate under the cover and
in gas takeoff ducts reducing the gas-withdrawal  capacity of the exhaust
system.  If gas passages in the control equipment are plugged on either open
or covered furnaces, gas capture will be less  efficient.
2.   Variability of Furnace Emission Rates During Shutdowns and Startups
     Because of the complexity of the heavy mechanical  and electrical
equipment associated with a modern submerged-arc  furnace, close supervi-
sion and maintenance are required to prevent frequent furnace shutdowns.
The furnaces are designed to operate continuously to maintain satisfactory
metallurgical and thermal equilibriums.
     Normal furnace shutdowns on an annual basis  may average 5 to 10 per-
cent of the operating time and are caused by such situations as electrode
installations, prevention and repair of water  leaks  at electrode contact
plates, mix chute failures, furnace hood or cover failures, taphole  problems,
electrical or other utility failures, crane failures, pollution control, and
ladle or chill problems.  In general, furnace  interruptions are relatively
short in duration, usually not more than several  hours.   Following such
interruptions, the furnace usually returns to  normal operation with  normal
emissions in a period of time approximately equal to the  length of the
interruption.
     Greater-than-normal emissions may occur when power is returned  to the
furnace after a lengthy interruption caused by a  major furnace operational
problem.  These problems may include electrode failure that makes it
                                  VI-11

-------
necessary to dig out an electrode stub or to bake at a reduced load for
self-baking electrodes, serious mixture blows of the furnace, metallurgical
problems that require a furnace burndown to return it to normal operation,
serious water leaks that flood the furnace with water, furnace hearth
failure, major taphole problems, and transformer or major electrical system
failure.  When starting up a new furnace, one with a cleaned-out hearth, or
one with a cold hearth after a long shutdown, heavier-than-normal emissions
may last from a few days up to a month before the furnace operates in an
optimum manner.
     Semi-enclosed furnaces are operated with the cover doors open and mix
seals empty during startups, shutdowns, and electrode burndowns.  Totally
enclosed furnaces are also operated with cover doors open during these
operations.  Consequently, higher-than-normal emissions may occur during
these periods.  However, open furnaces with air pollution control devices
should emit no additional pollutants during these shutdown or startup
periods because the control system remains in operation during these times.
3>   Data from Questionnaires
a.   Quantities of Emissions from Electric Furnaces Reported - Ferroalloy
manufacturers have voluntarily provided information on 120 submerged-arc
furnace operations representing about 70 to 80 percent of the furnaces In
the United States.  The information submitted in response to questionnaires
includes the quantities of particulate emissions based on test data or esti-
mates from ferroalloy smelting, and performance data and estimates for
emission control equipment.  Table VI-2 shows the types of control equip-
ment now in general use in the United States.  In 1971 approximately 50
percent of the furnaces were equipped with one or more of these types of
control devices.
                                 VI-12

-------
          Table VI-2.   TYPES OF CONTROL SYSTEMS USED ON FERROALLOY FURNACES
                               IN THE UNITED STATES16
        Semi-enclosed and
       covered  furnaces
  with withdrawal  and cleaning of
          unburned gases
Control device
Wet scrubbers
       Products
HC ferromanganese
50 to 75% Ferrosilicon
Calcium carbide
HC ferrochrome
                                         Open furnaces
                                  with withdrawal  and cleaning of
                                          burned gases
'•• Control  device
 Wet scrubbers
                                            Cloth filters
                                             Electrostatic
                                               precipitator
       Products
50 to 75% Ferrosilicon
Silicomanganese
HC ferrochrome
Ferrochrome-silicon
Silicomanganese
Ferromanganese silicon
75% and higher grades
  of ferrosilicon
Silicon metal
Ferrochrome-silicon
HC ferrochrome
Ferrochrome-silicon
    Only two electrostatic precipitators are currently used in the United States
    and were installed after the questionnaire survey was  completed.
                                      VI-13

-------
     Because the quantity  of emissions will  vary with  the product,  the
following 14 products  have been  categorized  into four  product  groups:
                            Silicon  Alloys
                                 Calcium Silicon
                                 Silicon metal
                                 65-75%  Ferrosilicon
                                 50% Ferrosilicon
                                 SMZ (Silicon Manaanese  Zirconium)
                                 Silvery Iron (15-22%  FeSi)
                            Manganese AlToys
                                 High-Carbon (HC)  Ferromanganese
                                 Ore/lime melt  (used to  make MC ferromanganese)
                                 Silicomanganese
                                 Ferromanganese silicon
                            Chrome Alloys
                                 Ferrochrome-silicon
                                 HC  Ferrochrome &  charge ferrochrome
                                 Ore/lime melt  (used to  make LC ferrochrome)
                            Other Products
                                 Calcium Carbide
     The questionnaires  submitted provide estimates &  data  about  gaseous  emission
characteristics and indicate the variations  in  particulate  emission rates for
each product.  This information  has  been tabulated and summarized in  Tables
VI-3 through VI-8.
     Table VI-3 provides estimated  uncontrolled emission factors  for
each product along with  the corresponding production factors.  The
production factors show  the average  amount  of electrical energy required
to produce one ton of ferroalloy and the number of tons  of  feed mixture
needed to produce one ton of ferroalloy. These production  factors
are averages and may vary up to  15  percent.   Using losses reported by
questionnaires, typical  energy consumption  figures, and  typical feed
charge figures, caluclations have been  made to  determine the
                                   VI-14

-------
                    Table VI-3.   PRODUCTION  AND  EMISSION,EACTORS
                          FOR UNCONTROLLED OPEN  FURNACES10
Product
Silicpn alloys
CaSi
Si
SMZ
(65-75%)FeSi
50% FeSi
Silvery iron
(1^22% FeSi)
Manganese alloys
FeMnSi
SiMn
(HC) FeMn
Mn ore/lime
melt
Chrome alloys
FeCrSi
(HC) FeCr and
charge chrome
Cr ore/lime
melt
Other
CaC2
Production factors
Electrical
Energy,
mw-hr/ton
product
(average)

11.8
14.0
8.'8
8.8
5.0
2.6
5.4
4.4
2.4
1.6
7.4
4.2
1.2
2.6
Ratio,
tons charge/
ton product
(average)

3.9
4.9
4.5
4.5
2.5
1.8
4.3
3.1
3.0
3.5
3.4
4.0
1.2
1.6
Emission factors
Parti culates,
Ib/ton
product

1343
1200a
No datab
915
446
116
315
219
335
133
831
335
11
No datab
Parti culates,
Ib/ton
charge

344
245a
No datab
203
179
64
73
71
84
38
244
84
9
No datab
Parti culates
Ib/mw-hr

114a
86a
No datab
104
89
45
58
50
62
83
112
62
9
No datab
Questionnaire data not conclusive.   Numbers presented are estimates by the
ferroalloy industry.

No uncontrolled particulate emission reported in questionnaires.
                                        VI-15

-------
average emission factor in pounds of participates  per ton of ferroalloy
produced, pounds of particulates per ton of charge material  to the furnace,
and pounds of particulates per megawatt-hour electrical  input.  The emission
factor is usually in the high range for those ferroalloys that require the
largest amount of electrical  energy to produce a ton of product.   The
products in each product group have been arranged  in descending order of the
amount of electrical energy input to determine if there is also a descending
order in the amount of emissions.  Questionnaire data were not sufficient to
determine a definite correlation for some product  groups, but a direct rela-
tionship was noted in most other instances.  The summary calculated from the
questionnaires shows that particulate emission factors, in pounds per megawatt-
hour ranged from a high of 114 for CaSi down to 9  for the chrome ore/lime melt.
The particulate emission factor for silicon alloy  products increases when
the silicon content in the product is increased.  In addition, the emission
factor of particulates per ton of silicon metal may vary considerably due to
normal swings in silicon recovery.  Normally silicon is recovered from the
silicon dioxide charged to the furnace with an efficiency ranging from 70
to 80 percent.  Based on one ton of Si02  charged, the theoretical calcula-
tions for silicon metal recovered and the associated silica fumes are shown:
Basis:  One ton of SiCL charged to silicon furnace
Recovery of Si from SiO?
%

70
75
80
Si produced,
Ib

654
700
746
Loss of Si02,
/

30
25
20
SiO? fumes3 Theoretical

. IB/ton product
1,835
1,429
1,070
h
lb/mwD
131
102
76
 Assumes all fumes produced are
3This theoretical emission rate is based on an average production factor of
 14 mw-hr per ton silicon produced.
                                   VI-16

-------
      For 5JO percent ferrosilicon production, metallurgical re$ults indicate

 a normal silicon recovery from 90 to 95 percent.   Based on one ton of Si02

 charged and a product analysis of 48.5 percent Si, the theoretical calcu-

 lations for metal produced and the associated silica fumes are shown

 below:

Basis:   one  ton Si02 charged to  5Q%  FeSi furnace

Recovery of Si from Si Op
90
95
Si produced,
Ib
1,732
1 ,828
; i
Loss of Si09, i
i °i L- i
| * \
i i
10 ;
5 !
SiOp fumes3 (Theoretical)
Ib/ton product
231
109 I
i
i
lb/mwb
46
aAssumes all fumes produced are Si09.
i                                   C.
 This theoretical rate is based on an average production factor of 5 mw-hr
 per ton FeSi produced„
                                   VI-17

-------
     The potential yearly quantities of participate emissions can be estimated
by using emission factors and known production figures.  These calculations
for .1971 are shown in Table VI-4.  If all furnaces had been uncontrolled,
total emissions for 1971 would have been 342,000 tons.  This figure is slightly
                                                                            20
higher than that reported in a study made for the year 1968 by a contractor,
who estimated potential emissions as 250,000 tons and actual emissions, based
on 80 percent control for 50 percent of the furnaces, as 150,000 tons.  The
difference between the two studies is primarily due to the use of different
emission factors and the possible exclusion of calcium carbide in the 1968
estimate.  The emission factors used for the 1968 estimate were determined
from fewer data, some of which differed widely from those used in this study.
     Table VI-5 summarizes questionnaire data on uncontrolled emissions from
open furnaces. It shows the reported range of concentrations in grains per
standard cubic foot (gr/scf) and mass emission rates in pounds per megawatt-
hour (Ib/mw-hr) coming off the furnace.  These ranges are based on particulate
emission tests and estimates.  The highest reported uncontrolled mass emission
rates are from the silicon alloy group of furnaces and range from 20 up
.to 324 Ib/mw-hr.  Although emissions of this high magnitude are not likely
to occur, they may do so for a short period of time.  Likewise some of the
low figures in this group, i.e., 21 Ib/mw-hr for a silicon furnace, appear
much too low and unlikely when compared to the average figures shown in Table
VI-3.  The manganese alloy furnaces reportedly have the second highest uncon-
trolled mass emission rates, ranging from 14 up to 191 Ib/mw-hr.
     Table VI-6 summarizes questionnaire data on controlled emissions from
open furnaces.  As can be seen, very few data were reported.  There are
                                  VI-18

-------
             Table VI-4.   POTENTIAL PARTICIPATE EMISSIONS (1971)
Product
Silicon alloys
CaSi
Silicon metal
65-90% FeSi
50% FeSi
Silvery iron
(15-22% FeSi)
Chrome alloys
FeCrSi
HC FeCr
LC FeCr

Manganese alloys
HC FeMn
LC FeMn
FeMnSi
SiMn

Other
CaC2
Production,
- net tons

10,309
88,888
109,951
377,403
94,801


66,685
113,664
96,611


266,376
106,019
44,818
150,383


625,000e
Uncontrolled
emission factors,
Ib/ton alloy

l,343b
1 ,200C
673C
446b
116C


831 b
335b
60d


335b
133b
31 5b
21 9b


100C
Potential
emission,
tons/yr

6,900
53,300
37,000
84,200
4,700
186,100

27,700
19,000
2,900
49,600

44,600
7,000
7,000
16,500
75,100

31 ,200
Totals
2,150,910
342,000
aPrice-Waterhouse data.
 Emission factors determined from questionnaire data.
 Estimates.
 Emission occurring from ladle reactions.
 Department of Commerce, Census Bureau.
                                           VI-19

-------
       Table  VI-5.   RANGES OF  UNCONTROLLED  PARTICIPATE  EMISSIONS
                     FROM OPEN  FURNACES16
Product
Silicon alloys
CaSi
Sil icon
65-75% FeSi
50% FeSi
SMZ
Silvery iron
(15-22% FeSi)
Manganese alloys
FeMnSi
SiMn
HC FeMn
Mn ore/lime melt
Chrome alloys
FeCrSi
HC FeCr
Charge chrome
Cr ore/lime melt
Other
CaC2
No.
of open
furnaces
reported
3
12
6
12
1
4
1
12
4
4
15
3
3
6
None
Range of (
gr/scf
0.33 to 0.91
0.15 to 1.1
0.16 to 0.25
0.30 to 1.3
0.36
0.30 to 0.7
1.0
0.17 to 4.0
0.05 to 4.0
NRb
1.05 to 1.86
1.07 to 1.60
NR
0.1 to 0.5
--
emissions
Ib/mw-hr
111 to 115
21 to 323
40 to 191
20 to 324
25
20 to 70
58
43 to 147
14 to 191
NR
42 to 180
62 to 117
NR
5 to 15
--
 Includes  emission  data from open  furnaces  equipped with control  devices.
 (Inlet data  only to control  devices)
3NR - none reported.
                             VI-20

-------
     Table VI-6.  RANGES OF CONTROLLED PARTICIPATE EMISSIONS REPORTED
                  FOR CONTROL DEVICES SERVING OPEN FURNACES16
Product
Silicon alloys
CaSi
Sil icon
65-75% FeSi
50% FeSi
SMZ
Silvery iron
(15-22% FeSi)
Manganese alloys
FeMnSi
SiMn
HC FeMn

MC & LC FeMn
Chrome al loys
FeCrSi
HC F.eCr and
charge chrome
Cr ore/lime melt
Other
CaC2
No. of
control
sys terns
reported
0
3
1
1



1
3
2
1
1

1
1
0
0
Type of
control
None
Baghouse
Baghouse
Baghouse
None
None

Baghouse
Scrubber
Baghouse
c
Scrubber
Baghouse
Baghouse
Scrubber
Scrubber
None
None
Range of emissions
gr/scf

NRa
NR
NR
'
—

NR
0.02 to 1.0b
NR
1.0b
NR
NR
0.1
0.02
--
--
Ib/mw-hr

NR
NR
NR
--
—

NR
0.76 to 37b
NR
49b
NR
NR
1.9
1.1
--
--
aNR - none reported (collection efficiency reported as 99 percent plus.)
 High figures reported not typical  of scrubbers serving ferroalloy furnaces.
cScrubber homemade.
                                    VI-21

-------
several control  systems equipped with baghouses none of which reported out-
let emission data.  Apparently, these data are lacking because it is difficult
to conduct stack tests on the open type of baghouse that is typical  in the
ferroalloy industry.  The lowest reported mass emission rate from controlled
open furnaces was 0.76 Ib/mw-hr from a venturi scrubber serving a silico-
manganese furnace..  The lowest reported outlet concentration was 0.02 gr/scf,
also from the same scrubber.   This scrubber was later tested by EPA, and
the-results averaged 0.33 Ib/mw-hr and 0.01/gr/scf.
     Table VI-7  provides information on the ranges of particulate emissions
reported for semi-covered furnaces with mix seals.  Although there are a
considerable number of semi-covered furnaces, all of which have scrubbers,
very little information has been reported on the amount of particulate
emitted into the atmosphere from these scrubbers.  The lowest reported
scrubber outlet  emission rate was 0.13 Ib/mw-hr.  This was from a high-
energy venturi scrubber operating at about 80 inches H20 pressure drop
serving a large  furnace producing 50 percent FeSi.  Data submitted do not
show how efficient a similar venturi scrubber system would be on a furnace
in the chrome or manganese groups.  Questionnaire data reported on outlet
mass emission rates are insufficient to allow a comparison of controlled
emissions for the different groups of alloys.  However, tests made by EPA
in Norway on covered furnaces producing FeMn and SiMn and equipped with
                                           22
venturi scrubbers were under 0.04 Ib/mw-hr.    The table shows that the
lowest reported loss for a Buffalo Forge centrifugal scrubber was
                                                                        i-
0.21 Ib/mw-hr.
                                  VI-22

-------
l!
                            VI-23

-------
     Dust and fume losses from mix seals on semi-enclosed  furnaces may  vary
widely, as shown in Table VI-7.  These emissions  are    *f   Ted.   The ma^s
emission rates of particulates from the mix seals varied from 14  to  462 Ib/hr.
The high measured loss of 462 Ib/hr appears much  too high  in  relation to  the
size of the furnace.  The next highest reported loss 	 27C  IL/hr.  The
lowest reported loss of 14 Ib/hr was from a 50 percent FeSi furnace.  The lower
reported emissions are probably due to better draft on the furnace produced
by a scrubber system of adequate size and at the  same time sufficient mix at
the mix seals.  Also, the furnace may have been operating  smoothly during the
stack test.  The particulate concentrations of the uncontrolled gas  stream
coming from the mix seals ranged from 0.04 to 0.6 gr/scf.   The concentrations
of particulate in the gas stream from the mix seals are dependent upon  the
amount of dilution air added and do not reflect the mass emission rate.
     Comparison of Tables VI-5 and VI-7 presents  some indication  that the
quantity of particulate emissions from an uncontrolled semi-covered  furnace
is less than that from an uncontrolled open furnace.  The  ranges  of  total
scrubber inlet and mix seal losses shown in Table VI-7 are lower  than the
ranges of uncontrolled losses shown in Table VI-5 for open furnaces.
     The average exhaust system volumes on semi-enclosed and  open furnaces
shown in Tables VI-8 and VI-9 are based on standard cubic  feet per minute per
megawatt (scfm/mw).  With gas volume rates based  on this unit, thei? tables
may be used to determine the gas volume expected  for a typical air pollution
control system serving a larger or smaller size furnace.   For example,  by
using the unit volumetric rate of 220 scfm per megawatt for collected gas
                                  VI-24

-------
                     Table VI- 8. AVERAGE EXHAUST-SYSTEM GAS VOLUMES
                                  FROM SEMI-ENCLOSED FURNACES16
Product
HC FeMn
65-75% FeSi
SiMn
HC FeCr
50% FeSi
CaC2
Number of
furnaces
reported
7
3
4
4
7
6
Range of
furnace
sizes, mw
5.9 to 13
9.5 to 15
6 to 9.5
10 to 25
11.3 to 38.5
8.5 to 20.8
Type of
control
system
Scrubber
Scrubber
Scrubber
Scrubber
Scrubber
Scrubber
No. of
control
systems,
7
3
4
3
7
6
Gases from
fugitive
exhaust
system,
scfm/mw
8,600
4,000
10,000
3,750
2,650
3,360
Gases from
air pollution
control
system,
scfm/mw
220 .
210
200
190
180
140
Fugitive fumes are considered to be those fumes which are not collected by the primary
air pollution control system and excludes tapping fumes.
                                            VI-25

-------
                       Table  VI-9.   AVERAGE EXHAUST-SYSTEM GAS VOLUMES
                                   FROM OPEN FURNACES10
Product
Silicon alloys
Silicon
CaSi
75% FeSi
50% FeSi
SMZ
Silvery iron
(15-22% FeSi)
Manganese alloys
FeMnSi
SiMn
HC FeMn
Mn ore/lime melt
Chrome alloys
FeCrSi
HC FeCr and
Charge chrome
Cr ore/lime melt
Number of
furnaces
reportedj
controlled &
uncontrolled
12
3
6
12
1
4
1
12
4
4
15
6
6'
Range of
furnace
sizes, mw
7 to 16
8.7 to 12.5
9 to 30
7 to 35
10
7.5 to 20
18
5 to 25
6.3 to 9.3
7 to 18.5
10 to 22
7 to 25
7.3 to 16
Type of
control
system
Baghouse
NRa
Baghouse
Baghouse
NR
NR
Baghouse
Baghouse
Scrubber
Baghouse
Scrubber
Baghouse
Scrubber
Scrubber
NR
No. of
control
systems
3
1
1
-
"
1
2
3
1
1
1
1
1
+
Gases from
uncontrolled
exhaust
system,
scfm/mw
31,600
29,200
11,500
10,700
5,700
9,700
NR
28,000
86,400
NR
11,500
10,000
4,100
Gases from
air pollution
control
system,
scfm/mw
16,800
18,600
9,200
-
"
6,700
12,200
4,800
13,200
5,500
8,100
3,400
4,800
-
NR-none reported.
                                            VI-26

-------
from a semi-enclosed furnace producing ferrornanganese as shown in the last
column of Table VI-8, the volume of gas coming from a 30-mw size furnace is
calculated to be 6,600 scfm.  Similarly, from Table VI-9 it can be seen that
the expected volumes of gas from the baghouse on a 30-mw open ferromanganese
furnace would be approximately 396,000 scfm.   Volumes from open furnaces will
vary greatly, depending on the type of control equipment used, on the gas
cooling method, and particularly on the proximity of the hooding to the
furnace.
     Table VI-10 shows the types of control  systems used by the ferroalloy
industry as reported in the questionnaires.   For some products, three types
of control systems are noted (as in the case of SiMn, where semi-enclosed
furnaces are equipped with scrubbers, and open furnaces are equipped with
a baghouse or a scrubber).  Generalization about technology transfer cannot-
be made at this time because data are incomplete.  Of the 47 control
systems reported, 30 are scrubbers serving semi-enclosed furnaces making
six different products.  Since the 1970 questionnaire, SiMn is no longer
made in a "semi-enclosed" furnace.
b.   Reported Estimated Quantities of Emissions from Material Handling -
Emissions to the atmosphere from other than the basic ferroalloy production
process itself were reported for 16 ferroalloy plants.  Summaries of estimated
emissions from handling the raw materials (up to the furnace process) and
from processing the ferroalloy product after the reduction state are shown
in Tables VI-11 and VI-12.
     Table VI-11 shows that the average raw material loss from receipt and
storage is 0.1 percent of raw material handled.  It can be assumed that a
                                  VI-27

-------
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                                                            VI-29

-------
part of this material  loss enters  the atmosphere as  airborne  dust  and some
of the heavier particles drop to the ground within the plant  property.   Raw
material preparation equipment includes crushers for reducing large pieces,
screens for size control, and dryers for moisture removal.  As shown in the
table, most of the preparation equipment has emission abatement equipment,
and the questionnaires indicate that collection efficiency is from 90 to 99
percent.  The average industry-wide dust loss from both controlled and
uncontrolled material  preparation operations is estimated as  0.1 percent.
Questionnaire data show that when uncontrolled, the emissions to the
atmosphere from raw material preparation equipment can range  up to 1 percent
of the material handled.  Equipment for weighing the raw materials by
batches and delivering them to the furnace in most cases did  not have emission
abatement equipment, and the dust loss to atmosphere was reported to be 0.1
percent.  Because of insufficient data and the many differences of feed
preparation from plant to plant, the overall average dust loss from material
handling cannot be accurately derived as the sum of these three averages.
However, another study indicates the overall losses from uncontrolled material
handling are the same as those from the iron and steel industry — 10 pounds
per ton of metal produced or 0.5 percent.20
     Table VI-12 shows that losses from treating molten ferroalloy in the
ladle with chlorine or other gases amount to 0.47 percent of the product.
This figure may be a little greater than normal, however, as  the loss at
one plant was much higher than at the other plants.  The fume losses during
ladle treatment are particulates which have characteristics similar to par-
ti cul ate emissions from ferroalloy furnaces.
                                  VI-30

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-------
     The normal loss of molten ferroalloys to the atmosphere during casting
operations is reported to be 0.01  percent, and the loss to atmosphere of
metal fines through crushing and sizing operations reportedly averages 0.03
percent.  About one-half of the crushing and sizing systems have emission
control equipment.
4.   Data from EPA Source Measurements
     a.  Quantities of Emissions from Electric Furnaces - The EPA Office
of Air Programs awarded a contract to an independent company to perform
a series of source emission tests  on nine electric furnaces.  These tests
were arranged with the cooperation of The Ferroalloys Association.  The
following considerations were used in selecting the furnaces:
         1.  The furnaces tested should be equipped with effective emission
             control equipment.
         2.  At least one of every type of emission control system
             in service should be tested.
         3.  Since emissions will  vary with different products, tests should
             be conducted on furnaces producing different products.
         4.  The tests should be distributed among the various producers
             to the fullest extent possible.
         5.  A limited number of tests on furnaces with no emission control equip-
             ment should be made to verify the questionnaire data and estimates.
     To meet all the requirements of this plan, the original schedule called
for testing a total of 17 furnaces at 10 locations.  However, time and cost
considerations allowed testing of only nine furnaces at seven U. S. plants
over a  14-month period.  Seven of the nine furnaces tested had emission
                                  VI-32

-------
control equipment.  In addition, tests were made by EPA personnel  on the gas
scrii!>bing systems of two Jotally enclosed furnaces operating in Europe.   All
of these tests are described in more detail in Appendix A.   The alphabetical
designations of the tests follow chronological order; i.e., the first test,
made on May 18-19, 1971, Is designated Furnace A, and the last test, made on
August 23-25, 1972, is designated Furnace L.  Measurements  were made of
particulate mass emission rates, sulfur oxide content, carbon monoxide
content, and particle sizes.  Collected samples were also analyzed with
either the atomic absorption method or the optical emission spectrograph.
Particle size and chemical analysis are covered in more detail in
Appendices D and E.
     All EPA test data for particulate shown in this section of the report are
based on that portion collected in the front half (probe, cyclone  and filter)
of the EPA sampling train.  For results based on collection in the total
sampling train, refer to Tables A-2 through A-5 in Appendix A.
     The initial two tests in the sampling program were made on"uncontrolled
furnaces A and B.  Furnace A was producing ferrochrome-silicon. Furnace B
was a chrome ore/lime melt furnace and was the only open-arc furnace tested.
The average concentration of particulate from the uncontrolled FeCrSi
furnace was 0.21 gr/scf, and the mass emission rate was 29  Ib/mw-hr,   The
average gas flowrate from this uncontrolled system was 159,150 scfm dry.
The average concentration of particulate from the uncontrolled chrome ore/
lime melt furnace was 0.16 gr/scf, and the mass emission rate was  6 Ib/mw-hr.
The average gas flowrate from this uncontrolled system was  41,200  scfm dry.
     Furnace C, a large, open, hooded furnace producing 2 percent  carbon-grade
silicomanganese, was controlled by two flooded-disc scrubbers installed
                                  VI-33

-------
in parallel and normally operated at 57 inches  water  pressure  drop.   Tests
were conducted with the scrubbers adjusted to operate at  57, 47,  and  37
inches HpO pressure drop.  For 57 inches HpO pressure drop, the
average outlet concentration and mass emission  rate were  0.01  gr/scf  and
0.33 Ib/mw-hr, respectively, with an average dry gas  flowrate  of  115,000
scfm.  For 47 inches H? 0 pressure drop, the average  outlet concentration
and mass emission rate were 0.015 gr/scf and 0.54 Ib/mw-hr, respectively,
at an average dry gas flowrate of 118,000 scfm.   Particulate removal
efficiency decreased very little when the scrubber was operated at 47
inches H -0 pressure drop, possibly because inlet concentrations  to the
scrubber were higher at this pressure drop than they  were at 57 inches
HpO pressure drop.  Scrubber performance differed noticeably,  however,
when the scrubber was operated at 37 inches H?  0 pressure drop.   At this
setting, the average outlet concentration and mass emission rate  were
0.044 gr/scf and 1.45 Ib/mw-hr, respectively, at an average dry gas volume
flowrate of 110,000 scfm.
     Furnace D, a large, open, hooded FeCrSi furnace, used an  open, pressure-
type baghouse for emission control.  This type  of baghouse is  commonly used
in the ferroalloy industry.  The furnace tapping station  was also vented  to
this baghouse.  Measurements of the average concentration and  mass emission
rate at the baghouse outlet showed 0.003 gr/scf (including dilution air)  and
0.42 Ib/mw-hr, respectively.  The gas flowrate  into the baghouse  was  178,000
scfm (dry) and, after dilution at the baghouse, the outlet flowrate was  383,000
scfm (dry).
                                 VI-34

-------
                                                                             21
     Emissions from Furnace E, called the "largest U.S.  ferrochrome furnace,"
were controlled by an electrostatic precipitator.   The tapping station was
also controlled by this precipitator.  A 120-foot  conditioning tower preceded
the precipitator.  The open, hooded furnace could  be almost completely
enclosed with sectional, vertically sliding doors.  The average concentration
and mass emission rate of particulates from the precipitator were 0.016 gr/scf
and 0.64 Ib/mw-hr, respectively.   The measured gas flowrates at the precipi-
tator stack outlet averaged 156,000 scfm (dry).
     Furnace F produced silicon metal.  Silicon metal  furnaces are the most
difficult and costly to control because the process generates large volumes
of hot gases heavily laden with extremely fine silica fumes.  Furnace F
had a high canopy hood and was controlled by the only type of control system
used on silicon furnaces - a baghouse.  Tests averaged 391,000 scfm (dry)  exhaust
gases treated by three parallel-installed baghouses.   After this amount of
gas passed through the cloth filter bags, dilution air increased the baghouse
outlet volume to 610,750 scfm.  Total filter area  was  344,000 square feet.
These baghouses are the typical open, pressure type with a roof monitor.
Average outlet particulate concentration (including dilution air entering  at
the baghouse) was 0.003 gr/scf (dry) and the average mass emission rate was
0.94 Ib/mw-hr.
     Furnace G was a small open furnace producing  silicomanganese, well-
enclosed and equipped with an Aeronetics scrubbing system.  The hot, fume-
laden gases were first ducted to a heat exchanger  where heat was transferred
to a high-pressure water stream.   This water stream was then used in a two-
phase (steam/water mist) jet nozzle located downstream of the heat exchanger.
                                 VI-35

-------
This jet nozzle not only cleaned the dirty gases but also pumped  the exhaust
gases through the air pollution control  system, precluding the need  for
exhaust fans.  Another exhaust system vented the tapping station  and tapping
fumes to the top part of the furnace hooding, where it helped  to  supply
combustion air for burning the carbon monoxide furnace offgas  to  carbon
dioxide.  Gas flowrate from the scrubber was 15,500 scfm (dry) at an average
participate concentration amd mass emission rate of 0.08 gr/scf and  1.48
Ib/mw-hr, respectively.
     Furnace H was a very large semi-enclosed furnace producing 50 percent
FeSi.  The control system serving this furnace consisted of two parallel-
installed Chemico venturi scrubbers operating at 80 to 85 inches  H?0 pressure
drop.  The cleaned 7,000 scfm (dry) gases with high carbon monoxide  content
were flared at roof level.  Particulate concentration before flaring was 0.06
gr/scf (dry) and mass emission rate from the scrubber exhaust  was 0.08 Ib/mw-hr.
The measured mix seal losses from Furnace H varied from 136 to 569 Ib/hr
(3 to 13.5 Ib/mw-hr).
     Furnace J was a semi-enclosed furnace producing calcium carbide.   This
furnace had hollow electrodes through which smaller size lime  and coke were
fed into the furnace.  The larger materials were charged through  openings
around the electrodes.  This method of charging raw materials  reportedly
reduces the dust load going to the scrubber.  Furnace emissions were con-
trolled by a Buffalo Forge rotary scrubber.  Average exhaust gas  rate from
the scrubber was 1,585 scfm (dry) at an average particulate concentration
and mass emission rate of 0.03 gr/scf (dry) and 0.02 Ib/mw-hr, respectively.
The measured loss from mix seals on Furnace J varied from 44 to 50 Ib/hr
(1.8 to 2.2 Ib/mw-hr).
                                  VI-36

-------
     Furnace K located in Norway was a totally enclosed furnace with fixed
electrode seals.   The furnace was producing FeMn when tested by EPA.  Emissions
                    •k
from this furnace were controlled by two identical  Warkaus scrubber systems
installed in parallel.  Each system consisted of a  three-stage venturi
scrubber.  No exhaust fan was necessary because aspiration of gases was  pro-
vided by water injection at the venturi.  Tests were made when both scrubber
systems were in operation and when only one scrubber system was in operation.
Average exhaust gas rates were 5,559 scfm (dry) with both scrubber systems
operating and 5,322 scfm (dry) with only one scrubber system operating.
The average concentration and mass emission rate of particulates in
the cleaned gas while both scrubber systems were operating were 0.013 gr/scf and
0.024 Ib/mw-hr, respectively.  With only one scrubber system in operation, the
average outlet emission was 0.018 gr/scf (dry), which is equivalent to  0.031
Ib/mw-hr.  Infrequent puffs of fumes escaping from  the electrode fixed  seals
were estimated to be less than 10 percent opacity.
     Furnace L located in Norway was a 27-mw totally enclosed furnace with
electrode seal's.   The furnace was producing 1 percent carbon-grade silicomanganese
when tested.  Emissions from this furnace were controlled by a system consist-
ing of two venturi scrubbers operating in series.  The first low-pressure
venturi (2 inches H20 pressure drop) acted to condition the gas stream  before
it entered the high-pressure venturi (50 inches f^O pressure drop).  The
average exhaust flowrate was 2,417 scfm (dry) and the average emission  was
0.01 gr/scf (dry), which is equivalent to 0.01 Ib/mw-hr.  The very small
volumes of gases  escaping from the electrode fixed  seals were estimated to be
less than 10 percent opacity.
                                   VI-37

-------
     Table VI-13 shows production data relating  to  the EPA tests.   The first
seven furnaces shown (A through G) are open and  are equipped  with  high or  low
canopy hoods.  The last four (H through L)  have  covers.   All  furnaces  were
operating at or near rated capacity.   A continuous  recording  chart provided
the furnace's electrical power input  in megawatts;  the average megawatt
figures are shown for the test periods.  The last two columns in this  table,
tons product per hour and tons charge per hour,  were derived  from  data in  the
preceding three columns.  For example, the  1.35  tons/hr of FeCrSi  product
for Furnace A was obtained by dividing the  average operating  load  (10  megawatts)
by the electrical energy production factor  (7.4  mw-hr per ton of alloy).   The
4.6 tons/hr of charge material was obtained by multiplying the product
(1.35 tons/hr) by the charge-to-product ratio (3.4 tons/ton alloy).
     Table VI-14 summarizes EPA particulate test results.  These  test  data
correspond in time to the furnace production rates shown in Table  VI-13.   The
first two furnaces (A and B) were uncontrolled.   The last two furnaces tested
(K and L) were the best controlled.  Overall control efficiencies  shown in
this table include losses from the furnace plus  those from the' tapping
station  unless otherwise  specified.   All scrubber  systems  serving  the  four
covered  furnaces had  an estimated scrubber  collection efficiency of over  99
percent  based  upon  the  use  of  uncontrolled  emission  factors  for inlet  loadings.
Because  of heavy fume losses from the  mix seals, estimated overall efficiencies
(excluding tapping  emissions)  from Furnaces H and  J  were  lower, 89 and 96
percent  respectively.   For  open  furnaces equipped  with  hoods,  the  highest
overall  particulate collection efficiency  (excluding tapping  emissions
(ttained  was  99.1 percent.   Overall particulate  collection  efficiencies for
furnaces with  open  hoods  are based on  the losses from the  control  device  plus
                                   VI-38

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-------
the estimated losses escaping the hood.
     Efficiencies of control devices cannot be used very well to compare
losses from furnace to furnace because of the differences in furnace sizes.
The most equitable comparison is based on the amount of loss related to
furnace energy input.  Using pounds per megawatt-hour as an emission rate
unit, the lowest emission rates from the gas cleaning system were those from
the scrubbers serving the four covered furnaces.   For covered furnaces, the
rates ranged from 0.01 Ib/mw-hr for a venturi serving a SiMn furnace to 0.08
Ib/mw-hr for a venturi serving a 50 percent FeSi  furnace.  For open furnaces,
the emission rates from the gas cleaning system ranged from 0.33 Ib/mw-hr
for a venturi serving a large SiMn furnace to 1.48 Ib/mw-hr for a venturi
serving a small SiMn furnace.  The emissions from the two baghouse systems
tested on open furnaces were 0.42 Ib/mw-hr for FeCrSi and 0.94 Ib/mw-hr
for silicon.
     Fugitive fumes escaping from the mix seals on Furnaces H and J wene
measured.  (These losses are not shown in Table VI-14.)  The measured mix
seal losses from Furnace H (50 percent FeSi) varied from 136 to 569 Ib/hr
(3 to 13.5 Ib/mw-hr).  The measured loss from the mix seals on Furnace J
(calcium carbide) varied from 44 to 50 Ib/hr (1.8 to 2.2 Ib/mw-hr).  These
measured losses from the mix seals were somewhat  higher than the ranges
reported in questionnaire data, particularly for  the 50 percent FeSi
furnace (see Table VI-6).  During the test, the furnace did not appear to
operate smoothly at all times, and this may have  resulted in heavier-than-
normal emissions.
                                 VI-41

-------
     Uncontrolled tapping losses were measured from Furnaces C,  H and J.
Losses from Furnace J producing CaC^ (continuous  tapping)  varied from 45
to 54 Ib/hr.   Losses from Furnace H producing 50  percent FeSi  varied from
18 to 30 pounds per tapping period (12 to 17 minutes).   Losses from
Furnace C producing Si'Mn varied from 17 to 59 pounds per tapping period
(28 to 32 minutes).  On Furnaces D, E, and G, the tapping stations were
served by the primary air pollution control systems.
     Except for periods when there were visible emissions of approximately
10 percent opacity from the electrostatic precipitator serving Furnace E,
no emissions  were visible from any of the control systems tested under
normal operating conditions.  The uncontrolled fume emissions from the
mix seals of furnace H caused visible stack emissions estimated in the range of
20 to 60 percent opacity, but during short periods of rough furnace operation
the visible emissions were as high as 100 percent. These readings were taken on
a random basis.  Visible emissions from the electrode seals on the two furnaces
in Norway were normally less than 10 percent opacity at the furnace area; at
times there were no visible emissions.  Visible emissions from all furnaces
without tap fume control varied during the tapping cycle from 10 to TOO percent,
     Temperatures of furnace gas entering the air pollution control devices
varied depending on furnace hooding and the extent of precooling.  The
temperature of the gas stream entering a conditioning tower preceding an
electrostatic precipitator  (Furnace E) varied from 429 to 492°F during the
EPA tests.  Temperature of  the gas stream entering a venturi scrubber on
an open silicomanganese furnace  (Furnace C) varied from 541 to 645°F.
Gas temperature from a closely hooded furnace producing silicomanganese.
                                   VI-42

-------
(Furnace G) was purposefully high to recover heat.   Temperature in the
furnace outlet exhaust duct was between 1100 and 1133°F, but after passing
through a heat exchanger and before entering a two-phase jet scrubber, it
decreased to 320 to 358°F.   Temperatures of gas streams entering baghouses
on Furnaces D and F ranged  from 306 to 330°F, and the gas streams were cooled
to these temperatures by dilution air at the hood and by radiant cooling
while the gas passed through several hundred feet of ducting.
     Five ASME samples were obtained using the ASME power test code method
and compared with results obtained by the EPA test method.   All samples were
collected from the hot, heavily dust-laden gas stream from the furnace.  The
two methods compared favorably for three tests, but no correlation could be
determined for the other two tests (see Appendix A).  Only the front half (probe
and cyclone) particulate catch in the EPA train was compared with the ASME samples.
     Emissions from the nine furnaces tested in the United States compare
within normal ranges with the information provided by the questionnaires
for similar products (see Table VI-15).  Emissions from eight of the
furnaces tested were lower than the average of the questionnaire information;
no questionnaire data were  available on the calcium carbide furnace for com-
parison.  The one product that differed markedly was FeCrSi.  Test results
obtained by EPA were much lower than those reported on the questionnaires.
The fact that fines were screened from the FeCrSi charge material for the
furnaces tested by EPA may account for the difference.
     b.  Particle Size Determinations - Determinations of particle size
distribution of uncontrolled and controlled furnace fume emissions were
made at several ferroalloy plants while emission tests were conducted.
                                  VI-43

-------
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                                            VI-44

-------
Samples for evaluation of particle size distribution were collected
Initially with the Andersen Stack Sampler, but most of the data were
based on the samples collected by the Brink Cascade Impactor.  Because
of the heavy and fluctuating dust load from the furnace, sampling time
at the inlet of the control devices was short and may not have been
representative of an average hourly sample.  Initially, the sampler was
modified with a dilution system to obtain longer sampling times at the
inlets, but high temperatures caused equipment failure.  More representa-
tive particle size analyses were obtained at the control equipment outlets
because longer sampling times were possible.  Table VI-16 shows the furnaces,
products, control equipment, and number of samples obtained by each sampler.
     Very little published information exists on the size distribution of
part'iculate matter from ferroalloy furnaces.  Person and Silverman state
                                                      17 1R
that most particles are less than 0.5 micron diameter.  '    EPA verified
this number by use of the cascade impactor.
     Cumulative weight percentages for each stage of the cascade impactor
were arithmetically averaged, and the combined size distributions are shown
1n Table VI-17.  From a furnace producing ferrochrome (see Figure A-6,
Appendix A), 50 percent of the outlet fume weight is composed of particles
smaller than 1.68 micron diameter.  Fumes from two furnaces producing
FeCrSi contain somewhat smaller particles, with 50 percent of the weight
normally composed of particles smaller than 0.9 micron.
                                  VI-45

-------
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-------
c.   Chemical Analysis - During the test program, EPA collected several
samples for chemical analysis to determine percent of sulfur dioxide in
the gas stream and percent metals content of the collected dust.   In addition,
metals analysis was performed on two manganese ore samples, two chrome ore
samples, and a sample of ferromanganese slag used as part of the charge  to
a SiMn furnace.  No significant sulfur dioxide concentrations were found
in the exhaust gas for the first five furnaces tested by EPA (A through  E).
The SCL loss from furnaces equipped with control devices did not exceed
7 pounds per hour.  For Furnace A (FeCrSi), the SOp concentration
ranged from 14 to 17 ppm.  No SCL was found in the gas from the chrome
ore/lime melt furnace.  The SCL content in the gas from Furnace C (SiMn)
was less than 1 ppm.  The SCL in the gas from a FeCrSi furnace (Furnace  D)
ranged from 8 to 9 ppm and was quite similar to Furnace A, which also produced
FeCrSi.  The SCL concentrations in the gas from an HC FeCr furnace ranged
from 1 to 8 ppm.  Because concentrations in these five furnaces were low,
no additional SCL analyses were made.  The SCL samples were analyzed
with the modified Shell Development method.
     Particulates collected by the EPA sampling train were analyzed for metals.
The analytical results for particulate collected on the glass fiber filters
are presented in Table VI-18.  This table shows that the particulate speci-
mens from furnaces producing different products are distinctly different
in chemical composition.  Gas samples analyzed were collected at both the
inlets and outlets of the control devices.  Samples collected at scrubber
outlets differed markedly in sodium and potassium content.  Samples from
scrubbers using recycled water were high in potassium and sodium.
                                   VI-48

-------
?l

                                                                                                S"  :
                                                                                                       i.  g.

-------
By comparison, the concentrations  of sodium and  potassium  in  samples  obtained
from scrubber outlets for Furnaces K and L, which  use  only fresh  water, were
very low.  Sodium and potassium compounds are highly soluble  in water and  are
thus difficult to remove by water  treatment.   Hence, the concentrations of
soluble compounds in the water recycled to the scrubber will  build  up and
may be stripped out when the scrubber water contacts the high-temperature
gases; emissions will increase accordingly.  Sodium fumes  are extremely fine
in the solid state and are difficult to remove,  as demonstrated by  the samples
collected from the inlets and outlets of a baghouse serving a FeCrSi  furnace.
The sodium in the outlet was found to be 12.7 percent, but the inlet  sample
contained only 0.23 percent sodium, indicating the fractional collection
efficiency was very low for sodium fumes.
     Residue samples from untreated scrubber water were obtained  from the
high-energy scrubber at Furnace C  (SiMn).  The metals  contained  in  higher
percentages in the water sample appeared to match  the  metals  contained in
higher  percentages in the scrubber outlet sample.
6.   Data from Other Sources^
a.   Quantities of Emissions from European Furnaces -  All  major types of
control systems are used in Europe to control emissions.
     A plant located in Germany prefers to use electrostatic  precipitators.
One of their newer units serves a 20-mw ferrochrome silicon furnace with
                                                      19
a reported dust loss ranging from 2.0 to 2.5 Ib/mw-hr.
                                 VI-50

-------
     Operation of a high-energy venturi  for cleaning the collected gas on a
closed 45 percent ferrosilicon furnace located in the USSR results in a re-
ported dust concentration in the cleaned gas of 0.001 to 0.009 gr/scf and a mass
emission rate varying from 0.015 to 0.10 Ib/hr.  The reported flow rate varies
from 1000 to 1300 scfm.   The total system's water flowrate is 150 to 225 gallons
per minute (gpm) with a  scrubber pressure drop of 70 to 95 inches water.
The furnace load and sampling method are not specified.  It is assumed that the
furnace is not totally enclosed because  of the marked decrease in gas volume
with increase in undercover pressure.
     An electrostatic precipitator used  on an open 75 percent ferrosilicon
furnace located in Switzerland reportedly cleans the exhaust gas to 0.035
to 0.066 gr/scf corresponding to 2.5 to  4.8 Ib/mw-hr.  The gases are pre-
scrubbed and conditioned by passing through a 15-centimeter wetted layer
of glass balls.    Higher emissions occur 3 minutes every hour, when the
plates are washed.
     Reaction furnace gases from a totally enclosed calcium carbide furnace
located in Germany are cleaned and used  as synthesis gas. The collected gases
are cleaned with ceramic cylinder filters called "filter candles."  The furnace
gas is cooled to 932°F before entering the filters.  The high-temperature gases
prevent formation of condensate on the filter.  Condensates in the gas stream
are removed downstream of the collector  by water-cooled condensers.  Dust
deposits are alternately removed from the filters in the compartments of the
collector by heating part of the cleaned gas stream and passing it through
the filters in a reverse direction to the normal flow.   The system is
designed to reduce the dust concentration in the cleaned gas to less than
0.004 gr/scf.25
                                  VI-51

-------
     An electrostatic precipitator serving an open silicon furnace in
Norway has encountered corrosion problems caused by water condensate and
small amounts of SO,,.  The ESP unit is preceded by a large treatment chamber
that cools the gases with water and adds gaseous ammonia.  It was  verbally
reported that tests have shown this ESP system to be 97 percent effective
when the inlet gas temperature is decreased to 158°F and 18 pounds per hour
                               O c
of anhydrous ammonia are added.
     Several ferroalloy plants in Europe use baghouses on open furnaces
but no baghouses are known to be used on covered furnaces in Europe.  Test
results for baghouse outlet loadings, if available, have not been  reported.
b.  Reported Quantities of Emissions from Japanese Furnaces - The  Japanese
ferroalloy industry in recent years has built several  totally enclosed
furnaces and achieved an excellent level of air pollution control  from these
units as well as other areas within the plant.  In general, this control
has been accomplished by a combination of furnace design, seals at the
electrodes, furnace-feed pretreatment, control of emissions from pretreatment
processing equipment, control of furnace tap fumes, and control of emissions
from product crushing and sizing equipment.
     Table VI-19 shows reported emission levels from a select group of well-
controlled Japanese furnaces, most of which are totally enclosed.   In most
of the installations, the cleaned furnace gas is used as fuel for  raw
material dryers and plant boilers, or it is sold to neighboring chemical
plants.  The gas volume for furnace 4 is not listed, but that furnace is
closely hooded and allows only enough induced air to combust the reaction
                                 VI-52

-------
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gases coming from the furnace.   Although furnace 15 has  electrode seals,
it is classified as an open furnace because the electrodes  are sealed to  an
open canopy hood, which extends down to the top of the furnace and limits
the amount of combustion.
     In Japan the most commonly used air pollution control  equipment consists
of venturi scrubbers, pressurized fabric filters, electrostatic precipitators,
Theisen centrifugal scrubbers or various combinations of these devices.
Fabric filter collectors,  in conjunction with furnace and/or ladle hooding,
are used in some installations to control furnace tapping fumes.   When
observed by EPA personnel, the furnaces listed in Table VI-18 had no visible
emissions.  Reported emission rates were obtained by use of the Japan
Industrial Standard test method.  Concentrations of emissions to the atmos-
phere from air pollution control systems for cleaning the collected furnace
gases varied from 0.001 to 0.035 gr/scf while mass emissions varied from
0.002 to 1.5 'Ib/mw-hr.
                                    VI-54

-------
                   VII.   DESCRIPTION OF CONTROL SYSTEMS
     For 40 years various types of participate emission control  systems
have been used on a limited basis by the ferroalloy industry to reduce
the high levels of suspended particulate matter often existing near
plant sites and causing ambient air problems.   During this time the
industry has sought an economical means for controlling particulates and
has tried systems using scrubbers, filters, and electrostatic precipitators,
Over-the years, four different control  systems have been used by the
industry:
         1.  Scrubbers serving open furnaces,
         2.  Cloth filters serving open furnaces,
         3.  Scrubbers serving covered  furnaces, and
         4.  Electrostatic precipitators serving open furnaces.
A.  SCRUBBERS SERVING OPEN FURNACES
     The most prevalent type of wet collector used for cleaning the large
gas volumes from open furnaces is the high-energy venturi scrubber.  Of
the several designs of venturi scrubbers, the one now generally used in
the United States is the flooded-disc scrubber (see Figure VII-1).   The
adjustable disc can be raised or lowered to decrease or increase scrubber
efficiency.  A two-phase jet scrubber system has also been developed and
used to reduce emissions from several furnaces.
     Because large quantities of submicron particulates are emitted from
ferroalloy furnaces, venturi scrubbers  require pressure drops of about
                                   VII-1

-------
VI [-2

-------
60 inches water gauge to obtain a removal  efficiency of 96 to 99 percent.
     The venturi scrubber is capable of absorbing gas temperature peaks
by evaporating more water.  Multiple units may be required if water
distribution across the throat is inadequate.   Improved performance can be
obtained by increasing either the scrubbing water or the gas velocities.
One of the greatest advantages of scrubbers over other types of collectors
is this operational flexibility.
     However, scrubbers also have some disadvantages.  Steam plumes are
usually noticeable in the exhaust gases entering the atmosphere because
the hot furnace gas evaporates large quantities of scrubber water and the
moisture is often condensed in the cooler  atmosphere.  Large quantities
of scrubber water are necessary, and to minimize water usage it may become
necessary to recirculate dust-laden water  to the cooling-spray zones of the
scrubber system.  When this happens, previously captured dust in the re-
cycled water is released into the gas stream,  and scrubber efficiency is
            27
thus reduced.  Another disadvantage of scrubbers is the potential  trans-
formation of an air pollution problem into a water pollution problem.   The
power required to operate these high-energy scrubbers is equivalent to about
10 percent of the total power supplied to  the  furnace.
     Because most venturi scrubbers recirculate the scrubbing liquor,  water
usage is held to that exhausted in the gas stream plus that bled off with
the collected solids.  The scrubbing liquor containing the collected solids
is clarified in thickeners or settling ponds.
     A new type of dust-removal system uses waste heat from the furnace
to provide the energy for gas scrubbing without the use of exhaust fans.
This system is shown in Figure VII-2.  At  one  plant, four such units have
                                 VII-3

-------
VII-4

-------
recently been installed to serve four ferroalloy furnaces.  'In brief,  the
combusted reaction gases pass through a heat exchanger, a nozzle,  and  a
separator before the cleaned gas is discharged to the atmosphere.   To
describe the process in more detail, heat from the reaction gases  is
transferred to the water in the heat exchanger, increasing  the temperature
of the water to 350 or 400 F and increasing water pressure  to about
300 pounds per square inch (psi).   As the heated water is expanded through
the nozzle of the scrubber, partial flashing occurs, and the remaining
liquid is atomized.  Thus, a two-phase mixture of steam and small  droplets
leaves the nozzle at high velocity.  At the same time, reaction gas from
the furnace is aspirated by this high-velocity two-phase mixture,  and
in the subsequent mixing, the high-velocity water entrains  the particulates
that had been contained in the reaction gas.  The mixture of steam, gas,
and dust-laden water droplets then passes through a separator where the
water and dust are separated from the gas-steam mixture.  Cleaned  gas
leaves the separator through the stack and dirty water is discharged from
the separator to a waste-water treatment system.  Chemicals and other
treatment are applied to settle solids and other contaminants from the
water, and fluid waste is discharged to settling ponds.  The water is  then
deionized, filtered, and returned to a pump for recycling to the heat
exchanger.  Makeup water is added to replace any losses.
B.  CLOTH FILTERS SERVING OPEN FURNACES
      In a cloth filter system, dust and condensed fumes are retained  on
the "dirty gas" side of the filter, and cleaned gas passes  through the
                                  VII-5

-------
filter to the "clean gas" side.   Collected  dust  particles  are  then
removed from the fabric by pneumatic or mechanical  devices.  Fabrics
                                   R        R        R
used are cotton, wool, nylon,  Orion , Dacron , Nomex ,  acetates,  fiber-glass,
etc.  Synthetic fibers are either produced  as a  continuous filament,  then  spun
and woven into yarn in the usual  manner, or they are cut  into  short
lengths or "staple," which may be spun, woven, or impacted into a felt.
Woven fabrics are identified by thread count and by weight of  fabric
per unit area.  Felts are identified in terms of thickness and weight
per unit area.
     The ability of the filter medium to pass clean air is stated as
"permeability," which is the volume of clean air in cubic  feet per minute
that is passed through 1 square foot of the filter at  a pressure  differential
of 0.5 inches water gauge.  The amount of furnace gas  that a fiber-glass cloth
filter can handle without blinding is a maximum  of about  2 actual cubic  feet
per minute (acfm) per square foot of filter area.  This low air-to-cloth
ratio can result in the use of thousands of bags so that  baghouses  serving
ferroalloy furnaces require large areas.  A baghouse also  has  many moving
parts, because the bags must be flexed or shaken to discharge  the dust.
Conveying the collected dust from the baghouse  hopper to  a dust  storage
bin requires several enclosed screw conveyors and an enclosed  elevator.
     The baghouse in Figure VII-3 is typical of those used in  the ferroalloy
industry.  The walkway access area around the bottom part  of  the  compartment
is shown as being solid, but these walkways are  normally grated  to  allow
outside cooling air to enter and mix with the hot filtered gases  at
approximately a 1-to-l ratio.  The resultant cooling effect within  the
                                 VII-6

-------
                      FILTERED GAS
                                                  FABRIC
                                                  CLEANING
                                                  MECHANiSM

                                                  SERVICE
                                                  WALKWAY
                                                  DUSTUBES
                                               DIRTY  GAS
                                     REVERSE  FLOW
Figure VII-3.  Typical baghouse. (Courtesy of
Wheelabrator-Frye, Inc.)
              VII-7

-------
baghouse compartment makes it easier for personnel  to replace bags
during operation.
     Unequal bag life necessitates frequent bag replacement.   Baghouses
in the ferroalloy industry are designed with compartments so  that one
compartment can be shut down for maintenance while  other compartments
continue to operate.  Means for easy access to the  bags are also included
in the original design.  In most cases, open, pressure-type baghouses
are used; the fan is located on the dirty gas side  of this kind of
baghouse.  Bag replacement is facilitated with this type of baghouse
because a leaky bag is easier to locate when the gas flows-from the inside
of the filter bags.
     Gas temperatures are limited to about 500°F for treated  fiberglass.
Gases from the furnace must often be cooled-by heat transfer  surfaces or
by air dilution before entering the filter media.   Figure VII-4 illustrates
one type of cooling system.  In some cases, arresters are used to prevent
overheated particles from reaching the fabric.  Cooling the gas by water
spray is possible, but requires a reliable spray control system to prevent
condensation of moisture on the fabric filters and  subsequent blinding.
     Cloth filters with air-to-cloth ratios ranging from 1.5  to 2 acfm
per square-foot of cloth have been installed on 12  large ferroalloy
furnaces in recent years.  Because of the high percentage of  submicron
particulates and the high electrostatic charge, pressure drops across the
filters are high, ranging from 10 to 18 inches of water.  However, the
pressure drops for cloth filters are lower than those for venturi scrubbers
                                  VII-8

-------
VII-9

-------
with equivalent efficiencies and gas flows;  consequently,  the power
required for the cloth filter exhaust system is less.
C.  SCRUBBERS SERVING COVERED FURNACES
     A covered ferroalloy furnace has a water-cooled cover that seals  the
top of the furnace, including the electrodes, mix spouts,  and access
openings.  This seal prevents the induction  of ambient air that would
otherwise burn the gases coming from the reduction process.   The dust-laden
furnace gas is withdrawn from under the cover, cleaned, and either used
as fuel or flared above the furnace building.  The quantity of gas that
needs cleaning from a covered furnace can be only 3 to 5 percent of that
from an open furnace.
     Two types of covered ferroalloy furnaces are currently in operation.
Developed in the 1930's, the initial version of the covered ferroalloy
furnace has mix seals at the electrodes and  is generally called a semi-covered
or semi-enclosed furnace (see Figure VII-5).  A later version is essentially
the same as the earlier one except that tight or fixed seals are used  in
place of mix seals at the electrodes.  This  configuration is called a  totally
enclosed furnace (see Figure VII-6).  However, mix seals are maintained
within the chutes at the cover of the totally enclosed furnace by choke-
feeding the material.
     With a semi-enclosed furnace, the mix is charged to the furnace through
the annul us around each electrode, and an air gap is established between  the
furnace cover and the mix chute to prevent an electrical current flow.  If
enough mix is added to keep this space filled, it acts as a seal that
prevents or limits the gases under the cover from escaping through the mix
                                     VII-10

-------
  MIX SEAL
 FORMED BY
RAW MATERIAL
FEED AROUND
ELECTRODES
COVER
CLEANED
  GAS
TO FLARE
                                     I  SLURRY TO
                                     ^"THICKENER
    Figure VI1-5.  Covered furnace with mix seals.
                ELECTRODES
      FIXED
      SEALS

       MIX
      FEED
  CLEANED
    GAS
  TO FLARE
  COVER
 TAP  	i
HOLE  '	\
                                         SLURRY TO
                                         'THICKENER
   Figure VII-6.  Covered furnace with fixed seals.
                    VII-11

-------
around the electrodes; hence the term, "mix seals."  To minimize emissions
at the mix seals, the air pollution control  system should be designed  with
enough flexibility to maintain a slight,  negative pressure under the cover.
The degree to which furnace emissions escape from the mix seals  may also be
influenced by the quality of charge materials and by the operating condition
of the furnace.  Particulate losses from mix seals are reported  to range from
2 to 12 percent of the dust and fumes generated in the furnace.   Semi-enclosed
furnaces are used in the United States to produce calcium carbide, ferrosilicon
containing 50, 65, and 75 percent silicon, ferromanganese, silicomanganese,
HC ferrochrome, and ferrochrome-silicon.
     In a totally enclosed furnace, seals are fixed insulators around  the
electrodes and cover which allows the air pollution control system to  collect
essentially all of the dust and fumes.  These furnaces are used  at several
foreign installations to produce calcium carbide, ferromanganese, silicomanganese.
ferrochrome, and several grades of ferrosilicon to a limited extent.
     No silicon metal or ferrosilicon alloys with 80 to 90 percent silicon
are produced in either semi-enclosed or totally enclosed furnaces due  to the
hot furnace conditions and complications in stoking the furnace.
     The quality and size of the raw materials used in the feed mixture have
a major influence on the operation of a covered ferroalloy furnace which may
adversely affect the gas scrubbing system.  Favorable operation requires
the use of charge materials with porsity and non-fusing properties that will
permit the uniform release of gases from the reduction process and free
flow of feed materials into the super-heated zone at the electrode tips.
Bridging of the mixture through fusion may cause gas pockets to form within
                                   vn-12

-------
the furnace burden.  Upon their collapse, heavy or violent hot-gas blows
may suddenly occur which cannot be handled by the gas removal system.
Stoking breaks up fused material and controls gas blows.  Occasionally, the
power may be turned off a semi-enclosed furnace for a short period and the
cover doors opened to permit stoking.  Totally enclosed furnaces in foreign
installations have been found to be rarely if ever stoked.  The frequency
of stoking in a covered furnace is dependent upon the furnace operating
conditions, the type of product, the quality of material, feed preparation,
and furnace design.
     Nine tests by EPA show that total particulate losses from two semi-
enclosed furnaces equipped with scrubbers are higher than the losses from
five well-controlled open furnaces and are-considerably higher than  those
from two totally enclosed furnaces equipped with scrubbers.  The particulates
in the fugitive fumes from the mix seals of the two semi-enclosed furnaces
tested averaged 342 Ibs/hr and 58 Ib/hr respectively.  The weight of parti-
culates represented  a computed loss of 8.7 percent and 6.7 percent of the
total particulates generated in open furnaces of the same size and products
based on the emission factors, Table VI-3.  A reduction in the fugitive fumes
from the two semi-enclosed furnaces tested is required to meet the control
equipment performance measured in the other seven EPA tests.  Emission reduction
may be accomplished by one or more of several methods; improved furnace
operation, more advance furnace design, or the use of secondary emission
control.
     In a covered furnace design using a shaft kiln, 80-90 percent of the
                                      r
dust containing 32.5 percent of MnO from a HC ferromanganese furnace is re-
ported to be retained in the furnace feed mixture and returned to the
        oc
furnace.     As  illustrated  in Figure VI1-7, dust is collected by impaction
                                  VII-13

-------
    DUST MOSTLY
    RETAINED BY
  FEED MATERIALS
                                      FURNACE
                                       FEED
                                     MATERIALS
PARTIALLY
 CLEANED
   GAS
                                     FEED CONTROL
ELECTRODE-

Figure VII-7.  Shaft kiln on HC ferromanganese furnace.
                             VII-14

-------
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on the feed as the gas stream is exhausted from the furnace.   The benefits
of this system have not been verified.
     In the United States, gases from semi-enclosed furnaces  are often
cleaned in a centrifugal scrubber consisting of a multi-stage centrifugal
fan equipped with water spray nozzles.  The two pictures in Figure VII-8
show the exterior and interior views of a typical centrifugal scrubber
used in the ferroalloy industry on several semi-enclosed furnaces.  Uncleaned
gases enter on the left and after passing through four cleaning states,
the cleaned gas is discharged from the "inlet" of the wheel on the right.
Although these and other scrubbers generally remove most of the particulates,
they do not remove all the tars.  Usually, the cleaned gas is flared, and
as a result, the tarry material is burned.  Absence of visible emissions
in the low volume of flared gas indicates that no significant discharge
of particulates occurs.  However, centrifugal scrubbers are limited to a
capacity of about 2800 acfm, which is comparable to gas flowrates from a
medium-sized covered furnace.  The volumes of gases from larger covered
furnaces can be controlled by the use of two or more centrifugal scrubbers.
Power and water requirements of a centrifugal scrubber are generally greater
than those of a venturi scrubber.  A centrifugal gas scrubber when used on a
covered furnace that produces calcium carbide and other alloys compatible
with the scrubber's limitations, has a particulate removal efficiency of
up to 99 percent.  Venturi scrubbers currently serving covered furnaces
and operating at pressure drops up to 80 inches water have been found to
be somewhat more efficient than centrifugal scrubbers.
     Scrubbers used to clean the gas from a covered furnace collect the dust
in the water.  Consequently, treatment facilities are required to remove
sludge from the waste water before it is discharged into public waterways.
                               VII-16

-------
     Cleaned gas from covered ferroalloy or calcium carbide furnaces has
significant value as fuel  if the gas can be used within a reasonable
distance of the furnace.  Fuel value of the gas, based on the cost of an
equivalent amount of coal, may exceed $100,000 per year for a moderate-sized
ferroalloy furnace.
     Retrofitting an open  furnace to a covered furnace generally cannot be
done without completely rebuilding it to include additional head room, which
provides space for the cover itself.  In addition, head room is required so
that the electrode suspension mechanism may be raised to provide working space
over the cover.  The mixture supply system also requires increased head room
since the mixture flows by gravity into the furnace, and the chutes need to
be clear of the electrodes.  Usually, self-baking electrodes are used for
covered furnaces, and ample head room is needed to provide a working area
for installing the metal electrode shells and an overhead crane for handling
electrode materials.
D.  ELECTROSTATIC PRECIPITATORS SERVING OPEN FURNACES
     Theoretically, the electrostatic precipitator has the lowest pressure
drop of any large-volume device capable of removing micron-size particles
from gas streams.  As a result, precipitators usually have lower power and
operating costs than other devices of comparable efficiency.  Precipitators
are also able to operate at higher temperatures than fabric filters.  Figure
VII-9 shows a cutaway view of a typical high-voltage electrostatic precipitator.
     In the precipitation  process, particles suspended in the gas are
electrically charged and passed through an electric field where electric
forces move the particles  toward the collection surface.  The particles
are retained on the collection electrode and subsequently removed from the
                                VII-17

-------
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                                          VII-18

-------
predpitator.  Various physical configurations are used to accomplish
these basic functions of charging, collection, and removal, depending
upon the type of application and properties of the dust and gas.
     Electrical resistivity of the dust is an important factor in the
performance of electrostatic precipitators in the ferroalloy industry.
If the resistivity of the collected dust is high, excessive sparking or
reverse corona can occur, thereby limiting precipitator performance.
     High conductivity of the dust is another property necessary for
satisfactory dust removal in a precipitator.  Two distinct types of
electrical conduction occur.  One type is conduction by free electrons
within the dust particles.  This type of conduction depends upon the
electron activation energy, which is a material property varying with
temperature.  Most of the particulates in the gas streams from the
ferroalloy furnaces are composed of metallic oxides and have low
activation energies.  The electrical conductivity of these particulates
is low at temperatures of 300 to 400°F, but is improved substantially
when temperatures are between 450 and 500°F.
     The second type of conduction occurs over the particle surfaces
because of the adsorption of moisture or of certain chemicals such as
ammonia.  Adsorption increases with decreasing temperature; hence,
particle conductivity also increases with decreasing temperature.  Moisture
is often referred to as the primary conditioning agent, and other chemical
adsorbates are called secondary conditioning agents.
     Unfortunately, most ferroalloy furnace fumes at temperatures below
500"F have too high an electical resistivity for satisfactory precipitator
operation.  Resistivity is in an acceptable range on-ly if the gas temperature
is maintained above 500"F.  The alternative to operating at high temperatures
                              VII-19

-------
is to humidify the furnace gases along with adding a secondary conditioning
agent, like ammonia.  Humidification of the furnace gas by water sprays
requires good atomization and sufficient residence time and heat to obtain
vaporization.  Thus, a conditioning tower physically larger than the
precipitator may be required (see Figure VII-10).  Stainless steel  construc-
tion would be required for the conditioning tower and interior surfaces of
the precipitator in order to control corrosion.  The conditioning tower
performs like a scrubber and in actuality removes 20 to 30 percent of the
particulates from the gas stream.  This system thus requires a waste-water
disposal system as well.
     Only two modern precipitators are in operation on ferroalloy furnaces
in the United States.  These are on open furnaces.  The dust-removal
efficiency of these precipitators on open furnaces in the manufacture of
chrome alloys under optimal conditions can be expected to be about 98 percent.
E.  WASTE-WATER TREATMENT
     Large quantities of water are used in the operation of both the
ferroalloy furnaces and the wet-type air pollution control devices
(scrubbers and electrostatic precipitators).
     Furnace cooling services require by far the largest portion of'the
water used in ferroalloy manufacturing processes.  From 700 to 5,000 gallons
per minute may be needed to cool the furnace and certain components of the
electrical conductors.  Additional water is, of course, required for
wet-type air pollution control devices, and approximately one-third of the
furnaces in the ferroalloy industry use such devices.  For the year 1968,
the U.S. Census Bureau tabulated water intake for the electrometallurgical
industry (20 out of 34 establishments reporting) as 298.2 billion gallons

                               VII-20

-------

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with gross water usage of 320.3 billion gallons.   Since some plants  are
equipped with their own steam electric generators, 185.3 billion  gallons
of this total were used for this purpose.   Total  water discharged was
296.1 billion gallons.
     Water quantities needed for furnace cooling  and for scrubbers range
widely from 3,000 to 10,000 gallons per megawatt-hour and from 500 to
3,500 gallons per megawatt-hour, respectively.   Since each ferroalloy
plant may differ in its water needs, typical  water requirements are
difficult to establish.  Water use may range  from 0.5 million gallons
per day for a small plant up to 100 million gallons per day for a large
plant with steam electric generators.
     Treatment facilities for the scrubber water differ, depending on
the product being made and the type of scrubber system used.  Water
pollutants from a ferroalloy plant may include  one or more of ihe following:
suspended insoluble metal compounds, soluble  metal compounds, cyanides, acid  or
basic effluents, tars, and thermal pollution.  Chemical and physical treatment of
the waste streams is usually sufficient; biological treatment methods  are not
normally considered necessary.  Scrubber water  is always clarified to  remove  the
dust scrubbed from the ferroalloy furnace fumes.   The solids consist of
burden fines ranging from less than 1 micron  up to 10 microns. The  slurry
bleed-off rate from a scrubber ranges from 200  to 500 gallons per minute.
Concentration of suspended solids in the slurry bleed-off varies  considerably
not only from plant to plant but also from hour to hour from the  same
ferroalloy furnace; a typical range is 3,000 to 17,000 ppm.  A well-designed
clarifier can reduce the concentration of suspended solids to less than
       OQ
50 ppm.
                                 VII-22

-------
     In some plants, thickened sludge from the clarifier is dewatered by
vacuum filters.  In some foreign installations, 
-------
                CHLORINE
               COMPOUNDS
                           POLYELECTROLYTES(FLOCCULENTS)
              !  CYANIDE"  "!
                REMOVAL
                  CYANIDE
               |_ REMOVAL  j

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                                       EFFLUENT

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                                    5% SOLIDS
         PONDS OR DRYING BEDS
                      FURNACE COOLING WATER.


                           RECYCLE
                                           STREAM

Figure VI1-11. Flow diagram of typical waste-water treatment facility.
                             VII-24

-------
of the Act requires the achievement by July 1,  1977,  of effluent
limitations which require application of the "best  practicable  control
technology currently available," and the achievement  by July  1, 1983, of
effluent limitations which require application  of the "best available
technology economically achievable."  In addition to  setting  effluent standards
for existing point sources, EPA also sets standards for new point  sources.
F.  SOLID WASTE DISPOSAL
     The application of more highly efficient air pollution and waste-water
treatment facilities in the industry intensifies  the  solid waste problem.
This means that wet and dry air pollution control equipment that is  only
95 percent efficient will potentially collect 342,000 tons per year  of
solid waste.  The industry also disposes of slag  when it cannot be used
in other processes.  The industry produces about  450,000 tons per  year of slag.
Slag from some operations is crushed and used as  road material.  Also,
waste slag from ferroalloy manufacture has been used  to construct  docks
and reclaim land.
     Presently very little use is made of collected ferroalloy  particulates.
Most of the collected dust is deposited in refuse lagoons and landfill areas.
In the dry state the collected material, which  contains considerable
quantities of submicron fumes, can easily become  reentrained  when  transported
to open dumps.  Therefore, dust collected in the  dry  state should  be mixed
with water or pelletized before disposal.
                                 VII-25

-------
                   VIII.  EMISSION CONTROL GUIDELINES

A.  FIELD SURVEILLANCE GUIDELINES FOR AIR POLLUTION CONTROL OFFICIALS
1.  Typical Emission Control Regulations Pertaining to the
    Ferroalloy Industry
     Particulate matter is the principal air contaminant emitted by
ferroalloy plants.  These particulates are primarily metallic oxides and
originate mainly from the electric smelting process.  Unless adequately
controlled, ferroalloy plant emissions are usually noticeable as a cloud
mass formed from several individual plumes and, depending upon weather
conditions, can prevail downwind for several miles.  Most of the partic-
ulates are submicron in size and produce extensive light scattering;
consequently, low particulate concentrations are necessary before the
furnace fumes become invisible.
     Most state regulations pertaining to allowed particulate emissions
are based on the weight of materials introduced into a specific process.
Table VIII-1 summarizes the general regulations for the states where most
ferroalloy plants are located.  The regulations express allowable emissions
in pounds of particulate matter that can be emitted per hour as a function
of the total pounds per hour of raw material process weight rate.  Included
in this table is the percent opacity allowed by those states that have
opacity restrictions.
                                 VIII-1

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     Since process weights are not easily obtained for electric smelting
furnaces, an indirect approach can be used with reasonable success.   This
approach is based on the stoichiometry of ferroalloy smelting, which pro-
vides a relationship between process weight and electrical energy input
(obtainable from control room instruments) required to produce a unit
weight of product.  These relationships are expressed as factors that vary
with the product made and are shown in Table VIII-2.  This table provides
the range of raw material usage and electrical energy requirements
experienced in furnaces normally used to produce general classes of ferro-
alloys.  Average factors are shown for convenience in applying them to
process weight information and furnace capacity in megawatts.
     Process weight (in pounds per hour) for each individual product in
Table VIII-2 may be determined by multiplying the average integrated
furnace load in megawatt-hours (obtained from instruments at the furnace)
by the appropriate factor from the table (column 7).  Likewise, net tons
of the ferroalloy produced may be determined by multiplying the average
integrated furnace load in megawatt-hours by the listed factor (column 6).
Uncontrolled mass-rate emissions may then be estimated by multiplying
the net tons of ferroalloy produced by the emission factor shown for the
appropriate ferroalloy in Table VI-3.
     State emission control regulations for particulates vary to some degree
but are generally based on process weight for each operating furnace or
source.  Because they do vary, however, a careful study of the emission
control regulations and a general knowledge of the plant operation,
including furnace loads and products, are needed to determine allowed
                                VIII-3

-------
Table VIII-2.  FACTORS FOR PROCESS WEIGHTS AND FERROALLOY PRODUCTION



               RELATED TO FURNACE KILOWATT CAPACITY
1
Product
Silvery
iron
50% FeSi
65-75% FeSi
Silicon
metal
SMZ
CaSi
HC FeMn
SiMn
FeMnSi
Mn ore/lime
melt
Chg Cr
HC FeCr
Cr ore/lime
melt
FeCrSi
Ca carbide
2
Charge
Ib/lb
Range
1.7-1.9
2.3-2.5
4.3-4.5
4.6-5.0
4.3-4.5
3.8-4.0
2.9-3.3
2.7-3.3
4.2-4.4
3.2-3.6
3.7-4.1
3.7-4.1

3.2-3.6
1.5-1.7
3
weight, l
alloy
Approximate
average
1.8
2.5
3.6
4.9
4.5
3.9
3.0
3.1
4.3
3.5
4.0
4.0
1.2
3.4
1.6
4 :
Furnace
KW-hr/lb
Range
1.2-1.4
2.4-2.5
4.2-4.5
6.0-8.0
4.2-4.5
5.7-6.1
1.0-1.2
2.0-2.3
2.4-3.0
0.6-1.0
2.0-2.2
2.0-2.2
0.5-0.7
3.6-3.8
1.3-1.4
5
load ,
alloy
Approximate
average
1.3
2.5
4.4
7.0
4.4
5.9
1.2
2.2
2.7
0.8
2.1
2.1
0.6
3.7
1.3
6
Product,
Ib/Mw-hr
770
400
227
144
227
170
834
454
370
1350
476
476
1670
270
770
7
Charge
weight,
Ib/Mw-hr
1380
1000
1020
700
1020
660
2500
1410
1590
4280
1900
1900
2000
920
1230
                             VIII-4

-------
losses from each individual plant.
2.  Process Description and Sources of Emissions
     A general description of the ferroalloy industry has been given in
Chapter V.  The operations important to the air pollution control in-
spector are the submerged-arc furnaces, the raw material preparation and
handling system, and the product sizing and handling.  Figure VI-1  in
Chapter VI shows a typical flow diagram for ferroalloy production.
     Ferroalloys are alloys of iron and some other metal or metals,
such as manganese, chromium and silicon.  They are produced by reducing
an ore of the alloying element with carbon in the presence of heat and
iron from scrap steel.  A submerged-arc furnace provides the high-
temperature vessel for the carbon reduction process.  Furnaces are rated
by electrical energy input and vary in size from about 7,000 to 50,000
kilowatts, depending upon furnace use and age.
     Raw materials from open storage piles are conveyed to overhead bins
in the mix house, where charge material is mixed and weighed for each
individual furnace.  The lump size of the raw materials varies from
approximately 0.25 to 4 inches.  In some plants, part of the mix materials
are dried before they are conveyed to the mix house; in this case,  up to
3 percent of the material charged may be lost as particulate unless proper
air pollution control equipment is used.  However, under ordinary circum-
stances when no intermediate operations are performed, the dust generated
during conveyance of material to the mix house can be held to a low level
with proper handling.
     Raw materials in the mix house are weighed into larry cars or  conveyors
according to the mix required for product specifications.  The small amount of
                                VIII-5

-------
dust generated during mix preparation 1s generally confined  to the mix
house.  The Tarry car next dumps the mix into a skip hoist,  which in turn
lifts the contents to an overhead belt conveyor within the furnace build-
ing.  If there are several furnaces within the building,  the conveying
system is designed to transport the mix to the correct furnace mix bins.
Charge material from the overhead mix bins is normally gravity-fed into
the furnace through several enclosed chutes, although a few  open furnaces
charge mix materials with manually operated skip loaders.
     The principal source of emissions is the submerged-arc  furnace.
Emissions vary widely 1n type and quantity, depending upon the product
being made, the type of furnace used, and the power input to the furnace.
Gas containing large quantities of carbon monoxide, metallic oxide fumes,  and
dust is continuously generated; gas flow will vary with furnace operation.
In an open furnace, large gas volumes result when the carbon monoxide
is burned to carbon dioxide at the surface of the charge.   In a covered
furnace, the unburned carbon monoxide is withdrawn and may be used as
fuel or flared.
     Another source of fumes associated with ferroalloy furnaces Is
the tapping operation, which occurs every 1 to 5 hours, depending on
the product, and lasts for 10 to 15 minutes.  After being tapped into a
ladle, the molten material may be transferred by overhead crane to
another ladle for repouring, which results in additional  fume emissions.
In some processes, still additional ladle operations involve slag-
metal reactions, chlorination, and oxidation, all of which produce
emissions.
                                VIII-6

-------
     The molten product is poured into chills or molds,  during which
time fumes are generated.   After solidifying in chills,  the product
is either manually sized or mechanically crushed and screened to size
before shipment.  The crushing and sizing system (jaw crushers, cone crushers
and screens) generates sufficient dust to require an air pollution control  system.
3.  Emission Control Systems
     Emission control systems are described in Chapters  VI and VII.  The
major emission problem of the ferroalloy industry concerns the capture
and collection of fumes from electric furnaces.  Control sytems are in
use on both open and covered furnaces.  Fumes from an open furnace are
collected by a canopy hood located 5 to 6 feet above the furnace and are
ducted through stacks to an emission control device.  The combustion
taking place at the surface of the unreacted charge material results in
large quantities of gases.
     Most conventional control devices have been used on open furnaces.
Several push-through baghouses are used on open furnaces producing
different products and, in the absence of other suitable devices, have
been found to be particularly adaptable for silicon metal and high-
silicon alloys.  High-energy scrubbers are used on furnaces producing
silicomanganese, HC ferrochrome, and ferrochrome-silicon.  Two electro-
static precipitators are in service on domestic furnaces producing
HC ferrochrome and ferrochrome-silicon.
     Particulate emission rates from the better controlled open furnaces in
the United States range from 1.0 to 1.5 pounds per megawatt-hour.  Particulate
emission rates from the most efficient air pollution control systems cleaning
collected gases from semi-enclosed furnaces are much lower, ranging up to 0.1
                                   VIII-7

-------
pound per megawatt-hour.   Unless losses from the mix seals  are controlled
however, semi-enclosed furnaces generally are not as well  controlled as
the better controlled open furnaces.
     The covered furnace restricts air ingestion so that the reaction gases,
consisting of a high percentage of carbon monoxide, are mostly unburned.   Gas
quantities from a covered furnace are from 2 to 5 percent of those from an
equivalent-size open furnace.   Consequently, a control  device serving a closed
furnace is small compared to one on an open furnace.  High-energy venturi
scrubbers and centrifugal scrubbers are generally used to control emissions
from covered furnaces.
     All ferroalloy products cannot presently be produced in covered furnaces.
The semi-enclosed furnace (with mix seals) is used in the United States for
the production of calcium carbide, HC ferromanganese, silicomanganese, 50-
percent ferrosilicon, and several other ferroalloys with relatively low gas
evolution.  In general, however, the high-silicon alloys (75 percent silicon and
higher) and silicon metal are not produced in covered furnaces either in the
United States or abroad.
4.  Maintenance and Operating Problems
     Even the most effective emission control systems in the ferroalloy
industry, whether serving open or covered furnaces, occasionally will
have operating problems during which the allowed losses may be exceeded.
These operating problems may be caused by equipment failures, plugged
ducts, electrical difficulties, or some other type of problem.  In some
instances, the proper performance of the control equipment bears a
direct relationship to the manner in which the furnace is operated.  For
example, if rough furnace operation suddenly increases the normal
exhaust gas temperature, the performance of an electrostatic precipitator
                                 VIII-8

-------
may be adversely affected.
     Ferroalloy furnaces are costly and complicated pieces of heavy equip-
ment that require a well-planned maintenance program.  Their operation requires
large quantities of selected feed materials, considerable amounts of electrical
power that is converted into heat, and rapidly circulated cooling water to
prevent heat damage to the equipment.  The complexity of the furnaces causes
some operating problems even when the equipment is operated by qualified
personnel and preventive maintenance is performed.
     Principal furnace operating problems may involve equipment failures,
furnace tapping problems that may cause the electrodes to be higher than normal,
water leaks, furnace interruptions for equipment repairs followed by startup
periods, mixture feed problems, electrode failures, electrical difficulties,
and electrical power shortages.  Although the majority of furnace operating
problems cause interruptions of less than an hour, major furnace operating
difficulties do occur and production may then be interrupted for several
days.  When a furnace with a cold hearth is starting up after a long
shutdown, emissions will be heavier than normal for up to a week.  In
general, ferroalloy furnaces operate from 90 to 95 percent of the time
on an annual basis.
     Baghouses usually contain several thousand cloth bags with a usable
life of about 2 years.  Bags are normally replaced as they wear out; replace-
ment may be necessary daily.  Sometimes locating the torn bags requires a
prolonged search, frequently under limited light conditions.
     Scrubber systems use large exhaust fan motors to drive high-speed
fans that require continuous monitoring because imbalances may occur.
Close control of the scrubber system's water supply is also necessary
to ensure desired performance.  Both recirculated water and waste water
                                VIII-9

-------
require treatment before discharge.
     When electrostatic precipitators are used, the gas usually requires
preconditioning before passing through the electrical  fields of the pre-
cipitator in order to reduce electrical resistivity of the particulate
matter.  Monitoring is necessary to ensure that the gas is correctly
preconditioned.  Other reasons the precipitators may not achieve design
efficiency are improper gas flow, inadequate rapping,  electrode mis-
alignment, adhesion of collected material to interior  surfaces, blocked
hoppers, and failure of the high-voltage electrical supply.  Most ferro-
alloy furnaces are capable of producing different products, but the
high resistivity of some fumes may prevent a precipitator from attaining
required collection efficiency.
5.  Monitoring Instruments
     Because emission monitoring instruments are complex and difficult
to maintain, they are used on only a limited basis in  the ferroalloy
industry.  Opacity meters, which measure the attenuation of light beams
caused by particulate matter suspended in stack gases, are used to a
limited extent.  To have reliable readings these instruments must be
cleaned frequently.  Although continuous monitoring instruments
indicating the mass emission rate of particulates are  available on the
market, the adequacy of these instruments for use in the ferroalloy
industry has not been fully demonstrated.
     Newer furnaces usually have emission control equipment, sample ports
in the exhaust ducts, and platforms and ladders to permit stack sampling.
     The furnace kilowatt-hour meter or kilowatt-load chart is used to
determine quantities of electrical energy consumed by furnace operation.

                                 VIII-10

-------
Usually, no other process control  instruments can be related to the
furnace production rates or process charge weights.   Furnace pro-
duction rates and process weight rates can be computed from the
furnace power consumption, as shown in Table VI-4.
B.  PROCEDURES FOR REDUCING EMISSIONS DURING EMERGENCY AIR POLLUTION
      EPISODES
     Air pollution control measures are promulgated  to meet national
ambient air quality standards during normal meteorological conditions.
However, adverse meteorological  conditions may cause a buildup of  air
pollutants.  To avoid a catastrophe in this event, each State is
responsible for establishing emergency episode procedures.  These  State
procedures will be necessary until emergency provisions of the Clean
Air Act Amendments of 1970 have  been fully implemented.
     The objective of an emergency episode plan is the immediate reduc-
tion of emissions.  Control strategies specify the control actions and
the degree of control required for each source.  These measures are
necessarily selective, requiring emergency curtailment of nonessential,
easily controlled sources first  and postponing drastic measures until
initial curtailments are obviously insufficient.
     Following is an example of an episode criteria  plan used as a
guide for conditions justifying  the proclamation of  an air pollution
                                                         30
alert, air pollution warning, or air pollution emergency:
     (a)  "Air Pollution Forecast":  An internal watch by the
          Department of Air Pollution Control shall be actuated
          by a National Weather Service advisory that Atmospheric
          Stagnation Advisory is in effect or the equivalent
          local forecast of stagnant atmospheric condition.
                                  VIII-11

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(b)  "Alert":   The  Alert  level  is  that  concentration of
     pollutants at  which  first  stage control actions are
     to  begin.  An  Alert  will be declared when any one
     of  the  following  levels  is reached at any monitoring
     site:

         SOp -- 800 yg/m   (0.3  p.p.m.), 24-hour average.

         Particulate -- 3.0 COHs or 375 yg/m3, 24-hour average.

         SOp and  particulate  combined -- product of SO, p.p.m.,
         24-hour  average, and COHs equal to 0.2 or proauct of,
         SOp --  yg/m  , 24-hour average, and particulate yg/m  ,
         24-hour  average  equal  to  65 X  10  .

         CO  --  17 mg/m (15 p.p.m.), 8-hour average.

         Oxidant  (0,)  --  200  yg/m  (0.1 p.p.m.) — 1-hour average.

         NOp — 1130 yg/m3 (0.6 p.p.m.), 1-hour average, 282 yg/m3
         (0.15  p.p.m.)) 24-hour average.

     and meteorological conditions are  such the pollutant con-
     centration can be expected to remain at the above levels
     for twelve (12) or more  hours or increase unless control
     actions are  taken.

(c)  "Warning":  The warning  level indicates that air quality
     is  continuing  to  degrade and  that  additional control
     actions are  necessary.   A  warning  will be declared when
     any one of the following levels is reached at any
     monitoring site:

         S02 -- 1,600  yg/m3  (0.6 p.p.m.) 24-hour average.
                                           3
         Particulate -- 5.0 COHs or 625 yg/m  , 24-hour average.

         SOp and  particulate  combined -- product of SOp p.p.m.,
         24-hour  average  and  COHs  equal to 0.8 or product of
         SOp yg/m , 24-hour average and,particulate yg/m  , 24-
         hoar average  equal to  261 X 10 .

         CO  —  34 mg/m (30 p.p.m.),8-hour average.

         Oxidant  (03)  --  800  yg/m  (0.4 p.p.m.), 1-hour average.
         NO
         56
2 — 2,260 yg/m  (1.2 p.p.m.)  —  1-hour average;
5 yg/m  (0.3 p.p.m.), 24-hour  average.
     and meteorological  conditions  are  such  that  pollutant
     concentrations can  be expected to  remain  at  the  above
     levels for twelve (12) or more hours  or increase
     unless control actions are taken.
                           VIII-12

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      (d)  "Emergency":   The emergency level  indicates  that
           air quality is continuing to degrade toward  a level
           of significant harm to the health  of persons and that
           the most stringent control actions are necessary.  An
           emergency will be declared when any one of the fol-
           lowing levels is reached at any monitoring site:

               S02 -- 2,100 yg/m3 (0.8 p.p.m.), 24-hour average.
                                                  •3
               Particulate -- 7.0 COHs or 875 yg/m ,  24-hour  average.

               S02 and particulate combined -- product  of S02 p.p.m.,
               24-hour average and COHs equal to 1.2  or product of
               S0? vg/m . 24-hour average and pacticulate yg/m  ,
               24-hour average equal to 393 X 10 .

               CO -- 46 mg/m  (40 p.p.m.), 8-hour average.

               Oxidant (03) — 1,200 yg/m  (0.6 p.p.m.), 1-hour average.
                                2
               NO, -- 3,000 yg/m  (1.6 p.p.m.), 1-hour  average;
               750 yg/m  (0.4 p.p.m.), 24-hour average.

           and meteorological conditions are  such that  this condition
           can be expected to remain at the above levels for  twelve
           (12) or more hours.

      (e)  "Termination":  Once declared,  any status  reached  by
           application of these criteria will remain  in effect
           until the criteria for that level  are no longer met.
           At such time, the next lower status will be  assumed.
      Additional  information relative to air pollution  emergency  episodes

is reported in the Federal  Register,  August 14,  1971, and the  amendment

of October 23, 1971.
      A ferroalloy plant can curtail  atmospheric pollution during an
episode in a number of ways:

      1.  A plant with both well-controlled and  uncontrolled furnaces
           should shut down the uncontrolled furnace(s) first.
      2.  A plant with no controlled  furnaces should consider  shutting

          down one or more furnaces in preference to an overall reduction

          of loads.  The worst polluting furnaces should be the first to


                               VIII-13

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         be shut down.   For example,  if there  are  four furnaces
         and a 25-percent reduction in  emissions is  required,
         better emission reduction can  be attained by shutting down
         one of the furnaces than by  cutting the operating load 25
         percent on all  four furnaces.   Also,  the  furnace with the highest
         emission levels to the  atmosphere  should  be the first to shut
         down.
     3.   Curtail or stop the material handling system as much as possible.
     4.   Curtail or stop the alloy sizing operations.

Furnaces can shut down  almost immediately by stopping the electrical
power input.  Once this is done, emissions  are immediately lowered
substantially and will  gradually disappear  over a  few hours.
                                  VIII-14

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                    IX.   ECONOMICS OF EMISSION CONTROL
A.  INTRODUCTION
     Under the Clean Air Act (1970) each State has  the primary responsibility
for assuring air quality within the geographic confines of that State  by for-
mulating and adopting, after formal approval  by the Administrator of the
Environmental Protection Agency, implementation plans  for achievement  of
primary and secondary ambient air quality standards.   These plans contain
emission regulations and timetables of compliance for  industrial  sources,
among other provisions,  such as monitoring air quality and enforcement,  for
the attainment of the ambient air quality standards.
     Ferroalloy plants are subject to implementation plans as required under
the Clean Air Act.  Air pollution control equipment has been installed in a
few plants for the past several years.  This  chapter is a study of the better
controlled facilities in the industry.  It provides that basis for estimating
the investments and annual expenditures that  will be incurred over the next
two to three years to meet emission regulations that will be adopted by
state implementation plans.
     To provide a general economic profile of the industry, present ownership,
type, and location of plants will be given.  Three  major products—ferro-
manganese, ferrochromium, and ferrosilicon--will be analyzed for supply-demand
characteristics, growth, and price movements.  Model plants will  then  be
presented along with their control requirements, associated investment costs,
and annualized costs.  Finally, economic repercussions will be discussed in
terms of impact on income and the ability of  the firm  to pass along the  costs.
     In order to reduce labor costs and to remain competitive, the ferroalloy
industry in the United States in recent years has constructed very large sub-
merged-arc furnaces with well-developed mechanical  equipment for handling
                                  IX-1

-------
raw materials and the finished product.   The more efficient furnaces are
expected to be retrofitted with control  devices such as baghouses and
high-energy scrubbers.   A number of smaller, inefficient furnaces may be
shut down and replaced with larger furnaces (e.g., a single new furnace of
30,000 to 50,000 kw size replacing several  smaller existing furnaces).
B.  FCONOMIC PROFILE
1.  Introduction
     The economic scope of the ferroalloy industry is international  and
highly complex.  Probably no other activity linked to steel making is so
completely subject to the forces of world trade.  Normally the ores  and
other raw materials, the finished ferroalloys, and even the final steel
products are all international commodities.  More than 50 different
alloys and metals, in hundreds of various compositions and sizes, are
produced for use in the manufacture of iron, steel, and nonferrous metals.
Most of the products are classified into three aeneral groups—ferromanganese,
ferrochromium, and ferrosilicon.  This sector of the chapter will present
a picture of the industry's structure followed by an analysis of the current
economic situation for each of the three ma.ior product groups.  An estimation
of the frequency of new installations will  also be made.
2.  Industry Structure
     The ferroalloy industry is comprised of establishments that reduce
oxidic ores with carbon, for the most part, to obtain the various ferroalloy
products.  The sources of carbon are most commonly byproduct coke or
low-volatile coals.  The ores are either imported, like manganese or
chromium ores  used to produce ferromanganese and ferrochromium, or mined
domestically,  like quartz used to produce ferrosilicon.  After reduction
                                   IX-2

-------
1n the electric furnace, the product is cast and crushed to meet
consumer specifications.
     As of January 1, 1972, there were approximately 44 known plants in
the United States, owned by 24 firms.   Table IV-1 outlines plant ownership,
geographic location, general run of products, and types and numbers of
furnaces producing both ferroalloys and calcium carbide.  As shown, there
are 145 ferroalloy furnaces and 13 calcium carbide furnaces.  This
tabulation should be reasonably accurate, although the companies involved
frequently change their product lines  or take furnaces in and out of
production according to demand.
     The smaller ferroalloy companies  are not diversified and rely
principally on sales of ferroalloys for their income.   The larger companies,
however, have other interests, such as the manufacture of industrial gases,
chemicals, and steel, and their ferroalloy sales comprise only a part
of their income.  In any case, the cost of controlling emissions to
atmosphere to meet new air pollution standards will have a major effect
on ferroalloy production costs and may force closure of marginal ferroalloy
plants, especially those that have open furnaces with no dust hoods and
ductwork for handling the furnace's gaseous emissions.  Furnaces of this
type cannot be effectively equipped with emission control equipment without
completely rebuilding the furnace and  extending the building height to
provide the head room required for the dust hood, ducts, and more
mechanized electrode columns.  Rebuilding a ferroalloy furnace requires
substantial new capital investment, and currently weak markets for
ferroalloys do not justify such an investment.

                                     IX-3

-------
a.  Ferromanganese - Silicomanganese
The Ore - Except for a small quantity of metallurgical  oxide nodules
shipped from stocks by The Anaconda Company and made several years ago from
Montana carbonate ore, no manganese ore, concentrates,  or nodules  have
been produced or shipped in the United States since 1971.  Thus  the U.S.  is
now totally dependent on foreign sources of manganese ore.   The  effect of
recent monetary fluctuations on ore prices is not known.   Principal suppliers
are Africa, 50 percent; Brazil, 30 percent; and India,  5  percent.   None
of the countries is noted for its hard currency.  Table IX-1 traces
the recent volume and price history of manganese ore supplies.
     Under the "Kennedy round" of General Agreement on  Tariffs and Trade
(GATT), tariffs were reduced on January 1, 1972, from 0.22 cent  per pound
of contained manganese to 0.12 cent per pound.   Actually, with only one
exception, no tariffs have been imposed since June 1964 because  of con-
gressionally approved suspensions.  The exception is a  special tariff
of 1.0 cent per pound of contained manganese on ores from the U.S.S.R.
and mainland China, deterring their import.
     U.S. consumption of metallurgical-grade ore has been cyclical, depending
upon the domestic market situation for ferromanganese and steel.   The
market for ores became progressively weaker during the  latter half of the
sixties, and imports generally decreased.  Prices followed the downward
trend, with the average value of imports at the foreign port falling from
$34 per gross-weight ton in 1962 to $22 in 1971, a drop of 35 percent.
All manganese ore prices are negotiated because they are  dependent, in part,
on the characteristics and quantity of ore offered, delivery terms, and

                                    IX-4

-------
     Table IX-1.   SOURCES AND VALUES  OF  ORES  CONTAINING   .
                  35 OR MORE PERCENT  MANGANESE,  1962-197V
Year
1971
1970
1969
1968
1967
1966
1965
1964
1963
1962
U.S.
production, ,
short tons x 10
b
5
6
11
13
14
29
26
11
25
Imports
(gross weight) ,o
short tons x 10
1914
1735
1960
1828
2059
2554
2575
2064
2093
1970
Value,3
$/ton
22
20
20
25
27
30
43
37
32
34
At foreign port.
1971 production 142 tons.
                              IX-5

-------
fluctuating shipping rates.   Transportation is a major cost item, with
ocean freight rates comprising roughly one-third of the price of imported
ore at eastern seaports.   Including domestic rail transportation, the
price of ore now reaching the domestic processing plant is probably about
$30 per gross ton.
     The outlook is for price stability in the world markets.  At present,
supply about equals demand and prices should halt their decline.  Current
and near-term prices are showing some strength.  The Bureau of Mines
estimates that nearly stable prices are expected to prevail through the
end of the century.  Given current technology and projected growth rates
for steel, by the year 2000 the U.S. may need over 3.5 million tons of
ore per year.
The Product - Over 90 percent of the imported manganese ore is used to
make ferromanganese (75 percent) and other alloys (15 percent).  The
consumption of ferromanganese and silicomanganese is tied closely to
the steel industry, which consumes 95 percent of the output.  These alloys
are needed principally to counteract the effects of sulfur in cast iron
and steel.  They also improve the characteristics of steel during rolling
and add strength and toughness to the finished product.  The remaining
5 percent of the output is used in electric dry batteries and in chemicals.
     Approximately one-half of the total U.S. ferromanganese output is from
electric submerged-arc furnaces, and ferromanganese production is usually
integrated with silicomanganese production.  Annual production of
ferromanganese has fallen every year since 1965.  Silicomanganese production
                                     IX-6

-------
peaked in 1968 and has since dropped 42 percent.   Table IX-2 presents
these recent trends.  However, with the already evident recovery of the
steel industry, the two ferroalloys should display recovery trends in
1972 and 1973.
     Over the last few years there has been a slow attrition in the number
of U.S. companies and plants.  As steel consumption recovers, it is
difficult to assess how much of the required ferromanganese and silicomanganese
will be provided by domestic production and how much by imports.  Several
factors account for increasing foreign competition.  Low transportation
costs are available to foreign producers as many of their plants are located
near seaports.  A few countries, particularly in northern Europe, have cheap
hydroelectric power.  As power costs vary from 15 to 40 percent of the
manufacturing cost (depending on, the product), a cost difference of 4 to
5 mils per kilowatt-hour can amount to $10 to $20 per ton of product,  which
offers a considerable advantage to the foreign producer.
     Tables IX-3 and IX-4 present recent values of both domestic production
and imports of ferromanganese and silicomanganese over the last several
years.  As these tables show, both silicomanganese and ferromanganese
are under considerable price pressure.
b.  Calcium Carbide
     Calcium carbide, while not related chemically to the ferroalloys, is
considered in this study because it is also manufactured in the electric
submerged-arc furnace.  Over 90 percent of the calcium carbide produced
                                  IX-7

-------
Table IX-2.  ANNUAL PRODUCTION OF FERROMANGANESE
              AND SILICOMANGANESE
                  (short tons)
Year
1971
1970
1969
1968
1967
1966
1965
Growth
rate
Ferromanganese
759,896
835,463
852,019
879,962
940,927
946,210
1,148,011
-5.5%
Silicomanganese
164,682
193,219
222,877
284,499
245,798
253,134
240,667
-6.1%
                         IX-8

-------
          Table IX-3.   SOURCES AND VALUES OF FERROMANGANESE

Year
U.S.
production,3
short tons
Value, b
$/ton
Imports,9
short tons
Val uec
$/ton

1971
1970
1969
1968
1967
1966
1965
759,896
835,463
852,019
879,962
940,927
946,210
1,148,011
168
167
143
159
147
148
146
242,778
290,946
301,956
203,212
216,279
251 ,972
257,339
133
108
105
104
122
117
122

aBureau of Mines,  Mineral  Yearbook (includes  both  electric  and  blast
 furnace output and all carbon content grades).

 Value of shipments without freight or container cost.

°Value in foreign  port of  origin.
                                IX-9

-------
          Table IX-4.   SOURCES AND VALUES  OF SILICOMANGANESE

Year
U.S.
production,3
short tons
Valueb
$/ton
Imports9
short tons
Value0
$/ton

1971
1970
1969
1968
1967
1966
1965
164,682
193,219
222,877
284,499
245,798
253,134
240,667
195
185
162
159
159
146
148
29,928
14,539
32,040
25,412
34,936
35,771
17,491
132
122
no
105
118
117
109

aBureau of Mines, Mineral  Yearbook.




 Value of shipments without freight or container cost.




cValue in foreign port of origin.
                               IX-10

-------
domestically comes from Air Reduction Company and Union Carbide Corporation.
Other companies producing this chemical  are Midwest Carbide (a subsidiary
of Chemetron Corporation) in Keokuk, Iowa,  and Pryor,  Oklahoma, and
Pacific Carbide and Alloys in Portland,  Oregon.
     Table IX-5 presents the recent domestic production, import, and price
history of calcium carbide.  The import  tariff for non-Communist nations
is $4.20 per short ton.  U.S. production has dipped 43 percent from
1,098,000 tons in 1965 to 625,000 tons in 1971,  an annual  growth rate of
-8.0 percent.  Production capacity dropped  from 1,195,000 tons in 1955
to 963,000 tons in 1970?1
     The greatest use for calcium carbide is in the manufacture of acetylene,
a major chemical building block.  However,  it is fast  losing ground to
acetylene made from petrochemicals.
c.  Ferrochromium
The Ore - Commercial grades of chrome ore,  a strategic and critical
commodity, are found only in limited areas  of the world.  North American
deposits are of poor quality and cannot  compete economically with foreign
ores.  No chromite ore has been mined in the United States since 1961,
when a small amount was produced under the  Government  Defense Production
Act.  The world's largest deposits are found in the Transvaal area in
the Republic of South Africa.  Other major  ore deposits are located in
Rhodesia, the U.S.S.R., and Turkey.  As  detailed in Table IX-6, the
United States must import all of its chromite needs.  As specified in
Tariff Classification 601.15* no rate of duty is placed upon chrome ore
imports.
                                      IX-11

-------
      Table  IX-5.   SOURCES  AND  VALUES  OF  CALCIUM  CARBIDE
Year
1971
1970
1969
1968
1967
1966
1965
U.S.
production,
short tons
625,000
791 ,000
856,000
942,000
912,000
1,063,000
1,098,000
Value,
$/ton
90
81
78
94
94
87
89
Imports,
short tons
20,000
18,600
17,900
6,900
8,300
20,200
10,500
Value,
$/ton
75
70
68
70
69
65
70
 Current Industrial  Reports,  Department  of Commerce,  Bureau  of the
 Census.

3U.S.  Imports  for Consumption and General  Imports,  U.S.  Department
 of Commerce,  Bureau of the  Census,  FT 246 (Calcium Carbide  TSUSA
 4181400).
                                IX-12

-------
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                                                       IX-13

-------
     The chief market for chrome ore is in the manufacture of chrome
ferroalloys, with this sector consuming over 60 percent.   Other uses include
the manufacture of refractory products and the production of bichromates
within the chemical industry.  Chromite ore has been traditionally classified
into three general grades—metallurgical,  refractory, and chemical—depending
to a large extent upon chromium content,  impurities, and  the chromium/iron
ratio of the deposit.  Although the Republic of South Africa accounts
for the greatest percentage of U.S. imports, deposits in  the Transvaal
region are mostly of chemical grade due to the low chrome-iron ratio.
Consequently, lesser amounts of ore from this source are  used by the
ferrochromium industry.  Metallurgical-grade ore is normally imported from
the U.S.S.R., Rhodesia, and Turkey.
     United States consumption of chromite ore has been cyclical, depending
upon the domestic market for ferrochromium and the international political
situation surrounding ore-exporting nations.  From 1960 to 1966 chromite
ore imports and ore consumption generally increased at yearly rates of
about 5.0 percent and 3.5 percent, respectively.  Average ore prices
remained relatively stable throughout this period, ranging between $33 and
$36 per short ton of chromium content (see Table IX-7).  In December 1966,
however, the United Nations Security Council passed a resolution calling
for an economic boycott of Rhodesia by member nations, declaring that the
apartheid policies of that country's government constituted a threat to
peace.  Pursuant to the U. N. resolution, a Presidential  Executive Order
was issued in early 1967, imposing sanctions upon trade with Rhodesia.
As shown in Table  IX-8, which presents import data for metallurgical-grade
                                    IX-14

-------
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ore, chromite shipments from Rhodesia ceased entirely in 1968.   The boycott
caused a general decrease in the supply of ore and severe price increases
for metallurgical-grade chromite between 1967 and 1971.   Although U.S.  ore
imports diminished during this period, domestic consumption remained
relatively constant, causing a general decrease in consumer inventories.
     This situation may be alleviated in the near future because in late
1971 the United States Congress passed a military procurement bill
containing an amendment that removed Presidential authority to ban imports
of Rhodesian chromite after January 1, 1972.  The amendment, which forbids
embargoes on any strategic material that is also imported from a communist-
dominated country, could eventually lead to an improvement in the raw
material cost/product price relationships for ferrochromium producers.
A small amount of Rhodesian chrome ore entered the United States in 1972;
however, political factors have so far prevented normal  shipments.
The Product - Ferrochromium is used in various percentages for producing
iron castings and all types of steel, with about 70 percent going into
stainless steel.  Substantial quantities are consumed in the production
of superalloys, and small amounts are used in nonferrous alloy production.
Output is normally in the forms of HC ferrochromium, LC  ferrochromium,
or ferrochromium silicon, depending upon the alloy usage and the undesirability
of excess carbon as an impurity.
     Table IX-9 shows production, shipments, and price statistics for
ferrochromium from 1963 to 1970.  Although the industry  encountered several
problems during this period, domestic output of all ferrochromium products
                                  IX-17

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showed rather steady growth.  Yearly Increases were attained through 1967,
after which a cyclical  pattern set in for the remainder of the decade.
Linear regression shows a growth rate from 1963 to 1970 of approximately
3.2 percent per year, with total domestic production presently about
400,000 short tons per year.
     Because of its close relationship with stainless steel  (for which
market researchers predict long-term growth at a greater rate than for
raw steel), ferrochromium should have the most favorable outlook of any
of the major ferroalloys.  However, three interrelated problems may plague
the domestic producers in the near future:  (1) Higher chrome ore prices
and tightening supplies of metallurgical-grade lump, caused by the
Rhodesian boycott, have forced the domestic industry to raise alloy prices.
As measured by quotations for LC ferrochromium (maximum carbon content
0.025 percent), prices have increased from 25.5 cents per pound of contained
chromium in early 1968 to 39.5 cents per pound in late 1971, a jump of
some 55 percent.  (2) Such price increases may stimulate higher levels  of
alloy imports since foreign producers have a cost advantage going into  the
marketplace.  Ferrochromium imports have in fact grown at a rate of about
4.0 percent per year from 1963 to 1970, although the statistics show large
fluctuations.  Norway, Sweden, and the Republic of South Africa are major
suppliers, having easy access to low-cost electric power and/or indigenous
raw materials.  West Germany, France, and Japan also export substantial
quantities to the United States.  (3) The rising prices for ferrochromium
and nickel have forced parallel increases in quotations for stainless
steel, estimated to be costing U.S. consumers an extra $100 million per
                                   IX-19

-------
annum.  The domestic steel  industry,  with mounting competition  from
abroad, has also lost a substantial  part of its stainless steel  markets.
As shown in Table IX-9, stainless steel  imports have risen dramatically
from the 1963 level, even with allowance for the programs of voluntary
steel import quotas underway since 1969.  For 1971, stainless steel
imports stood at 191,000 tons, up about  8 percent from the 1970 level.
     If international political  problems can be settled,  the prospects
for ferrochromium appear to be favorable.  If Rhodesian ore supplies
become available once again, the prices  for chrome ore should drop and
the ore markets should stabilize.  Ferrochromium prices should  follow a
similar downward pattern, which would benefit both alloy producers and the
domestic steel industry.  Over the long  run, growth in demand for ferro-
chromium should exceed the rate of expansion in steel  output, reflecting
continued efforts to upgrade certain  qualities of steel,  particularly
corrosion resistance and increased strength.  Between 1968 and  2000,
the U.S. Bureau of Mines predicts a growth of demand for ferrochromium
of 2.0 to 3.3 percent yearly.  However,  the United States will  remain
dependent upon foreign sources of chrome ore, a situation that  will
continue to be a potential  problem.
d.  Ferrosilicon
The Ore - Silica raw materials are widely distributed throughout the  world,
and the processing required to retrieve  the ore is relatively simple.
United States domestic supplies are plentiful, and the quarrying of quartz,
quartzite, and sandstone is essentially  a domestic industry.  Consequently,
ferrosilicon is one of the few ferroalloys made from an ore that is not
                                    IX-20

-------
subject to the fluctuations of international  political  and economic
forces.  Conventional  processing consists of removing the material  with
power equipment, followed by crushing, sizing, and washing.
     United States production and consumption statistics for silica gravel
or crushed rock are not regularly collected.   However,  with  an assumed
production ratio of 3  to 1  for guartzite converted to silicon contained
in all ferroalloys, the U.S. Bureau of Mines estimated  that  approximately
1.5 million tons of silica  raw materials were guarried  in !QfiB.   Because
these raw materials are commodities having a low value-to-bulk ratio,
transportation costs are a  major item and in most cases can  determine
the source and the distance the material can be hauled.  Prices  for
quartz or quartzite are dependent to a large degree upon chemical
analysis, sizinq, quantity, and negotiated contracts.  For 1%8, guoted
prices including transportation ranged from $R to $12 per ton in various
locations throughout the nation.
     The outlook for silica rock is continued stability.  Domestic  raw
materials will be in ample  supply well beyond the year  2000.  The United
States will not have to depend upon imports for any part of  its  supply.
The Product - It is estimated that about QO percent of  all silicon  is
consumed by the iron and steel industry in the form of  ferrosilicon alloys,
Ferrosilicon is regularly used to deoxidize the molten  metal and remove
dissolved gases.  It is also used to produce hiqh-silicon "alloy"  steels
                                   IX-21

-------
with greater corrosion resistance and improved strength, and low-iron-loss
steels for electrical transformers and motors.  Ferrosilicon is also
used in gray iron foundries to increase the amount of silicon in the iron,
as it is necessary to add silicon when using scrap steel charge in the
cupola.  Products are normally classified as silvery pig iron (15 to 20
percent silicon), ferrosilicon (21 to 95 percent silicon), and silicon
metal (96 to 99 percent silicon), with several percentage grades made
in each class.  No silvery pig iron is now made in blast furnaces, but
it is produced in the submerged-arc furnace.  The major market for silicon
metal is the aluminum casting industry.  Because iron is unacceptable
in aluminum alloys, silicon metal is added to aluminum instead of the
normal grades of ferrosilicon to improve corrosion resistance, weldability,
and casting and machining properties.  Secondary aluminum producers are
the largest consumers, accounting for some 65 percent of the demand for
silicon metal in 1969.
     Table IX-10 gives production, shipments, imports, and price statistics
for two classes of ferrosilicon from 1965 to 1971.  Based upon simple
linear regression, the growth rate for domestic production of silvery
pig iron dropped 4.4 percent while that for ferrosilicon rose 3.3 percent
per year from 1965 to 1971.  Growth in shipments of silvery pig iron,
some 85 percent of which is consumed by the gray iron foundry industry,
followed the trend in cast iron output from foundries, where production
has been slowly receding since 1955.  Domestic shipments of 21 to 95 percent
ferrosilicon increased about 3.3 percent per year, while prices ranged
                                     IX-22

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-------
from 15 to 18 cents per pound of contained silicon.   Markets  for
ferrosilicon have been growing chiefly because steelmakers  have increasingly
demanded a wider variety of specialized ferrosilicon grades to be used
for high-silicon alloy steels.
     As reflected in Table IX-10, imports have not been a major influence
upon ferrosilicon markets..  Overseas shipments were normally  less than
inflows until 1970, when exports exceeded imports.  Most of the trading
is with Canada and the United Kingdom.  The Norwegian Ferrosilicon
Producers Association announced in 1972 that it has adopted a major
marketing program to penetrate the U.S. market.
     The outlook for ferrosilicon products is somewhat favorable.  Future
demands for silvery pig iron and 21 to 95 percent ferrosilicon are expected
to follow the trends in iron and steel growth, estimated at 4 percent per
year.  Because raw materials are plentiful and silica is relatively
inexpensive, there is little likelihood that silicon alloys will be
replaced by substitute products.  Furthermore, technological  advances
may even increase the use of ferrosilicons for replacement  of the more
expensive corrosion-resisting additives such as chromium.
3.  New Units
     Concrete projections of the number of new units to be  installed by
the industry are not readily available in the literature.  However,
predictions can be made based upon the growth rates of the  various product
classes and by a consideration of the replacements needed for older
furnaces.  Although the growth rate for ferromanganese and  silicomanganese
products has been negative in recent years, consumption should keep pace
                                  IX-24

-------
with the 4 percent annual  long-term trend of steel  industry growth.
However, only 50 percent is currently supplied by electric furnace.
If this ratio holds, it will mean a net growth of one 30-mw furnace
every 2 years if all the increase can be obtained by domestic producers.
However, in the recent past domestic producers have only supplied about
80 percent of the domestic market for ferromanganese and 90 percent
of the silicomanganese market.
     Generally it is made in the same type of equipment as ferromanganese
and silicomanganese.  However, no new units are anticipated for the  express
purpose of producing this material.  One source quoted by the Chemical
Economics Handbook believes that acetylene derived from calcium carbide
may cease to be used for the production of chemicals.  The only thing
that might reverse this trend would be a jump in the price of the competing
light hydrocarbons due to the energy shortage.
     Growth rates of approximately 3 percent for ferrochromium and ferro-
silicon products seem to dictate that this segment of the industry will  need
approximately one large furnace (30,000 to 40,000 kw) in alternate years.
     There are a total of about 150 existing furnaces in the industry;
assuming an average furnace life of 30 years, about five furnaces per
year should have to be replaced.  The trend in the industry, however, is
to replace smaller furnaces (average size estimated to be about 10,000 kw)
with much larger units (probably around 40,000 kw).  Given a size ratio
                                 IX-25

-------
of 4 to 1  for old-to-new furnaces, it is expected that approximately one unit
per year will be needed for replacement purposes.  In  total,  about 5 to 8
new ferroalloy furnaces are estimated to be installed  in the  next 5 years.
C.  CONTROL COSTS
1.  Introduction
     Capture of pollutants is the critical  factor in designing-atmos-
pheric emission control systems for ferroalloy plants.  The major
source of emissions is the carbon reduction of metallic oxides in the
submerged arc furnace.  Carbon monoxide is  generated continuously
along with other reaction gases and fumes.   The carbon monoxide from
the furnace reaction zone may be withdrawn  by an exhaust system with-
out combustion provided a furnace has a closed water-cooled cover
and seals around the electrodes.  The covered ferroalloy furnace may
only be used for a limited number of products but offers the  advantage
of producting smaller gas volumes to clean  than an open, hooded furnace.
The small volume of dirty gases from a covered system  is typically
cleaned by high-energy scrubbers.
     The open-furnace system allows induced air to mix with and burn the
carbon monoxide above the charge.  Depending on design of this particular
furnace type, evolution of gases may result in flows of 20 to 50
times those generated by the covered system.  The volume of gas flow
depends on the hood design, the vertical opening required for stoking
the charge, and the diameter of the furnace.  In addition, open furnaces
with provisions for adding electrode sections under electrical load,
require a protection area for electrode installation.   Some older open
furnaces add electrodes under no  load conditions at which time venting
occurs directly through roof monitors.  To control such a system,

                                  IX-26

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hooding requirements call for a much greater volume of gas than would be
required if a hood were placed at a lower elevation.  Collection devices
for open furnaces include fabric filters, scrubbers, and electrostatic
precipitators.
     In the following sections, costs will  be discussed for scrubbers on
covered furnaces, and scrubbers and fabric  filters on open systems.   Not
enough data are available to discuss electrostatic precipitator costs.
It is important to point out that covered systems work only for a limited
number of products—ferromanganese, silicomanganese, 50 percent ferro-
silicon, some grades of HC ferrochrome and  calcium carbide.
2.  Model Plants
     Model furnaces were developed to evaluate the control cost.  Because
the trend in the industry is toward larger  furnaces than in the past,
the size chosen for the models is large - 30 megawatts.  Table IX-11
shows the pertinent design parameters associated with the model furnaces.
Since silicomanganese (SiMn) can be made in the same furnace inter-
changeably with high-carbon ferromanganese  (HC FeMn), we have assumed that
the control equipment for the SiMn furnace  will be the same as for the
HC FeMn furnace.
                                  IX-27

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                 Table IX-11.  MODEL FURNACE PARAMETERS
Product
Parameter
Power rating, mw
Product rate,3 tons/yr.
Gas volume from
HC FeMn
30
99,000
5,non
SiMn
30
44,000
5,noo
50% FeSi
30
47,500
6,000
HC FeCr
30
51,000
5,000
CaC?
30
91 ,000
4,000
  totally enclosed
  furnace,& scfm

Gas volume from open     350,000  350,000°  450,000     250,000   200,000
  furnace,b acfm
  O 400°F

Tapping fume gas          60,000   60,000    60,000      60,000    60,000
  volume from all
  furnace types, acfm
  0 150°Fd
aAt 90 percent of full capacity.

 The gas volumes represent typical values obtained
 from the industry survey questionnaires.

°Assumed to be the same as for HC FeMn since the furnace
 may be designed to produce either product.

 The figures shown for the tap fume collection are additive to the open
 furnace volume, based on an open furnace configuration with the
 collection hood 5 to 7 feet above the furnace deck.
                                  IX-28

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     Another emission source that must be controlled besides the furnace
itself is the furnace tapnina operation.   The method of control assumed
for this cost analysis depends on the furnace type.   For open furnaces
the tapping fumes can be collected with a separate hood and vented into
the main control  device.  For other furnaces a separate fabric filter
control  system would be the most probable method of control.
     In  addition  to the costs for the model  plants,  costs are presented
for a large, totally enclosed furnace that is currently under construction
in North America.  These data should represent the most up-to-date costs
experienced by industry for construction  of a totally enclosed furnace
in this  part of the world.
3.  Open Furnace  Control Costs
     Control costs for the model open furnaces shown in Table IX-11
were developed for two types of control devices - fabric filters and
wet scrubbers.
a.  Fabric Filter Control Costs - Estimates of investment and operating
costs required to control open furnaces using fabric filter systems are
shown in Table IX-12.  These costs were developed from information sub-
                                                              op
mitted to EPA by the Industrial Gas Cleaning Institute (IGCI).    The tap-
ping fume control system is vented into the fabric filter, and the costs
for that system are included.  The assumptions that form the basis for
these cost estimates will be discussed below.  The industry's cost esti-
mates for fabric filter systems are higher than the figures in Table IX-12
because additional eguipment and installation factors are considered.  The
industry's cost estimates are shown in Table IX-13 and will be discussed in
the second part of this section.
                                    IX-29

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      Table IX-12.   CONTROL COSTS FOR FABRIC FILTERS  ON OPFN  FURNACES
                                                     Product
                                 HC FeMn
  Cost item                     and SiMn       50% FeSi       HC FeCr      CaC
                                                                            2
Capital cost
  Fabric filter                 $ 682,000    $ 832,000     $ 532,000  $ 449,000
  Auxiliary equipment             226,000      275,000       176,000    149,000
  Installation                  1,142,000    1,393,000       892,000    752,000
Total capital cost            S 2,050,noO  $ 2,500,000   $ l,600,nno $1,350,000
Annual cost
Operating labor
Maintenance (6%)
Electricity
Capital recovery
(15 yr. life, 8% interest)
Administration (2%)
Taxes and insurance (2%)

53,000
123,000
87,000
240,000

41,000
41,000

53,000
150,000
106,000
292,000

50,000
50,000

53,000
96,000
68,000
187,000

32,000
32,000

53,000
81 ,000
57,000
158,000

27,000
27,000
Total annual cost               $ 585,000    $ 701,000     $ 468,000  S 403,000
                             HC FeMn  SiMn
Annual cost per ton          * 5.91  $ 13.30  $ 14.76        $ P.18     S 4.49
                                   IX-30

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4.0
2.0

1.0
0.8
0.4
0.2
0.1
  20
40        60     80   100               200
        INLET GAS VOLUME TO COLLECTOR, acfm x 103
400
600
     Figure IX-1.  Capital costs of open furnace control with fabric filters.
                                       IX-31

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     The capital costs for fabric filter installations as received from
the IfiCI were plotted against the associated collector inlet volumes, and
the graph is shown in Figure IX-1.  The capital  cost for each model  furnace
may be determined from Figure IX-1 by finding the capital cost that
corresponds to the gas volume flow rate for that model.  The capital  costs
from the IGCI study are based on a new plant situation (I.e., a simple
duct run, no space limitations, etc.).  The costs for the furnace hood
and the incremental electrical substation are not included.  The capital
costs for the fabric filter installations include the baghouse, fans,
upstream mechanical collector, dust storage bins with 24-hour capacity,
dust hoppers and conveyers, foundation support,  ductwork connections, and
stack.  The charges for engineering design layout, electrical and piping
tie-ins, insulation, erection, performance testing, and startup are  all
included.  Fiber glass bags with a temperature resistance of 500 F are
assumed to be used.  The baghouse is also assumed to contain one extra
compartment, which permits shutdown for maintenance.
     The following assumptions concerning annual costs of operation  apply
to operation of the control facility for open furnaces.
     1.  Replacement parts and maintenance were estimated at 6 percent
         of the original plant investment for the purpose of replacing
         50 percent of the bags and 10 percent of the air valves per
         annum, and for unknown contingencies.
     2.  Manpower requirements were estimated to be 1/2 man per shift.
     3.  Electricity costs account for sufficient power to push the gas
         into the baghouse with 10 to 12 inches pressure loss for HC
         FeCr and 15 to 20 inches pressure loss for FeSi.  Electrical
         costs were based on 1 cent per kilowatt-hour.

                                   IX-32

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     4.   Depreciation and interest charges are accounted for by the use
         of a capital recovery factor based on 15 year life and on 8
         percent interest rate.
     5.   Administrative costs of 2 oercent of original investment and
         another 2 percent for property tax and insurance were assumed.
     The ferroalloy industry has reported higher costs for fabric filter
installations due to the following factors:
     1.   The industry's cost figures are based mainly on installations
         at existing plant sites.  Since these installations must be fit
         into the available space, certain cost items such as ducting will
         be more expensive.
     2.   The industry's figures also include items that were not included
         in the IGCI cost estimates.  These items are the furnace hood cost,
         electrical substation expansion costs, equipment startuo costs,
         and company engineering and contingency costs.
Including these items and assuming a retrofit installation, the capital costs
can be as much as 50 percent higher than the IGCI costs.  Table IX-13 shows
the industry's cost estimates for the model furnaces.
     If the average of the IGCI costs and the industry's costs are used,
the annual cost per ton ranges from a low of $5.12 per ton for calcium
carbide to $17.73 per ton for 50 percent ferrosilicon.
b.  Wet Scrubber Control Costs -  Estimates of the investment and operating
costs required to control open furnaces using wet scrubbers are shown in
Table IX-14.  These estimates are derived from information from the
                                        3?
Industrial Gas Cleaning Institute (IGCI)   and are based on equipment and
                                  IX-33

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   Table IX-13.   CONTROL COSTS FOR FABRIC FILTERS ON OPEN FURNACES
                 (REPORTED BY INDUSTRY)
                               HC FeMn
  Cost item                   and S1Mn       50% FeSi        HC FeCr        CaC2
Capital cost
  Fabric filter             $ 1,000,000    $ 1,265,000  $   700,000    $   630,000
  Auxiliary equipment           360,000        455,000      255,000        220,000
  Installation                1,640,000      2,080,000    1,145,000      1,050,000
Total capital cost          $3,000,000    $3,800,000  $ 2,100,noo    $1,900,000
Annual cost
Operating labor $
Maintenance (6%)
Electricity
Capital recovery
(15 yr. life, 8X interest)
Administration (2%)
Taxes and insurance (2%}

53,000
180,000
87,000
350,000
60,000
60,000

$ 53,000 $
228,000
106,000
444,000
76,000
76,000

53,000
126,000
68,000
245,000
42,000
42,000

$ 53,000
114,000
57,000
222,000
38,000
38,000
Total annual cost            $  790,000     $  983,000   $  576,000     $  522,000
                           HC FeMn   SiMn
Annual cost per ton        $ 7.98   $17.95      $ 20.69     $ 11.29        $ 5.74
                                   IX-34

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operating requirements to meet the process weight standard published
in the Federal Register of August 14, 1971.  The costs have been adjusted
from I6CI data to reflect the gas flows of the model plants presented in
Table IV-11.  The costs in Table IX-14 are based on a new plant installa-
tion and do not include the furnace hood or additional electrical
substation costs.  The industry's experience confirms the costs as
presented in Table IX-14.
     Plots of investment cost data for scrubbers developed by the IGCI
are shown in Figure IX-2 for HC ferrochrome and 50 percent ferrosilicon
furnaces.  The cost curve for ferrochrome was used to develop the costs
for all the other alloys except 50 percent ferrosilicon.  The investment
costs include a venturi scrubber, a fan with at least 20 percent excess
capacity, and entrainment separator, aftercoolers, a slurry settler, two
filters to dewater the slurry product, and tapping emissions control.  The
charges for engineering design layout, electrical wiring, piping, insula-
tion, erection, performance testing, and startup are all included.  It
should be noted that the water treatment equipment may not necessarily be
enough to meet EPA's proposed effluent standards.
     The annual cost per ton of product ranges from a low of $7.08 per
ton for calcium carbide to a high of $34.38 per ton for 50 percent ferro-
silicon.
4.  Totally Enclosed Furnace Control Costs
     Capital and annual costs are presented in this section for control
devices on totally enclosed furnaces.  Since the furnace has a tight cover
with seals around the electrodes, the gas volume going to the control device
is much smaller than for an open furnace.  Thus, the cost of the control

                                   IX-35

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Table lk-14.  CONTROL COSTS FOR WET SCRUBBERS ON OPEN FURNACES
Product
Cost item
Capital cost
Scrubber $
Auxiliary equipment
Installation
Total capital cost $
Annual cost
Operating labor S
Maintenance (7%)
Electricity
Water
Capital recovery
(15 yr. life, 8% interest)
Administration (2%)
Taxes and insurance (2%}
Total annual cost $
HC
Annual cost per ton
of product $8.
HC FeMn
and SiMn

110,000 $
290,000
1,400,000
1,800,000 $

26,000 $
126,000
290,000
155,000
210,000
36,000
36,000
879,000 $
FeMn SiMn
88 $19.97
50% FeSi

190,000
510,000
2,450,000
3,150,000

26,000
220,000
595,000
298,000
368,000
63,000
63,000
1,633,000

$34.38
HC FeCr

$ 96,000
254,000
1,250,000
$ 1,600,000

$ 26,000
112,000
225,000
118,000
187,000
32,000
32,000
$ 732,000

$14,35
CaC2

$ 87,000
233,000
1,130,000
$ 1,450,000

$ 26,000
102,000
190,000
99,000
169,000
29,000
29,000
$ 644,000

$ 7.08
                                IX-36

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    4.0
    2.0
    1.0


    0.8

CNJ
a
-  o.e
    0.4
    0.2
    0.1
      20
                                                        FERROCHROME
40        60      80    100              200


           INLET GAS VOLUME, acfm x 103
400
600
       Figure  IX-2.  Capital  costs of open furnace control with wet scrubbers.32
                                         IX-37

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device is much smaller than for the open furnace.   The higher  cost of a
covered furnace compared to an open furnace will  be discussed  in  Section 6.
In addition to the furnace control  device,  a separate fabric filter to
control taphole emissions is included.
a.  Wet Scrubber Control Costs for  Furnace  Gas  Cleaning - The  capital  and
annual cost for two types of wet scrubber control  systems are  discussed
in this section.  Both systems are  considered best demonstrated technology,
but one system includes two parallel control systems which increase the
cost.  The costs are based on actual costs  reported for foreign installations
of HC FeMn furnaces updated to 1973 U.S. dollars.   However, European con-
struction costs will be generally lower than similar installations in the
United States because of differences in building  standards, labor rates,
safety requirements, accounting procedures, and tax structure.
    System A consists of two parallel control devices each capable of
handling the total gas flow.  The control device  is made up of three stages
of venturi scrubbers.  The draft for this system  is provided by aspiration
when water is injected at the venturi throats.  The capital cost includes
the complete scrubber system and the necessary water treatment facilities
and flare stack.  The annual cost includes  operating labor and materials,
maintenance, depreciation, interest on capital, administrative costs,
property tax and insurance.  Ho credit has  been taken for the  heat recovery
value of the carbon monoxide (CO),  which can be a significant  amount pro-
vided conditions permit use of the  gas.  For example, the heat value of
5000 scfm of gas (assuming 60 percent CO) from the HC FeMn furnace is about
$180,000 per year based on production at 90 percent of full capacity and a
heat value of $0.40 per million Btu.
                                  IX-38

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     The total reported capital costs for system A was about $630,000, which
was about 9 percent of the total furnace installation cost of $7.2 million.
The reported annual cost for system A was about $225,000.
     System B is another foreign installation consisting of a two-stage
venturi scrubber with a fan to supply the necessary pressure.  The capital
costs include the control system, flare stack, and water treatment
facilities.
     The reported capital cost of control system B was about $260,000, which
was about 6 percent of the total furnace installation cost of 4.5  million.
The reported annual cost was about $77,000.  Again, no credit has been taken
for the heat value of the CO.  This furnace was installed at an existing
site where some of the existing equipment could be adapted for use with
the new furnace.
b.  Fabric Filter Control Cost- A few overseas companies use fabric filters
as the control device on totally enclosed furnaces.  This method of control
has not been used in the U.S., and the domestic industry does not expect
to use this method of control for totally enclosed furnaces.  The estimated
capital cost for a conventional fabric filter control system consisting of
a radiant cooler, cyclone, fan, fabric filter, dust removal and storage
equipment, water seal tank, and flare stack is about $250,000.  However,
this system would have to be specially designed because of the high con-
centration of CO gas.  These added design considerations could double or
triple the cost.
C.  Tapping Fume Control Cost- The estimated capital and annual costs
presented in Table IX-15 are based on a separate fabric filter control
system for emissions generated during the furnace tapping operation.   The
                                  IX-39

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           Table IX-15.  CONTROL COSTS FOR A SEPARATE TAPPING
                         FUME COLLECTION SYSTEM
     Cost item                                     Cost
Capital cost
  Fabric filter                                $   85,000
  Auxiliary equipment                              55,000
  Installation                                    260,000
Total capital cost                             $  400,000
Annual cost
Operating labor
Maintenance (10%)
Electricity
Capital recovery
(15 yr. life at 8% interest)
Administration (2%)
Taxes and insurance (2%)

$ 10,000
40,000
23,000
47,000
8,000
8,000
Total annual cost                              S   136,000
                                    IX-40

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assumed flowrate was 60,000 acfm at 150°F.  The system includes a hood,
fan, fabric filter, and dust removal and storage equipment.
     Because the tapping operation can be scheduled with some flexibility,
this control system could serve more than one furnace.  Possibly two
tapping fume hoods could be vented to the same fabric filter, and this
would reduce the control cost per furnace.  However, for this analysis
a separate tapping fume control system for each furnace has been assumed.
5.  Semi-enclosed Furnace Control Costs
     The main difference batween a semi-enclosed furnace and a totally
enclosed furnace is the method of sealing the area around the electrodes.
On the semi-enclosed furnace, the seal is made by maintaining the feed
mix around the electrodes.  The furnace gases drawn from under the cover
require treatment in the same manner as the totally enclosed furnace gas.
In addition, hoods may be constructed to capture the emissions that
escape around the electrodes.  This gas stream can be controlled by com-
bining it with the taphole gases and venting the combined stream to a
fabric filter.
     One way to illustrate the cost of control for the semi-enclosed
furnace is to examine the differences in control cost between the semi-
enclosed furnace and the totally enclosed furnace.  The capital cost of
semi-enclosed furnace installation is lower than the totally enclosed
furnace by about the amount of the mechanical seals.  On the other hand,
electrode and taphole emissions from the semi-enclosed furnace may require
a fabric filter that is about twice as large as the fabric filter for the
taphole emissions from the totally enclosed furnace.  For a 30 mw furnace,

                                   IX-41

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the cost of these two factors approximately cancel  each other.   In general,
the control cost for the semi-enclosed furnace is equal to or slightly
greater than that for the totally enclosed furnace.  The annual  cost for
the semi-enclosed furnace would be higher by the amount of the operating
cost to run the larger fabric filter.
6.  Case Study of a Totally Enclosed Furnace
     As shown by the previous models, the cost of the air pollution control
equipment for the totally enclosed furnace is considerably less  than the
open furnace cost.  The main reason is that the gas volume from the totally
enclosed furnace is much smaller.
     However, the pollution control equipment is not the only consideration
when comparing the open and totally enclosed furnace.  Actually the open
and totally enclosed furnaces require two different sets of process equip-
ment of which the pollution control system is one part.
     In order to make a complete comparison of the two furnace types, one
should look at the total system from both the process side and the air
pollution control side.  On one hand the totally enclosed furnace requires
a more expensive furnace installation with a larger building, a more complex
feed handling system, and a more complex furnace cover,  fin the other hand,
the totally enclosed furnace can be controlled with a much smaller and less
expensive air pollution control system.  In this section the costs for a
totally enclosed furnace are compared to the costs for an open furnace to
Illustrate this point.
     The costs in this section are for a large totally enclosed furnace
under construction in North America.  These costs should he more represen-
tative of the costs that would be experienced at a U. S. location than

                                  IX-42

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some of the previously presented costs for totally enclosed furnaces which
were based on overseas installations.  The maximum power rating for this
furnace is 33 mw for HC FeMn and 38 mw for SiMn.
     The primary control system for the totally enclosed furnace consists
of the sealed furnace cover, a water spray cooler, a mechanical dust
separator, and a variable-throat venturi scrubber followed by a mist
eliminator.  The pressure drop across the scrubber is in the range of 75 to
80 inches of water.  The gas flow from the furnace is about 6600 scfm, and
the gas flow at the scrubber is about 9700 scfm.  The cleaned gas stream,
which is high in CO, can be used as a fuel source in the feed pretreatment
plant or diverted to a stack.  A complete water treatment system is
included; the treated water is recycled to the scrubber and the filter cake
of solids is recycled to the sintering plant.
     The furnace tapping system is designed with a hood over each of four
tapholes.  A total flow rate of 30,000 acfm is combined with another 20,000
acfm vent stream and sent to a fabric filter collector.
     Table IX-16 shows the costs for the totally enclosed furnace and its
control equipment compared to the company's estimated costs for an open
furnace with a fabric filter collection system.  The prorated share of the
project's utilities, electrical and engineering expense for the control
system is included in the control system cost.  In addition to the furnace
collection system and the tapping emission collection system, the company
reported two other cost factors for the totally enclosed furnace that are
different from the open furnace.  The first is the incremental furnace
cost which includes such items as a more complex feed system, a taller
building, and larger and more complex electrode columns and electrical equip-
ment.  The second item is an incremental feed pretreatment cost which includes
ore and coke dryers and a sinter plant.

                                   IX-43

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             Table IX-16.   COMPARISON OF CAPITAL AND ANNUAL COSTS FOR AN OPEN
                   AND A TOTALLY ENCLOSED HC FeMn AND SiMn  FURNACE
                   PRODUCING HC FeMn OR SiMn
                                                           Totally enclosed
     Cost item                       Open furnace               furnace
Comparison of total capital costs9
Basic furnace and associated
process equipment
Incremental furnace cost
Incremental feed pretreatment
Air pollution control systems
$8,500,000
3,500,000
$12,000,000
S 8,500,000
1,400,000
3,000,000
2,100,000
$15,000,000
Comparison of control  equipment costs

  Capital  costs3

    Primary system                  $ 3,500,000            $ 1,700,000
    Taphole system                (included in above)           400,000
    Incremental furnace cost             --                  1,400,000
                                    $ 3,500,000            $ 3,500,000

  Annual costs

    Operating cost                  $   143,000            $   135,000
    Maintenance (6%)                    210,000.               210,000
    Capital recovery                    409,000°               390,000°
      (at 8% interest)
    Administration (2%)                  70,000                 70,000
    Taxes and insurance (2%)             70,000                 70,000

                                    $   902,000            $   875,000

  Annual cost per ton  ($/ton)

    HC FeMn                                9.11                  8.84®
    SiMn                                  20.50                 19.896


aLetter from Mr. D. J. Maclntyre, Manager, Environmental Affairs, Union
 Carbide Canada Limited.   March 9, 1973.

 Based on 30 row for HC FeMn and 34 mw for SiMn, both at 90% operating rate.

Depreciation lives:  10 years - furnace cover, 15 years - pollution control system
 20 years - incremental furnace costs.

 Depreciation life:  15 years.
eThis does not include the annualized investment cost or operating cost of the
 incremental feed pretreatment equipment.  The ferroalloy industry has indicated
 that the total manufacturing cost per ton of product is about equal for both
 the open furnace with control and the totally enclosed furnace with control and
 feed preparation.
                                      IX-44

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     The decision to use the incremental  feed pretreattnent must be made after
evaluation of the overall process.   Drying and sintering allow the use of
coke and ore fines and the recovered particulates from the air pollution
control systems.  Through the use of these feed pretreatment steps the
furnace can be operated in a smoother and safer manner.  Some foreign plants
with totally enclosed furnaces have these additional feed pretreatment steps
and some do not.  It is even hard to define exactly what should be included
as incremental feed pretreatment equipment.  For example, some open furnaces
have dryers and some do not (depending on the availability of dry materials).
Thus, dryers may or may not be considered as incremental equipment for
totally enclosed furnaces.  The incremental feed pretreatment cost could be
considered as part of the air pollution control cost, or could be considered
a process addition for which the economics must be justified in each
individual case.
     In Table IX-16 the capital cost for the incremental feed pretreatment
is shown, but these costs are not included in the presentation of the annual
cost of the air pollution control equipment.  After an overall evaluation
was made, this particular plant decided that the totally enclosed furnace
with the additional feed pretreatment was the best choice in this case.
     It is not possible to generalize from this case to say that in all cases
the totally enclosed furnace with feed pretreatment would be the best choice.
For example, in the case where a furnace is to be added at an existing plant
an open furnace could possibly use the existing feed preparation and
delivery system whereas a totally enclosed furnace might require a new,
separate feed pretreatment system.  Also, the open furnace could possibly
be installed in an existing building while the taller, totally enclosed
furnace would probably require a new or expanded building.  These or other
differences at any specific site could affect the costs enough to change
the best choice of furnace type to an open furnace.
                                   IX-45

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D.  ECONOMIC IMPACT
1.  Introduction
     The impact of abatement costs will be analyzed in this section, and
the model plant approach will be continued through development of income
statements before and after control for the five hypothetical  plants.  The
ability of the firm to raise the capital necessary for control will then
be discussed.  Finally, a general overview of the industry will cover
important trends and prospects.
     Sufficient data describing the profitability of the ferroalloy industry,
particularly with regard to individual products, are difficult to obtain.
Three firms that were not diversified have been chosen to represent the
industry, so distortion from other product groups is precluded.  Table IX-17
presents aggregate operating data for these three firms in terms of percent
of sales for the period 1963 to 1971.  As can be inferred from the table,
operating costs for the 9 years have averaged approximately 93 percent of
sales, with earnings before taxes around 7 percent of sales.  Net income
after taxes has averaged approximately 3.89 percent of sales,  and cash" flow,
about 8.19 percent of sales.  These average results will be used to generate
model income statments for the five hypothetical plants.
2.  Model Income Statements
     Tables IX-18 and IX-19 present earnings statements for the model plants
based on costs presented in Tables IX-12 and IX-13, respectively.  Sales
figures for ferroalloys were calculated using annual capacities of the
30 mw furnaces and the value per ton of shipments from quotations in the
1973 American Metals Market.  These values were:  HC ferromanganese, $200.00;
silicomanganese, $210.00; HC ferrochrome, $264.00; and 50% ferrosilicon,
$175.00.  All prices are based on short tons.  These sales figures were
                                   IX-46

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then used to derive operating costs and profits based on the historical
percentages in Table IX-17.  Tables IX-18 and IX-19 then compare the
"before" and "after" affect of imposing control costs on the five
model plants.
3.  Economic Impact on Model Plants
     As shown in Table IX-18, which is based on the lower costs developed
in Table IX-12, control costs in the absence of product price increases
will reduce profits and cash flows significantly.  Reduction in net earnings
after taxes ranges from 42 percent for HC FeMn to 114 percent for 50% FeSi.
Similarly, reductions in cash flows (i.e., the sum of depreciation charges
and after-tax earnings) range from approximately 20 percent for HC FeMn
to 54 percent for 50% FeSi.
     However, if the profit figures are based on costs from Table IX-13
which include retrofit expenses and off-site items, the effect is more
drastic.  In Table IX-19, silicomanganese and 50 percent ferrosilicon show
a net loss, while HC FeMn and HC FeCr show 57 percent and 53 percent re-
ductions in net income, respectively.  Cash flow reductions range from 25 to
76 percent.  Although application of aggregate corporate operating ratios
to the calculation of income statements for individual products may distort
the results for any or all of these products, the interpretation of this
analysis would remain the same with better data; i.e., control costs are
significant relative to the thin profit margins and can only be supported
by very substantial price  increases.
4.  Economic Impact on the Domestic Ferroalloy Industry
     The preceding section concluded that pollution control for the model
plants would have to be supported by price increases to maintain even the
                                  IX-50

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current low profit margins.  In this section, the total economic impact of
emission control on the domestic ferroalloy industry is discussed.  The
ability of the industry to pass control costs along to the user in the form
of higher prices is likewise considered.
     The better control systems (baghouses and high-energy scrubbers)
installed by industry in recent years have average costs for amortization
and operation that total $9.30 (1971 dollars) per ton for ferroalloys
having relatively favorable dust-removal properties, such as the products
used for the models.  Control costs for high-silicon alloys, which have
difficult dust-removal properties, average $61 per ton of product for
recent installations (see Table IX-20).  Emission control costs range from
2 to 9 percent of sales for specific ferroalloys.
     The ultimate total cost of emission controls to meet state implementa-
tion plans is estimated at approximately $30 million per year for the 2
million tons of ferroalloys produced.  This estimate is based on a product
mix characteristic of recent industry experience and on unit control costs
derived from actual plant visits.   These data are shown in Table IX-20.
Since annual costs run approximately 25 to 28 percent of required capital
costs, the ultimate capital costs will approach $120 million.
     As of 1971 only about 20 percent of the total production capacity
(based on megawatt ratings) can be regarded as well enough controlled to
meet the state implementation plans.  Such plants must include good hooding
enclosure and high collection efficiency of captured pollutants.  The
amount of particulate emissions from all ferroalloy furnaces has been
estimated to be 150,000 tons annually.  Installation and operation of the
most effective control systems on all furnaces would ultimately decrease

                                   IX-51

-------
         Table IX-20.   PERCENTAGE  OF PRODUCTION  AND  CONTROL  COSTS
Control costs
Product
HC FeMn
SiMn
LC FeMn
HC FeCr
LC FeCr
FeCrSi
Up to 30% Si
50% FeSi
65% FeSi
75% FeSi
85-90% FeSi
Si Metal
MgFeSi
Ca alloys0
All other Si
Totals
Portion of productions3
net tons
348,000
194,000
138,000
148,000
126,000
86,000
124,000
494,000
26,000
106,000
10,000
116,000
58,000
14,000
12,000
2,000,000
Historical ,
$/ton
$ 5.00
9.00
7.15
6.15
-
11.25
8.00
10.00
10.00
20.00
61.00
61.00
10.00
61.00
20.00
-
Recent,
$/ton
$ 8.00
18.00
10.00
12.00
-
15.00
16.00
20.00
20.00
30.00
61.00
61.00
20.00
61.00
20.00
-
Average total
cost,
$
$ 2,262,000
2,619,000
1,183,000
1,343,000
-
1,129,000
1,488,000
7,410,000
390,000
2,650,000
610,000
7,076,000
870,000
854,000
240,000
$30,124,000
 Based on Price Waterhouse Statistical  Reporting Program, 1971,
   adjusted from 1,632,835 net tons to  2,000,000 net tons.

 The Ferroalloys Association.

°Excluding calcium carbide production.
                                   IX-52

-------
the estimated emissions to 8,000 to 10,000 tons annually,  based on  1971
production.
     The domestic ferroalloy industry is faced with serious economic
problems in  addition to air pollution control.  Slackened  demand for
many of the products, increased competition from foreign ferroalloy pro-
ducers, rising electrical  power and coal costs, and higher wages have
combined to reduce profit margins significantly.  A large  proportion of
the industry has shut down in recent years as a result.
     Foreign imports, mostly manganese and chromium products,  accounted
for 19 percent of domestic consumption in 1971.  Imports of silicon
products, historically on the order of 3 to 5 percent of domestic consumption
for this product class, jumped to 10 percent in 1971.  Several  factors account
for increasing foreign competition.  Low transportation  costs  are available
to foreign producers, as their plants are located near the seaports.  Some
countries, particularly in northern Europe, have cheap hydroelectric power.
As power costs vary from 15 to 40 percent of the product manufacturing cost,
depending upon the product, a cost difference of 4 to 5  mils per kilowatt-
hour or greater between U.S. power rates and overseas hydroelectric rates
can amount from $10 for HC FeMn to as high as $70 per ton  for silicon, which
offers a considerable cost advantage to the foreign production.
     High-quality metallurgical coal and coke, which are used in significant
quantities by the industry, have become expensive in recent years.   Of
course, foreign producers have been paying higher prices for these  coals,
too.  Increased prices of ores, machinery, and parts have  also been im-
portant factors in raising manufacturing costs for the domestic industry.
                                  IX-53

-------
     There are also qualitative factors that may contribute to the
stagnation of the industry.   The expectation of increased costs for
emission control, the difference in government policies among various
countries toward taxation, subsidy payments for promotion of industrial
growth, advances in foreign  technology leading to production efficien-
cies, and different latitudes in various countries with respect to
pollution control regulations all cannot be measured adequately in
numeric terms, but are postulated as important factors in the economic
setting of the industry today.
     Of the groups analyzed, only silicon and ferrosilicon manufacturers
seem to be in a position to  pay for emission control by raising product
prices.  The quartz used to  produce silicon alloys is plentiful domes-
tically,and demand for silicon products, particularly the silicon metals,
appears strong, as measured  by an expected annual growth rate of 4 to 6
percent.  Lastly, imports are still less than 10 percent of the market
measured in terms of domestic shipments.  Some of the control costs for
silicon products could thus  probably be passed on to the consumer.  How-
ever, silicon and ferrosilicon manufacturers are also facing the greatest
costs.
     Faced with low growth rate in demand by the steel industry for their
products and stiff foreign competition, ferromanganese and ferrochrome
producers will be forced to absorb most of their emission control costs.
Only through increased production efficiency in the form of higher
mechanization and larger plants can ferromanganese and ferrochrome
producers hope to retain current profit margins and simultaneously absorb
control costs.  It is likely the smaller and more marginal plants (i.e.,

                                   IX-54

-------
those faced with higher power costs,  labor problems,  and other  cost-
associated problems) may either shut  down  in  the  face of expected  air
pollution abatement costs,  shift to other  product lines, install more
efficient manufacturing facilities, or build  in other countries which
have more lenient standards and lower costs.
                                  IX-55

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           X.  RECOMMENDED RESEARCH AND DEVELOPMENT PROGRAMS
A.  INTRODUCTION
      Previous sections of this cooperative study have evaluated known control
technology, control technology now being tested in commercial  operations,
and the economic effects of using various methods of emission  control.
      Present knowledge indicates the various known control  methods are not
each broadly applicable to controlling emissions from the manufacture of
all products.  Existing controls result in the accumulation  of substantial
amounts of wastes in the form of either dusts or drained slurries,  without
proper disposal, the dry dusts can be entrained by wind, and the drainage
from slurries can become a water pollution problem. With the advent of
new source performance standards and the increasingly stringent levels of
control generally required under the Clean Air Act Amendments  of 1970,
the problem of handling and disposing of collected dusts can become more
acute.
      The technology of covered furnaces is applicable to the  manufacture
of almost all products except some high-silicon ferroalloys.  However,
the use of covered furnaces for different product lines has  been noted
to vary to some extent from country to country; in Japan, for  example,
covered furnaces have been used to produce silicon alloys containing up
                                 >,
to 75 percent silicon.  A worldwfde evaluation should be made  of furnace
designs, operating techniques, manufacturing limitations and capabilities,
control technology, and economic factors.  The goal of such  an evaluation
would be to determine the extent to which covered furnaces can be applied
to the manufacture of high-silicon alloys.
                                       X-l

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B.  RECOMMENDATIONS
     The following recommendations are presented for further research and
development.
     1.  Process Modifications
         a.  Determine the relationship of the cost of control  to
             particle size of emissions.  This might include an
             investigation of agglomeration techniques by sonic,
             electrostatic, or other means that would increase
             particle size and, presumably, decrease costs.
         b.  Examine methods that would decrease the rates of furnace
             exhaust gas to be handled by control devices, since
             costs normally decrease when the volumes decrease.
         c.  Examine the economics of raw materials (ores, coals,
             etc.) used as ferroalloy charge stocks and their
             effects on gaseous and particulate emissions.  If
             possible, develop data on the economic feasibility
             of using raw materials that would result in the
             lowest quantity of particulate emissions.
     2.  Applications of Control Techniques
         a.  Examine other types of available control techniques
             and collection systems besides recognized venturi
             or other liquid scrubbing systems, baghouse filters,
             and electrostatic precipitators.  This would include
             examination of all available liquid-contacting
             nozzle-ejector systems for effectiveness, reduction

                                        X-2

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        in costs,  and applicability to a  broader  range  of
        dusts.   Examine combination two-stage  systems such
        as electrostatic precipitator  treatment preceding
        a low-pressure venturi  scrubber.   Examine the
        possible domestic application  of  other systems
        developed  outside the United States, such as multi-
        stage scrubbers and the charging  chute (shaft kiln).
    b.   Examine methods for reducing pressure  drop across
        baghouse collectors.
    c.   Develop a  fiberglass fabric resistant  to  higher
        temperatures or find other fabrics more suitable  to
        ferroalloy dust-filtering operations,  with emphasis
        on extended life of the fabric.
    d.   Develop a  preconditioner additive for  electrostatic
        precipitators that may  be more effective  than the
        currently  used ammonia.
3.  Waste Utilization
    a.   Search for new uses of  particulates recovered from various
        product lines and by various recovery  methods.  Uses  for  dry,
        fluffy dusts and the settled-slurry fine  particulates
        should be  included in this search. Examine the chemical
        content and physical form of the  recovery products and search
        for additional uses in  agriculture, industry, and other
        areas not  now in evidence.  Examine collected materials
        for other  elements of possible economic value.
                                    X-3

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    b.  Examine in greater depth the possibility of preparing,
        by extrusion or other means, recovered participate for
        recycling to the submerged-arc furnace.   The problem
        of possible wind entrainment is particularly severe
        with dry dusts.  Certain positive values, particularly
        chromium and manganese, are contained in the dusts and
        might be recovered for use.  Although pelletized chromium-
        and manganese-containing dusts may not be fully acceptable
        as desirable charge stock, the stockpiling of these dusts
        in the pelleted form would prevent their becoming entrained
        by wind.  Such stockpiles could be an important source
        of raw material for furnace feedstock when other supplies
        are not available.
4.  Waste Heat Utilization
    a.  Investigate methods for using the sensible heat of
        reaction gases as well as heat from the combustion of
        carbon monoxide therein.
    b.  Develop methods for achieving greater utilization of the
        heat produced within the furnace itself, possibly
        through the use of water walls.
5.  Emission Measurements
    a.  A much higher volume sampler is needed at the collector
        outlet to more quickly obtain an adequate weight of
        particulate.  A sampler should be developed that is simple
        to apply and that will accurately and quickly reflect the
        results of control measures.
                                    X-4

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b.  Develop continuous-reading monitors of reliable accuracy
    for hour-to-hour measurements of outlet particulate
    concentrations.
                            X-5

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                               APPENDIX A
                      Description of  EPA Source Tests

     All  the data compiled by EPA tests are a part of this Appendix.
Furnaces  A through J were tested  in the United States.   Furnaces K
and L (ferromanganese and siliconnanganese)  were tested in a plant
located in Norway.  A brief description of  the process and a flow
diagram showing test points are included for each plant tested.   Re-
sults of each individual  sample analysis from tests made on these
furnaces  are shown in Tables A-2  through A-5.  The source of the
samples shown in these tables is  given in Table A-l.   The amount of
submicron particulate matter in the gas stream flowing either to or
from an air pollution control system was obtained from the back  half
(impinger catch) of the sampling  train; this information is presented
in Tables A-6 through A-ll.  Wherever inlets and outlets were tested
simultaneously, the percent collection efficiency (impinger catch only)
is shown  for each furnace tested.   These efficiency rates indicate
that the  three types of control devices (baghouses, scrubbers, and
precipitators) used on these furnaces are effective in removing  a high
percentage of submicron particulates.
     Table A-l2 shows the actual  gas flow rates and temperatures of
the furnace gas streams measured  during each individual test run.
                                    A-l

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                  FURNACE A
             Ferrochrome Silicon
               (Uncontrolled)
     The initial atmospheric emission  tests
made by the EPA contractor were conducted
May 18 to 19, 1971, on an uncontrolled
ferrochrome silicon furnace.  The  furnace
has a hood for collecting the furnace  fumes,
and it was about 100-percent effective in
capturing the fumes.  Two exhaust  ducts
connected at opposite sides of the hood  are
equipped with blowers that discharge the gas
into the open atmosphere through two stacks
terminating above the building roof.   The
tap-hole hood was about 95-percent effective
in capturing generated tapping fumes.   This
SAMPLE
POINT 1
                                                Figure A-1. Uncontrolled ferrochrome silicon
                                                -fitcnae.?
hood was vented into the uncontrolled  furnace
exhaust duct.  Figure A-1  shows  the  uncontrolled exhaust system and
test points.  The charge material  to the  furnace was a mixture of
chrome ores, quartz, coke, and wood  chips.   The two exhaust stacks
were sampled simultaneously  for  approximately  two hours to cover the
tapping cycle.  Both the EPA train and the  ASME particulate train
were used for comparison of  results.  The two  tests with the EPA train
showed emissions to be  197 pounds  per  hour  (0.14 gr/scf) and 438 pounds
per hour (0.32 gr/scf).  The higher  emissions  for the second test were
caused by more furance  gas blows than  normal because one of the two
stoking machines broke  down. However, the  quantity of emissions for
                                     A-2

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both tests was considered lower than normal for this alloy and has
been attributed to screened ores used in the furnace mixture.  The
ASME train showed a slightly higher particulate emission rate than
the EPA train (28 percent for the first test and 2 percent for the
second test).  The percentage of particulates collected in the
impingers (back half) of the EPA train was approximately 50 percent
during the first day's test at sample point 1 but varied from two
to five percent in all other samples.  The EPA train was not com-
pared with the ASME train when the high fraction of sample was
obtained in the impingers.
     The mass media particle size of the fumes emitted varied from
0.62 to 0.67 microns (see Table VI-16 and Appendix D)
     Visible emissions ranged from 60 to 100 percent.  One of the
two stacks serves not only the furnace hood but also the tapping
station.  Consequently, the larger volumes of gases in this stack
dilute the concentration of particulates and results in fewer visible
emissions.
     Chemical analysis was made of the exhaust gases coming from the
furnace and the particulates collected on the filter of the particu-
late sampling train.  Sulfur dioxide ranged from 11 to 17 parts per
million.  Carbon dioxide and carbon monoxide were 0.8 percent and
0 percent, respectively.  Chemical constituents of the collected
dust are shown in Table VI-17.
                                     A-3

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                      FURNACE B
           Chrome Ore/Lime Melt Furnace
                  (Uncontrolled)
     On May 20, 1971, a chrome ore/lime melt fur-
nace was tested.  Dried and screened chrome ore
mixed with lime is charged into an open-arc tilt-
ing electric furnace with a pouring spout at the
top.  The furnace is periodically tilted and the
melt falls by gravity into a large ladle,
where subsequent ladle reaction with ferrochrome
silicon produces a low-carbon ferrochrome (see
Flow Diagram, Figure V-3, page V-7).  Two test
runs were made with results of 50 pounds per hour
(0.14 gr/scf) and 61 pounds per hour  (0.175 gr/
scf).  At the same time an ASME sampling train
      SAMPLE
       POINT
     \
  TAP
 LADLE
          TILTING
          OPEN-ARC
          ELECTRIC
          FURNACE
Figure A-2. Uncontrolled chrome
ore/lime melt furnace.
was used with test results of 60.4  pounds  per  hour and 72.3 pounds per
hour.  Capture of the fumes by the  hooding and exhaust system was
judged very poor.  With the use of  a  high-volume filter to determine
the particulate concentration and an  estimate  of the volume of the
uncaptured gases escaping the exhaust system,  it was shown that emis-
sions escaping the exhaust system varied from  9 to 65 pounds per
hour.
     Chemical analysis was made of  the gases coming from the furnace
and the particulates collected on the filter of the particulate sampling
train.  The analysis showed no sulfur dioxide  or carbon monoxide, and
only 0.1 percent carbon dioxide.  Chemical analysis of the collected
particulate sample is shown in Table  VI-18.
     Particle size was determined by  the use of a cascade impactor.
                                    A-4

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FURNACE C
           Silicomanganese Furnace
                  (Scrubber)
    A series of tests were conducted be-
tween July 27 and August 4, 1971, on a
furnace making silico manganese, 2-percent-
carbon grade.  The furnace fumes are con-
trolled by two Research Cottrell flooded
disc scrubbers discharging into a common
stack.  Figure A-3 shows the flow diagram
of the furnace and scrubber system.  Three
test runs were made at each scrubber pres-
sure drop setting of 57,47 and 37 inches H20
pressure. Figure A-4 shows the collection
efficiency curves as a result of these
tests.  The mass emission rates in pounds per hour were 9.8  (0.01
gr/scf), 16.7 (0.02 gr/scf)> and 44 (0.05 gr/scf) for pressure  drops
of 57 inches H20, 47 inches H20, and 37 inches H20, respectively.  The
percent efficiencies were 99.1  (57 inches H20), 99.1 (47  inches Ufl),
and 96.3 (37 inches H20).  The  efficiencies were the same for 57 inches*
HpO and 47 inches hUO, but the  concentration of dust into the scrubber
when testing at 47 inches HJ) was 60 percent higher.  Even though pres-
sure drop varied across the scrubbers, velocities and temperatures
remained relatively constant.   The average scrubber inlet particulate
loading was 1355 pounds per hour.
     Particulate emission rates were also determined for  tapping.  Tap-
ping time varied for each tapping test from 28 to 32 minutes.   There
                             Figure A-3. Scrubber system serving Silico-
                             manganese furnace.
                  A-5

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are two tap holes with exhaust systems,  but only one  tapping  station
was in use.  Therefore, it was necessary to test both stacks  simul-
taneously to obtain the total  tapping emissions.   Tapping losses  for  each
tapping period were 59 pounds  (32 minutes), 27 pounds (30 minutes), and  17
pounds (28 minutes).  The average tapping losses (34  pounds)  exceed the  con-
trolled losses (average over three different pressure drops)  by 22 pounds.
     Gas analysis made at the  scrubber outlet showed  sulfur dioxide
emission levels generally below 1 ppm.  Carbon monoxide was negligible,
and carbon dioxide varied between 2 and 3 percent.
     The filter catch of the EPA particulate sampling train was analyzed
for chemical constituents by use of a microscope, qualitative electron-
beam X-ray microanalysis and atomic absorption.  The  quantities of
sample materials were very small, making analysis difficult.   The glass
fiber of the filter became intermixed with the particulate matter im-
bedded in the filter, and no accurate silicon analysis could  be made.
Details concerning the specific elements can be found by referring
to Table VI-18.
     Several samples were obtained by a cascade impactor to determine
particle size.  The mass median diameter (MMD) of the particulates at
the scrubber exhaust varied from about 0.2 to 0.7 micron.  The MMD
of particulates from the furnace varied from 0.6 to 5.0 microns.
Because of the short sampling time and the varying loading of the gas
stream from the furnace outlet, the MMD particle size reported may not
reflect a true average particle size from the furnace.  However,  most
of the samples analyzed showed a MMD of less than 1 micron.  Table VI-17
                                     A-6

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and Appendix D shows the particle size of samples collected.
     No emissions were visible from the scrubber when it was  operated
at 57 and 47 inches H?0 pressure drop, but a slight trace of  emissions
was reported at 37 inches H20.
                                   A-7

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    0.08
                                  100
    0.07
    0.06
    0.05
a

to
z


1  0.04



te

a

i—
LLl


t  0.03
    0.02
EFFICIENCY
    0,01
                                  99
                                  98
                                       I
                                      UJ

                                      o
                                  97
      27                       37                      47


                             VENTURI PRESSURE DROP, in. H20



               Figure A-4.  Scrubber efficiency as function of pressure drop.



                                            A-8
                            57
                                                                                       96

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                  FURNACE D
             Ferrochrome Silicon
                 (Baghouse)
                                                CLEAN AIR TO ATMOSPHERE (
     Three test runs were made  on  Aug-
ust 31 to September 1, 1971, on an air
pollution control system with a 12-
compartment push-through baghouse  con-
trolling the fume emissions from a FeCrSi
furnace.  An air curtain is provided
around the periphery of the hood over
the furnace with the air provided  coming [j\rr
from the exhaust system serving the tap-
ping station hood (see Figure A-5).  The
larger particle sizes in the exhaust
system serving the furnace settle  out
                                               I 1 II 1 I iTTl TiTTll 1 1 1 I 1 1 1 11 1 I I I
     12-COMPARTMENT
       BAGHOUSF
              SPARK
             IRJJESTOJ
 AIR
COOLER
Figure A-5. Baghouse serving ferrochrome
silicon furnace.
in the spark arrester. A  very small  amount settled out in the spark
arrester hopper; at the time  of the  tests, it had not been emptied
after several months of operation.   The effluent gas stream then passes
through two indirect forced draft air coolers, although it had not
been necessary to use these as coolers.  The dust-laden gas then is
directed into a 12-compartment baghouse with a total of 1728  (11-1/2
inch X 30 foot) fiberglass  bags.  Mechanical shakers clean the bags in
each compartment once every 78 minutes.
     Three EPA particulate  sampling  trains were spaced equal distances
apart at the baghouse-roof  monitor outlet in order to obtain a represen-
tative sample.  Simultaneous  sampling with the three samplers showed
that particulate emissions  to the atmosphere varied considerably in
                                   A-9

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three test runs, ranging from 18.1  to 37.9 Ib/hr with  an  average
of 30 Ib/hr.  The average grain loading was only 0.009 grains  per
standard cubic foot.   The collection efficiency of the baghouse was
96.5 percent.  The percentage of participates collected in the im-
pinger (back half) of the EPA train was high for an unknown reason
and quite consistent for nine samples, ranging only from 63 to 74
percent.  The impinger water residue from the sampling train was
analyzed by the Sulfaver-Turbidimetric procedure and found to  be
33 percent sulfate ion (SO }.  Optical emission spectrography  has
shown most of the material in the water residue to be Fe, Na,  Ca,
Si, Al, Mg, and K.  The sample volume through the sampling train
was 88.72 standard cubic feet of dry gas with an SO  concentration
of 0.69 mg/cubic foot.  The impinger water thus contained enough
S02 to potentially ionize 91 mg sulfate ion.  Total material col-
lected in the impinger weighed 20.4 mg.  With the possibility  that
particulates may have formed from the reactants in the impinger portion,
the amount of particulate matter reported going into the atmosphere
should be based on the fraction collected in the front half (filter  and
probe) of the EPA train.  In this case, the emissions for the  three  test
runs would be 11.0 Ib/hr (0.0035 gr/scf), 9.4 Ib/hr (0.0025 gr/scf), and
5.8 Ib/hr (0.0014 gr/scf), resulting in a collection efficiency of  98.7%.
     Particle size determinations were made by use of a cascade im-
pactor.  The mass median diameter (MMD) for the baghouse exhaust was
approximately 0.7 to 0.8 microns.  The MMD for the furnace exhaust  was
0.3 and 3.2 microns during taps and between taps, respectively.
     The baghouse exhaust flow rate was too low to measure accurately
with a pitot tube.  Because air is induced into the baghouse and
                                  A-10

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mixed with the cleaned furnace gases after passing through the cloth
filters, it was necessary to measure the induced air by use of a vane
anemometer.  The volume of gases from the baghouse was determined by
adding the measured volume of dirty gases from the furnace going into
the baghouse to the measured volume of induced air.  Induced air was
found to be over half the volume leaving the baghouse.  These volumes
were verified by use of a heat balance.  Another method for determin-
ing the amount of dilution air is measuring the concentration of CO
into and out of the baghouse.  The C02 readings into and out of the
baghouse were 1.2 and 0.5 percent, respectively, which also compared
very closely.  Including induced air, the baghouse outlet volume was
383,000 SCFM.
     The quantity of particulates contained in the air induced into
the bottom of the baghouse was determined by use of an ambient air
                                    3
particulate sampler to be 1400 mg/nM , which means that this con-
centration of dust was added to the cleaned gases exiting the baghouse.
Subtracting the amount of dust in the induced ambient air from the
total outlet emissions would only reduce the emissions by slightly
less than one pound per hour.
     The baghouse was in good operating condition during the tests,
and no emissions were visible.
                                  A-ll

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              FURNACE E
       HC Ferrochrome Furnace
    (Electrostatic Precipitator)
     Three test runs were made on
September 21 to 23, 1971, on a
HC ferrochrome furnace equipped
with an electrostatic precipitator
for controlling furnace fumes.  The
precipitator is preceded by a gas
conditioning tower because of the
Figure A-6. Electrostatic precipitator
serving HC 'srrochrome furnace.
high resistivity of the ferroalloy fume.  The gas conditioner,  similar
to a scrubber tower in construction, removes approximately  40 percent
of the furnace fume.  Resistivity of the fumes  is reduced by  spraying
170 gallons per minute of water into the gas conditioner.   Water
adsorbing on the dust particles forms a liquid  surface  film through
which electrolytic conduction of the accumulated charge can occur.
Since this type of dust does not readily adsorb moisture, a small
amount of ammonia is added to enhance the moisture  adsorption capacity.
The dry precipitator consists of three sections in  series with  discharge
electrodes of negative polarity and positively  charged  collecting
surfaces at ground potential.  The furnace hood is  equipped with
water-cooled, vertically operated doors to minimize the excess  air
required for effective furnace emission collection.   Two tapping holes
120 degrees apart are both vented to the air pollution  control  system.
     The tests showed that the air pollution control  system removes
15.4 tons per day of dust and fumes.  Average emissions from  the pre-
cipitator to the atmosphere were 21 pounds per  hour with a  concen-
                                 A-12

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tration of 0.0183 grains per standard cubic foot.   The average inlet
loading to the conditioning tower and precipitator was 1312 Ib/hr and
1.87 gr/scf.   The collection efficiency was 98.1  percent.   The fraction
of particulates collected in the water impinger section of the EPA train
varied from 8 to 20 percent in the outlet sample and from 0.7 to 3.2
percent in the inlet sample.
     Particle size distributions of furnace fumes  and precipitator ex-
haust fumes are shown in Table VI-16 and Appendix D.  Average size (mass
medium diameter, MMD) of individual particles from the furnace was typically
from one to two microns.  Frequently, there was little difference between
the sizes measured before and following the air pollution control system.
The MMD of the fumes at the precipitator outlet varied from 0.38 to 2.54
microns.
     Chemical analysis was made of the gas and the filter catch of the
sampling train.  The average sulfur dioxide analysis from the furnace
was 8 ppm.  Carbon monoxide varied from 200 to 500 ppm.  The percent
of carbon dioxide varied from 1.6 to 2.4 percent.   The major con-
stituents found on the filter using atomic absorption methods of
analysis were found to be Cr, Mg, Al, and Si02.  The major conclusion
is that the sample is a mixture of oxides: Si02, Cr^O.,, MgO, and
A120_.  The sum of the percent values, after conversion to equivalent
oxide values, is 84 percent, which indicates adequate closure in the
sense that all the major constituents have been taken into account.
The remaining 16 percent could well be accounted for by water of hy-
dration or by the presence of chlorine, carbon, and titanium.  Analysis
of a dust sample collected by the precipitator unexpectedly found 4.22
percent sodium and 5.95 percent potassium (see Table VI-17).
                                   A-13

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     Chemical analysis made by the company of the collected dust samples
showed a difference between the dust collected in the conditioning
tower and that collected in the electrostatic precipitator.  This is
shown in Table A-13.  It was speculated the conditioning tower collects
the larger dust particles, which are primarily from the mix charge
materials, while the electrostatic section collects the fumes from
the furnace reactions.
                 Table A-l    TYPICAL DUST AND FUME ANALYSIS FOR
                                          FURNACE E28
1
Product
Cr203
FeO
Si02
A12°3
MgO
CaO
C
Conditioning tower
dust, %
28.3
7.6
10.2
25.7
15.8
3.9
6.0
Precipitator
fume, %
5.4
6.7
24.2
7.1
38.8
12.3
2.3
                                     A-14

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                     FURNACE F
                  Silicon  Furnace
                    (Baghouse)
     A series of  three  test runs were conducted
on January 17 to  20,  1972,  on a three-baghouse
system (3744 bags,  11-1/2"  diameter X 30' long)
serving a silicon furnace.   Figure A-7 shows a
plan view of this system.   Baghouse B was se-
lected for sampling simultaneously with four
EPA particulate samplers  as the cost would be
high to test all  three  parallel-operated bag-
houses.  The trains were  equally spaced in the
roof monitor.  A  representative
sample was obtained from  all 8 com-
partments by traversing over the
monitor 24 sampling points.  The
inlet sample was  obtained at the
furnace outlet exhaust  duct.  The
three tests showed  the  emissions
from Baghouse B only were 11.27,
   HOOD OVER Si
    FURNACE
                                ROOF
                               MONITOR
                              TRAVERSE
                               POINTS
                     BAGHOUSE B
                      BAGHOUSE A
               SAMPLE POINT
TRAVERSE
 POINTS
 TOTAL
28 POINTS
                        SECTION OF
                         FURNACE
                       EXHAUST DUCT
Figure A-7. Plan view of baghouse system on
silicon furnace.
13.82, and 10.3  pounds  per hour.  Based on the measured  gas flow rates
into all three baghouses,  and assuming all three baghouses  were equally
as efficient  in  particulate removal as Baghouse B, the total  amount of
emissions to  the atmosphere for each test run would calculate to be
28.6, 30.9, and  23.5  pounds per hour.  The concentration of particulate
emissions to  the atmosphere from Baghouse B was 0.006, 0.006, and 0.004
grains per cubic foot.   The three baghouses collect 14.6 tons per day
                                     A-15

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of participates from the submerged-arc furnace producing a silicon pro-
duct.  The collection efficiency of the baghouse averaged 98.9 percent
for the three test runs.
     Two other particulate samplers were used at the baghouse outlet
for the purpose of comparison.  A Boubel high-volume source test sampler
was used adjacent to an EPA sampler, and a high-volume ambient air sampler
was suspended at the outlet of the same baghouse compartment.  Comparison
of filter catch only for all three samplers found the EPA train collected
59 percent and 67 percent more than the Boubel and high-volume samplers
respectively, during one test.  The other two times, the EPA train was
compared only with the high-volume sampler and was found to be 53 per-
cent and 17 percent higher.
     An ASME sampler at the baghouse inlet was compared with the EPA
sampler, and the EPA train collected 19 percent more particulates based
on pounds per hour of emissions.  The difference may be attributed to
the fact that the ASME testing was started about halfway through the
EPA test.  The ASME train continued to be used for a sampling period
equal to the amount of time that the EPA train was used.
     The operating condition of the baghouse sampled appeared good
even though there was a small bag leak in one of the end compartments
during the first two tests.  The results of testing reflect this higher
emission.  Emissions from the baghouse for test runs one and two were
10 to 35 percent higher than those for test run three.  Disregarding
the area containing the leaky bag, the baghouse system appeared to be
capable of reducing particulate emissions to approximately 0.004 gr/scf
or approximately 23 Ib/hr.
                                   A-16

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     Laboratory analysis of the 12 outlet samples of participates
from the impinger train (percent of total) varied from 22 to 77
percent and averaged half the total weight.
     The plan and side view of the baghouse in Figure A-8 shows where
the sampling points were traversed when using four EPA samplers
simultaneously.  Each sampler determined the quantity of particulate
emissions from two baghouse compartments.
                                   A-17

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                                  SAMPLER i4 REQUIRED)

                                      SAMPLER PLATFORM
                     SIDE VIEW







/ OPEN GRATING LOCATED
/ AT BOTTOM FOR DILUTION
1 AIR AND WALKWAY
i «rr5r° ° ° °
\ ^T-fro §o
; \oo6
' V3 O O
r S S S S S S S S S S S f S f J








;
J
J
k
2 1
4 3
6 5
8 7
10 9
12 11
14 13
IB 15
17 18
20 19
22 21
24 g 23
1-












"*)
a (
~B > SAMPLING POINTS
-c)
-A
-B
„ ^ 	 ROOF OF
"L BAGHOUSE
-A
-
-A
-B
-C

                                                         A'
                    PLAN VIEW
Figure A-8.  Eight-compartment, open-type baghouse
showing sampling points.
                  A-18

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              FURNACE  G
            SiMn Furnace
              (Scrubber)
     The test conducted on  February
1 and 2, 1972, was on  an Aeronetics
scrubbing system.  As  dust-laden gas
(1100-1200 F) flows from the  ferro-
alloy furnace, a standard heat-
exchanger (see Figure  A-8)  transfers
heat from the gas to high-pressure
water that then enters a two-phase
jet nozzle.  The pressure and temper-
ature of the scrubbing water  entering
                           CLEAN GAS
    TWO-PHASE
   fJET NOZZLE
            CHEMICAL
            ADDITIVES
        HEAT
      EXCHANGER
                         SLUDGE
DIRTY GAS
    Figure A «). Aeronetics scrubbing system.
the jet nozzle at a rate of  82  gallons  per minute averages 320 pounds per
square inch and 375°F.  A  two-phase mixture (steam and water) occurs
as the high-pressure heated  water  passes  through the jet nozzle which
is located at the inlet of the  mixing duct.  The mixture thus leaves
the nozzle at high velocity,  and as it  passes through the long venturi
section, dust-laden gases  are intermixed  with the moisture.  Concurrently,
transfer of momentum of the  mixture to  the furnace gas stream results
in a pressure rise across  the mixing section, which produces the force
to move the fumes from the furnace into the scrubbing system.  The tap-
ping hood is served by an  exhaust  fan that discharges into the top part
of the furnace cover and helps  to  supply  combustion air to the furnace
for the conversion of carbon  monoxide to  carbon dioxide.  The conversion
process in turn provides heat necessary to drive the scrubber exhaust
system.  The tapping-hood  exhaust  system  was estimated to be 40-percent
                                     A-I9

-------
effective In capturing tapping fumes.
     The emission concentration, including the entire catch of the
EPA sampling train, varied from 0.05 to 0.11 grain per standard
cubic foot and averaged 0.086 gr/scf.  Considering only the front
half (probe and filter) of the EPA train, the mass emission rate and
concentration varied respectively from 5.8 to 13.6 pounds per hour
and from 0.04 to 0.10 gr/scf.  The gas cleaning efficiency varied
from 92.6 to 97.6 percent.  Two of the tests at the control inlet showed
lower-than-normal emission factors for this product; the effeciency
would thus be correspondingly lower.  Particle sizing of the particu-
lates in the scrubber outlet and inlet was obtained during the test
by using a Brink cascade impactor.  The mass median diameter of the
particulate samples varied from 2.41 to 5.1 in the inlet and from
0.18 to 0.50 micron in the stack outlet.
                                    A-20

-------
                 FURNACE H
             50% FeSi Furnace
                (Scrubber)
     Tests were made on February 15, 16,
and 17, 1972, on a covered 50 percent
ferrosilicon furnace served by two par-
allel-installed Chemico scrubbers opera-
ting at 80 to 85 inches H20 pressure
drop.  The total volume of furnace exhaust
gas is approximately 7000 scfm.  Three
test runs were made at the sampling point
located in the common outlet duct of the
  BLOWER
        5 HOODED
        ^TAPPING
          STATION
                         BLOWER
Figure A-10.  Covered ferrosilicon
furnace with scrubbers.
 two  scrubbers.  Three test runs were also made  in the three outlet ducts
 of the  secondary,  uncontrolled exhaust system.  The  secondary  uncontrolled
 exhaust system captures the  fugitive furnace  fumes that escapes  from  the  cover
 and  discharges them directly to the atmosphere.  Also tested was the  uncontrolled
 tapping station.   Figure A-10 shows a schematic diagram of the furnace with  the
 five exhaust  stacks and test points.  The blowers on the  scrubber exhaust
 were injected with kerosene  to prevent binding  of the rotors.  Any resi-
 dual kerosene carryover is combusted when flared.  All three test runs
 at the  scrubber outlet were  of short duration because the filter in
 the  sampling  train became quickly  loaded.   The  filter location was changed
 over to the impinger outlet  in the sampling train during  test  runs 2  and  3
 with very  little extension of testing time.
      The results of the particulate loading in the collected aas before flarina
were 86.1,  11.2,  and 8.25 pounds  per hour.   The corresponding grains per standard
                                    A- 21

-------
cubic foot were 0.856, 0.115, and 0.085.  Analysis of the filter catch
showed a high percentage of combustibles that should have been burned
by the flare.  When the flare was off, a very distinct emission was
visible.  No visible emission occurred with the flare on.  An attempt
was made to determine the inlet loading to the scrubbers by collecting
water samples coming out of the scrubbers.  The results did not come
close to typical inlet loadings for this size furnace; thus the
efficiency of the scrubber cannot be precisely determined.  However,
emission factors indicate that the scrubber is about 98.5 percent
efficient, and the efficiency is even higher if the combustibles are
not included.
     Losses from the secondary hooding varied from 136 to 569 pounds per
hour and averaged 342 pounds per hour.  Tapping losses averaged 20 pounds
per tap.  The average tapping time was 15 minutes.
     As an experiment, an IKOR sampler was used for cnmnarisnn of particulate
loading during the samolina of the secondary hnnriinn <=tacks and thp tarmina
     35                                                   	         J
stack.  This instrument gives instant readout, and it showed wide
fluctuation of the particul ate loading in the secondary hooding stacks.
     Carbon monoxide concentrations appeared stable in the scrubber
exhaust but varied considerably in the fugitive fume exhaust ducts,
ranging from 50 to 75 ppm with peaks up to 130 ppm.
     Because the test of the scrubber outlet was somewhat influenced
by kerosene injection into the blower, tests were repeated on July 18 and
19, 1972, without injecting kerosene.  Three test runs were made; each lasted
approximately one hour.  The results were 3.9, 3.6, and 3.6 pounds per
hour and on a pounds per megawatt basis were 0.09, 0.08, and 0.07.
                                     A-22

-------
                 FURNACE J
              Calcium Carbide
                (Scrubber)
     Tests were made on February 22, 23,
and 24, 1972, on a scrubber outlet stack,
four fugitive-fume hood stacks, and a
tapping stack all serving a covered cal-
cium carbide furnace.  The fume collec-
tion system consists of a pair of
identical Buffalo Forge (centrifugal)
scrubbers, with only one on line and the
other one used as a spare.  The tapping
operation is continuous, and the hood
Figure A-l L Covered calcium carbide furnace
with scrubber.
over this area directs all fumes directly to the atmosphere.  The molten
product pours directly into molds, then is cooled and dumped from the
molds in an automatic operation.  Figure A-11 shows a schematic diagram
of the furnace with the six exhaust stacks and test points.
     Three test runs conducted at the scrubber outlet Were very con-
sistent and averaged only one-half pound per hour of particulate emis-
sions for the collected gas.  The outlet particulate concentration averaged
0.036 grain per standard cubic foot.  Fugitive fumes (fumes uncaptured by the
scrubber exhaust system) amounted to an average of 58 pounds per hour.  The
average particulate concentration of these fumes was 0.06 grain/scf.
The average tapping particulate emissions of three test runs was 48
pounds per hour with an average concentration of 0.20 grain/scf.
Samples of the scrubber effluent water showed that an average of 689
                                 A-23

-------
pounds of participate rratter per hour was  collected by  the  scrubber,
indicating a scrubber efficiency of 99.9 percent.  No solids  measure-
ment was taken on the inlet water.
     Flue-gas conditions were stable in the scrubber exhaust, but were
very erratic and unstable at other  locations.   Carbon monoxide  levels
in the fugitive-fume ducts were extremely  variable across the area  of
the traverse; they ranged from 50 ppm to more  than 500  ppm.  The levels
of carbon monoxide in the tapping exhaust were more stable,  generally
in the range of 35 ppm with occasional peaks up to 150  ppm.
                               A-24

-------
               FURNACE K
            Ferromanganese
              (Scrubber)
     This furnace, rated at 27 MW, was
tested August 12 to 21, 1972, by EPA
personnel in a plant located in Norway.
Figure A-12 shows only one scrubber system,
but an identical system is located on the
opposite side of the furnace.  This furnace
operating at its rated loading of 27 mw was
tested under two conditions, first with only
                                             SCRUBBER
one scrubber system in operation, and then    WATER
                                                                    FLARE/
                                                HIP
                                              Figure A-12 .Covered ferromanganese furnace
                                              with sealed electrodes served by three
                                              Venturis in series.
both scrubber systems in operation.  The
design is based on the use of water jets only, which eliminates need for  the
exhaust fan found in conventional fan-scrubber systems.  The last two  stages
act as ejectors inducing the movement of gas through the entire exhaust system.
The cleaned gas containing a high percentage of carbon monoxide is either flared
or sold as a fuel to a nearby chemical plant.
     Six test runs were conducted with only one scrubber system in operation. The
concentration of particulates for the collected gas in the  scrubber outlet
ranged from 0.009 to 0.037 gr/scf and averaged 0.018 gr/scf.  The average pounds
per megawatt -hour was  0.031.
     Two test runs were conducted with both scrubber systems in operation.  The
concentration of particulates in the scrubber outlet was 0.010 and 0.016   and the
average pounds per megawatt -hour was 0.024.
     Normally only one scrubber system is used.  The company will not
                                     A-25

-------
Install  two systems on future furnaces.
     Excluding incidents of uncontrolled tapping, no emissions were
visible from the furnace except for a few instances during test runs
1 and 2 when emissions were less than 10 percent opacity from fugitive
fumes.
                                     A-26

-------
                  FURNACE  L
          Silicomanganese Furnace
                 (Scrubber)
     This covered furnace equipped with
sealed electrodes is  located in Norway.
It is used to make silicomanganese or
ferromanganese.   During the tests made by
EPA personnel on  August 23  and 24, 1972,
the furnace was making silicomanganese and
operating between 22.5 and  23 megawatts.
The air pollution control  system serving
the furnace consists  of a two-stage
venturi scrubber, two 200-HP exhaust fans,
                   2ND
                  STAGE
                 VENTURI
Figure A- 1 3, Covered silicomanganese
'furnace witn sealed electrodes served by
two-stage venturi scrubbers.
and two 150-HP booster  fans.   The pressure drop across the  first-
stage venturi is approximately 2 inches f^O and across the  second
stage approximately  50  inches I-^O.
     Because of operating  difficulties in the control system  during
the fourth test run,  data  are limited to the first three test runs.
The particulate concentration for the collected gas in the  scrubber-
outlet gas stream ranged from 0.00811 to 0.0113 grain per standard cubic
foot and averaged 0.01  gr/scf (probe and filter catch only).   On a
pound-per-megawatt basis the  average emission was 0.009.  No  emissions
were visible from the stack.
                                  A-27

-------
Table A-2.  KEY TO SAMPLE NUMBERS  FOR TABLES  A-3  THROUGH  A-12

' Furnace
: kilowatts
during
Furnace test
A 9,800
9,300

B 7,200

C 29,000
28,000
20,000
23,000
23,000
28,000
28,000
27,500
27,500
28,000
28,000
27,500
27,500
! ! !
1 ! i
1 Test
Furnace Control point
Product type equipment location
FeCrSi Open None Uncontrolled
stack
Uncontrolled
stack
Uncontrolled
stack
Uncontrolled
stack
Cr ore/ Open None Uncontrolled
lime melt stack
Uncontrolled
stack
SiMn Open Scrubber Outlet
Outlet
Outlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Sample
number
IE
1W
2E
2W
3

5
6
7
8
9
10
11
12
(discarded)
13
14
15
16
17
                              A-28

-------
Table A-2 (continued).  KEY TO SAMPLE NUMBERS FOR TABLES A-3 THROUGH A-12

Furnace
kilowatts
during
Furnace test Product
27,500
27,500
28,000
28,000
27,000
27,000
27,500
27,500
28,000
28,000
28,000
28,000
28,000
28,000
D 20,000 FeCrSi
20,000
20,000
20,000
22,000
22,000
22,000
22,000
20,000
i ! 1
Test
Furnace Control point
type equipment location
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
None Tapping
Tapping
Tapping
Tapping
Tapping
Tapping
Open Baghouse Outlet
Outlet
Outlet
Inlet
Outlet
Outlet
Outlet
Inlet
Outlet
Sample
number
18
19
20
21
22
23
24
25
26E
26W
27E
27W
28E
28W
29N
29C
29S
30
31N
31C
31S
32
33N
                                  A-29

-------
Table A-2 (continued).  KEY TO SAMPLE NUMBERS FOR TABLES  A-3  THROUGH A-12

Furnace
kilowatts
during
Firnace test Product
20,000
20,000
20,000
E • 32,000 FeCr (HC)
33,000
33,000
34,000
34,000
34,000
33,000
34,000
34,000
F Silicon










Test
Furnace Control point
type equipment location
Outlet
Outlet
Inlet
Open Precipitator Outlet
Inlet
Inlet
Outlet
Inlet
Inlet
Outlet
Inlet
Inlet
Open Baghouse Inlet
Outlet
Outlet
Outlet
Outlet
Inlet
Outlet
Outlet
Outlet
Outlet
Inlet
Sample
number
33C
33S
34
35
36 E
36W
37
38E
38W
39
40 E
40W
41
42E
42EC
42WC
42W
43
44E
44EC
44WC
44W
45
                                   A-~30

-------
Table A-2 (continued).   KEY TO SAMPLE NUMBERS FOR TABLES A-3 THROUGH A-12

Furnace
kilowatts
during Furnace Control
lace test Product type equipment

•



i 7,800 SiMn Open Scrubber
7,800
7,800
7,800
7,800
7,800
40,500 FeSi (50%) Covered Scrubber
39,500
39,500
50,200 None
50,200
48,700
48,700
« 01
i
Test
point
location
Inlet
Outlet
Outlet
Outlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Outlet
Outlet
Outlet
Fugitive
fume
Exhaust
ducts
Fugitive
fume
Exhaust
ducts
Fugitive
fume
Exhaust
ducts
Fugitive
fume
Exhaust
ducts
Sample
number
46
47E
47EC
47WC
47W
48
49
50
51
52
53
54
55
56
57N
57S
58N
58C

-------
Table A-2 (continued).  KEY TO SAMPLE NUMBERS FOR TABLES A-3 THROUGH A-12

Furnace
kilowatts
during
Furnace test Product
48,700
52,300
52,300
52,300
50,000
50,000
50,000
40,500
39,500
42,000
J 24,000 CaC2
23,800
Test
Furnace Control point
type equipment location
Fugitive
fume
Exhaust
ducts
Fugitive
fume
Exhaust
ducts
Fugitive
fume
Exhaust
ducts
Fugitive
fume
Exhaust
ducts
Fugitive
fume
Exhaust
ducts
Fugitive
fume
Exhaust
ducts
Fugitive
fume
Exhaust
ducts
None Tapping
Tapping
Tapping
Covered Scrubber Outlet
Outlet
Sample
number
58S
59N
59C
59S
60N
60C
60S
61
62
63
64
65
                                    A-32

-------
            Table A-2 (continued).   KEY TO SAMPLE NUMBERS FOR TABLES A-3 THROUGH A-12
Firnace
 Furnace
kilowatts
 during
  test
Product
Furnace
  type
 Control
equipment
  Test
 point
location
Sample
number
           23,500

           22,800




           22,800




           22,800




           23,000




           23,000




           23,000




           23,000




           21,500




           21,500
                                     None
                                               A-33
                                     Outlet

                                     Fugitive
                                       fume
                                     Exhaust
                                       ducts

                                     Fugitive
                                       fume
                                     Exhaust
                                       ducts

                                     Fugitive
                                       fume
                                     Exhaust
                                       ducts

                                     Fugitive
                                       fume
                                     Exhaust
                                       ducts

                                     Fugitive
                                       fume
                                     Exhaust
                                       ducts

                                     Fugitive
                                       fume
                                     Exhaust
                                       ducts

                                     Fugitive
                                       fume
                                     Exhaust
                                       ducts

                                     Fugitive
                                       fume
                                     Exhaust
                                       ducts

                                     Fugitive
                                       fume
                                     Exhaust
                                       ducts
                                           66

                                           67NE




                                           67NW




                                           67SW




                                           68NE




                                           68NW




                                           68SE




                                           68SW




                                           69NE




                                           69NW

-------
            Table A-2 (continued).   KEY TO SAMPLE  NUMBERS  FOR TABLES  A-3  THROUGH  A-12
Furnace
 Furnace
kilowatts
 during
  test
Product
Furnace
  type
 Control
equipment
  Test
 point
location
Sample
number
           21,500




           21,500




           24,000

           23,800

           23,800
                                     None
                                     Fugitive
                                       fume
                                     Exhaust
                                       ducts

                                     Fugitive
                                       fume
                                     Exhaust
                                       ducts

                                     Tapping

                                     Tapping

                                     Tapping
                                           69SE




                                           69SW




                                           70

                                           71

                                           72
                                               A-34

-------
         Table  A-3.
['ARTICULATE EMISSION CONCENTRATIONS  AND RATES FROM UNCONTROLLED TEST POINTS
urnace
A



B

C








D


[





F



G


H
J
Sample
nuniier
IE
1W
2E
2W
3
4
9
11
13
15
17
19
21
23
25
30
32
34
36E
Probe and
cyclone
gr/scf j
0.052
0.023
0.069
0.046
0.117
0.137
0.180
0.386
0.98
0.98
0.99
1.25
0.17
0.56
0.23
0.13
0.06
0.06
0.48
36W j 0.59
38E
38W
40E
40W
41
43
45
46
48
50
52


0.40
0.39
0.43
0.35
0.085
0.052
0.085
0.078
0.47
0.31
0.42


Ib/hr
30.1
18.5
42.7
34.3
41.8
47.6
161.0
319.0
439.0
823.0
875.0
1123.0
134.0
407.0
189.0
199.0
81.5
84.7
322.0
415.0
292.0
253.0
315.0
253.0
297.0
193.0
286.0
266.0
65.0
43.7
59.5


Probe,
and
gr/scf
0.220
0.047
0.376
0.249
0.141
0.175
1.05
0,423
2.22
1.92
2.10
2.06
0.965
1.66
1.91
0.66
0.12
0.40
0.892
1.09
0.819
0.835
1.107
0.782
0.815
0.538
0.742
0.723
2.15
1.38
1.33


cyclone,
filter
Ib/hr
126
37
232
188
50
61
940.4
349.8
1918.0
1611.0
1857.0
1846.0
752.6
1209.0
1553.0
996.4
173.2
594.4
597.0
761.0
600.0
538.0
811 .0
573.0
2840.0
1980.0
2490.0
2470.0
296.1
194.8
188.1


Impi nger
gr/scf
0.005
0.040
0.012
0.014
0.014
0.003
0.01
0.04
0.01
0.03
0.02
0.01
0.02
0.03
0.01
0.79
0.40
0.59
0.03
0.02
0.01
0.01
0.01
0.01
0.009
0.007
0.004
0.025
0.04
0.02
0.02


Ib/hr
3
31
8
10
5
1
8.9
33.9
8.0
25.0
18.0
10.0
13.3
22.0
9.0
1194.6
583.5
882.9
20.0
16.0
6.0
6.0
6.0
5.0
30.0
30.0
20.0
90.0
5.5
2.8
2.8


Total per
sample point
(includes water
: residue)
; gr/scf : Ib/hr
i
' 0.225 129
0.087 , 68
| 0.388 ' 240
, 0.263 198
, 0.154 55
0.178 62
1.06 949.3
i
; 0.464 383.7
' 2.23 1926.0
1.95 1636.0
2.12 1875.0
i 2.07 1856.0
0.982 765.9
1.690 1231.0
1.920 1562.0
1.448 2191.0
0.520 75t>.7
0.990 1477.3
0.922 617.0
i 1.113 777.0
, 0.827 606.0
0.845 . 544.0
1.114 817.0
0.789 578.0
!
0.824 2870.0
0.545 2010.0
0.746 2510.0
0.748 2560.0 i
2.19 301.6
1 .40 197.6
•1.35 190.9


Total from
furnace
gr/scf

0.15

0.29
0.15
0.18
1.06
0.46
2.23
1.95
2.12
2.07
0.98
1.69
1.92
1.45
0.52
0.99

1.07

0.84

0.95
0.82
0.55
0.75
0.75
2.19
1.40
1.35


Ib/hr

197

438
55
62
949
384
1926
1636
1875
1856
766
1231
1562
2191b
757b
1477b

1394

1150

1395
2870
2010
2510
2560
302
198
191


Estimated
emissions
not
captured,
percent

0.5

0.5
53
52
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5b
0.5b
0.5b

0.5

0.5

0.5
5
5
5
5
2
2
2
9C
6C
 Does not  include tapping fume losses  unless otherwise indicated.
 Includes  tapping fura losses.
cNo inlet  sarples obtained with EPA  sampler.  Percent loss  based on emission factor and  samples obtained of
 fugitive  fu ,e hood.
                                                    A-35

-------
Table  A-4.     r.wr:-." ire EMISSION C(«CEKTRATIO:IS KIO RATES TO ATMOSPHERE FROM CONTROLLED TEST POINTS

n
c












D








E


r











c


H


J


Sairple

5
C
7
8
10

1?
14
16
18
?0
??
21
29H
29C
MS
31H
3K
31S
3X1
33C
335
35
37
39
42E
42EC
42WC
42W
44E
4irr
44UC
44U
47E
47EC
47WC
47W
49
SI
S3
S4
55
S6
54
es
66


Scrubber 57" PD
Scrubber 57" PU
Probe


0.010
0.007
Scrubber 57" PD 0.011
Scrubber 57" PD 0.003
Scrubber 57" PD 0.009
i
Scrubber 47" PD
Sarplc
Scrubber 47" PD . 0.015
Scrubber 47" PO O.Ola
Strui,b»r 17" PD
0.011
Scr..bl'er 37" PO 0.013«
Tr.rubber 37" PD 0.037
Scrubber 37" PD
Ba'jhousc*
Gaghouse3
Bjghouse*
Baghouse*
Baghousea
Baghouse*
Bd^ltouse*
Eaghouse
Bughouse*
PreclpHator
Precipitator
PrecipHator
8aghouseb
Baghouse*
Baghouse
Baghouse
Baghouse
P-jllOtKP1"
Baghouse
Baghouse
Ba;houseb
Baghouse
Baghouse
Hajhouse1'
Scrubber
Scrubber
Scrubber
Scrubber
Scrubber
Scrubber
Scrubber
Scrubber
Scrubber
O.OCO
0.0035
0.0042
0.0023
0.0038
0.0028
0.0020
0.0023
0.0014
0.0016
0.029
0.009
0.010
0.007
0.0032
0.0015
O.OOIS
0.0067
0.0014
0.0023
0.0014
0.0026
0.0018
0.0017
0.0015
0.040
0.093
0.102
0.668





and filter
| Ib/hr
10.0
6.8
11.2
8.1
8.4

discarded
15.2
17.7
11.8
13.5
35.4
70.6
11 .5
13.8
7.6
12.5
9.2
6.6
7.6
4.6
5.3
36.3
12.5
14.2
4.2
1.9
0.9
0.9
5.2
1.0
1.4
0.9
1.5
1.1
1.0
0.9
S.8
12.4
13.6
67.0





Inplnger
gr/scf
0.007
0.004
0.001
0.002
0.002


0.002
0.002
0 002
0.0006
0 008
0.005
0.008
0.010
0.007
0.008
0.007
0.006
0.004
0.004
0.003
0.002
0.003
0.003
0.007
0.002
0.0005
0.0001
0.004
0.003
0.002
0.003
0.001
0.004
0.002
0.002
0.009
0.008
0.005
0.188





Ib/hr
6.1
3.7
1.6
1.6
l.S


2.0
1.7
1.8
0.6
7.3
4.5
28.3
30.5
21.9
27.2
23.0
19.0
12.8
11.5
12.4
3.1
3.2
3.0
2.4
0.6
0.2
0.1
1.6
1.3
1.1
1.
0.6
2.4
1.3
1.4
1.3
1.0
0.6
19.0





! Total per
sample point
, (Includes water
residue)
gr/scf
0.017
0.011
0.012
0.010
0.011

-•
0.017
0.020
" 0.013 '
0.0144
0.045
0.08S
0.012
0.014
0.009
0.01?
0.010
0.008
0.006
0.005
0.005
0.031
0.012
0.013
0.014
0.005
0.002
0.002
0.011
0.004
0.004
0.004
0.004
0.006
0.004
0.004 ,
0.049
0.101
0.107
0.856
0.115
0.085
0.043
0.031
0.034
Ib/hr
It.l
10. i
12.8
9.7
9.9

"
17.2
19.4
13.6
14.1
42.7
75.1
39.8
44.3
29.$
39.7
32.2
25.6
20.4
16.1
17.7
39.4
15.7
17.2
6.6
2.5
1.1
1.0
6.8
2.3
2.5
2.3
2.1
3.5
2.3
2.3
7.1
13.4
14.2
86.1
11.2
8.3
0.6
0.4
0.5
i
Totll Into
atmosphere
«r/$cf
0.02 '
0.01
0.01
0.01
0.01


0.02
0.02
0.01 '
0.01
0.05
0.09

0.01


0.01


0.005

0.03
0.01
0.01

0.01



0.01



0.01


0.05
0.10
0.11
0.86
0.12
0.09
0.04
0.03
0.03
Ib/hr
16.1
Efficiency

10.5
12.8
9.7
9.9


17.2
19.4
13.6
14.1
42.7
75.1

37.9


32.5


18.1

39.4
15.7
17.2

11.2



13.9



99.0
97.5


99.0
99.0
99.4
98.1
96.4
95.2

98.0


95.0


98.9

97.2
98.6
98.8

99.1



98.5



10.2


7.1
13.4
14.2
86.1
11.2
8.3
0.6
0.4
0.5
99.1


97.6
93.2
92.6






 'three samplers  used during each run  designated N, C,  and  S.  Total enfs:fons  are based on results of each sanpl*.
  Total for ejch  rjn i; the average of tt, C, and S.

 brour samplers used d^ing p,ich run designated E. EC.  WC,  and V.  Ea:h s*r.pler covers emissions  from two compartmen
  Total emissions  for each tcit run are  the su-*i'3tion of  the result* of E.  EC,  KC, and U.
                                                      A-36

-------
             Table  A-5.   PARTICIPATE LOSSES FROM THE FUGITIVE FUME HOOD*
1
Sample
Furnace number
H 57N
57C
57S
58N
58C
58S
59N
59C
59S
SON
60C
60S
0 67NE
67NW
67SE
67SW
68NE
68NU
. 68SE
68SW
69NE
69NW
69SE
69SW
I
; Probe and filter
; gr/scf
0.095
Sample
0.110
0.423
0.337
0.565
0.054
0.358
0.740
0.078
0.077
0.163
0.161
0.037
Sample
0.050
0.079
0.018
0.046
0.029
0.079
0.021
0.037
0.039
|
• Ib/hr
40.6
rejected -
! 45.5
i 186.1
: 157.7
' 225.4
22.3
159.9
275.5
36.0
36.8
63.3
15.8
20.4
rejected -
29.2
8.1
9.5
13.2
15.7
: 9.1
10.8
9.9
20.1
Impinger
gr/scf
0.008
Ib/hr
3.6
Total
sample
gr/scf
0.103
per
point
i
! Ib/hr
1
! 44.2
glass probe broke ;
0.015
0.028
0.016
0.035
0.061
0.064
0.014
0.033
0.031
0.008
0.003
0.004
6.0
12.2
7.2
13.9
25.1
28.6
5.1
15.5
14.4
3.1
0.4
2.1
0.125
0.451
0.353
0.600
0.115
0.422
0.754
0.111
0.108
0.171
0.164
0.041
51.5
198.3
164.9
, 239.3
47.4
188.5
280.6
j 51.5
I 51.2
! 66.4
I
: 16.2
, 22.5
| Total Into
: , atmosphere
!
gr/scf i Ib/hr

0.11 293.06
.
i
0.47 602.5
j
i
!
' 0.43 516.5
j
I
0.13 169.1

0.09 69. 0C
glass probe broke
0.002 '
0.007
0.001
0.005
0.015
0.007
0.003
0.001
0.030
1.1
0.8
0.7
1
1.4
8.5
0.7
1.7
0.5
15.7
0.052
0.086
0.019
0.051
0.044
0.086
0.024
0.038
0.069
30.3
8.9
10.2
' 14.6
24.2
9.8
12.5
10.4
35.8
i

0.05 64.0


0.05 68.5


Fumes not captured by  air pollution scrubber system.

Fugitive fume hood discharges uncontrolled fumes to atmosphere through  three stacks.  Total
Into atmosphere is summation of samples N, C, and S.  Total  of 293  Ib/hr would be higher If sample
57C were added.

Fugitive fume hood discharges uncontrolled fumes to atmosphere through  four stacks.  Total Into
atmosphere is summation of samples NE, NW, SE, and SW.  Total  of 69 Ib/hr would be higher if sample
67SE were added.
                                             A-37

-------
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                                                                A-38

-------
            Table A-7.   COLLECTION EFFICIENCY ( IMPINGER SECTION ONLY)3
                         OF SCRUBBER SERVING FURNACE C
Scrubber
pressure
drop,
nches H20
57





47








37









Sample
point
Inlet

Outlet
Inlet

Outlet
Inlet

Outlet
Inlet

Outlet
Inlet

Outlet
Inlet

Outlet
Inlet

Outlet
Inlet

Outlet

Sample
No.
9

8
5


7


8


9


10


11


12



Impinger
catch, %
1

16
9

15
1.5

12
1

9
0.5

13
1.7

4
1.8

17
0.5

6

Total
parti culates,
Ib/hr
949

9.7
384

9.9
1636

17.2
1875

19.4
1856

13.6
766

14.1
1231

42.7
1562

75.1

Parti cul ate
from impinger
section only,
Ib/hr
9.5

1.6
34.5

1.5
24.5

2.1
18.8

1.7
9.3

1.8
13.0

0.6
22.0

7.2
7.8

4.5

Collection
efficiency
(back half
only), %

83


96


91


91


81


95


68


42


Efficiencies  shown  are  calculated from samples collected in the impinger section
 (back half only)  of the EPA sampling train and were based on inlet and outlet
 samples of the  air  pollution control device.
                                           A-39

-------
      Table A-8.   COLLECTION EFFICIENCY (IMPINGER SECTION ONLY)
                     OF BAGHOUSE SERVING FURNACE'U


Sample
point
Inlet

Outlet
Inlet

Outlet
Inlet

Outlet


Sample
no.
a

b
a

c
a

d


Impinger
catch, %
40

71
40

71
40

68

Total
particulates,
Ib/hr
827a
k
38b
827a

32. 5C
827a
H
18°
Particulates
from impinger
section only,
Ib/hr
330

27
330

23
330

12
Collection
efficiency
(back half
only) %

92


93


96

 Average of samples  30,  32,  and  34  obtained on  8-31  and 9-1-71
^Average of samples  29N, 29C,  and 29S  obtained  on  8-31-71.
cAverage of samples  31N, 31C,  and 31S  obtained  on  9-1-71.
 Average of samples  33N, 33C,  and 33S  obtained  on  9-1-71.
                                      A-40

-------
Table A-9.  COLLECTION EFFICIENCY (IMPINGER SECTION ONLY)  OF PRECIPITATOR SERVING FURNACE E


Sample
point
Inlet

Outlet
Inlet

Outlet
Inlet

Outlet


Sample
No.
36

35
38

37
40

39


Impinger
catch, %
2a

8
i.oa

20
0.8

17

Total
parti culates,
Ib/hr
1394

39.4
1150

15.7
1395

17.2
Parti culates
from impinger
section only,
Ib/hr
27.9

3.1
11.5

3.1
11.1

2.9
Collection
efficiency
(back half
only), %

89


73


74

        Average of two test points,
                                            A-41

-------
Table A-10.  COLLECTION EFFICIENCY (IMPINGER SECTION ONLY) OF BAGHOUSE SERVING FURNACE F

Sample
point
Inlet

• Outlet
Inlet

Outlet
Inlet

Outlet

Sample
No.
41

42
43

44
46

47

Irnpinger
catch, %
1.1

22
1.3

46
3.4

54

Total
parti culates
Ib/hr
2870

29
2010

28
2560

23
Particulates
from impinger
section only,
Ib/hr
31.6

6.4
26.1

12.9
87.0

12.4
Collection
efficiency
(back half
only), %

80


51


86

                                            A-42

-------
Table A-11.    COLLECTION EFFICIENCY (IMPINGER SECTION ONLY)
               OF SCRUBBER SERVING FURNACE G
Sample
point
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Sample
No.
48
49
50
51
52
53
Impinger
catch, %
1.8
17.6
1.4
7.7
1.5
4.6
Total
parti culates,
Ib/hr
301.6
7.08
197.6
13.42
190.9
14.21
Parti culates
from impinger
section only,
Ib/hr
5.40
1.25
2.76
1.03
2.75
0.65
Collection
efficiency
(back half
only), %
77
63
77
                             A-43

-------
       Table  A-12.  PARTICULATE EMISSIONS  (IMPINGER SECTION ONLY) FROM FURNACE Ha
?un no.
1

2


3


4


1
2
3
1
2
3
Impinger
catch, %
8.1
11.6
6.1
4.3
5.8
52.9
15.1
1.8
30.0
28.1
4.7
4.1
28.0
1.3
22
41

Parti culates to
atmosphere based
total catch,
Ib/hr
44.2
51.5
198.3
164.9
239.3
47.4
188.5
280.6
51.5
51.25
66.4
105.2
76.6
90.7
86.1
11. 2C
8.25C
Parti culates to
atmosphere based on
impinger section only,
Ib/hr
3.6
6.0
12.2
7.2
13.9
25.1
28.6
5.1
15.5
14.4
3.1
4.3
21.4
1.1
19.0
--
--
Source of
parti culates
Mix seals

Mix seals


Mix seals


Mix seals


Tapping
Tapping
Tapping
Scrubber exhaust


'inlet to  scrubber  not  sampled.
'Three exhaust  ducts  vent  mix seal  fumes  directly  to  atmosphere.
"After run No.  1, filter relocated  in  test  train after  silica  gel  impinger.
                                           A-44

-------
                     Table A-13.  FURNACE GAS VOLUMES
Product
FeCrSi
FuCrSi
Cr ore lime melt
Cr ore lime melt
SiMn
SiMn
SiMn
SiMn
SiMn
SiMn
SiMn
SiMn
SiMn
FeCrSi
FeCrSi
FeCrSi
FeCr (HC)
FeCr (HC)
FeCr (HC)
Si
Si
Si
Si
SiMn
SiMn
SiMn
FeSi (50%)
FeSi (BOX)
FeSi (50%)
CaC2
CaC2
CaC2
Average
megawatts
(test period)
9.8
9.3
7.2
7.2
23
28
27.5
28
27.5
27.5
28
27
27.5
20
22
20
33
34
34
17
17
17
17
7.8
7.8
7.8
42
41
45
24
23.8
23.5
Type of
furnace,
0-open
C-closed
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
C
c
c
c
c
c
Temperature,
°F
280
261
123
154
599
674
607
631
633
629
655
654
541
331
323
336
460
470
445
300
300
310
307
1133
1100
1106
a
a
a
a
a
a
Gas
volume,
acfm
196,000
202,000
47,000
49,000
224,000
203,000
215,000
216,000
230,000
232,000
205,000
199,000
192,000
273,000
271 ,000
282,000
295,000
297,000
310,000
595,000
630,000
590,000
590,000
51,300
51 ,400
51.700
7,600b
7,600b
7,600b
1,443b
1 ,443b
1 ,443b
a i«o.  test conducted at inlet.
  Volumes (scfm) based on outlet test.
                                 A-45

-------
                                 APPENDIX B


                     SAMPLING  AND ANALYTICAL TECHNIQUES




     The  procedures and equipment used by EPA  personnel or by  contractors


working for EPA to measure  particulate and other emissions are described in


the appendix of the Federal Register, 42CFR Part 466, Proposed Standards


of Performance for New Stationary Sources (Vol.  36, No. 159, August 17,


1971).  The applicable test methods are reprinted below.


     A suitable sampling site and the required number of traverse points


were determined according to  Method 1.  The volumetric flow rate of the


total effluent was obtained by using Method 2.   For each run,  the average


concentration of particulate  matter was determined by using Method 5.


A limited number of tests were also made for the determination of sulfur


dioxide by Method 6.


     Because of the configuration of ducting at certain sample points, it


was sometimes necessary to  deviate from  the procedures set forth in


Method 1.   The sampling points in these situations were located in


the only  possible or usable places, but care was taken that representa-


tive samples were nevertheless obtained.


     Sample ports and procedures for all tests were approved by the EPA


project officer in charge of  testing.



FEDERAL REGISTER, VOL 36, NO. 159—TUESDAY, AUGUST 17, 1971—TEST METHODS


  METHOD I-SAMPU: AND VELOCITY TRAVERSES         d   h  exttaotlon of a representative
         FOR STATIONARY SOURCES               sample
   1. Principle and applicability.                  1.2 Applicability. This method should be
   1.1 Principle. A sampling site and the        applied only when specified by the test pro-
  number of  traverse points are selected to        cedures for determining  compliance  with
                                   B-l

-------
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-------
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                                    B-3

-------
                                                  PROPOSED  RULE  MAKING
43   OaVrtlivte  the pitot tube  coefficient  then the other pointed down-trcnm. Ufe the
                                          pitot tube only it the two cc efficients differ
                                          by no more than  001.
                                             5. Calculations.
                                             Use Equation 2 -2 to calculate the stack gas
using Equation 2-1

       f     __<"•
       Cl""l~  '•li
                             equation 2-1
where:
  C,,,.t = P!tot tub*  coefficient of  Type  5
            pitot tube.
   C»,,j = Pltc units
                                                  •<»„„_ ^lb moi^-R^   are used.
                                             Cp-Pitot tube coefficient, (limensionlrss.
                                             T, = Ahtcilulf M:ick r,es temperature, °R.
                                             Ap=Vrlodty head of stack pas, In HiO (sec fig. 2-2).
                                             1',= Abwlutc flock pivs prc^tire. In Up.
                                              M.-
                                                      uliir wt
                                                                     .
                                                            t of stack giis, Ib./lfo -mole,
PLAI
DAT
RUN
STA<
BAR
STAT
OPER
MT 	
E r-
NO.
:K DIAMETER. In.
D.Y:TRIC PRESSURE, in. Hg.
1C PRESSURE IN STACK (P0). In. Hg.
ATORS




SCHEMATIC OF STACK

Traverse point
number





















Velocity head,
in. H2O





















AVERAGE:
vs;










*











CROSS SECTION
Stack Temperature
iy °F






















  Figure 2-2 shows a cample recording r.heet
for velocity traverse data. U-c the ftverar<*s In
the last two columns of Figure 2 2 to deter-
mine the average  stack evs  velocity from
Equation 2-2.
  6.  References.
  Mark,  L. S. Mechanical  Engineers'  Hand-
book. McGraw-Hill Book Co., Inc., New York,
1951.
  Perry, J H. Chemical Engineers' Handbook.
McGraw-Hill Book Co., Inc., New York, 1060.
  Shlgehara, R. T..  W.  P.  Todd, and  W. S.
Smith. Significance of Errors In Stack Sam-
pling Measurements.  Paper presented at  the
Annual Meeting of the Air Pollution Control
Association, St. Louis, Mo.,  June  14-19, 1970.
  Standard  Method for Sampling Stacks for
Paniculate  Matter. In:  1971 Book of ASTM
standards. Part 23. Philadelphia,  1971. ASTM
Designation D-2928-71.
  Vcnnard, J. K. Elementary Fluid Mechanics.
John Wiley and Sons, Inc., New York, 1947.
METHOD  3	GAS ANALYSIS FOtt CAIU1ON DIOXIDE,
   EXCESS AIR, AND DRT MOLECITLAR WKIGHT
  1.  Principle and applicability.
  1.1  Principle.  An  integrated or  grab  gas
sample is extracted from  a sampling point
and  analyzed for its  components using  an
Orsat analyzer.
  1.2  Applicability. This method should be
applied only when specified by the  test pro-
cedures for determining compliance with New
Source Performance Standards.
  2.  Apparatus.
  21  Grab sample (Figure 3-1).
  2.1.1   Probe—Stainless  steel  or  Pyrex1
glass, equipped with a filter to remove par-
ttculate matter.
  2.1.2   Pump—One-way  squeeze   bulb,  or
equivalent,  to transport gas sample to ana-
lyzer.
  2.2  Integrated sample (Figure 3-2).
  2.2.1   Probe—Stainless  steel  or  Pyrex'
glass equipped with  a filter to remove par-
ticulate matter.
  2.2.2   Air-cooled   condenser—To  remove
any excess moisture.
  2 2.3  Needle valve—To adjust flow rate.
  2 2.4   Pump—Leak-frie,  diaphragm type,
or equivalent, to pull gas.
  2.2.5   Rate meter—To measure a flow range
from 0 to 0 035 c.f jn.
  2.2.6   Flexible bag—Tedlar,"  or equivalent,
with ft capacity of 2 to 3 cu. ft. Leak test the
bag  in the  laboratory before using.
  2.2.7   Pitot tube—Type  S, or equivalent,
attached to the probe so that the sampling
flow rate can be regulated proportional to the
stack gas velocity  when velocity Is varying
with time or a sample traverse is conducted.
  2.3  Analysis.
  2.3.1   Orsat analyzer, or equivalent.
  3. Procedure.
  3.1  Grab sampling.
  3.1.1   Set  up the equipment as shown in
Figure 3-1.  Place the probe In  the stack at a
sampling point and purge the  sampling Jme.
                         Figure 2-2.  Velocity traverse data.
                                                                                            1 Trade name.
                                   FEDERAL REGISTER,  VOL 36, NO.  157—TUESDAY, AUGUST  17,  1971
      Uo.169-Pt.il-
                                                                B-4

-------
                                                  PROPOSED RULE  MAKING
                   PROBE
                   PJV
                                             FLEXIBLE TUBING
    ERIG
FILTER (GLASS WOOL)
                                            SQUEEZE BULB
                          Figure 3-1.  Grab-sampling train.

                                             RATE METER
               5. References
TO ANALYZER   Altshuller.  A.  P., et al. Storage of Oos.t.
             and Vapors in Plastic  Bags.  Int  J. Air *
             Water Pollution. 6:75-81. 1903.
               Conner, William D., and J. S. Nader. Air
             Sampling with Pla-stic Bags.  JournaJ of the
             American  Industrial  Hygiene  As.-delation
             25 291 -297. May-iunc 1964.
               Devorkln, Howard, et  al.  Air  Pollution
             Source Testing Manual.  Air Pollution Con-
             trol Di-strlct. Los  Angeles. November 1903.


             METHOD  5.—DETERMINATION  OF  PNRTICULATE
                  EMISSION'S FHOM STATIONARY SOURCES
         AIR-COOLED CONDENSER
     PROBE
                                                                  QUICK DISCONNECT
FILTER (GLASS WOOL)
                                                                                          1.  Principle and opp
                                                                                          1.1 Principle. Participate matter is with-
                                                                                        drawn Isokinetlcally from the soxirce and Its
                                                                                        weight is determined  gravimetrically after
                                                                                        removal of uncombined water.
                                                                                          1.2 Applicability. This method Is applica-
                                                                                        ble  for  the determination  of particulate
                                                                                        < missions from stationary sources only when
                                                                                        specified by  the  test procedures for deter-
                                                                                        mining  compliance with New Source  Per-
                                                                                        formance Standards.
                                                                                          2.  Apparatus,
                                                                                          2.1 Sampling train. The design specifica-
                                                                                        tions of the particulate sampling train used
                                                                                        by EPA  (Figure 5-1) are described in APTD-
                                                                                        05S1. Commercial models of this train  are
                                                                                        available.
                                                                                          2.1.1  Nozzle—Stainless steel (316) with
                                                                                        sharp, tapered lending edge.
                                                                                          2.1.2  Probe—Pyrex ' glass  with  a heating
                                                                                        system capable of maintaining a gas tempera-
                                                                                        ture  of  250'  P.  at  the exit end during
                                                                                        sampling.  When  temperature or   length
                                                                                        limitations  are encountered,  316  stainless
                                                                                        steel, or equivalent, may be used, as approved
                                                                                        by the Administrator.
                                  RIGID CONTAINER
                Figure 3-2.  Integrated gas - sampling train.
  3 1.2  Draw sample Into the analyzer.
  3 2   Integrated sampling.
  3.2.1  Evacuate the flexible bag. Set up the
equipment as shown In Figure 3-2 with the
bag disconnected. Place  the probe in the
stack  and purge the sampling line. Connect
the bag, making ST>^ that  all  connections
are tight and that there are  no  leaks.
  3.2 2  Sample at a rate proportional to the
stack gas velocity.
  3.3   Analysis.
  3.3.1  Determine the CO?, 02, and CO con-
centrations as soon as possible. Make as many
passes as are necessary to give constant read-
ings. If more than 10 passes are  necessary,
replace the absorbing solution.
  3.3.2  For Integrated sampling, repeat the
analysis  until  three consecutive runs vary
no more than 0.2 percent by volume for each
component being analyzed.
  4. Calculations.
  4 1   Carbon  dioxide. Average the  three
consecutive  runs and report result to the
nearest 0.1 percent CO2.
  4.2   Excess air. Use  Equation 3-1 to cal-
culate excess air, and average the runs. Re-
port the  result to  the nearest  0.1 percent
excess air.
_ _ (r0o.)-o.s(%co)          . nft
0.264 ( % N,) - (% 0,) +0.5(% CO) X 1UO
                             equation 3-1
                                            where:
                                              %EA=Percent excess air.
                                              %O,=Percent  oxygen  by  volume,  dry
                                                      basis.
                                              %N,=Pereent  nitrogen  by volume,  dry
                                                      basis.
                                              TtCO=Percent  carbon monoxide by  vol-
                                                      ume, dry basis.
                                              0.264=Ratlo ot oxygen to nitrogen in air
                                                      by volume.
                                              4 3  Dry  molecular weight. Use Equation
                                            3-2  to calculate dry molecular weight  and
                                            average the runs. Report  the result to the
                                            nearest tenth.
                                                  Ma = 0.44(% C0,)+032(% O.)
                                                       + 0.28(% N,+ %CO)
                                                                         Equation 3-2
                                            where:
                                                 Md = Dry   molecular   weight,   lb./lb.-
                                                       mole.
                                              %CO,=Percent carbon dioxide by volume,
                                                       dry basis.
                                               %O,=Percent oxygen  by volume,  dry
                                                       basts.
                                               TcNj=Percent nitrogen by volume, dry
                                                       basis.
                                                0.44 = Molecular weight of carbon dioxide
                                                       divided by 100.
                                                0.32 = Molecular   weight   ot   oxygen
                                                       divided by 100.
                                                028=Molecular  weight   of  nitrogen
                                                       divided by 100.
                                 FEDERAL REGISTER, VOL. 36, NO.  159—TUESDAY, AUGUST  17,  1971
                                                                B-5

-------
                                                  PROPOSED  RULE  MAKING
  2.1.3  Pilot  tube—Type S, or equivalent,
Bt Inched  to  probe  to monitor  stnck gas
velocity.
  2.1.4  Filter  holder—Pyrex1  glass  with
healing system capable of maintaining niijr
temperature to & maximum of 225* f.
  21.5  Itnplngurs—Pour   Impingers  con-
nected In scries with glass ball Joint fittings.
The first, third, and fourth Impingers are  of
the Orecnburg-Smlth design, modified by rc-
     piaclng the lip with a 'i-lnch. ID gla'a tube
     extending to ^-Inch from the bottom of the
     fia.sk. The r-ocond Implnger is of the Grccn-
     burg-Snnth dc:.Jgu with the sUindard tip.
       2 1.6  Metering  system—Vacuum  gauge,
     Icak-ficc  pump,  thermometers capable  of
     measuring temperature to within 6" P., dry
     gas meter with 2 percent accuracy, and re-
     lated equipment, or equivalent, as required
     to maintain an Isoklnotic .sampling rate and
     to determine sample volume.
                             HEATED AREA  FILTER HOLDER   THERMOMETER
       PROBE
REVERSE-TYPE
 PITOT TUBE
             PITOT MANOMETER

                       ORIFICE
IMPINGERS             ICE BATH
        BY-PASS.VALVE
                                                                VACUUM
                                                                 GAUGE
                                                        MAIN VALVE
                                                                            CHECK
                                                                            VALVE
                                                                              VACUUM
                                                                               LINE
                         DRY TEST METER
     AIR-TIGHT
       PUMP
                           Figure 5-1.  Particulale-sampling train.
   2.1.7 Barometer—To measure atmospheric
 pressure to ±0.1 In. Hg.
   2.2  Sample recovery.
   2.2.1 Probe brush—At least  as  long as
 probe.
   2.2.2 Glass wash bottles—Two.
   2.2.3 Glass sample storage containers.
   2.2.4 Graduated cylinder—250 ml.
   2.3  Analysis.
   2.3.1 Glass weighing dishes.
   2.3.2 Desiccator.
   2.3.3 Analytical balance—To  measure to
 ±0.1 mg.
   2.3.4 Beakers—250 ml.
   1 Trade name.
       2.3.5  Separatory  funnels—500 ml.  and
      1,000 ml.
       2.3.9  Trip  balance—300 g. capacity,  to
      measure to ±0.05 g.
       2.3.7  Graduated cylinder—25 ml.
       3. Reagents.
       3.1  Sampling
       3.1.1  Filters—Glass fiber. MSA 1106 BH,
      or  equivalent, numbered  for  Identification
      and preweighed.
       3.1.2  Silica gel—Indicating  type.  6 to  16
      mesh, dried at 175* C. (350* F.) for 2 hours.
       3.1.3  Water—Deionized, distilled.
       3.1.4  Crushed Ice.
       3.2  Sample recovery
       3.2.1  Water—Deionized, distilled.
  322  Acetone— Reagent grade.
  3 3  Analysis
  331  Water— DcionUcd, distilled
  332  Chloroform—Ronsent grade.
  3 3.3  Ethyl ether—Roaeent grade.
  334  Dc.slccant—Drlerite,' Indicating.
  4. Procedure.
  4.1  Sampling.
  4 1.1  After selecting the sampling site and
the  minimum number of sampling points,
determine the stack pressure,  tempciature,
moisture, and range of velocity head.
  4.1.2  Preparation   of  collection   train.
Weigh to the nearest gram approximately
200 g. of silica gel. Label a  filter of proper
diameter,  desiccate3 for  at  least 24  hours
and \veigh to the nearest 0.5 mg. In a room
where the relative humidity  Is less  than
50 percent. Place  100 ml. of water In each of
the first two Impingers, leave the third 1m-
pinger empty, and place  approximately 200
g. of prewclghed silica gel in the fourth 1m-
pinger. Save  a portion of the water for use
as a blank in the  sample analysis. Set up the
train without the probe as In Figure 5-1.
Leak check  the sampling train at  the sam-
pling site by plugging the inlet to  the filter
holder and pulling a  15-ln.  Hg vacuum. A
leakage rate  not in excess of 0.02 c f m at a
vacuum of  15-in. Hg  is  acceptable. Attach
the probe and adjust the heater to provide a
gas  temperature  of about  250° F. at the
probe outlet. Turn on the filter heating sys-
tem. Place crushed ice around the impingers.
Add more ice during the run to keep the tem-
perature of the ga^es leaving  the last im-
pinger at 70"  F. or less.
  4 1.3  Participate train operation  For each
run record the data required  on the example
sheet  shown in Figure  5-2. Take readings
at each sampling  point at least every 5 min-
utes and when significant changes in  stock
conditions   necessitate  additional  adjust-
ments in flow rate. To begin sampling, po-
sition the nozzle at  the  first traverse  point
with the tip pointing directly  into the gas
stream. Immediately start the pump and ad-
Just the flow to isokmetic conditions. Main-
tain  Isokinetic  sampling throughout the
sampling period.  Nomographs  are  available
which aid In the rapid  adjustment of the
sampling rate without other computations.
APTD-0576 details the procedure for  using
these nomographs. Turn off the pump at the
conclusion of each run and record  the finaj
readings. Remove the probe and nozzle from
the stack and handle in accordance with the
sample recovery process described in section
4.2.
                                                                                          »Dry using Drierite ' at 70° ±10' F.
                                  FEDERAL REGISTER VOL.  36, NO. 159—TUESDAY,  AUGUST  17,  1971
                                                           B-6

-------
                                                    PROPOSED  RULE  MAKING
           PLANT	

           LOCATION	


           DATE..	
           f.UN NO.	
           SA.V.PLE BOX NOj..
           men i>ox NO.__
                                                    AVBItNT TEMPI:r,ATURE_

                                                    BAROViTRICPRESSURE_

                                                    ASSUVED MOISTURE. 8_

                                                    IIEA1ER BOX SETTING	

                                                    MODE LENGTH, in.	

                                                    NOZZLE DIAMETER, in. ._

                                                    PROBE HEATER SETTING_
           CFACTOR	
                                                    SCHEMATIC OF STACK CROSS SECTION
TRAVERSE POINT
KUV.BEB












TOTAL
SAMPLING
TIME
to), min.













AVERAGE
STATIC
PRESSURE
[Psl. in. Ha.














SfACK
TEMPERATURE
(Tsl.'F














VELOCITY
HEAD
I A PS).














PRESSURE
DEFERENTIAL
ACROSS
ORIFICE
METER
UH),
In, H20














GAS SAMPLE
VOLUME
(Vml, It3














GAS SAV.PLE TEMPERATURE
AT DRY GAS METER
INLET
ITm,D).°F












Avg.
OUTLET
(Tmout1.°F












Avg,
Avg.
SAMPLE BOX
TEMPERATURE,
°F














IMPINGER
TEMPERATURE.
"f














  4.2  Sample recovery. Exercise care in mov-
ing the collection train from the test site to
the sample recovery area to minimize the loss
of collected sample or the gain of extraneous
particulate matter. Set aside portions of the
water and acetone used in the sample recov-
er7 as  blanks for analysis. Place the samples
In containers as follows:
  Container No.  1. Remove the niter from its
holder, place in  this container, and seal.
  Container No. 2.  Place loose particulate
matter and acetone washings from all sam-
ple-exposed surfaces prior to the filter in this
container and seal. Use a  raaor blade, brush,
or rubber policeman to loosen adhering par-
ticles.
  Container No.  3. Measure  the volume of
water  from the first  three  Implngers  and
place the water in this container. Place^'ater
                                                               Figure 5-2.  Paniculate Held data.
rinsings of  all sample-exposed  surfaces be-
tween the filter and fourth impinger in this
container prior to sealing.
  Container  No. 4. Transfer the silica gel
from the fourth  impinger to  the  original
container and  seal. Use a rubber policeman
as an aid in removing silica gel from the
impinger.
  Container No. 5. Thoroughly rinse  all sam-
ple-exposed surfaces between the filter and
fourth  impinger  with  acetone,  place the
washings in this container, and seal.
  4.3  Analysis. Record the data required on
the  example  sheet shown  In  Figure  5-3.
Handle each sample container as follows:
  Container No. 1. Transfer the filter  and any
loose particulate  matter from  the  sample
container to a tared glass weighing dish, des-
sicate, and dry to a constant weight. Report
results to the nearest O.S ing.
   Container No.  2. Transfer  the acetone
washings to a tared beaker and evaporate to
dryness  at  ambient temperature and  pres-
sure. Dessicate and dry to a constant weight.
Report results to the nearest 0.5 mg.
  Container No. 3. Extract organic particulate
from the impinger solution with three 25  ml.
portions of chloroform.  Complete the  en-
traction with  three 25  ml. portions of  ethyl
ether. Combine the ether and chloroform  ex-
tracts, transfer to a tared beaker and evapo-
rate at 70* P. until no solvent remains. Des-
sicate, dry to a constant weight, and report
the results to the nearest 0.5 mg.
  Container No.  4. Weigh the spent  silic
gel and report to the nearest gram.
                                  FEDERAL REGISTER, VOL.  36, NO. 159—TUESDAY, AUGUST 17, 1971



                                                                B-7

-------
                                                 PROPOSED RULE  MAKING
                             PLANT.

                             DATE.

                             JiU'J N0._
CONTAINER
NUMBER
1
2
3a"
3b"»
5
TOTAL
WEIGHT OF PARflCULATE COLLECTED.
ing
FINAL WEIGHT





^>~
-------
                                 PROPOSED RULE MAKING
                                                                                          o
                                                                                          3
                                                                                          <

                                                                                          >-"
                                                                                          <
No 159-
        n
                                          B-9

-------
                                                  PROPOSED  RULE MAKING
  23.1  PlpcMos—Transfer tjpe, 5 ml. and
10 ml. s,\7.cs (0.1  ml. dlvl.-lons) and  25 ml.
fcbo (02 ml. divisions).
  2 3.2  Volumetric flasks—50  ml., 100 ml.,
and 1,000 ml.
  233  Burettes—5 ml and 50 ml.
  234  Erlcnmeycr fln«,h—125ml.
  3. Reagents.
  3.1   Sampling.
  31.1  Water—Deionlzed, distilled.
  3.1.2  Isopropanol, 80 percent---Mix 80 ml.
of isopropanol with 20 ml. of distilled water.
  3.1.3  Hydrogen peroxide, 3  pciccnt—dilute
100 ml. of 30 percent hydrogen peroxide with
900 ml. of distilled water. Prepare fresh daily.
  3.2   Sample recovery.
  3 2.1  Water—Deionlzed, distilled.
  3 2.2  Isopropanol, 80 percent.
  3.3   Analysis.
  3 3.1  Water—Deionlzed, distilled.
  3.3.2  Isopropanol.
  3.33  Thorin indicator—l-(o-arsonophen-
jlazo) -2-naphthol-3, 6-disulfonic acid, diso-
dium  fcftlt  (or  equivalent).  Dissolve  0.20 g.
in 100 ml. distilled water.
  33.4  Barium  perchlorate   (0 OliV)—Dis-
Eolve   1.95  g.   of   barium   perchlorato
I3a(ClO,), SHjOJ  in 200  ml. distilled water
and dilute to 1 liter with isopropanol. Stand-
ardize with sulfuric acid.
  3 3.5  Sulfuric   acid  standard  (O.OINf—
Purchase  or standardize  against a primary
standard to ± 0.00021V.
  4. Procedure.
  4.1   Sampling.
  4.1.1  Preparation of collection train. Pour
16 ml. of  80  percent Isopropanol  Into the
midget bubbler and 15 ml. of 3 percent hydro-
gen peroxide to each of the first two midget
Impingers. Leave  the final midget  Impinger
dry. Assemble the train as shown In Figure
6-1. Leak check  the sampling train at the
sampling site by plugging the probe inlet and
pulling a 10-m. Hg vacuum. A leakage rate
not In excess  of  1 percent of  the sampling
rat* \s acceptable. Carefully release the probe
Inlet  plug  and turn  off the  pump. Place
crushed ice around the impmgers. Add more
ice during the  run to keep the temperature
of the gases leaving  the last Impinger at
70' F. or less.
  4.1.2  Sample collection. Adjust the sam-
ple flow rate proportional to  the stack as
velocity. Take readings at least every 5 min-
utes and  when significant changes In stack
conditions  necessitate  additional  adjust-
ments In flow rate. To begin sampling, posi-
tion the nozzle with the tip pointing directly
Into the gas stream and start  the pump. Sam-
ple proportionally throughout the run. At the
conclusion of each run, turn  off the pump
and record the final  readings. Remove the
probe from the stack and disconnect It from
the train. Drain the Ice bath and purge the
remaining part of the train by drawing clean
ambient air through the  system for 15 min-
utes.
  4.2   Sample  recovery. Disconnect the Im-
pingers after  the purging  period. Discard
the contents  of  the midget bubbler. Pour
the contents of  the midget Impingers into
a polyethylene shipment bottle. Rinse the
three midget impingers and the connecting
tubes with  dKtlllcd  water and add these
un-',hin£s to the same ''oragc  container.
  43  S.imple  analysis.  Trnii'-fcr the  con-
tents of the storage  container to  a 50-ml.
volumetric flask. Dilute to the  mark  with
delonixed, distilled water.  Pipette  a 10 ml.
aliquot  of this solution  to a  125-ml. crlen-
mycr flask. Add 40 ml. of Isopropanol and 2
to 4 drops of  thorln  indicator. Titrate  to a
pink endpolnt using  0 01JV barium perchlo-
rate.  Run  a  blank  with  each series  of
fcamples.
  5. Calibration.
  5.1  Use standard methods and equipment
approved by the Administrator to  calibrate
the orifice meter, pitot tube, dry gas meter,
and probe  heater.
  5 2 Standardize the sulfuric acid with po-
tassium acid phthalate as  a primary stand-
 ard.  Standardise  the  barium  perchlorate
with 26 ml. of standard sulfuric acid  con-
taining  100 ml. of ibopropanol.
  6. Calculations.
  6.1  Dry gas volume.  Correct  the  sample
volume  measured  by the dry  gas  rneter to
standard conditions  (70*  P.  and  29 92  in.
Hg) by using Equation 6-1.
        v  (Tiii
        • DO I  rn
      /   7   °R  \V,Pb.,
      V.     in. Hg/   TV   equation  6-1

where:
  Vm.,a=Volmne of gas sample through the
           dry gas meter (standard condi-
           tions) , cu. ft.
     V» = Volume of gas sample throvgh the
           dry gas meter (meter conditions),
           cu. ft.
   Ttld=Absolute temperature at standard
           conditions, 530* B.
     T»=A\erage dry gas meter temperature,
           •B.
    Pblt=Barometric  pressure at the orifice
           meter, in. Hg.
       4 = Abso)ute pressure at standard con-
           ditions, 29.92 In. Hg.
  6.2  Sulfur dioxide concentration.
 /           Ib 1 \
 ( 7.03X10-'^)
 \           g.-DlI./
                              equation 6-2
       V.cin = Total solution vohi^nc of sulfur
             dioxide, ml.
         V«=:Volume  of   pajnple   aliquot
             titrated, ml.
      Vmtta~Volume of gas sample through
             the dry gas meter  (standard
             conditions), see Equation 6-1,
             cu. f».

  7.  Relaenca.
  Atmospheric Emissions from Sulfuric Acid
Manufacturing Processes. U.S. DIIEW, PHS,
Division of Air Pollution. Public Health Serv-
ice  Publication No.  999-AP-13.  Cincinnati,
Ohio. 1965.
  Corbett,  P. P.  The Determination  of  SO,
and  SO, In Flue Gases. Journ.il of the In-
stitute Of Fuel. 24.237-243. 1961.
  Matty, B.  E. and  E.  K. Dlehl.  Measuring
Flue-Gas SO, and  SO,. Power  iW:94-97.
November 1957.
  Patton, W. F. and J.  A. Brink. Jr. New
Equipment  and Techniques  for Sampling
Chemical Process Gases. Paper presented at
the 55th Annual Meeting of APCA. Chicago,
HI. May 20-24, 1962.
 where:
        Cso2 = Concentration  of  sulfur  di-
             oxide at  standard conditions,
             dry basis, Ib./cu. ft.
  7. 05 X10-t = Conversion   factor  Including
             the number of grams per gram
             equivalent  of sulfur  dioxide
             (32 g./g.-eq.) , 453.6 g./lb.,  and
             1,000 ml./l, Ib.-l./g.-ml.
         V,= Volume of barium perchlorate
             tltrant used for the sample, ml.
        V,,= Volume of barium perchlorate
             tltrant used for the blank, ml.
          K= Normality of barium  perchlo-
             rat« titrant, g.-eq./l.
                                  FEDERAL  REGISTER. VOL. 36, NO.  159—TUESDAY, AUGUST 17, 1971



                                                               B-10

-------
                               APPENDIX C
    VISIBLE EMISSIONS REPORTED FROM EPA TESTS AND QUESTIONNAIRE DATA
     Visible emissions were read by the EPA project engineer on a random
basis during EPA tests.  Figure C-l shows the points of discharge where the
emissions were read.  Table C-l reports the emissions in percent opacity
corresponding to the emission points numbered in Figure C-l.  Point 2 in the
figure is used to indicate the furnace is without a control  device whereas
Point 4 shows that the furnace is equipped with a control  device.  Covered
furnaces H and J have mix seals.  Above the mix seals are  located a hood and
uncontrolled exhaust systems to remove the escaping dust-laden gases from
the mix seals.  This is shown as Point 6 in Figure C-l.  The opacity of these
emissions ranges from 10 to 100 percent.  Covered furnaces K and L are
equipped with fixed seals and do not have hooding and uncontrolled exhaust
systems.  In these two cases no emissions from the building were notice-
able
   In most instances, there were no, or very insignificant,  noticeable
visible emissions from the control equipment.  Most noticeable emissions
were from uncontrolled furances A and B, the uncontrolled exhaust systems
serving the tapping stations, and the uncontrolled exhaust system serving
to remove the fugitive fumes from the covered furances with mix seals (H
and J).
     Table C-2 is a summary of visible emissions reported by the ques-
tionnaires submitted by the industry. The reported opacity of the
                                 C-l

-------
fugitive fumes escaping from the mix seals ranged from 0 to 60 percent.
The reported opacity of uncontrolled emissions from open furnaces
ranged from 10 to 100 percent.
     Whenever possible, emissions were read using the visible emission
recording sheet shown in Figure C-2.  The second page of Figure C-2 is
in reality printed on the reverse side of the visible emission record,
and the necessary data relative to the opacity are filled in at the time
of the readings.
                                  C-2

-------
                               Table C-).  OPACITY OF EMISSIONS REPORTED FROM  EPA TESTS
                                                         (I)




urnace
A

B



C











D


E


F


6


H


J


K




L





Test
run
1
2
1


2
1
2
3
4
5
7
8
9
10
11
12

1
2
3
1
2
3
1
2
J
1
2
3
I
2
3
1
2
3
1
2
3
4
5
1
I
1


\ Type

ro uct
FeCrS!

Cr ore/
lime
Belt

SIMn











FeCrS!


rIC FeCr


Silicon


S1Hn


aOi FeSt


CaC2


FeHn




SIMn


of
urnace
0

0



0











0


0


0


0


C


C


C




C


Uncontrolled fumes
Outlet of| Outlet of
furnace tapping
exhaust exhaust
system | system
r1
b
Outlet of
fugitive
fume exhaust
system
po nt
Controlled fumes
i
; Tercent
opaci tv of
' Degree uncap tured
Type of fumes fumes at
control captured roof moni tor-
1
None
50 to 100 b
SO to 100 b ! 100C None


i
50 to lOoi b ' 100C













































Venturl(57"PO)' 99 0
\ Venturi (57"PO)
















100
100
100
10 to 80
10 to 60
10 to 80






100"
100"
100"
100d
,00"
100"
too"
100"
Venturi (57"PO)>
Venturi(57"PD)j
Venturt(5;"PD)|
0
0
0
0
Venturi (47"PD) 99 0
Ventun(47"PD)'
Ventun(4r'PD)

0
0
»enturt(37"PD)' 99 0
\ Venturi(37"PD)
Venturl(37"PO)
i
0
0

Baghouse 99 0
J 8aghouse

Baghouse
0
0
Preclpltator ' 99








10 to 100
10 to 100
10 to 100
10 to 100
10 to 100
10 to 100








PrecipUator
Preclpltator
Baghouse 95
Baghouse
Baghouse


to 99 10 to 20
10 to 20
10 to 20
Venturi 99 0
99 0
99 0
Ventun 85 ! See point 6
Venturi
Venturi
Scrubber
Scrubber
Scrubber
Venturi 10
Venturi
Venturi
venturf
Ventur!
Venturi 1C
Venturi
Venturi
i
i See point 6
; See point 6
!
!
1
0 0
0
0
0
0
K) 0
Q
0

"PercenT "
opacity of
control
equipment
outlet-







0
0
0
0
0
0
0
0
< 10
< 10
< 10

0
0
0
< 5
5 to 20
5 to 20
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
*Q • open,  C a  closed.
 Tapping fumes  vented to main uncontrolled exhaust system.
cUncaptured fumes escaping through roof monitor.
Tlo exhaust system at tapping point.
                                                        C-3

-------
                   table C-2   OPACITY 01 EMISSIONS HEPORfi.ll I R0» yiJf.1 IOMKAIW  WUA
"

Questionnaire
	
82
85
46
44
45
64
65
66
70
71

73
83
6
IS
103
79
84
68
72
91
60
55
54
59

8
91
47
52
5
7
10
11
13
14
44
74
76

100
90
67
69
75
77

53
56
57
61
62
98
3
114

as


Product
	





«C FeHn









6S-75S FeS<


jjn fsi1










St Fin










FeCrSi

FeCr




c.c2





LC i MC feFIn
CfOrt/HM
melt
SIHnZ
I
Outlet of
furnace

80 to 100
80 to 100
20 to 80
20 to 80
20 to BO








20 to 60
20 to 60











10
80 to 100
20 to 80

20 to 60
20 to 60
20 to 60
20 to 60
20 to 60
20 to 60




80 to 100












5 to 50
60 to 80

60 to 60
ncontrollcd fume
Outlet of
tapptmj
No data report-
ed

























































"ruiiVtlvc
fuOKS






0 to 20
20 to 40
35
10 to 50
5 to 30

5 to 25
0 to 10


40 to 60
20 to 40
20 to 40
S to 10
15 to 30
25
10 to 20
10 to 20
10 to 20
10 to 20




20 to 40






20 to 40
20 to 60




20 to 30
20 to 40
20 to 30


20 to 40
10 to 35
20 to 40
20 to 40
10 to 35
10




ton troll

Type of






BF^sc rubber
Br scrubber
BF scrubber
BF scrubber
BF scrubber

BF scrubber
BF scrubber


BF scrubber
BF scrubber
BF scrubber
BF scrubber
BF scrubber
BF scrubber
BF scrubber
BF scrubber
BF scrubber
Venturl
scrubber



BF scrubber






BF scrubber
BF scrubber
Venturf
scrubber

Ventun
8F scrubber
BF scrubber
BF scrubber
Venturl
scrubber
BF scrubber
BF scrubber
BF scrubber
BF scrubber
BF scrubber
BF Scrubber




ed funcs
Control
equipment







































0


0 to 20



0











'>F scruMxr • Guffllo Forgi icrubb.r.
                                     C-4

-------
ONTROL
EQUIP.
                                               ROOF MONITOR
                                                                                     TAPPING
                                                                                       HOOD
SCRUBBER
  ,wV\V\//#t\\V'ff\\\vwmvv//U\\Wf\WW/\W«W


                         OPEN FURNACE                             COVERED FURNACE
           Figure C-1.  Emission points where visible emissions were read during EPA tests on open
           and covered furnaces.
                                                 C-5

-------
                               ENVIRONMENTAL PROTECTION AGENCY
 COMPANY NAME	

 EQUIPMENT LOCATION ( ADDRESS)_

 TIME OF OBSERVATION: FROM	
                                                  RECORD OF
                                                  VISIBLE EMISSIONS
 A.M.
.P.M. TO.
 A.M.
.P.M.   DATE .
s«"Vhour
R. No.
6
4*
4M
4K
4
3*
3V,
3M
3
2*
2V,
2K
2
w
m
IK
1
*
v>
%
0
1
% Min. 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20
100
9$
90 I
65
80
75
70
65
60
55
50
45
4o
35
30 ] 	
25
20
15
10
5
0 - - - --

SlarVhour
R. No.
6
4%
4Vi
4!4
4
3H
3K
3)4
3
2%
2Vi
2V>
2
1H
1V4
1%
1
K
fc
'/.
0
% Min. 21 22 23 24 25 26 27 28 29 3
TOO
95
90
85
80
75
70
65
60
55
50
45
40
35
30
r 25
20
15
16
£
0
start/hoor
R. .No.
5
4%
4V4
4M
4
3X
3tt
3«
3
2N
2H
2%
2
IX
154
1H
1
X
Vt
%
0
% Mm. 41 42 43 44 45 46 47 48 49 £
iop
95
90
65
,8S 	
75
iJo
68
60
55
~5fl
45
46
sT
."30 r
"25
" K 1
15
TtT"
5
0























0 31 32 33 34 35 36 37 38 39 40
T" 1" "*"




















i
rO 51 52 53 54 55 56 57 58 59 60





















NOTE:  Each small square represents an individual reading of intensity corresponding to that shown in the left-hand column
over a time span of % minute.  Insort an "S" in the top row of blank squares to indicate the exact minute of the start of
observation. In the next square after the "S", insert the hour in which the measurement was made.  Each page of this form
can thus be used to record 1  hour of measurements.
      Figure  C-2.    Visible emissions  recording sheet.
                                              C-6

-------
 ource of Air Contaminants.
 ype of Air Contaminants	
 oint of Discharge:   Stack |	|       Other .
 oint of Observation:
   Distance to Base of Point of Discharge, feet
  Height of Point of Discharge Above Ground Level, feet
 ackground Description	
 eather:   Clear j	|     Overcast!	|     Partly Cloudy I	I      Other
          Wind Direction	;   Wind Velocity, mi/hr _
 lume Description:
  Detached:   Yes I   I   No LJ
  Color:  Black I   I     White LJ      Other
  Plume Dispersion Behavior:   Looping |	|        Coning |	|         Fanning |	|
                             Lofting |	|        Fumigating |	|      See Comments I
  Estimated Distance (feet) Plume Visible (Maximum)	(Minimum)	
lomments
iigned	  Title
   Figure  C-2.  (continued)   Visible emissions recording sheet.
                                                C-7

-------
                                 APPENDIX D
                           PARTICLE SIZE ANALYSIS
     Determination of the size distribution of particles suspended in
gases from a submerged-arc furnace is important and is helpful  in
designing an optimum dust-removal system.  Unless capture and recovery
is excellent, significant quantities of small  particles can be emitted
to the atmosphere since nearly all of the particles are less than  1
micron.  Very little published information exists on the size dis-
tribution of particulate matter from ferroalloy furnaces.   Person  states
                                             20
that most particles are less than 0.5 micron.     This was verified In en
EPA-contracted study made by TRW, Inc.  This study's data, presented in
this appendix, were obtained during the same time tests were made  to
determine mass emission rates.
     Samples of particulates in the gas streams from five electric
furnaces and at the outlets of four air pollution control  devices  were
collected by a cascade Impactor to determine particle sr s d^tr^1 ••
The first nine samples were collected using the Andersen sampler.   Because
the particles were smaller than expected, the  majority of the particles
passed through the sampler and were deposited  on the filter.  The
Andersen sampler was therefore discarded in favor of the Brink sampler,
which was used in gathering the remaining samples.
                                  D-l

-------
     The basic design of the cascade impactor  sampler  has  been described
in detail in literature.  The cascade impactor is  constructed of a
succession of jets, and each jet is smaller than the preceeding one.  The
sampler is small enough that it can be inserted through a  small port  in the
stack and positioned in the gas stream so that the sample  is collected in
conditions as close as possible to isokinetic.
     The gas streams take a turning path through the impactor.  When  the
velocity of an entrained particle is high enough to overcome aerodynamic
drag and escape from the laminar streamline, the particle  impacts on  a
collection area of the plate.  If the particle is  too  small and its inertia
too low for removal from the stream, it proceeds with  the  gas through an
orfice in the next plate, and its velocity and inertial effects are
increased.  Fractionation is not based on physical diameter only, but
also on "aerodynamic diameter," which takes into account density and
shape.  Aerodynamic diameter, in fact, is probably more related to
atmosphere behavior and the operation of particulate collection devices
than its physical diameter.
     The Andersen impactor has a stainless steel sampling  head containing
nine circular plates, each with several hundred jet-orifices.  The size
of the orifices becomes progressively smaller  in each  succeeding down-
stream plate, so that the velocity of the gas  streams  that pass through
the orifices increases correspondingly.  The top part  of the  photograph
of the Andersen sampler in Figure D-l shows the relative size of the
assembled sampler.  The lower part of the photograph  shows the  sampler
when disassembled.
                                   D-2

-------

         Ij* J^i.,
                     rfc
                     .*4~* <
                                                                    , ,J_,
Figure D-1.  Andersen sampler showing assembled and disassembled sections.
                                  D-3

-------
     The second sampler, the Brink cascade impactor,  has a  single jet
orifice for each stage.   Each orifice uses a  collection cup as  an impac-
tion surface rather than the solid areas  of the next  plate.   Velocities
are higher through the single orifices of the Brink than through the
multiple orifices of the Andersen, so the cups normally have adhesive
coatings.  The manufacturer indicates that the Brink  impactor collects and
classifies particles down to 0.25 micron, with more cuts in the fine-
particle range than the Andersen sampler.  Because it was  found that most
of the particles from air pollution control devices were below  0.7  micron,
the Brink impactor was selected to obtain most of the samples.  The charac-
teristic diameter of an aerosol particle  for  each impactor stage  (i.e.,
Dpc) has been calculated for pressure drops across the impactor of  5 and 10
inches of mercury (based on a spherical particle of density one).   The
impactor has five in-line stages as shown in  Figure D-2.   The top part
of the figure shows the relative size of the  impactor; the lower  part
shows an enlarged view of the five jet stages.  When  the pressure drop
across the impactor is at 5 inches of mercury, the particles collected are
in the size range of 3.4, 2.0, 1.36, 0.69, and 0.42 microns. When  the
pressure drop across the impactor is at 10 inches of  mercury, the sizes
of the particles collected are 3.06, 1.80, 1.23, 0.63, and 0.38 microns.
     During the tests, the cascade impactor was mounted on a probe  and
connected to vacuum pumps by rubber tubing.  Metering valves were installed
on the inlet side of the pump to adjust the air flow  through the  samplers.
Magnehelic gauges were inserted in the system to measure pressure drops
across the sampler.  Figure D-3 illustrates a typical particle  sizing
train.  Volumetric flow rates through the sampler were measured for long
                                   D-4

-------
Figure D-2.   Brink  sampler  showing  assembled and disassembled sections.




                              D-5

-------
                            MAGNEHELIC
                              GAUGE
STACK
                          Figure D-3.  Particle sizing train.
                                    D-6

-------
durations using the dry gas meter and for short  durations  using  the
pressure drop across the sampler.
     The particle size tests made while  measuring  mass  emission  rates  from
furnaces A, C, D, E and G in the field testing program  indicate  that the
particle size is largely submicron and that particle  size  distribution
varies for different products.   The mass median  diameter  (MMD) in microns
is less for ferroalloys that contain silicon as  a  major component  (for
example, ferrochrome-silicon and silicomanganese)  than  it  is  for HC
ferrochrome, which has a relatively low  silicon  content.
     Size distributions are defined by two parameters:   (1)   the intercept
of the curve with the 50 percent probability (mass mean particle diameter),
and (2) the polydispersity factor or geometric standard deviation, defined
as:                0    = diameter of particle at  50% probability
                          diameter of particle at  15.87% probability
     Figures D-4 through D-14 show graphical presentations of particle size
test data, that is, log-probability plots of cumulative percent  less than
stated micron size versus the Dpc for each fraction collected by a cascade
impactor.  The intercept of these curves at 50 percent  probability indicates
that, on a weight basis, one-half of the particles are  below  the micron
size shown at this intercept and one-half are above.
     Table D-l shows the particle size versus the  collection  efficiency of
EPA-tested control equipment.  It is interesting to note that the efficiency
of scrubber G (Aeronetics scrubber system serving  a silicomanganese furnace)
becomes markedly less when the particle  size is  under 0.6  microns.  It is
also interesting to note that if an efficiency curve  vs. particle  size were
to be drawn for the baghouse indicated in the table,  there would be a
                                   D-7

-------
slight dip in the curve at the particle size range  between  0.3  to  1.0  microns.
This drop in efficiency appears to be typical  according to  the  article
"Design and Performance of Modern Gas Cleaning Equipment" Journal  of the
Institute of Fuel, February 1956.
     Tables D-2 through D-ll  show the particulate emission  losses  in pounds
per hour for various sources  according to particle  size ranges.  These losses
were calculated from the mass emission rates of particulates  based on  EPA
tests and from Figures D-4 through D-14 of this appendix.
                                   D-8

-------
           Table D-l.   PARTICLE SIZE VS.  COLLECTION EFFICIENCY
                       OF ERA-TESTED CONTROL EQUIPMENT

                                   (percent)
Particle
size range,
microns
0 to 0.3
0.3 to 0.6
0.6 to 1.0
1.0 to 1.5
+1.5
Overall
Control equipment
Scrubber3
Cl
98.5
99.3
99.7
99.8
99.9
99.5
C2
93.4
96.5
97.7
98.2
98.2
97.4
C3
90. Ob
92.8
94.1
98.7
98.9
96.1
Baghouse
D
99.4
98.1
97.8
97.7
99.6
98.7
Preci pita tor
E
98.4
98.8
99.1
99.2
99.0
99.0
Scrubber
G
NIL
64
91
98
99
96
 Scrubber  C tested at theee pressure  drops:   C,  at 57",  C9  at 47",  and  C,
 *+ IT"  u  n                                              to
 at 37"  H20.

'Assumed.   Actual  calculations  above  93%.
                                D-9

-------
Table D-2.  PARTICULATE EMISSIONS BY PARTICLE SIZE
            FROM UNCONTROLLED FeCrSi FURNACE
                        (Ib/hr)
Particle size
range, microns
0 to 0.3
0.3 to 0.6
0.6 to 1.0
1.0 to 1.5
+1.5

Total, Ib/hr
Sample no.
Al
16
44
49
28
26

163
A2
59
122
119
67
A3
76
126
105
59
53 . 54

420

420
                    D-10

-------
             Table D-3.   PARTICULATE EMISSIONS  BY  PARTICLE  SIZE
                         FROM THE SCRUBBER  INLET OF  A  SiMn  FURNACE
                                        (Ib/hr)
Particle
size, microns
0 to 0.3
0.3 to 0.6
0.6 to 1.0
1.0 to 1.5
+1.5
Total, Ib/hr
Sample no.a
C-l
223
427
464
316
427
1857
C-2
484
502
372
202
297
1857
C-3
55
83
in
120
1477
1846
C-4
b




1611
C-5
290
218
181
133
387
1209
C-7
545
61
48
36
519
1209
Average
319
258
235
161
621
1594
aSample numbers C-l  and C-2 obtained  at  port 1,  C-3  at  port  2,  C-4  at  port  3,
 C-5 at port 4, and  C-7 at port 5 (not simultaneously).
1234
~
                                                  ,., Sample Ports

                                                 __ Sampl e Points
             Cross section of inlet duct  showing  sampling  ports.
5Data points are at the extremities of the graphs,  either  less  than  15%  or
 greater than 85% of stated size.   Reliable particle  sizes could  therefore
 not be determined from these data.
                                  D-ll

-------
Table D-4.  PARTICULATE EMISSIONS BY PARTICLE  SIZE  FROM
            SCRUBBER OUTLET OF A SiMn FURNACE
                        (Ib/hr)
Particle
size,
microns
0 to 0.1
0.1 to 0.2
0.2 to 0.3
0.3 to 0.4
0.4 to 0.5
0.5 to 0.6
0.6 to 0.7
0.7 to 0.8
0.8 to 0.9
0.9 to 1.0
1.0 to 1.2
1.2 to 1.5
+1.5
Total, Ib/hr
Sample number and scrubber pressure drop,
inches water
C-8
57"
1.65
1.32
0.99
0.66
0.58
0.41
0.33
0.25
0.25
0.16
0.25
0.33
1.08
8.26
C-9
57"
1.59
2.35
1.68
1.01
0.59
0.42
0.25
0.17
0.08
0.04
0.03
0.02
0.16
8.39
C-12
37"
<0.30
0.40
2.12
3.54
4.24
4.24
3.54
3.18
2.48
2.12
3.18
2.80
3.28
35.4
C-13
47"
2.00
2.00
1.42
1.06
0.83
0.59
0.47
0.47
0.35
0.24
0.47
0.47
1.43
11.8
C-14
47"
10.6
15.2
10.6
7.1
5.0
3.5
3.5
2.1
2.1
1.5
2.1
2.8
4.5
70.6
C-15
37"
1.5
5.7
9.2
8.5
7.1
5.7
5.0
3.5
3.5
3.5
3.5
4.9
9.0
70.6
C-16
3/"
5.6
8.5
10.6
7.1
7.1
5.0
4.2
3.5
3.0
2.1
3.5
3.5
6.9
70.6
C-17
37"
1.5
5.0
7.8
7.1
7.1
7.1
5.0
4.2
3.5
3.5
5.0
4.9
8.9
70.6
                       D-12

-------
       Table D-5.   PARTICULATE EMISSIONS BY PARTICLE SIZE FROM
                   UNCONTROLLED TAPPING OF A SiMn FURNACE
                               (Ib/tap)
Particle size
range, microns
0 to 0.3
0.3 to 0.6
0.6 to 1.0
1.0 to 1.5
1.5 to 2.0
2.0 to 3.0
3.0 to 6.0
6.0 to 10.0
+10
Total Ib/tap
Sample no.
C-18
4.2
6.4
6.9
6.4
4.8
6.4
9.0
3.7
5.2
53. Oa
C-19
11.7
9.5
8.0
5.8
3.7
4.8
5.3
2.1
2.1
53. Oa
C-20
4.2
4.8
5.3
4.8
4.2
5.8
9.0
5.8
9.1
53. Oa
C-21
12.2
9.5
7.4
6.4
3.2
5.3
4.8
2.1
2.1
53. Oa
Average tapping loss per tap based on 3 test runs.
                              D-13

-------
           Table  D-6.   PARTICIPATE  EMISSIONS  BY  PARTICLE  SIZE  FROM
                       A  FeCrSi  FURNACE AT  INLET TO  BAGHOUSE

                                   (Ib/hr)
Particle size
range,
microns
0 to 0.3
0.3 to 0.6
0.6 to 1.0
1.0 to 1.5
+ 1.5
Total, Ib/hr
Sample no.
D-l !
161
125
101
71
136
594
D-2a |
1
36 '
48
54
48
408
594
D-3a[
- j
101 j
101
95
65
232
594
D-4b
131
119
89
77
178
594
T n-5^
j u °
i 327
113
71
36
47
594
r i
D-6C
178
125
95
59
137
594
D-7C
296
77
54
30
137
594
D-8d
107
77
71
65
274
594
D-9d
184
83
65
48
214
594
 Samples  0-2 and  D-3 collected  simultaneously between furnace taps.
'Samples  D-4 and  D-5 collected  simultaneously during furnace tap.
"Samples  D-6 and  D-7 collected  simultaneously during furnace tap.
 Samples  D-8 and  D-9 collected  simultaneously between furnace taps.
                                    D-14

-------
       Table D-7.   PARTICULATE  EMISSIONS  BY  PARTCLE  SIZE  FROM
                   BAGHOUSE  EXHAUST  ON  FeCrSi  FURNACE

                               (Ib/hr)
Particle size
range,
mi crons
0 to 0.1
0.1 to 0.3
0.3 to 0.6
0.6 to 1.0
1.0 to 1.5
1.5 to 2.0
2.0 to 3.0
3.0 to 6.0
6.0 to 10.0
+10
Total, Ib/hr

D-10
~-
< 0.55
1.43
1.87
1.65
1.32
0.66
1.76
0.66
1.10
n.o ;

D-ll
--
<0.66
1.65
2.10
1.76
1.54
1.32
1.43
0.44
0.10
11.0

D-13
0.56
1.78
2.35
1.41
1.03
0.66
0.85
0.75
0.38
0.19
9.96

D-14
0.28
1.31
1.88
1.69
1.22
0.85
0.94
0.85
0.28
0.01
9.31

D-15
1.88
1.88
1.41
0.94
0.66
0.47
0.56
0.75
0.28
0.57
9.40 ,

D-163
- •
<0.70
2.08
2.43
1.56
0.87
0.70
0.26
--
—
8.7b ,
*

D-173
0.26
1.30
1.83
1.56
1.21
0.78
0.70
0.78
0.17
0.11
8.7a
 D-16 and D-17 samples  obtained simultaneously.
^Average of three test  runs.
                                 D-15

-------
Table D-8.  PARTICULATE EMISSIONS BY PARTICLE SIZE
            FROM  HC  FeCr FURNACE AT PRECIPITATOR
            INLET
                     (Ib/hr)

Particle
size,
mi crons
0 to 0.3
0.3 to 0.6
0.6 to 1.0
1.0 to 1.5
+ 1.5

E-l
159
125
114
102
638
Sample no.
! E-2 !
83
i 97
180
194
830

E-3
138
207
221
193
625
i
i
i Average
; 126
143
172
163
698
Total, Ib/hr    1138    1384    1384    1302
                       D-16

-------
   Table D-9.  PARTICULATE EMISSIONS BY PARTICLE SIZE FROM
                HC  FeCr FURNACE AT PRECIPITATORS OUTLET
                           (Ib/hr)
Particle size,
microns
0 to 0.1
0.1 to 0.2
0.2 to 0.3
0.3 to 0.4
0.4 to 0.5
0.5 to 0.6
0.6 to 0.7
0.7 to 0.8
0.8 to 0.9
0.9 to 1.0
1.0 to 1.2
1.2 to 1.5
+ 1.5
Sample no.
E-4
- •
0.38
0.62
0.88
0.75
0.75
0.62
0.62
0.62 '
0.38
0.38
0.88
0.88
4.74
E-5
1.25
0.75
0.50
0.38
0.38
0.38
0.25
0.25
0.13 ;
0.25 i
0.25
0.50
7.23
E-6
0.43
0.57
0.71
0.57
0.57
0.43
0.43
0.43
0.43 ;
0.28
0.57
0.85
7.93
E-7
0.57
0.71
0.71
0.57
0.57
o
0.57
0.57
0.28 ,
0.43
0.28
0.57
0.43
7.94
E-8
0.57
0.85
0.71
0.71
0.71
0.57
0.57
0.43
0.43
0.43
0.57
0.85
6.80
Total, Ib/hr
12.50    12.50    14.20    14.20    14.20
                             0-17

-------
Table D-10.  PARTICLE EMISSIONS BY PARTICLE SIZE FROM SiMn FURNACE
                   AT AERONETICS SCRUBBING INLET

                              (Ib/hr)
Particle
size,
microns
0 to 0.3
0.3 to 0.6
0.6 to 1.0
1.0 to 1.5
+1.5
Total, Ib/hr
Sample no.
6-1
2
10
20
27
136
195
6-2
1
3
9
11
164
188
Average
2
7
15
19
150
193
                                D-18

-------
Table D-ll.   PARTICULATE EMISSIONS BY PARTICLE SIZE FROM SiMn FURNACE
                    AT AERONETICS SCRUBBER OUTLET

                               (Ib/hr)
Particle
size,
microns
0 to 0.1
0.1 to 0.2
0.2 to 0.3
0.3 to 0.4
0.4 to 0.5
0.5 to 0.6
0.6 to 0.7
0.7 to 0.8
0.8 to 0.9
0.9 to 1.0
1.0 to 1.2
1.2 to 1.5
+1.5
Total, Ib/hr
Sample no.
6-3
0.18
0.53
0.76
0.76
0.70
0.53
0.41
0.35
0.29
0.18
0.35
0.29
0.50
5.83
6-4
0.03
0.09
0.58
1.05
1.23
0.93
0.76
0.41
0.29
0.18
0.18
0.09
0.01
5.83
6-5
3.59
3.09
1.73
1.11
0.74
0.49
0.37
0.25
0.25
0.12
0.25
0.12
0.27
12.38
                                 D-19

-------
!
s
s
     3.0
     2.0
1.0
0.9
0.8
0.7
0.6

0.5
     0.3
     0.2
            10
                 20
                      30     40    50     60     70

                       CUMULATIVE PERCENT < STATED MICRON SIZE

Figure D-4.  Particle size distribution of uncontrolled fumes from a FeCrSi furnace.
98
                                               D-20

-------
i
o
    50.0

    40.0


    30.0



    20.0
    10.0
     9.0
     8.0
     7.0
     6.0

     5.0

     4.0
.«   3.0
     2.0
     1.0
     0.9
     0.8
     0.7
     0.6
     0.5

     0.4


     0.3
     0.2
     0.1
        0
       0.82
       0.56
       5.40
     »3.40
       0.79
       2.35
       0.60
80
90
95
                           10         20      30      40    50     60     70

                               CUMULATIVE PERCENT < STATED PARTICLE SIZE

Figure D-5.  Particle size distribution of SiMn fumes entering  a scrubber serving an open furnace
                                               D-21

-------
£
 i
 O-
     4.0

     3.0




     2.0
1.0
0.9
0.8
0.7
0.6

0.5

0.4


0.3



0.2
      0.1
                                                                                         0.33
                                                                                         0.21
                                                                                         0.68
                                                                                         0.34
                                                                                         0.31
                                                                                         0.57
                                                                                         0.44
                                                                                         0.60
       10
              20       30     40     50     60     70       80

                          CUMULATIVE PERCENT < STATED MICRON SIZE
90
100
Figure D-6.  Particle size  distribution of SiMn fumes from a scrubber serving an  open furnace.
                                               D-22

-------
 M.
Q.
cc
LU
ce
2
     0.1
                  20
30     40     50     60    70      80          90


     CUMULATIVE PERCENT< STATED SIZE
100
    Figure D-7.  Particle size distribution of uncontrolled tapping fumes from SiMn furnace.
                                              D-23

-------
2
                                                                                   0.62
                                                                                   3.20
                                                                                   1.01
                                                                                   0.79
                                                                                   0.26
                                                                                   0.30
                                                                                   0.59
                                                                                   1.30
                                                                                   0.73
               10
20     30     40     50    60     70      80

     CUMULATIVE PERCENT< STATED MICRON SIZE
                                                                            90
100
           Figure D-8.  Particle size distribution of FeCrSi fumes entering a baghouse.
                                            D-24

-------
 g
 &
'i
DC
UJ
O
     7.0
     6.0

     5.0

     4.0

     3.0
     2.0
1.0
0.9
0.8
0.7
0.6

0.5

0.4

0.3
     0.2
SAMPLE NO.
D-10
D-11
D-13
D-14
D-15
D-16
D-17
MMD, microns
1.50
1.26
0.74
0.86
0.48
0.83
0.80
                10         20      30     40    50    60     70     80

                              CUMULATIVE PERCENK STATED MICRON SIZE
                                                                        90
100
Figure D-9.  Particle size distribution of FeCrSi fumes from a baghouse serving  an open furnace.
                                             D-25

-------
     7.0
     6.0

     5.0

     4.0

     3.0



     2.0
o
LU
a:

-------
 I
'I
o
LU
O
I
Q.
     8.0
     7.0
     6.0

     5.0

     4.0

     3.0


     2.0
1.0
0.9
0.8
0.7
0.6

0.5

0.4


0.3



0.2
     0.1
                10         20      30     40    50     60     70      80

                              CUMULATIVE PERCENK STATED MICRON SIZE
                                                                        90
95
100
Figure D-11.  Particle size distribution of  (HC)FeCr fumes from a precipitator serving an open
furnace.
                                                D-27

-------
Q
LU
_l
O

cc
    9.0
    8.0

     '1.0

     6.0

     5.0


     4.0


     3.0




     2.0
     1.0
     0.9
     0.8

     0.7

     0.6

     0.5


     0.4
5
                 10
                                        SAMPLE NO.
                                           G-l
                                           G-2
MMD, microns
    2.4
    5.1
20       30      40     50      60      70       80


      CUMULATIVE  PERCENT< STATED MICRON SIZE
     90
95
Figure D-12.   Particle  size distribution of SiMn fumes entering a scrubber serving an open furnace.
                                                D-28

-------
 v>
 s
     3.0
     2.0
1.0
0.9
0.8
0.7
0.6
0.5

0.4
u
P   0.3
cc
cu
     0.2
     0.1
                10         20       30     40    50    60     70      80        90

                               CUMULATIVE PERCENT< STATED MICRON SIZE
                                                                                         100
Figure D-13.  Particle size distribution of SiMn fumes from a scrubber serving an open furnace.
                                            D-29

-------
          E-I.  CHEMICAL ANALYSES OF PARTICIPATE EMISSIONS


                                  FROM


                    FERROALLOY SMELTING OPERATIONS




1.  INTRODUCTION
                                                                    
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-------
                                                                 FURNACES A & B
                 £-11.   CHEMICAL ANALYSIS  OF EMISSIONS
                                 FROM
                   A FERROCHROMESILICON FURNACE  (A)
                AND A CHROME ORE/LIME MELT  FURNACE  (B)
1.   INTRODUCTION
     Participate fumes  and gaseous emissions are generated during the
smelting and pouring of a commercially important class of ferroalloy
materials called reactive metals.  The particulate portion of these
emissions has been collected on glass fiber filters, strategically
placed in the air stream of an exhaust system.  Fourteen such filters
from Furnaces A and B were analyzed by microscope, X-ray diffraction,
atomic absorption, electron beam X-ray microanalysis, and optical
emission spectroscopy.
     The analytical results are presented in the following sections where
it is shown that the particulate specimens from the two furnaces are
distinctly different from the standpoints of chemical composition and
crystallographic structure.  The samples from Furnace A consist princi-
pally of non-crystalline fused silica (Si02) with impurities.  Impurities
present in concentrations;-! weight percent are Mg, Cr, and Zn in decreas-
ing order.  In contrast, the samples from Furnace B contain crystalline
material with the inverse spinel structure such as typified by Fe304.
Instead of consisting mostly of Si02 as seen for the Furnace A specimens,
the specimens from Furnace B consist of chromium, silicon, magnesium,
iron, and zinc all in the 4 to 18 weight percent range along with chemical-
ly combined oxygen.  This is,  the specimens from Furnace B consist of
metal oxides.
                                     E-3

-------
                                                                FURNACES A & B
2.   TEST RESULTS

2.1  Optical Examination
     The specimens were examined at magnifications up to 100X.  Figure E-l
shows Specimen 25W-1 and shows the manner in which all specimens were
divided for individual analysis.  The specimens from Furnace  B  were yellow-
brown and distinctly different from the gray-colored Furnace  A   specimens.
2.2  X-Ray Diffraction Analysis
     X-ray diffraction occurs when a crystalline substance is exposed to a
beam of X-rays.  The angle between the diffracted beam and the incident
beam is always 20, or twice the angle of incidence.  By using monochromatic
X-rays of wavelength X,  the interplanar spacing d  of various planes in
a crystal  can be found by using Bragg's Law, X = 2d sin 0.   An electronic
detector or photographic film is used to record 0 angles and the intensities
of the diffracted beams.   Every crystalline substance has an unique X-ray
pattern comprised of many 9 angles (usually converted to d-spacings) and
associated intensity values.   Over 22,000 X-ray diffraction patterns have
been published to date.

     The diffraction samples  were prepared by removing the  powders  from
the individual filters,  thoroughly mixing each powder manually in a plastic
container with a wooden  tongue depressor, and pressing into 1/2-inch
diameter pellets under 80,000 psi.  This method of specimen removal from
the quartz (Si02) filter in no way disturbed the filter.  No filter particles
mixed with the specimens removed.  In fact, a small quantity of powder
remained on the filter after removal of the specimens.  These pellets were
analyzed on a G.E. XRD-5 X-ray unit.  The instrumental settings used are
listed in Table E-2.
     The diffraction patterns from all samples were weak; therefore, a
chromium tube was used as a source of X-rays in order to reduce background
radiation due to X-ray fluorescence.  The use of the chromium X-ray tube
and pulse height analysis maximized the signal/noise ratio.
                                    E-4

-------
                                                                   FURNACES A  & B
              FILTER
SIZE OF SAMPLE
TAKEN FROM EACH
FILTER FOR ELECTRON
BEAM MICROANALYSIS
                                    25W-1
                                                          SAMPLE FOR ATOMIC
                                                          ABSORPTION ANALYSIS
                                                          PETRI DISH
      SAMPLE FOR X-RAY
      DIFFRACTION ANALYSIS
SAMPLE FOR OPTICAL-
EMISSION SPECTROSCOPY
ANALYSIS
     Figure E-1. Drawing of condensate from ferrochrome operation showing
     area analyzed.
                                    E-5

-------
                                                            FURNACES A & B
                       TABLE  E-2.
             X-RAY DIFFRACTOMETER SETTINGS
X-ray Source:   Chromium Tube; 50KVP, 20 ma, no filter
Beam Slit:   1°
Soller Slit:  Medium Resolution
Exit Slit:  0.1°
Table Speed:   2°/Min; Chart Speed 2"/rnin.
Detector:  Flow proportional
Scale:  Linear 100
Pulse Height Selector:  El  = 2V   with Gain x 16.
                        AE  = 6V
                               E-6

-------
                                                                   FURNACES A & B
     The diffraction results are summarized in Figure E-2 which shows the
sample identification,  and the d-spacings and relative intensities of the
diffracted beams.   These patterns were then compared with tables of known
                     *
diffraction patterns.
     The X-ray results  can be summarized as follows:
     1.    All  specimens were largely non-crystalline as  evidenced by an
          absence  of a  diffraction pattern or very weak  diffuse patterns
          with very few lines.  No X-ray diffraction patterns were obtained
          from Specimens 25W-1, 25W-2, 25E-1, and 25E-2;  they were completely
                          **
          non-crystalline.

     2.    Another  eight samples had weak patterns,  but the  patterns could
          not  be  correlated in a meaningful way with any  known pattern
          from the diffraction file.   In a few instances, a force-fit
          might have been  possible but the choices  were hydrated crystals
          such as  Ca3Al8(PO,J8(OH)6-15H20.   It seemed unlikely that a
          highly hydrated  and complex  crystal  would have  formed during  the
          few  microseconds available for emissions  to condense from the
          gaseous  high  temperature effluent.   These eight patterns  were,
          therefore,  classified as unknown.
     3.    Recognizable  patterns were obtained  from  both specimens  from
          Furnace  B.   The patterns  belong  to  the  naturally occurring class
                                      ***
          of compounds  called spinels.     It  was  not possible to positively
          tell  which  particular spinel  oxide was  present  but  the best fit
          to the X-ray  data  include:
     Joint Committee  on  Powder  Diffraction  Standards,  Powder  Diffraction  File.
     Swarthmore,  Pennsylvania,  1969.
     The specimen numbers  designate  the  Furnace,  A   or  B, and  duct,  west
     or east,  from which specimens,  1  or 2,  were  taken simultaneously.  For
     example,  specimen 25W-1  is  Sample #1  taken from the west (W)  duct of
     Furnace   A .   Specimen  25E-1  was  taken  from  the east  duct of  Furnace A
     at the same  time specimen  25W-1 was taken.
     The spinel group includes  a large number  of  oxides of the general
     formula AB2C\.   The more familiar members of the  spinel  group are
     MgAl^,  ZnFe2Ou, CdFe^,  FeAl204, CoAl^, NiAlzO^, MnAl204,  and
     ZnAl204.   Inverse spinels  have  the  same X-ray  pattern, are  more common
     1n nature, and include  FeO-Fe203  also written  as  Fe3(V
                                    E-7

-------
                                                                   FURNACES  A & B

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-------
                                                                      FURNACES A &  B
                     Chromite:       FeO-[Crx  Al1_x]2  03   0.64
-------
                                                                     FURNACES A &  B
     The individual elemental concentrations obtained from the aqua regia
leach and the filtrate from the Na2C03 fusion were then summed for each
sample; these results are compiled in Table E-3.Samples 6E-1  and 6E-2 were
found to be Insoluble  in the Na2C03 flux and as a consequence of this, it
was not possible initially to obtain Si02 or further elemental analysis on
these two samples using the above method.  These two samples  were found to
be soluble  in a potassium pyrosulfate flux.  The samples were, therefore,
fused with approximately 0.5 gram  of potassium pyrosulfate,  and the resultant
fused samples were then dissolved in dilute HC1.  The solution was then
filtered; the filtrate made up to 100 cc volume, and subsequently analyzed
by Atomic Absorption Spectroscopy (A.A.)-  The residue on the filter paper
was then ignited in a muffle furnace at 900°C and the residue back weighed
as Si02.  The results of these analyses were added to the results found
for the acid extracted portion of the sample, and are tabulated in Table E-3.
Since the optical-emission spectroscopy analyses discussed later showed
that Specimens 6E-1 and 6E-2 contained considerable quantities of calcium,
A.A.  analyses for calcium were run on these two specimens also.  The instru-
mental parameters used for each element are listed in Table E-4. Nitrous
oxide-acetylene flames were used for Cr and Mg to eliminate inter-element
interferences.   Because of the small amount of sample collected (30-120 mg)
and the desirability of determining the toxic elements (Mn, Cd, Pb, As, Hg,
Be) in low concentration levels, it was found necessary to use the entire
sample for each of the above analyses.
     The choice of these elements was based on the combined considerations
of (i) expected presence in condensate, (ii) toxicity, and (iii) availability
of atomic absorption lamps.  The results are summarized as follows:
     1.   The samples from Furnace A   invariably contain at least 66 wt%
          Si02 with an average value of 73.6 wt%.  In contrast, the
          specimens from B  contained only -6 wt% Si02 as found in a
          supplemental optical-emission analysis.  The Si02 did not come
          from the filter paper because the sample was removed from the
          quartz (Si02) paper prior to analysis.
     Walter Slavin, Atomic Absorption Spectroscopy, Interscience Publishers,
     New York, New York, pp 79-189, 1968.
                                      E-10

-------
                                                                                                                             FURNACES A  &  B
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-------
                                            FURNACES A & B
       TABLE E-4.



INSTRUMENTAL PARAMETERS
ELEMENT
Cr
Mn
Cd
Pb
Hg
Be
V
Mg
Fe
Zn
Al
Ca
WAVELENGTH
o
(A)
3579
2801
2288
2833
2537
2348
3184
2852
2483
2138
3093
4227
FUEL OXIDIZER
SYSTEM
N20
air
air
air
air
N20
N20
N2°
air
air
N20
N2°
acetylene
acetylene
acetylene
acetylene
acetylene
acetylene
acetylene
acetylene
acetylene
acetylene
acetylene
acetylene
SLIT
WIDTH (A)
2
2
7
7
7
7
7
7
2
7
7
7
HOLLOW CATHODE
CURRENT (MA)
10
10
4
4
4
12
15
4
12
8
13
8












              E-12

-------
                                                                    FURNACES A & B
 2.    The chromium content ranged from 0.68 to 2.08 wt% from Furnace
       A  and the average value was 1.3 wt%.   The value from Furnace
       B is much higher at 7.2 wt%.
 3.    The average manganese content was 0.067 wt% in Furnace  A  and
      0.062 wt% in  B.   The values are virtually the same.

 4.    The magnesium content varied considerably among different
      samples.  It was  highest, 11.6 wt%,in the two 25E-1 specimens.
      These specimens also had the lowest Si02 levels (67.5 and
      66.6 wt%) from among the samples from Furnace A.
 5.    The iron content  in Furnace  B  was a full factor of 10
      higher than in Furnace   A-   The average values in Furnace B
      and   A are 3.75  and 0.34 wt%,  respectively.
 6.    The zinc content  in Furnace  A   varied  from 0.30 to 1.68 wt%
      with an average of 1.04 wt%.  The corresponding value for
      Furnace B  is 2.20 wt%.
 7.    The average aluminum content from Furnace  A   was 0.10 wt%
      and,hence, lower  than the 0.545 wt%  found in  the two  samples
      from Furnace B.
 8.    Mercury, beryllium, and vanadium, all toxic elements, were
      below the detectability limits  of 0.05  wt%, 0.001 wt%, and
      0.03 wt%, respectively.
 9.    The cadmium levels from Furnace  A  varied from below 0.0003
      wt% to 0.002 wt%.   The condensate from  Furnace B  contained
      an average of 0.0024 wt% cadmium which  was somewhat higher
      than that for Furnace  A  j,ut still  relatively low.   Cadmium
      is a toxic element.
10.    Calcium analyses  of Specimens 6E-1 and  6E-2 from Furnace  B
      were decided on only after it was seen  from the optical-emission
      spectroscopy results that the calcium levels  were very high
      compared to the Furnace  A  specimens.   The A.A.  analyses for
                                     E-13

-------
                                                                       FURNACES  A & B
          calcium yielded  10.6  wt%  and 10.7  wt%  for the  two specimens.
          Since  the  A.A. technique  is  more exacting than the optical-
          emission  technique, it  is the A.A.  calcium values which should
          be considered as being  the true calcium concentrations  in the
          Furnace B   specimens.
    11.    The total  concentration of elements from Furnace A   samples
          1s virtually  100% when  all the metal  values are converted to
                                       *
          equivalent oxide percentages.   This  means that all  the major
          elements  in the  emissions from this furnace were detected and,
          in addition,  a few minor but toxic elements (V, Hg,  Be, Cd) were
          also detected.
    12.    The total  concentration of elements from Furnace  B  after
          conversion to equivalent oxide percentages is  70%, a somewhat
          less satisfactory mass  balance situation than  for Furnace A  .
          This lack-of-closure  should not be taken to signify the presence
          of an additional but  undetected element.  No additional element
          of any consequence was  detected in either the  electron  microprobe
          or optical-emission techniques.  It is concluded that all the
          major elements are accounted for in Table E-3  and that  the lack-of-
          closure in samples from Furnace B   is  due to errors  associated
          with the  extreme difficulty encountered in dissolving the samples.

2.4  Electron Beam  X-Ray Microanalysis
     The electron microprobe is an  advanced  piece of equipment which uses
a small  beam of electrons  to produce characteristic X-ray emissions from a
sample volume with  a radius of  -1 micron. Curved crystal X-ray spectrometers
are used to analyze  the resultant characteristic X-ray spectra.  In these
analyses, the electron  beam was defocused to  a diameter  of 200 microns
(0.008 inch) to cover a larger  segment of the sample.
     Equivalent oxide percentages are obtained by multiplying the weight
     percent metal in Table E-3  by the  ratio  Mo/Mm where Mo is the molecular
     weight of the metal oxide and Mm is that of the metal.   The oxide
     formulae were taken to be A1203, ZnO, Fe^O,,, MgO, A203, and CaO.   Thus
     for Ca, the equivalent oxide percentage is 10.65 x  (40+16)/40.  Justi-
     fication for this conversion is  based on electron microprobe results.
                                       E-14

-------
                                                                     FURNACES A & B
     The electron beam Impinged in vacuum upon the untouched sample surface
as shown in Figure E-l. An examination was made of the complex spectrum of
X-rays given off by the specimen under electron beam excitation, and it was
found that the entire spectrum could be identified uniquely on the basis of
the elements shown in Table E-4. All portions of the X-ray spectrum in the
wavelength range 1-100A covering all elements except H, He, Li, and Be were
taken into account.
     The silicon and oxygen signals did not originate from the silica
filters although the latter were present in the electron microprobe chamber.
The electron beam penetrated about 2 microns (and absolutely no more than
20 microns) into the sample from the top surface.   The total sample thickness
was about 0.02 inch (-500 microns).  Thus, the silica filter material was
-500 microns away from the effective sensing depth of the electron beam.
     The major outcome of the electron microprobe analyses was that the
main elements were identified for the atomic absorption analysis already
discussed.   Thus, Fe, Cr, Si, Al, Ca, Mg, and Zn were found on the untouched
samples and were, therefore, selected along with other elements  for A.A.
analyses.
     A second outcome of the electron microprobe analyses was the detection
of oxygen  at roughly the 50% level  in the samples  from both furnaces.   This
means that the metals are present as oxides and is the basis for the
conversion of the metal  percent values in Table E-3 to equivalent oxide
percents.    The 50%  oxygen value  was strictly applicable only to the top
2-20 microns of the  untouched samples where the analyses were made.   However,
1t was assumed that the sample was  essentially a mixture of oxides
throughout its depth.  Such an assumption seemed reasonable when the
source of the samples was taken into account.
     The  50%  value was  obtained  in  a  10"6  torr vacuum.  Thus  oxygen was not  an
     occluded  atmospheric gas  but was  present as  an  oxide.
                                     E-15

-------
                                                                 FURNACES A & B
   Table E-5.  ELECTRON BEAM X-RAY MICROANALYSIS RESULTS FROM
                           QUALITATIVE  ANALYSES
Camnlp
   Elements Positively Identified  in X-ray Spectra
 25E-r
 25E-23
Fe, Cr,  0,  Si, Al. Ca, Mg, Zn, Na, Ba, K,  -,  -  -
Fe, Cr,  0,  Si, Al, Ca, Mg,  -,  -,  -, -, Ni,  -, -
Fe, Cr,  0,  Si, Al, Ca, Mg, Zn, Na,  -, -, Ni, Cl, S
     Ferrochromesilicon furnace (Furnace A).
     Chrome ore/lime melt furnace (Furnace b).
                                 E-16

-------
                                                                             FURNACES A & B
     The concentrations are not given in the electron microprobe  table (Table E-5)
 because, although the elements shown were present  throughout  the  depth
 of  the  samples,  their concentrations (particularly the metals) varied with
 depth  (i.e., the samples were non-uniform).  Thus, the atomic absorption
 analyses were used to determine the quantitative analyses on  properly
 composited samples while the electron microprobe qualitatively identified
 the elements.

 2.5  Optical-Emission Spectroscopy
     Optical-emission spectroscopy or arc-spark spectroscopy  consists of
 electrical excitation of the electrons of the elements in the sample.  When
the electrons return to their ground state,  light is  emitted.   The emitted
light is passed through a prism or diffraction  grating to separate it into
 its component wavelengths.   The spectrum is  then analyzed electronically
or optically on a photographic plate.   Each  line occurring at a definite
wavelength position on the spectrum designates  a specific element, and
 the intensity of light at that wavelength is proportional to the quantity
of that element present.
     Portions of the samples  were  subjected  to  optical-emission  analyses
to provide (1)  a check on the analytical  procedures (particularly the
lack-of-closure in  the atomic absorption  analyses  from Furnace g ),  and  (ii)
« more sensitive approach  to  trace element analysis than  that  provided by
electron beam X-ray  microanalysis.  The  spark emission results for the
isajor elements  agreed well  with  the atomic absorption and electron beam
results and,  in addition,  identified numerous trace impurities not found
1n the other  approaches.  The results  are compiled  in Table  F-6.
                                             E-17

-------
                                                                                                                    FURNACES  A  &   B
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                                                                   FURNACE C
               III.   CHEMICAL ANALYSIS OF EMISSIONS




                                  FROM




                        A SILICOMANGANESE FURNACE
1.  INTRODUCTION




    Particulate fumes and gaseous emissions are generated during the




smelting and pouring of a commercially important class of ferroalloy




materials called reactive metals.  The particulate portion of these




emissions has been collected on glass fiber filters, strategically




placed in the air stream of an exhaust system.  Six such filter samples




taken from a scrubber serving a SiMn furnace and an uncontrolled tapping




station were analyzed by microscope, qualitative electron beam X-ray




microanalysis, and atomic absorption.  The analytical results are presented




in the following sections.  Sample specimen designations  preceded by




MIE are filter samples collected at the scrubber outlet; those preceded




by WTE and ETE are samples collected at the tapping station.






2.  TEST RESULTS




2.1  Optical Examination




     The specimens were examined at magnifications up to 30X.  The




particulate matter could be seen intimately mixed with the quartz filter




fibers, and it was obvious that the particulate matter could not be




physically separated from the filter pad upon which it had been collected.




Under tungsten filament the specimens appeared as follows:MlE-6 (light




gray), M1E-T (dark gray), M1E-12 (yellow-brown) and ETE-2 (partly dark




brown, partly light brown).
                                   E-19

-------
                                                                  FURNACE C










2.2  Electron Beam X-Ray Microanalysts




     The electron microprobe is an advanced piece of equipment which uses




a small beam of electrons to produce characteristic X-ray emissions from




a sample volume with a radius of —1 micron.  Curved crystal X-ray




spectrometers are used to analyze the resultant characteristic X-ray




spectra.  In these analyses, the electron beam was defocused to a diameter




of 150 microns (0.006 inch) to cover a relatively large area of each




specimen and thereby obtain data which would be representative of the




entire sample.  The electron beam impinged in vacuum upon the untouched




sample surface.  An examination was made of the complex spectrum of X-rays




given off by the specimen under electron beam excitation, and it was found




that the entire spectrum could be identified uniquely on the basis of the




elements shown in Table E-7.A11 portions of the X-ray spectrum in the




wavelength range 1-100A covering all elements except H, He, Li, and Be




were taken into account.






     The analyses were conducted on small portions of the filter pads which




were not later digested for the atomic absorption analyses.  The small




samples for electron probe analyses are still intact.  The qualitative




analysis results are summarized in Table E-T.Several points seem germane:






     I.  The major elements are manganese, magnesium, calcium, and




         potassium.  The silicon signal could have come from either




         the filter pad or from the particulate matter.  The fibers




         of the pad were visible in the optical microscope which is




         attached to the electron probe.
                                 E-20

-------
                                                                 FURNACE  C
     2.   Distinct signals,  equivalent to several weight percent,




         were found for sulfur,  chlorine,  carbon,  sodium,  and




         potassium.












     3.   The presence of sodium  and chlorine frequently suggests




         salt and could have come from handling with bare  hands.




         However, it must be stated that the filters were  not




         handled with bare  hands during the chemical analysis




         effort.







2.3  Atomic Absorption Analyses




         Atomic Absorption  (A.A.) means that a cloud of atoms in  the




     un-ionized and unexcited state is capable of absorbing radiation




     at  wavelengths that are specific in nature and characteristic  of




     the element in consideration.   The atomic absorption  spectro-




     photometer used in these analyses consists of a series of lamps




     which emit the spectra of  the elements determined, a  gas burner




     to  produce an atomic vapor  of the sample, a monochromator to




     isolate the wavelengths of  interest,  a detector to monitor the




     change of absorption due to the specimen, and a readout meter  to




     visualize this change  in absorption.
                               E-21

-------
                                                           FURNACE C



    The filters with samples were weighed,  and the sample weights




calculated by subtracting the tare weights  written on the outside




of the Petri dish sample containers from the total weights.




Specimen identifications were as follows:   MlE-6,  M1E-7,  M1E-12,




and a composited specimen consisting of filters WTE-3,  ETE-1,




and ETE-2.
                          E-22

-------
                                                                                                            FURNACE  C
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-------
                                                                    FURNACE C
     The filters (both pad and participate) were extracted for 2 hours with
50 mis of 1:1 H^SO^; this solution was decanted and saved.  The filters were
then extracted for 2 hours with a boiling dilute Aqua Regia solution.*  This
solution was then combined with the H2$04 solution, filtered, taken to con-
stant volume in a volumetric flask, and analyzed by A.A.  The instrumental
parameters used for the individual elements are given in Table E-8 and the
results of the A.A.** analyses are shown in Table E-9.

     The A.A. results are normalized to compensate for the portion removed
for electron beam X-ray microanalyses.  Silica (Si02) analyses were not per-
formed since the entire Si02 filter pad with the intimately mixed specimen
was digested in acid in each case.  In order to determine if the acid diges-
tion process chemically attacks the Si02 filter, an unused filter will be
exposed to the digestion process and A.A.  analyses run on a blank to deter-
mine background concentrations.  A remote possibility exists that some K or
Na could have come from the filter material if it is not pure Si02.

     Note also that in Table E-9  only  one  specimen (M1E-6) adds up to 100%.
The other specimens most likely consist of metal oxides or a mixture of
metals and metal oxides; oxygen and silicon are therefore the likely
missing chemical components needed to bring the totals in all four cases
to 100%.

     A comparison of these results with the results reported for Furnace A
                                               immediately brings to light
certain differences between the two emissions.  The emissions from
 Furnace C      contain, in general, less  chromium but more manganese,
sodium, potassium,  chlorine, and,to be particularly noted, sulfur, than
 Furnace A emissions.
    R. J. Thompson, G. B.  Morgan,  and L.  J.  Purdue, "Analysis of Selected Ele-
    ments in Atmospheric Particulate Matter by Atomic Absorption",  Atornic
    Absorption NEWS Letter. Volume 9, No. 3, 1970
**
    Walter Slavin, Atomic Absorption Spectrescopy,  Interscience Publishers,
    New York, New York, pp 79-189, 1968.
                                   E-24

-------
Table E-8. Instrumental Parameters
                                            FURNACE C
Element
Cr
Mn
Mg
Fe
Al
Ca
Ba
Na
K
Zn
Wavelength
(I)
3579
2801
2852
2483
3093
4227
5536
5890
7665
2139
Fuel Oxidizer
System
Air-Acetylene
Air-Acetylene
N^O-Acetylene
Air-Acetylene
N20-Acetylene
NgO-Acetylene
NgO-Acetylene
Air-Acetylene
Air-Acetylene
Air-Acetylene
Slit 0
Width (A)
2
2
7
2
7
7
7
20
20
7
Hollow Cathode
Current (Ma)
10
10
4
12
13
8
7
10
10
8
           E-25

-------
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                                             E-26

-------
                                                                   FURNACE C
                     EN  RONMENTAL PROTECTION AGFj ^Y
                Reserr~.. Triangle Park,  North Carolina 27711

Reply to
Atln of:                                                     Date:  11-17-71

Subject:   Analysis of Samples for Mercury


   To:   K.  W.  Grimley, Division of Applied  Technology

THRU:   R.  E.  Lee, Jr., Chief, 3SFAB y\L^

        1.   Origin:   Furnace C

        2.   Date collected:  7/31 - 8/3/71

            Date analyzed:   11/10/71

        3.   These seven samples of scrubber exit  water were analyzed
        for mercury using flameless atonic  absorption.

        4.   Tests were run on both the clear liquid and the liquid
        and sediment.  There was no mercury detected in any of the
        samples run.

        5    The lower detectable limit is~.008 ug Hg/g.
        Kathryn il.  i'lac^eod
        Source  Sample £>na Fuels
          Analysis  Broach, DAS

        cc:   R.  Neligan
             A.  Altshuller
             J .  i-icGinnity
             D.  Shearer
             D.  von Le.'hmden
             D.  Slaughter
             R.  Atherton
             V7.  Kelly
             F.  Uilshire
                                        E-27

-------
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                                                              E-28

-------
                       ENVIRONMENTAL PROTECTION AGENCY         FURNACE C
.'•<> .'o
                                      •                             Dale: September  10, T

        Ore and Slag Samples  -  Furnace C
  To:    Or. K. t. Lee
        Source Sample and Fuels Analytical Branch
        Division of Atmospheric Surveillance


        1.  Origin:  Samples of two representative manganese ores  and  two
        ferromanganase slags from the prociuction of silicomanganese  alloy
        in Furnace C              during  the MCA- EPA emission  tests
        (July 27-A-.v;st 5, U'71).

        2.  Samp.les :   Sample 1 - Manganest Ore
                        Sample 2 - Manganese Ore
                        Sample 1 - Slag
                        Sample 2 - Slag

        3.  Analysis:   Please  analyze each  sample  separately for trace metals
        by both, neutrcr,  activation analysis and emission spectroscopy (on contract,
        if necessary).   Also analyze  a  representative  portion for beryllium by
        atomic  absorption.

             Trace ratals  are dsfinod  as ^h° following:  Sb, As, Ba4 Be,.B, Cd,
        Ca,  Crs Cu, Fe, Pb,  Hg,  fin.  Hg,  Ni , K, Se, Si, Na, Sr, S, Sn, V and Zn.

        4.  Results:  Forward results to the author.
         D. R. Patrick
         Chemica1
         cc:  VI. Basbagill
              J. Dealy
              S. Blacker
...pi. ?rl.rit» 1 MnxiM trinity I Jll~.it. Ock.r.
T™. fet. SI.. 1. >i CJ »t V ",. XI 'b tt :n LU ?b S« » F tl AS Sn re St Ml « C« 51 HI Al )
tn ~V» | O 1-3M <7M UX) M]»c 200 <100 100 O09 200 OO « »J 1 200 <1  to » 100  <100 100 <30 • M « 200 <1 <30 JX JOO MOO n 2000 (1 2000 }1
ttMfk«
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oa
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1	"luw«**«-.    Table E-ll.   METAL ANALYSIS  OF ORE  AND  SLAG SAMPLES.
                                      E-29

-------
                                                                      FURNACE  D
                      IV.  CHEMICAL ANALYSES OF EMISSIONS
                                        FROM
                           A FERROCHROMESILICON FURNACE
1.  INTRODUCTION
     Particulate fumes and gaseous emissions are generated during the process-
ing of a commercially important class of ferroalloy materials called reactive
metals.  The particulate portion of these emissions is collected on glass
fiber filters strategically placed in the air stream of a ventilation system.
Six such filters from samples collected on a FeCrSi furnace were analyzed by atomic
absorption and qualitative electron beam X-ray microanalysis.  Each of the six
filters prior to compositing was examined microscopically.
2.  TEST RESULTS
2.1  Optical Examination
     The loaded filters were examined at magnifications up to SOX.  Under
tungsten filament illumination the separate filters appeared as follows:
     ABD-1M      Dark gray powder with black particles-no quartz  (baghouse inlet)
                 fibers from the collector pad visible.
     ABD-2M      Light gray powder with very few black particles- (baghouse inlet)
                 no quartz fibers from the collector pad visible.
     ABD-3M      Dark gray powder with black particles-quartz fibers  (baghouse inlet)
                 from the collector pad visible.
     ANE-1M      Light gray powder with black particles-quartz fibers(baghouse outlet)
                 from the collector pad visible.
     ACE-1M      A few black particles among the quartz fibers.       (baghouse outlet)
     ASE-1M      A few black particles among the quartz fibers.       (baghouse outlet)
                                       E-30

-------
                                                                FURNACE D
The optical examination revealed that:

1.  Four filters had trapped a heterogeneous participate materia.
    consisting predominantly of a gray powder and a minor amount
    of black particles.

2.  The amount of sample collected in four cases was so small that
    the fibers from the filters could still be seen.  In fact, in
    two such samples, only a small amount of the black particles
    could be seen against a background that was predominantly the
    filter material.

Two different techniques were necessary to form composite samples:

1.  Simple Blending of Loose Powders
    Samples ABD-1M, ABD-2H, and ABD-3M were shaken, lightly scraped
    and copious amounts of loose gray material  were gathered, blended,
    and designated as Baghouse Inlet Duct Sample ABD-M.   A negligible
    amount of the collector filter material was included in the  blended
    sample.

2.  Dissolution in a Common Reagent
    Samples ANE-1M, ACE-1M, and ASE-1M were submerged (particulate
    matter and filter pads) in a common solution of sulfuric acid.
    A control experiment was also run on a unused filter pad to
    determine the contributions of the filter.   The composited sam-
    ple in this case was labeled Baghouse Outlet Stack Sample ABE-M.

    Small samples for electron beam X-ray microanalysis  were cut
    from every specimen prior to formation of any composite samples.
                                E-31

-------
                                                                      FURNACE D
2.2  Electron Beam X-Ray Microanalysis
     The electron microprobe is an advanced piece of equipment which uses a
small beam of electrons to produce characteristic X-ray emissions from a sam-
ple volume with a radius of ~1  micron.  Curved crystal  X-ray spectrometers
are used to analyze the resultant characteristic X-ray  spectra.   An examina-
tion was made of the complex spectrum of X-rays given off by the specimen
under electron beam excitation, end it was found that the entire spectrum
could be identified uniquely.   All portions of the X-rcy spectrum in the
wavelength range 1-100A covering all  elements except H, He, Li,  and Be were
taken into account.

     In these analyses, the electron  beam was defocused to a diameter of "150
microns (0.006 inch) to cover a relatively large area of the specimen and to
insure that both the gray condensate  and the black particles were analyzed.
The electron beam impinged in vacuum  on the untouched surfaces of three specimens:

     1.  Sample ABD-1M
         In this sample, the layer of particulate material was far too
         thick to allow penetration of the electron beam into the
         collector (filter) pad.  In  other words, only the condensed
         particulete material was analyzed in this case.
     2.  Sample ABD-3M
         The layer of particulate was sufficiently thin that a contri-
         bution from the collector pad may be present.
     3.  Sample ANE-1M
         A contribution from the collector was definitely present in
         this case because the fibers from the collector could be seen
         in the optical microscope viewing system attached to the
         electron microprobe.

     The qualitative results are compiled in Table E-12 and provide the basis for
selection of elements for quantitative analyses.  Note that a total of 15 ele-
ments were found* and that the stack sample  (ANE-1M  contained a  small  but
distinct amount of both sulfur and chlorine.  Special mention is made of these
   The spectral scans were conducted in a manner such that all elements except
   H, He, Li, Be, B, N could be detected.
                                     E-32

-------
                                                                                           FURNACE D
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                                             E-33

-------
                                                                     FURNACE D
elements because they were not included in the quantitative analyses which will
be described in the next paragraph.   Note also that oxygen was detected at
about the 50%, thereby suggesting that the particulate material was a mixture
of oxides.

2.3  Atomic Absorption Analyses
     Atomic Absorption (A.A.) means  that a cloud of atoms in the un-ionized and
unexcited state is capable of absorbing radiation at wavelengths that are speci-
fic in nature and characteristic of the element in consideration.  The atomic
absorption spectrophotometer used in these analyses consists of a series of
lamps which emit the' spectra of the elements determined, a gas burner to pro-
duce an atomic vapor of the sample,  a monochromator to isolate the wavelengths
of interest, a detector to monitor the change of absorption due to the speci-
men, and a readout meter to visualize this change in absorption.

     As stated previously, the two sets of samples were composited two differ-
ent ways for the atomic absorption analyses.  The detailed procedures for the
physically blended powders are as follows:
     1.  The particulate material from three specimens was either shaken
         loose or scraped from the filter pads with a wood tongue de-
         presser and blended in a polyethylene container.
     2.  Duplicate portions of the blended powder were digested in hot
         HC1-HN03.*  After cooling, the suspension was filtered.
     3.  The filtrate (soluble portion) was analyzed for the elements of
         interest by atomic absorption.  The precipitate (non-soluble por-
         tion) was analyzed by "large beam" electron microprobe analysis and
         flame photometry and found to be free of sodium or potassium.  This
         action was done because potassium acid sulfate  (KHSO.) v/as used in
         the next step.
     4.  The precipitate was blended with a known quantity of  KHS04 and ignited
          in a 850°C muffle furnace to form a fused mass which  subsequently was
          dissolved in HC1.  Solution was  not complete, and a  filtration step was
         needed to separate the solution  from a precipitate.
     5.  The solution was analyzed for the elements of interest by atomic
         absorption, and the results from this step were added to those from
         Step 3 to yield the total percentage of each element  in the parti-
          culate sample.
 *
   The  hot  solution  used was 8 ml concentrated HC1, 32 ml concentrated HNCL
   and  40 ml  distilled water.
                                     E-34

-------
                                                                     FURNACE D
     6.  The precipitate from Step 4 was checked for SiO? by a gas
         evolution technique.*  This technique selectively decomposes
         and volatilizes Si02 through reaction with hot H2S04, HH03
         and HF in a platinum crucible.   The portion of the sample
         that still remained after all these steps was labeled an
         insoluble residue in Table E-13.


     A different procedure was needed for those samples in which the quantity
of condensable particulate was insufficient for a physical separation.   In

this case the following procedure was used:


     1.  Three entire collector pads, with material in and on them,
         were digested in a common hot ^$04 solution.  An unused
         collector pad was submerged in  a second identical solution.

     2.  The steps described previously  were followed for both the
         unknown and the unused sample.   The results for the latter
         were corrected to account for the fact that three used pads
         were used with the unknown samples but only one unused pad
         was employed as a blank.

     3.  The concentrations of elements  in the condensable particulate
         material was obtained by subtracting the results for the
         "blank" from the total.
     The results of'the atomic absorption analyses are compiled in TableE-13.

The following are observations.


     1.  Both samples are predominantly silicon dioxide, Si02.  This
         conclusion is directly seen in the results for the Inlet Duct
         Sample where 76.4% of the material is SiOp.   The concentrations
         of the remaining elements are all low in comparison, and magnesium
         is the highest at an average 5.44« level.  The sum of all the
         percentage values is 100%, and this indicates excellent closure
         (mass balance).  The 100% value is achieved when all the metal
         percent values are converted to their equivalent oxide percent
         values.**
**
N. H.  purman, Editor, Standard Methods of Chemical Analysis, 6th Edition,
Volume 1, D.  Van  Nostrand Company, Princeton, N.  J.,  p.  950.

Equivalent, oxide percentages are obtained by multiplying the weight percent
metal  in Table 2 by the ratio Mo/Mm where Mo is the molecular weight of the
metal  oxide and Mm is that of the metal.
                                     E-;

-------
                                                                                                                              FURNACE  D
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                                                                  E-36

-------
                                                                     FURNACE D
      2.   The Stack Sample, in comparison with the Inlet Duct Sample, con-
          tains relatively more of every metal cation except magnesium.
          The absolute amount of 'the Stack Sample was far less and this
          had an impact on the sensitivity values.  Thus the lower limits
          for barium and titanium are 4% and 8% in the Stack Sample (rather
          than 0.4 and 0.8%) because the total sample mass was limited to
          "11 milligrams.

      3.   It must be emphasized that the values have been corrected to
          account for the  contributions from the filter pads.  In other
          words, the 12.7ft Ma value is for the particulate matter collected
          on a filter and  riot for the filter pad.


      Metals analysis was  also made on two chrome  ore samples using the  optical
emission spectrography method.  These are shown in Table E-14.
                                    E-37

-------
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                                                           E-38

-------
                                                                         FURNACE D
                           ENVIRONMENTAL PROTECTION AGENCY
                                   Office  of A1r Programs
                       Research  Triangle Park,  North  Carolina  27711
Reply to
 Attn of:  AID
Date, fay 5, 1972
 subject:  sojj   Analysis  of  Partlculate  Samples  from Furnace D

    To:  Wlnton  Kelly,  Chemical  Engineer,  Petroleum  4  Chemical  Section

              Two  sample fractions  (organic extract  and  Impinger water  residue)
         were  selected  for sulfate  analysis from each  of the  two sample tests,
         ANE-1 and ABD-2.   These samples were  first  analyzed  by the  Barium Perch-
         lorate  titratlort  method, which proved to be too In-sensitive.   Re-analysis
         by the  more  sensitive Sulfaver-Turb1dimetric  procedure gave the following
         results:                  (MO         M» en"
                                 Original      ng iU4  Weight   .    Sample
         Test  No.   Beaker  No.  Sample  Weight   Sample  Percent SO,  Fraction
ANE-1

ANE-1


ABD-2

ABD-2


31

43


35

47


8.1

18.8


35.8

42.4


<0.25

6.75


<0.25

5.55


< 3

33


< 1

13


•*
Organic
Extract
Impinger
Water
Residue
Organic
Extract
Impinger
Water
Residue
                                                                              BAGHOUSE
                                                                               OUTLET
                                                                              BAGHOUSE
                                                                                INLET
               An acid-base  tltratlon  of  beakers  35  and  47,  using  0.1009  N  NaOH,
          used less  than  one drop  per  sample,  Indicating both  samples were  very
          near neutrality.   Beakers  31  and  43  were not subjected to  an  acid-base
          tltratlon  due to a lack  of sample volume after the SO? analysis.

               Remnants of test  ABD-2  (beakers 35 and 47)  have been  sealed  to  pre-
          vent contamination and are located at the  IRL  Building sample storage
          area.  Any questions regarding  these samples or the  data can  be directed
          to me (X277) or found  1n the laboratory notebook located in Room  26, at
          the IRL Building.
                                                     ank  M11shire
                                                       Chemist
                                            Petroleum & Chemical  Section
                                            Emission  Testing  Branch,  ATD
          cc:   Mr.  W.  Grimley
               Mr.  H.  Crist
                                     E-39

-------
                                                                   FURNACE D
                     ENVIRONMENTAL PROTECTION AGENCY
               Research Triangle Park,  North Carolina   27711
Rtply to
Attn of:
                                    Dau:  5/3/72
 Subject:  Terro-Alloy Samples



   To:  Vfinton Kelly,  ETB
       Petroleum & Chemical Section
             The results of analyses  on  the above samples collected
        from  Furnace D                are  attached.


             Your samples are identified as follows:
       Battelle No,    EPA Test No,
                  Sample Fraction
       B-272
ABD-2
B-273
B-274
B-275
B-276
B-277
B-278
B-279
/•BD-2
ACE- 1
ABD- 1
ACE-1
ABD-1
ANE-2
ANE-2
Solvent extraction of im-
pinger water               >

Impinger water  residue   J

Solvent extraction of im- /'-
pinger water               J

Impinger water  residue   ^

Impinger water  residue

Solvent extraction of im-
pinger water

Impinger water  residue

Solvent extraction of im-
pinger water
                                                                      BAGHOUSE
                                                                        INLET
                                                                      BAGHOUSE
                                                                       OUTLET

                                                                      BAGHOUSE
                                                                        INLET

                                                                      BAGHOUSE
                                                                       OUTLET
                                                                      BAGHOUSE
                                                                        INLET
                                                                      BAGHOUSE
                                                                       OUTLET
                                      Howard L.  Crist
                           Chief,  Source  Sample  Analysis Section
                                         SSFAB,  DAS
       Attachment
       cc:   W.  Grimley
                                    E-40

-------
        Table E-15.  METAL AND OTHER ANALYSES OF COLLECTED PARTICULATES
                                FROM FURNACE D
                                 (ug/sample)
Determinations requested:

Type analysis:  VAS, OES
anions, water insolubles, organic material, trace
metals, pH

Be
Cd
As
V
Mn
Ni
Sb
Cr
Zn
Cu
Pb
B
Li
Ag
Sn
Fe
Sr
Na
K
Ca
Si
Sample designation
B272
<0.1
<5
10
3
100
30
<5
1000
150
10
200
3
<5
3
30
700
<5
1000
2000
150
100,000
B273
<0.1
<5
<10
<1
200
30
<5
1000
300
10
300
3
<5
1
10
300
<5
2000
2000
700
50,000
B274
<0.1
<5
<10
<1
<1
<1
<5
<1
<10
<1
<5
1
<5
<0.1
<5
5
<5
<10
<10
20
200
B275
<0.1
<5
<10
<1
200
30
<5
600
50
7
300
3
5
0.1
10
300
<5
800
1000
400
40 ,000
B276
<0.1
<5
<10
<1
10
2
<5
3
10
5
5
1
<5
<0.1
5
20
<5
100
30
100
200
B277
<0.1
<5
<10
<1
80
5
<5
600
30
5
30
5
<5
1
20
300
<5
300
800
200
120,000
B278
<0.1
<5
<10
<1
10
2
<5
10
20
7
5
1
<5
0.1
5
50
<5
100
30
200
200
B279
<0.1
<5
<10
<1
<1
<1
<5
<1
<10
<1
<5
<1
<5
<0.1
<5
1
<5
<10
<10
<1
5
                                      E-41

-------
   Table E-14 (continued),
 METAL AND OTHER ANALYSES OF COLLECTED PARTICIPATES
      FROM FURNACE D
       (ug/sample)
Determinations requested:

Type analyses:  VAS, OES
anions, water insolubles, organic material, trace
metals, pH

Mg
Bi
Co
Ge
Mo
Ti
Zr
Ba
Al
S04
Cl
NH4
N03
Water
insol-
uble
Organic
PH
Sample designation
B272
5000
5
1
<3
3
20
3
50
2000
<500
30
<30
<100
223,000
16,500
6.2
B273
15,000
2
1
<3
<1
3
<1
20
1000
24,000
1000
120
200
191,700
2000
6.1
B274
10
<1
<1
<3
<1
<1
<1
<1
10
< 500
<20
70
100
3500
1400
5.4
B275
12,000
<1
3
<3
<1
1
<1
10
1200
22,000
60
700
100
41,300
2000
4.5
B276
5
<1
<1
<3
<1
3
<1
2
40
6800
<20
1000
<100
2200
1000
3.2
B277
4000
<1
5
<3
<1
5
<1
50
1200
<500
<20
<30
<100
121,500
4000
6.3
B278
30
<1
10
<3
<1
5
<1
2
60
10,000
<20
750
100
None
1000
2.7
B279
<1
<1
<1
<3
<1
1
<1
<1
<3
<500
20
<30
<100
None
400
5.3
                                      E-42

-------
                                                                      FURNACE E
                        V.  CHEMICAL ANALYSES OF EMISSIONS
                                         FROM
                              AN HC FERROCHROME FURNACE
     Particulate fumes and gaseous emissions are generated during processn.b
of an important class of ferroalloy materials called reactive metals.   The
participate portion of the emissions is collected on glass fiber filters stra-
t^nically placed in the air stream of a ventilation system.   Two such  filters  of a
sample collected at the outlet of a  furnace producing HC ferrochrome were analyzed
by the combined techniques of a electron  beam X-ray analysis and atomic absorption
analysis, and the results are detailed in the following paragraphs.

2.   TEST RESULTS
2.1  Optical Examination and Compositing
     The two samples were gray and were labeled WCD and ECD.  Small  portions
were cut for electron microprobe analyses.  The remainder was shaken and a
copious amount of loose powder was gathered, blended, and designated  preci-
pitator   Inlet Duct CD-M.

2.2  Electron Beam X-Ray Microanalysis and Atomic Absorption
     The electron microprobe is an advanced piece of equipment which uses a
small beam of electrons to produce characteristic X-ray emissions from a sam-
ple volume with a radius of ~1 micron.  Curved crystal X-ray spectrometers
are used to analyze the resultant characteristic X-ray spectra.  In  these
analyses, the electron beam was defocused to a diameter of 150 microns
(0.006 inch) to cover a larger segment of the sample.  The electron  beam
Impinged in vacuum upon the untouched surfaces of small pie-shaped pieces of
sample-covered filter pads.  An examination was made of the complex  spectrum
of X-rays given off by the specimen under electron beam excitation,  and it
was found that the entire spectrum could be identified uniquely.  All  portions
of the X-ray spectrum in the wavelength range 1-100A covering all elements
except H, He, Li, and Be were taken into account.

                                     E-43

-------
                                                                     FURNACE  E
     Atomic Absorption (A.A.)  means that a cloud of atoms  in  the  un-ionized
and unexcited state is capable of absorbing radiation  at wavelengths  that  are
specific in nature and characteristic of the element in  consideration.   The
atomic absorption spectrophotometer used in these analyses  consists of  a
series of lamps which emit the spectra of the elements determined, a  gas bur-
ner to produce an atomic vapor of the sample, a monochromator to  isolate the
wavelengths of interest, a detector to monitor the change  of  absorption due
to the specimen, and a readout meter to visualize this change in  absorption.

     The qualitative electron  microprobe results are in  Table E-16, along with
the quantitative atomic absorption results.  The latter  were  generated  on  the
composited samples mechanically separated from the filter  (collector) pads
by shaking and lightly scraping the filters.  A negligible  amount of  collector
filter material was included in the blended sample, and  therefore no  unused
filter pad was needed.

     The sum of the percent values, after conversion to  equivalent oxide
values, is 84% and indicates adequate closure in the sense  that all the major
constituents have been taken into account.  The remaining  16% could well be
accounted for by the presence  of chlorine, carbon, and titanium.

     The major conclusion is that the sample is a mixture  of  oxides:  SiCL,
Cr203, MgO, and A1203.

     X-ray diffraction analyses were not executed, and hence  it is not  known
if the oxide mixture is amorphous (non-crystalline), crystalline  (spinel
structure), or partially amorphous-parti ally crystalline.

     A sample was  obtained from the precipitator  and analyzed for metals
by the Optical  Emission Spectrography  (OES) method.  This sample does not
necessarily  represent true emissions from  the  furnace  since some particulates
are  removed  by the conditioning tower preceding  the  precipitator.
                                      E-44

-------
                                 FURNACE E
Table E=16. QUALITATIVE ELECTRON BEAM X-RAY MICROANALYSIS AND ATOMIC -ABSORPTION
RESULTS FROM SAMPLE COLLECTED AT PRECIPITATOR INLET DUCT (FURNACE E)
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-------
                                                                     FURNACE F
                   VI.  CHEMICAL ANALYSIS OF EMISSIONS
                                     FROM
                             A SILICON METAL FURNACE
I.  INTRODUCTION
    Particulate samples were collected using an  EPA sampling  train  at  the
inlet and outlet of a baghouse serving a silicon metal  furnace.   Chemical
analyses were made of the particulates collected in each  section  of the
sampling train.  For the use of Table E-18,  sample  numbers  are  identified
as follows:
         Description of
         sample or sample
         fraction
               Sample No.
Baghouse inlet
Baghouse outlet
Probe wash residue
Glass fiber filter
Impinger aceton wash residue
Impinger water residue
Chloroform-ether extraction residue
165,188
(166,167,168,169),189
170,190
171,191
172,192
137,152
138,153
139,154
140,155
141
Sample numbers 137 through 141 were for a test run at the baghouse outlet.
Samples 152 through 155 were also for a test run at the baghouse outlet.
Samples 165 through 172 were for a test run at the baghouse inlet.  Samples
166, 167, 168 and 169 were combined into one sample.  Sample numbers 188
through 192 were analyzed representing a test at the baghouse inlet.

    The samples were water leached for the anion and NH4  analysis, and they
were acetone leached for the total organic analysis; portions of these
leaches were combined with a portion from an additional acid leach-scrubbing
step to obtain a sample for optical emission spectrograph (OES).  A portion
of each filter was water and acetone leached for the organics, anions, and
NH.+; a separate portion of each filter was acid extracted for the OES sample.

    The analysis of the filter and residue samples are shown in Table E-18.
Results are reported in micrograms per entire filter or residue.  The weights
                                     E-48

-------
                                                                    FURNACE F
of the samples analyzed are:




                                   Wt.  in Mg
137
138
139
140
141
152
153
154
155
165
166
167
168
169
170
171
172
188
189
190
191
192
153.6
10.4
23.1
21.2
3.4
13.1
16.8
27.5
25.0
486.3
1017.4
701.8
923.0
1404.4
30.7
59.6
68.6
9.5
18.8
20.6
23.2
1.0
                                       E-49

-------
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-------
                                                                     Furnace G
                     CHEMICAL ANALYSIS OF EMISSIONS
                                  FROM
                       SILICOMANGANESE FURNACE

I.  INTRODUCTION
     Inlet and  outlet scrubber samples collected by the use of the EPA
particulate sampler were chemically analyzed using optical  emission (OES)
and visual absorption spectrophotometry (VAS).  For the purpose of
identifying the results shown in Table E-19, the following  information is
given:
                           Description of samples or sample
            Sample No.	fraction analyzed	
            B-338
            B-339
            B-340
            B-341
            B-342
            B-343
            B-344
            B-345
            B-346
            B-347
            B-348
            B-349
            B-350
            B-351
Probe wash residue
Glass fiber filter
Glass fiber filter
Glass fiber filter
Impinger water residue
Chloroform-ether extract
Impinger acetone wash residue
Probe wash residue
Glass fiber filter
Impinger water residue
Chloroform-ether extract
Impinger acetone wash residue
Blank glass fiber filter
Blank glass fiber filter
     Sample numbers from B-338 through B-344 represented portions of one test
collected at the scrubber inlet.  Samples from B-345 through B-351 represents
portions of one test collected at the scrubber inlet.
     Filter samples B-339, B-340, B-341 and B-346 had in the packages mailed
to the contractor doing the analysis some loose material that had been
                                  E-52

-------
shaken from the filters during shipping and handling.   The loose material
and the filters themselves were analyzed separately for convenience, but
the data were combined into a single reported valie for each determination.
     The appropriate blank corrections were made in the data for the filter
samples, as indicated in the footnotes to Table E-18.   The very large
blank values for certain elements led to high "less than" values for the
filters with sample even though these elements are almost certainly
present in the sample, as indicated by their presence  in the loose material.
However, some particles of the glass fiber filters may also be in the
loose material, and so it is very difficult to determine the true net
amount of these elements in the actual sample.
     Material balance for these samples is not good, but this may be due to
the silicon content which cannot be determined for reasons given above.
                                  E-53

-------

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-------
                                                                    Furnace H
                VII.  CHEMICAL ANALYSIS OF EMISSIONS
                                  FROM
                       A 50% FERROSILICON FURNACE

     Chemical analyses were made on particulate samples collected from the
outlet gas stream of a venturi scrubber serving a semi-covered furnace producing
50% ferrosilicon.  The first tests were made on this scrubber on February 2,
1972, while kerosene was injected into the exhaust system blower, some kerosene
was collected in the sample.  The samples for these tests are identified as
253 through 257.
     The second group of tests were made on July 19, 1972, without kerosene
injection into the blower.   Combustible material in the sample collected with
kerosene injection was about 67 percent and without kerosene injection, about
50 percent.
     Sodium, potassium, and calcium analysis appeared to be too high, so a
check analysis was made on filter samples 134 and 140 by the atomic
absorption method.  The results in milligrams were:
Sample
134
140
Sample
weight,mg
98.3
103.1
Na
83
81
K
11
11
Ca
33
35
     This represents the amount of these elements extracted from the collected
particulate and the filter material.
                                  E-55

-------
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-------
FURNACE H

-------
                                         FURNACE H
E-62

-------
                                 FURNACE H
E.63

-------
           VIII.  CHEMICAL ANALYSIS OF EMISSIONS
                               FROM
                     A FERROMANGANESE FURNACE

     Chemical analyses were made on participate samples collected from
the outlet gas stream of a venturi  scrubber serving a sealed furnace
producing ferromanganese.
     Samples of three of the six test runs were analyzed for trace
metals, SO.", Cl", NO,", NH. ,  pH,  organics and water insolubles.  Chemi-
cal analyses were made of the particulates collected in each section of
the sampling train.  A total of five separate analyses were made to
determine the metals in each portion of the sampling train for one
test run.
     The samples were water leached for the anion and NH.   analysis, and
they were acetone leached for the total organic analysis; portions of
these leaches were combined with a  portion from an additional acid
leach-scrubbing step to obtain a sample for optical emission spec-
trography (OES).  A portion of each filter was water and acetone leached
for the organics, anions,  and NH.+; a separate portion of each filter
was acid extracted for the OES  sample.
     The analysis of the filter and residue samples are shown in Tables
E-24 and E-25.
                                E-64

-------
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                                  E-68

-------
                  IX.  CHEMICAL ANALYSIS OF EMISSIONS
                                 FROM
                            A SiMn FURNACE

     Particulate samples were taken at the outlet of a venturi scrubber
serving a silicomanganese furnace (sealed).  Samples were collected with
an EPA sampling train by EPA method 5 (described in Appendix B of this
report).  Chemical analyses were made of the collected particulates in each
fraction of the sampling train.  Metal analyses were made of the two test
runs.  Analyses of organics, anions,   NH. , and water insolubles were made
of three test runs.
     The samples were water leached for the anion and NH.  analysis, and
they were acetone leached for the total organic analysis; portions of
these leaches were combined with a portion from an additional acid leach-
scrubbing step to obtain a sample for optical emission spectrography (OES).
A portion of each filter was water and acetone leached for the organics,
anions and NH.+; a separate portion of each filter was acid extracted for
the OES sample.
     The analyses of the filter and residue samples are shown in Tables
E-26, E-27, and E-28.
                                  E-69

-------

-------
FURNACE L

-------

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-------
                               APPENDIX F




    Table F-l.   UNITED STATES IMPORTS OF REACTIVE METALS AND ALLOYS*
December 1971
Issued;



TSUSA
KO .
607.
3500







607.
3600
|







607.
3700







607.
''.700




!






CO.'^C'DITY
FF.RR OKA is G ANESE ,
under } 'is Carbon,
Commercial






FERROMANGANESE,
1-4% Carbon,
Commercial







F.ERR OMANG ANESE
over 4% Carbon,
Commercial






FKRROS1LJCON
MANGANESE,
Cornrnoi" ciul








COUKTKY
or
ORIGIN
IMPORTS FOR CONSUMPTION

CURREXT MOKTH
Short
T or>r> '••*
Franr« I 648
Japan
Rep. S, Africa
Sweden
West Germany


TOTAL

Canada
France
Italy
Japan
Norway
Rep. S. Africa
Sweden
West Germany
Yugoslavia
TOTAL
Belgium
Canada
France
India
Japan
Norway
Rep. S. Africa
TOTAL

Canada
France
Jr.pan
Mexico
Norv.-ay
Sweden
Yugoslavia
TOTAL
„
1)2

-


760

-
235
-
-
.-
-
851
-
-
1086
-
~
-
-
-
1345
100
1445

-
-
-
--
';8 ?-9'iV
659
2346
299?.T>
} 1C
:•; 1 4
39:>1
i
M

-------
Table F-l.  Continued
     December 1971
r 	 - -
TSUSA
K'O .
632.
3200




1
607.
3300









607.
3000








632.
J800



i

•
COMMODITY
MANGANESE
METAL
Commercial




FERROCHROME,
over 3% Carbon,
Commercial








FERROCHROME,
under 3% Carbon,
Commercial







CHROME METAL,
Commercial





COUNTRY
0?
ORIGIN
Australia
Canada
Cyprus
Japan
Netherlands
Rep. S. Africa
TOTAL
Belgium
Brax.il
Canada
Finland
France
Japan
Norway
Rep. S. Africa
Sweden
West Germany
TOTAL
Canada
France
India
Japan
Norway
Rep, S. Africa
Sweden
Turkey
Wcsl Germany
TOTAL
Canada
France
Japan
Netherlands
Un, Kingdom
V/ c fi t G e r r/*a ny
TOTAL
IJ-? PORTS FOR COWSUMPTIO:'
CURRENT HONTJI
S7hort j value
Tons''-'* £1000
10
-
-
114
-
82
206
_
-
-
-
-
-
-
-
220
55
275
_
-
~
-
-
-
-
-
142
142
-
-
41
-
35
-
76
27
-
-
45
-
34
106
_
-
-
-
-
-
-
-
51
33
64
_
-
~
-
-
-
-
-
215
215
-
-
87
-
63
-
150
	 JAN.__;
Short
10
24
15
800
50
1979
2878
310
1382
535
10903
4256
12992
301
7174
220
3 3697
49550
184
3086
2260
7389
3457
14632
5433
1320
5033
40594
17
90
605
2
818
102
1 6 3 4
:o D".v:
Vr.i'AK
27
2
6
343
23
828
1229
25
291
359
1138
1125
2923
85
956
51
1620
8373
43
-','/"
!',
b
393
] 1 4 7
6
1420
J ',. 2
2963
L _ 	
        F-2

-------
Table F-l.  Continued




     December 1971
'SUSA
NO.
07.
000

,07.
ilOO




607.
5200

607.
B.'iOO

632.
J200


,07.
5500

COMMODITY
FERROSILICON,
8 --60% Silicon,
Commercial

FERROSILICON,
60-80% Silicon
Commercial




FERROSILICON
80-90% Silicon,
Commercial

FERROSILICON
90% and over,
Silicon

SILICON METAL,,
Commercial


C M R O M I LI M S J I , I CO N


COUNTRY
OP
ORIGIN
Canada
i;'r.c> jn,u
Japa.n
Norway
W. Germany
TOTAL
Canada
China
Denmark
France
Japan
Norway
Rep. S. Africa
Sweden
W. Germany
Yugoslavia
TOTAL
Canada
Rep. S. Africa
TOTAL


TOTAL
Canada
Norway
TJn. K-'ngdom

TOTAL
Sxv u u e n

TOT AJ,
IMPORTS FOR CONSUMPTION
CURRKK
Short
Tons >'•••'<
74
16
50
55
195
44
69
165
-
278
„
-
-
-

-

-
-


| CUMULATIVE,
P MONTH j JAN. TO D/vTE
Value
S l.OOO
6
7
18
17
48
17
28
32
«t
-
77
_
-
-
-

-
-

-
-

-
Short
T.ons**
6038
1387
3587
685
277
11974
791
28
44
2837
50
2568
319
3115
444
2224
12420
60
14
74
-

-
174
22
2

198
772

772
Value
SJ.OOO
422
492
1111
213
75
2313
216
7
17
1 1 29
10
737
62
541
161
776
3656
18
3
21
|
i
!
1
I
	 -___]
74 i
8 !
^ !
i
84
207

207
        F-3

-------
Table F-l.  Continued



      December 1971
I


TSUSA
NO.
607.
7000
I
1 . ,
607.
6000


607.
6500

629.
2800

628.
1500

6.79.
0500





,S20.
6000










COMMODITY
FERROVANADIUM


FERROTITANIUM
Commercial


FERRO TUNGSTEN


TUNGSTEN,
Unwr ought

COLUM3IUM METAI


TANTALUM METAL






ZIRCONIUM METAL









COUNTRY
OF
ORIGIN
W. Germany

TOTAL
France
Italy
Un. Kingdom
TOTAL
Bxaxil
Sweden
TOTAL
Sweden
W. Germany
TOTAL
i
W. Germany
TOTAL

Canada
Japan
Mexico
Un. Kingdom
W. Germany
TOTAL

Canada
Japan
Netherlands
Sweden
Un. Kingdom
W. Germany
TOTAL
IMPORTS FOR CONSUMPTION

CURRENT MONTH
Short
Tons**
-

_
^
-
-
—
5
-
5
1
-
1.
(P
-
M
(P
_
-
_
-
-
_
(F
2047
44532
-
-
-
-
46579
Value
S1000
-

_
_
-
-
..
24
-
24
7
-
7
OUNDS &
-
..
OUNDS V.
-
~
-
-
~
„
OUNDS &
1126
144284
-
-
-
-
145410
CUMULATIVE,
JAN. TO DATK
Short
Tons**
69

69
50
20
17
87
6
12
18
7
44
:>!
DOLLAR:
450
450
:DOLLAP
763
792
22341
16020
175
40091
Value
$1000
360

360
23
15
116
154
29
69
98
66
539
605
5)
7227
7727
S)
ZZfjH
10456
47739
212355
4981
278799
DOLLARS)
4798
164124
12867
7209
240
36692
225930
-
4546
549800
11659
10805
1457
54572
632839
.
        F-4

-------
Table F-l.   Continued
      DLH:.::OK>cr J971




TSUSA
| NO.
629.
iiSOO





I


!
~












COMMODITY
TITANIUM. METAL,
Commercial






Government
Purcho.ee












COUNTRY
OF
ORIGIN
Austria
C/ct'UdUa
Japan
Netherlands
Un. Kingdom
USSR
W. Germany
TOTAL


TOTAL






i

"
IMPORTS FOR CONSUMPTION

CURRENT MONTH
Short
Tons**
_
•11
37
-
-
437
-
485

-
485








Value
.,..$1.0.00.

5
69
-
-
67
-
141

-
141








CUMUIv'.TIVK,
JAN. TO u.Vra
Short
Ton si*
5
117
2498
4
1ZO
1335
66
4145


4145








Value
__£1£LQ.O.._.
3
129
433]
3
130
316
68
4980

-
4980 i
i

i
1
i
i



         r-, C > '.-,
          F-5
                             • >!• f, -,- r. >:'

-------
Blocking Chrome
Charging
Charge chrome
Chrome ore/Time melt
Condensed fumes
Covered furnace
           APPENDIX G
            Glossary
     A high-silicon (10 to 12 percent) grade
of high-carbon ferrochromlum used as an additive
1n making chromium steel to block (I.e., stop)
the reaction 1n the ladle.
     The process by which raw materials (charge) such
as ores, slag, scrap metal reducing agents, and
limestone are added to the furnace.
     A grade of high-carbon ferrochrome, so called
because 1t forms part of the charge 1n the
making of stainless steel.
     A melt of chromium ore and Hme produced 1n
an open-arc furnace (tilting) and used as an
Intermediate charge material in the production
of low-carbon ferrochrome.
     Minute solid particles generated by the condensa-
tion of vapors from solid matter after volatiliza-
tion from the molten state.
     An electric furnace with a water-cooled cover
over the top to limit the admission of air to burn
the gases from the reduction process.  The furnace
may have sleeves at the electrodes (fixed seals)
with the charge introduced through ports in the
furnace cover, or the charge may be introduced
through annular spaces surrounding the electrodes
(mix seals).
                                        G-l

-------
Electrolytic process
Exothermic process
Ferroalloy
     A low-voltage direct current causes the simple
ions of the metal contained in an electrolyte of
modest concentration to plate on the cathodes as
free metal atoms.  The process is used to produce
chromium and manganese metal, which are included
with the ferroalloys.
     Molten silicon or aluminum or a combination of
the two combines with oxygen of the charge, generating
considerable heat and creating temperatures of several
thousand degrees in the reaction vessel.  The process
is generally used to produce high-grade alloys with
low carbon content.
     An intermediate material used as an additive or
charge material in the production of steel and other
metals.  Historically, these materials were ferrous
alloys, hence the name.  In modern usage, however,
the term has been broadened to cover such materials
as silicon, calcium silicon, calcium carbide, etc.,
which are produced in a manner similar to that used
for the true ferroalloys.
                                   G-2

-------
Induction furnace
Open-arc furnace
Open furnace
Pre-baked electrode
     Induction heating is obtained by changing the
frequency to electric conductors composing the
charge, and may be considered as operating on the
transformer principle.  Induction furnaces, with
low frequency or high frequency, are used to produce
small tonnages of specialty alloys through remelting
of the required constituents.
     Heat is generated in an open-arc furnace by the
passage of an electric arc either between two elec-
trodes or between one or more electrodes and the
charge.  The open-arc furnace consists of a furnace
chamber and two or more electrodes.  The furnace
chamber has a lining which can withstand the
operating temperatures and which is suitable for the
material to be heated.  The lining is contained
within a steel shell which, in most cases, can be
tilted or moved.
     An electric furnace with the surface of the
charge exposed to the atmosphere, whereby the
reaction gases are burned by the inrushing air.
     An electrode purchased in finished form, avail-
able in diameters up to about 152 cm (60 inches).
These electrodes come in sections with threaded ends
and are added to the electrode columns.
                                         G-3

-------
Reducing agent
Self-baking electrodes
Sintering
Slag
Stoking
     Carbon-bearing materials such as metallurgical
coke, low-volatile coal, and petroleum coke used
in the electric furnace to provide the carbon which
combine with oxygen from the metallic oxides in the
charge to form carbon monoxide.
     The electrode consists of a steel casing filled
with a paste of carbonaceous materials quite similar
to those used to make pre-baked amorphous carbon
electrodes.  The heat from the passage of current
within the electrode and heat from the furnace
itself bakes the electrode and volatilizes the
asphaltic binders in the paste.
     The formation of larger particles, conglomerates,
or masses from small particles by heating alone, or
by heating and pressing, so that certain constit-
uents of the particles coalesce, fuse, or other-
 wise band together.
     The more or less completely fused and vitrified
matter separated during the reduction of a metal from
its ore.
     The means by which the upper portion of the charged
materials in the furnace are stirred up.  This loosens
the charge and allows free upward flow of furnace gases.
                                    6-4

-------
Submerged-arc furnace
Tapping

Tapping period

Tapping station
     In ferroalloy 'reduction furnaces, the elec-
trodes usually extend to a considerable depth into
the charge; hence, such furnaces are called
"submerged-arc furnaces."  This name is used for
the furnaces whose loads are almost entirely of
the resistance type.
     A process whereby slag or product is removed
from the electric submerged-arc furnace.
     That period of time during which product or
slag flows from the electric submerged-arc furnace.
     The general area where molten product or slag
is removed from the electric submerged-arc furnace.
                                        G-5

-------
°F
acfm
scf
scfm
psig
gr

ppm
mg/m
ton

gross ton
kv-a
kw
Kw-hr
mw
mw^hr
Silvery iron
50% FeSi
MgFeSi
Si
CaSi
SMZ
HC FeMn
        ABBREVIATIONS
temperature, degrees Fahrenheit
actual cubic feet per minute
standard cubic feet measured at 70°F and 29.92 in.  Hg.
standard cubic feet per minute at 70°F and 29.92 in.  Hg.
pounds per square inch guage
grain (1 grain equals 64.8 milligrams) -
  7000 grains equal 1 pound
parts per million
micrograms per cubic meter (0°C and 760 mm Hg)
milligrams per cubic meter (0°C and 760 mm Hg)
weight of 2,000 pounds avoirdupois, also, short ton
  or net ton
weight of 2,240 pounds avoirdupois
kilovolt-ampere
kilowatt, 1,000 watts
kilowatt hour
megawatt, million watts
megawatt hour
15% to 20% ferrosilicon
50% ferrosilicon
magnesium ferrosilicon
silicon metal
calcium silicon
silicon manganese zirconium
high-carbon ferromanganese
                                     G-6

-------
MC FeMn
LC FeMn
SiMn
FeMnSi
Chg Cr
HC FeCr
LC FeCr
FeCrSi
Cr ore/lime melt
Chemical Symbols
A1203
CO
co2
CaC2
CaO
Cr203
Fe
H20
MgO
Mn
P
SO,,
medi urn-carbon ferromanganese
low-carbon ferromanganese
silicomanganese
ferromanganese silicon
charge grade ferrochrome
high-carbon ferrochrome
low-carbon ferrochrome
ferrochrome-si1i con
melted chrome ore and Hme (CaO) 1n oxide form

alumium oxide
carbon monoxide
carbon dioxide
calcium carbide
calcium oxide (quick lime)
chromium oxide
iron
water
magnesium oxide
manganese
phosphorus
sulfur dioxide
                                    G-7

-------
                                H.   REFERENCES

 1.  DeHuff, Gilbert L.   Ferroalloys.   In:   Mineral  Facts  and Problems.
     U.S. Bureau of Mines Bulletin  630, 1965 edition,   p.  330.
 2.  Ferroalloys:   Steel's All-Purpose Additives.   33/The Maqazine of
     Metals Producing  p.39-56.   February 1967.
 3.  Minerals Yearbooks.   U.S.  Bureau  of Mines,  1963-1971.
 4.  U.S. Department of Commerce, Bureau of the  Census.
 5.  Trends in the Use of Ferroalloys  by the Steel  Industry of the United
     States.  Washington, D.C.,  National Materials  Advisory Board (NAS-NAE),
     July 1971.
 6.  Watson, George A. (The Ferroalloys Association).   Ferroalloys — A Billion
     Dollar Industry.  Mining Congress Journal,   p.  140-143.   February 1971..
 7.  World Stainless Steel  Statistics.  London,  Metal  Bulletin Books, Ltd.,
     1972 edition.
 8.  A Systems Analysis Study of the Integrated  Iron and Steel  Industry.
     Battelle Memorial Institute.  Columbus, Ohio.   Contract No.  PH 22-68-65.
     May 15, 1969.
 9.  Mantell, C. L.  Electrochemical Engineering.   4th edition.  New York,
     McGraw-Hill, 1960.
10.  Durrer, R. and G. Volkert.  The Metallurgy of Ferro-Alloys.  Revised
     edition.  1972.
11.  Paschkis, V. and John Person.   Industrial Electric Furnaces  and Appliances.
     2nd edition.  New York, Interscience Publishers,  1960.
12.  Elyutin, V. P. et al.   Production of Ferroalloys  Electrometallurgy.   2nd
     edition.  Washington,  D.C., National Science Foundation and  Department  of
     the Interior (translated from  Russian by the Israel Program  for Scientific
     Translations), 1957.
                                      H-l

-------
13.  Hopper, Rex T.  The Production of Ferromanganese.   Journal  of Metals.
     p. 88-92.  May 1968.
14.  Wowk, Z. B.  Silicon  Alloy Production in Canada.   (Presented at the 1971
     Electric Furnace Conference.   Toronto, Canada.)
15.  Minerals Yearbooks.  U.S.  Bureau of Mines,  1960-1970.
16.  Questionnaires used in the ferroalloy industry study conducted by EPA
     and The Ferroalloys Association.
17.  Person, R. A.  Control of Emissions from Ferroalloy Furnace Processing.
     Union Carbide Corp.  (Presented at the 27th Electric Furnace Conference.
     Detroit.  December 10-12,  1969.)
18.  Silverman, L. and R.  A. Davidson.  Electric Furnace Ferrosilicon Fume
     Collection (pilot plant study).  Journal of Metals,  p.  1327-1335.
     December 1955.
19.  Retelsdorf, H. J., et al.   Experiences with an Electric  Filter Dust
     Collecting System in  Connection with a 20 MW Silicochromium Furnace.
     Source unknown,  p. 66-79.
20.  Participate Pollution System Study.  Midwest Research Institute.
     Kansas City, Mo.  EPA Contract No. CPA 22-69-104.   1971.
21.  The News and Courier.  Charleston, S.C.  April 12, 1971.
22.  Electric Submerged-Arc Furnaces for the Production of Ferroalloys and
     Calcium Carbide, Test Data Summary for New Source Performance Standards.
     Environmental Protection Agency.  1973.
23.  Test summary results  developed by study team from contractor's field
     testing reports.
24.  Dobryakov, M. Z., et al.   Operation of a Gas-Cleaning System on a Closed-
     Top Electric Furnace.  Steel' in the USSR.  p. 401-402.  May 1971.
                                      H-2

-------
25.  Dry Purification of Reaction Furnace Gases According to the SKW Filter
     Candle Process.  Dortmund, Germany, Friedrich Uhde G.m.b.H., May 1971.  5 p.
26.  Dealy, J. 0. and A. M. Kill in.  Observations of Covered Ferroalloy
     Furnaces Operating in Belgium and Norway.  Unpublished trip report.
27.  Kalika, P. W.  How Water Recirculation and Steam Plumes Influence
     Scrubber Design.  Chemical Engineering,  p. 133-138.  July 28, 1969.
28.  Scott, J. W.  Design of a 35,000 K.W. High Carbon Ferrochrome Furnace
     Equipped with an Electrostatic Precipitator.  The Metallurgical Society
     of AIME.  New York, N.Y.  Paper No. EFC-2.
29.  Lund, Herbert F. (ed.).  Industrial Pollution Control Handbook.  New
     York, McGraw-Hill, 1971.
30.  Federal Register.  Vol. 36, No. 158.  August 14, 1971.
31.  Calcium Carbide -- Salient Statistics.  Chemical Economics Handbook.
     724.5020C.  January 1972.
32.  Air Pollution Control Technology and Costs in Nine Selected Areas.
     Industrial Gas Cleaning Institute.  EPA Contract No. 68-02-0301.
     September 30, 1972.
33.  Moody's Industrial Manual.  Standard and Poor's Corporate Reports.
     1963-1971.
34.  Durkee, K. R.  International Trip Report, Survey of Japanese Ferroalloy
     Kurnaces.  August 9, 1973.
35.  Hyland, G. R.  Test for particulate emissions using an IKOR Continuous
     Particle Monitor (informal report)  June 6, 1972.
36.  Ferrari, Renzo.   Experiences in Developing an Effective Pollution Control
     System for a Submerged Arc Ferroalloy Furnace Operation.   Journal of
     Metals,  p.  99.   April  1968.
                                     H-3

-------
                                 TECHNICAL REPORT DATA
                           (Please read Instructions on the reverse before completing)
1. REPORT NO.
 EPA-450/2-74-008
                                                         3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
  Air Pollution Control Engineering  and  Cost
     Study  of the  Ferroalloy  Industry
                                                         5. REPORT DATE
                                                           May  1974
            6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
  James O. Dealy and Arthur  M.  Killin
                                                         a. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORG-VNIZATION NAME AND ADDRESS
                                                         10. PROGRAM ELEMENT NO.
  Office of Air Quality  Planning  and  Standards
  Control Programs Development  Division
             11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
  Office of Air Quality  Planning  and  Standards
  Control Programs Development  Division
  National  Environmental Research Center
                                                         13. TYPE OF REPORT AND PERIOD COVERED
             14. SPONSORING AGENCY CODE
           -:h  Triangle  Park.  N.C.  27711
15. SUPPLEMENTARY NOTES
16. ABSTRACT

    Report  includes a number of studies  of several  ferroalloy plants and
    provides information  of the following aspects of the  industry:
        1.  Atmospheric emissions from production of ferroalloys  and
           calcium  carbide.
       2.  Methods  and equipment used to  limit these emissions.
       3.  Cost  and  economic impact of air pollution  controls.
       4.  Industry  characteristics  such as  growth rate,  raw materials,
           processes,  consumer products,  and  number  and location of
           producers.
    Most of the information herein  was gathered from industry  questionnaires
    and EPA source  tests.
17.
                              KEY WORDS AND DOCUMENT ANALYSIS
                 DESCRIPTORS
                                            I).IDENTIFIERS/OPEN ENDED TERMS  C. COSATI 1 leld/Group
13. DISTRIBUTION STATEMENT

  Release unlimited
19. SECURITY CLASS (This Report/
   None
                                                                      21 NO OF PAGES
410
20 SECURITY CLASS (Thispage)
   None
                                                                      22. PRICE
CPA Farm 2220-1 (t-73)
                                         H-4
*U.S. Government Printing Office:  1974—747-795/364 Kegion NO. 4

-------