APTD-1511
    NATIONAL INVENTORY
                OF SOURCES
            AND EMISSIONS:
          VANADIUM -  1968
U.S. ENVIRONMENTAL PROTECTION AGENCY
    Office of Air and Water Programs
 Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711

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                                      APTD-1511

  NATIONAL  INVENTORY

                OF

SOURCES  AND  EMISSIONS:

      VANADIUM - 1968


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

       ENVIRONMENTAL PROTECTION AGENCY
       Office of Air and Water Programs
   Office of Air Quality Planning and Standards
       Research Triangle Park, N.C. 27711

              June  1971

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The APTD (Air Pollution Technical Data) series of reports is issued by
the Office of Air Quality Planning and Standards, Office of Air and
Water Programs, Environmental Protection Agency, to report technical
data of interest to a limited number of readers.  Copies of APTD reports
are available free of charge to Federal employees, current contractors
and grantees, and non-profit organizations - as supplies permit - from
the Air Pollution Technical Information Center, Environmental Protection
Agency, Research Triangle Park, North Carolina 27711 or may be obtained,
for a nominal cost, from the National Technical Information Service,
5285 Port Royal Road, Springfield, Virginia 22151.
This report was furnished to the Environmental Protection Agency
in fulfillment of Contract No. CPA-70-128.  The contents of this report
are reproduced herein as received from the contractor.  The opinions,
findings and conclusions expressed are those of the author and not
necessarily those of the Environmental Protection Agency.  The report
contains some information such as estimates of emission factors and
emission inventories which by no means are representative of a high
degree of accuracy.  References to this report should acknowledge the
fact that these values are estimates only.
                       Publication No. APTD-1511
                                   11

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                        PREFACE







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





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





tion Agency, Office of Air Programs.







This inventory of atmospheric emissions has been prepared to




provide reliable information regarding the nature, magnitude,





and extent of the emissions of vanadium in the United States for





the year 1968.







Background information concerning  the basic characteristics





of the vanadium industry has been assembled and included.  Pro-





cess descriptions  are given, but they are brief,  and are limited





to the areas that are  closely related to existing or potential at-





mospheric losses  of the pollutant.







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




plan was to  personally contact about thirty percent of the  com-




panies in each major emission source group to obtain the re-




quired information.   It was known that published data concerning




emissions of the pollutant was virtually  nonexistent, and contacts




with industry ascertained that atmospheric emissions were not  a




matter of record.
                                ill

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The vanadium emissions and emission factors presented are




based on the  summation of information obtained from produc-




tion and reprocessing companies that handle about twenty-five




percent of the vanadium consumed in the United States.  Vana-




dium emissions and emission factors are considered to be




reasonably accurate.
                              IV

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                 ACKNOWLEDGEMENTS







This was an industry oriented study and the authors express





their appreciation to the many companies and individuals in





the vanadium industry for their  contributions.







We wish to express  our gratitude for the assistance of the




various societies and associations,  and to many branches of





the Federal and State Governments.







Our expr.ess thanks  to Mr.  C. V. Spang]er,  Project Officer,




Office of Air Programs, for his helpful guidance.

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                       CONTENTS
SUMMARY
      Emissions by Source	,«...,.       2
      Emissions by States	       3
      Emission Factors  .  .  .  ,	,  .  .       4
SOURCES OF VANADIUM	       5

MATERIAL FLOW

      Material Flow Chart .	       7
      Mining and Processing ,  .  .  .  „	,       8
      Imports and Exports *...,....,.,       9
      Vanadium  Stocks	„  ~  .  ,  .      10
      Reprocessing  ,	  ^  .  „  .      11
           Carbon  Steel.  „„.......„..      11
           Alloy Steel   ,	„  .  ,      12
           Cast Iron	      13
           Nonferrous Alloys	      14
           Chemicals and Ceramics  ........      16
           Miscellaneous	      18

EMISSIONS

      Mining and Processing	      21
      Metallurgical Processing	      23
      Reprocessing	.,  ,  .  .  .      29
           Steel	,  „  .  .      30
           Cast Iron ..............      36
           Nonferrous Alloys  ..........      37
           Chemicals and Ceramics	,  ,      37
           Miscellaneous	      39
      Consumptive  Uses	  .  .  .  .      41
           Coal	      41
           Oil	      44
                            VI i

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APPENDIX  A
      Companies  Dealing in Vanadium and
        Vanadium Products	  .  .       50
TABLES

Table I
      Average Minor Element Contents of
        Coals from Various Regions of the
        United States  - ppm	„  „  .  .  ,       43
Table II
      Vanadium Content of Domestic Crude  Oils .  .       45
Table III
      Vanadium Content of Venezuelan Crude
        Oils.  .,.,,..	„  .  .       46
Table I-V
      Vanadium Content of Middle East Crude
        Oils.	       48
                             viii

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                           -1-
                       SUMMARY







The production and use of vanadium  in the United States has





been traced and charted for the year 1968.  The consumption





was 5,495 tons, exports 741 tons, and imports 652 tons.  About





80 percent (4, 350 tons) was used in  the production of steel.







Emissions  to the atmosphere during the year totaled  19,231




tons.  Emissions due to the combustion of fuel oil and coal




were 17, 000 tons and 1, 750 tons,  respectively. Emissions




resulting from the production of ferrovanadium were 144  tons




and those from the production of  steel were 236 tons.







Emission estimates for coal and  fuel oil combustion are con-




sidered to be reasonably accurate.  They are based on the





average vanadium  content of many coal and oil samples.

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                           -2-
                 EMISSIONS BY SOURCE
                          1968
Source Category
Mining and Processing
Source Group
Short Tons
                                      8]
Metallurgical
  Processing
                                     144
Reprocessing
                                     244
                     Steel
                       Blast Furnace               63
                       Open-Hearth Furnace       166
                       Basic Oxygen Furnace        7
                       Electric Arc Furnace        N

                     Cast Iron                       1

                     Nonferrous Alloys              3

                     Chemicals and  Ceramics
                       Catalysts                     2
                       Glass and Ceramics          N

                     Miscellaneous                  2
Consumptive Uses
                     Coal

                     Oil

                 TOTAL
                         ], 750

                        17,000
                                  18,750
                                  19,219
N - Negligible (less than 1 ton)

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                      -3-
           EMISSIONS BY  STATES
                     1968
      State                           Short Tons

New York                               3, 460

California                               1, 880

Massachusetts                          1, 740

New Jersey                             1, 730

Pennsylvania                            1,400

Georgia and Florida                     1,290

Illinois                                   760

Connecticut                               720

Delaware and  Maryland                    470

Indiana                                   430

Virginia                                   420

Ohio                                      360

All Other States                         4, 090

Undistributed                              469

           TOTAL                     19,219

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                           -4-
                  EMISSION FACTORS
Mining and Processing
25 Ib/ton of vanadium processed
Metallurgical Processing
61 Ib/ton of vanadium processed
Reprocessing

   Steel
     Blast Furnace
     Open-Hearth Furnace
     Basic Oxygen Furnace

   Cast Iron

   Nonferrous Alloys

   Chemicals and Ceramics
     Catalysts
1. 4 lb/1, 000 tons of pig iron produced
5. 1 lb/1, 000 tons of steel produced
0. 3 lb/1, 000 tons of steel produced

0. 22 Ib/ton of charge

12 Ib/ton of vanadium processed


20 Ib/ton of vanadium processed
Consumptive  Uses

   Coal

   Oil
6. 9 lb/1, 000 tons of coal fired

51 lb/ 1, 000 bbls of oil fired

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                            -5-
                SOURCES OF VANADIUM







Vanadium is a grayish malleable,  ductile element found com-





bined in many minerals.  It melts  at 1,900 C and has an atomic





weight of 50. 942.  It is used especially to form alloys.







Vanadium occurs in more than 65 vanadium-bearing minerals





and is widely distributed over the world with significant deposits





in Peru, South Africa, Russia,  and the United States.







Vanadium is found in the minerals patronite, bravoite, sulva-





nite,  davidite,  and roscoelite.  It also occurs as a secondary




element in such uranium-bearing sandstones as carnotite,




uravanite,  tyuyamunite, and hewettite;  in ferrophosphorus




derived from domestic phosphate rock; and in titaniferous




magnetite ores.







Ores  containing vanadium are found in the following states:




Alabama, Arizona,  Arkansas, Colorado,  CaJifornia, Idaho,




Montana, Nevada, New Jersey,  New Mexico,  New York, North




Carolina, Oregon,  Rhode Island, South Dakota,  Utah,  and





Wyoming.







The concentration of vanadium in ores varies-widely;  from





less than one percent to as high  as 25 percent.  In roscoelite,

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                           -6-
vanadium pentoxide (V2O5) accounts for 20 percent of the total





ore but in most of the vanadium-bearing titanium ores,  the





VoO,- content is from 0. 1 to 0. 3 percent and is removed as an





impurity.  The phosphate rocks of Idaho and Montana contain





from 0. 11 to 0.45 percent V2°5'







Vanadium is also found in coal and oil.  Vanadium compounds





are major constituents in some crude  oils.

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       SOURCES
       6. 149
 V2O5 RECOVERED
(Contained Vanadium)

        652
     IMPORTS
        741
     EXPORTS
        381
      STOCKS
         184
  UNACCOUNTED
                                   VANADIUM

                         MATERIAL FLOW  CHART  -  1968

                                    (Short Tons)
5.495
                         USES
                                                          1.092
                                                    CARBON STEEL
                         3.259
                    ALLOY STEEL
                                                           57
                                                       CAST IRON
                                                           459
                                                 NONFERROUS ALLOYS
                                                           168
                                                CHEMICALS & CERAMICS
                                                           460
                                                                                     CONSUMER
                                                    MISCELLANEOUS
                                     Figure  1

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                           -8-

                    M ATE RIAL  FLOW

                 MINING  AND PROCESSING

During 1968 the recoverable vanadium contained in uranium
and vanadium ores and concentrates received at mills,  plus
vanadium recovered from ferrophosphorus derived from do-
mestic phosphate rock, was 6,483 short tons.  Vanadium pent-
oxide,  the most common mill product, amounted to 6, 149 short
tons (contained vanadium)   /.

Four mills were in operation recovering vanadium from uranium-
vanadium ores  in Colorado, Utah, and New Mexico.  Two plants
in Idaho and Utah extracted it from ferrophosphorus and a new
recovery facility at Wilson Springs,  Arkansas processed vana-
diferous  clays   /.

     MINE PRODUCTION  OF  RECOVERABLE VANADIUM V
        .    ..                               Contained  V
        Location
                                            Short Tons
Colorado                                      3, 492
Utah                                             563
Arizona and Other States'                      2., 428
                 TOTAL                      6,483
*Includes  Arkansas, Idaho,  New Mexico, North Dakota, Oregon,
 South Dakota, and Wyoming.		
1- Minerals Yearbook;  Bureau of Mines;  1968.

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                           -9-
                  IMPORTS AND EXPORTS







During 1968 vanadium imports totaled 652  short tons consisting





of ferrovanadium, vanadium ore and concentrate,  principally





ferrovanadium.  Of the 621  short tons (V content)  of imported





ferrovanadium,  approximately 47 percent came from West Ger-




many,  45 percent from Austria, and the remaining 8 percent




from Belgium,  Luxembourg, France,  and  Sweden.  The 31  short




tons (V content) of vanadium ore and concentrate were imported




from Canada and the Netherlands Antilles  _/.







Exports were 278 short tons (V content) of ferrovanadium and




other vanadium alloying materials, and 463 short  tons (V con-




tent) of vanadium ores, concentrates,  oxides, and vanadates.




The total exports were 741 short tons   /.
1- Minerals Yearbook;  Bureau of Mines;  1968.

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                           -10-
                  VANADIUM STOCKS







Consumer stocks at the end of 1967 amounted to 1, 193 short





tons of contained vanadium.  Producers' stocks as fused oxide,





precipitated oxide,  vanadiferous slag, metavanadate, metal,





alloys, and chemicals totaled 2,231  short tons (V  content).  The





total amount of vanadium stocks was 3,424 short tons   /.







At the end of 1968 consumer stocks were 977  short tons and





producers1 stocks were 2,828 short  tons,  totaling 3,805 short





tons  /.   Therefore,  vanadium stocks increased 381 short tons





over the previous y.ear.
]•- Minerals Yearbook;  Bureau of Mines; 1968.

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                           -11-
                     REPROCESSING







The apparent consumption of vanadium in the United States dur-





ing 1968 has been reported at 5,495 short tons.  Of this amount





4, 350 short tons, or about 80 percent,  were used in making vari-





ous steels  /.







CARBON  STEEL




Ordinary carbon  steels depend mainly on their carbon content





for their properties and they represent the  largest proportion




of  steel produced.  In carbon steels in the United States there





are specified minimums and maximums for certain elements,





but there is no minimum specified for vanadium.  Vanadium is




chemically active,  easily forming oxides, nitrides, and car-




bides at elevated temperatures.  For  this reason vanadium is




used in sma]]  quantities in the steelmaking  process to obtain




uniform grain size, and to assist in the removal of oxygen and




nitrogen from the melt.







In  the United States during 1968 the consumption of vanadium





in  carbon steel was 1, 092  short tons contained vanadium _/.





This represents about 20 percent of the total va.nadium con-





sumed during the year.
1- Minerals Yearbook; Bureau of Mines;  1968.

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                           -12-
ALLOY STEEL





Vanadium is added during the production of some alloy steels in





order to control grain size and improve various properties.  It





will increase the strength at elevated temperatures and the alloy





will also be harder, tougher, and more wear resistant.  Gener-





ally the vanadium content ranges from  0. 1 to 0. 5 percent but, in





some instances,  as much as 4. or 5 percent is added.







During  1968 almost half of the vanadium produced in the United





States was used in a group of alloys known as high-strength,  low-




alloy steels.  Its purpose is  to increase the yield point from  the





usual 35, 000 psi to about 60, 000 psi, thus making the steel more





desirable for many construction  applications  such as bridges,





towers, and buildings.  It is also employed in the manufacture





of line pipe for high-pressure gas transmission pipe lines.   The





nominal vanadium content in high-strength, low-alloy steels  is





0. 1 percent.







High-speed and tool steels are another important group and





about 11 percent of the domestic vanadium supply was used for




this purpose.  Alloys in machine tools  for metal removing op-





erations such as  cutting, reaming, drilling, and hobbing con-




tain from 1 to 4 percent vanadium.  Cold work steels for wrenches,

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                           -13-
puncheS; arbors,  shock-resistant pneumatic tooling,  accurate




gages, and thread rolling dies typically contain 0.2 to 0. 3 per-





cent,  although one type containing 4. 5 percent vanadium is avail-





able.   Other  tool steel alloys are about the same;  usually they





contain only a small amount of vanadium.







Stainless steel has a great number of commercial and industrial




applications due to its corrosion resistance and pleasing appear-





ance.  One alloy,  type 422 containing 0. 3 percent vanadium, can





be hardened and tempered to provide a very stable material.





This stainless steel contains 12 percent chromium and is used





in steam power turbines for blades, rotors, and fasteners;  also





in jet engine  compressor parts.  It  is less  expensive  than nickel




high-temperature  alloys and has some  other advantages;  how-





ever, the operating temperature capability is lower.







In the United States during  1968 the consumption of vanadium  in




alloy  steel was 3, 259 short tons  (V  content); a little less than




60 percent of the total domestic supply  /.







CAST  IRON




Vanadium, one of the common alloying elements in cast iron,
1- Minerals Yearbook;  Bureau of Mines; 1968.

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                            -.14-
is generally used in amounts  between 0. 08 and 0. 2 percent in





combina.tion with other alloying elements  such as chromium,





molybdenum,  and nickel.







Vanadium increases the tensile strength and hardness of cast





iron and in combina.tion with chromium and molybdenum im-





proves heat-treatment hardenability,  wear resistance, and





higher temperature properties.  When used with molybdenum,





finer and more uniform graphite flakes result.  Vanadium co-





operates with chromium, molybdenum, and nickel to decrease





the tota] amount of ingredients needed for a good cast iron alloy.







In 1968 the cast iron industry in the United States  used 57  short




tons of contained vanadium, or approximately one percent of




the total consumption   /.







NONFERROUS ALLOYS




Vanadium is a good stabilizer in titanium  and  improves hot and





cold workability.  Thus the titanium alloys can be strengthened




by heat t peatmen!.  Molybdenum, tantalum, and columbium are





also used wit,h titanium, but vanadium has been the most popular




due to the following advantages:  (1) a lower melting temperature
1- Minerals Yearbook:  Bureau of Mines:   1968.

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resuJting in fewer segregation problems:  (2) stronger stabiliz-




ing power:  (3) lower density;  and, (4) cost.  Titanium alloys





are used in a  variety of industries: aerospace,  jet engine pro-





duction, airframes, desalination,  and chemical process equip-




ment.







High percentages of aluminum and vanadium occur in certain




commercially prepared alloys.  The vanadium content is either





2. 5, 5, 40, or 85 percent with the remainder  in aluminum and





fractional percentages  of silicon, iron,  and oxygen.  These al-





loys are used for control of thermal expansion,  grain size,





electrical resistivity and improvement of high-temperature





strengths.







Alloys based on vanadium are now being used  in the nuclear





industry as fuel cladding for experimental liquid-metal cooled,





fast-breeder reactors.  These alloys may replace austenitic




stainless steels in  this application due to vanadium's nuclear




characteristics.  It has a higher creep strength and may have




a greater  resistance to neutron damage than stainless steels.







Vanadium can also be alloyed with columbium and tantalum for




use in coatings to withstand high temperatures and for brazing.





These alloys a.re still generally  experimental.

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                            -16-
In. the  United States during 1968,   459 short tons of contained




vanadium were used in nonferrous alloys;  approximately 8 per-




cent of the total vanadium consumption  /.
CHEMICALS AND CERAMICS




Vanadium in the form of inorganic compounds is  important as a





catalyst in chemical manufacture.  The largest use is in the pro-





duction of sulfuric acid.  Vanadium catalysts have a higher effi-





ciency, better  immunity to poisoning by arsenic and chlorine,





longer life,  greater physical ruggedness, and good availability.







Vanadium catalysts are also used in the synthesis of phthalic




anhydride from napthalene or ortho-xylene.  Phthalic anhydride





is the basic raw material used in alkyd,  cellulose,  and vinyl




resins.  Alkyd resins are used in manufacturing  surface coatings




a.nd paints.  Cellulose and vinyl resins are used in a wide  variety




of products.  Maleic  anhydride, also produced by using  a vana-




dium ca.talyst.  is  important in the manufacture of resins and




plastics.  Adipic acid,  a basic ra.w  material in nylon production,




employs an ammonium metavanadate catalyst.







A recent, development is the use of vanadium pentox:ide and
1- Minerals Yearbook; Bureau of Mines; 1968.

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                           -17-
aluminum trioxide in afterburners for oxidizing hydrocarbons





in automobile exhaust gases.  Some vanadium catalysts are





also used to accomplish the cracking of petroleum.







Minute quantities of vanadium pentoxide in glass manufacture




give hues ranging from almost colorless  through various shades





of green,  yellow, tan, amber,  and gray.  A few of the vanadates





used in coloring glass are cobalt vanadate,  manganese vanadate,




copper vanadate, and nickel yanadate.  Vanadium has been one




of the least used elements listed among the fundamental glass





coloring agents.







Compounds of vanadium are used in the ceramic industry for




glazes and enamels.  Vanadium oxide mixed with vanadium




salts and zirconia produce a yellow color while other mixtures




can result  in a blue or red color.   Va.nadium pentoxide fritted





in the proper composition with tin produces a  yellow tin-




vanadium stain which has largely  replaced the uranium yellows.







During 1968 in the United States  168 short tons of  contained




vanadium,  or 3 percent of the total consumption,  were used





in chemical and ceramic  manufacture.

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                            -18-
MISCELLANEOUS





Permanent magnetic alloys of iron-cobalt materials with  10 to





15 percent vanadium have been  developed.  These materials are





used in computers where small components need very high field





strengths.  Some  iron-cobalt alloys have excellent magnetic





properties but poor  electrical resistivity and poor workability.





By using 2 percent vanadium  in these alloys,  they can be used





in receiver diaphragms and specialized small power transform-





ers for radar and radio.







Hardfacing is a process  of covering a specific area or a whole





surface with some composition  to accomplish more wear resist-




ance.  The process  is used where machinery is  subjected to





abrasive wear, inexpensive tough materials are needed, and





lubrication is impossible.  Such areas  of work include oil well





drilling, earth moving, and ore mining.







Hardfacing alloys  vary greatly in composition.   Vanadium is




used in a number of  grades with an iron base and is usually





present in amounts from 0. 5 to  2. 5 percent.







Some welding wires  have vanadium as a part of their  composi-




tion.  One  such wire contains vanadium, nicke], manganese,




and molybdenum and is used to  weld certain alloy steels.

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                           -19-
Another wire containing chromiurrij  molybdenum, and vanadium




is used to weld heat-treated, medium-carbon, low-alloy steels.





Vanadium in welding wire does not add special properties in the





weldment but is added only to match base metal composition.







Some vanadium is used in one of a number of cobalt-chromium




alloys that have been developed for tooling applications.  These





alloys cannot be hot-worked practically so they are used as cast-





ings.  The alloy used generally contains 38 to 40 percent cobalt,





25 to 32 percent chromium,  10 to 20 percent tungsten,  and 2 to





2. 5 percent carbon.  The alloy containing vanadium uses 3 per-





cent of this element.







Vanadium compounds in paint and varnish promote rapid drying




and produce a tough,  uniform,  smooth film.  A group of driers,




based on soluble vanadium salts,  are  fairly  strong surface-




drying catalysts and are used to a small extent,  more particu-




larly in printing inks.   Ammonium metavanadate is often used.







Vanadium chloride has been used  in photographic processes




for  toning silver bromide prints to impart a green color.







Compounds of vanadium have been used as antiseptics;  inhibi-





tors of germ and organism growth;  to treat abscesses, infected





wounds,  sores,  and ulcers;  destroyers of fermentation

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                           -20-
microbes;  to treat anemia;  boost appetite and improve nutri-




tion.  A University of Kansas Medical School research team ad-




vances the theory that vanadium salts tend to reduce deposits and




discourage production of cholesterol.







Small amounts of vanadium pentoxide are  used in textile print-




ing to give black dyes greater intensity and fastness.







Miscellaneous use of vanadium  in the United States during  1968




amounted to 460 short tons contained vanadium.   This is about




8 percent of the total consumption.

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                           -21-







                      EMISSIONS





                MINING AND  PROCESSING







Prior to 1948,  Colorado uranium-vanadium ores were mined




underground at a shallow depth on a highly selective basis.  The




operation was usually on a small scale and there was  little mech-





anization.  However, since that time the emphasis has shifted to




uranium recovery and mining methods have changed.  Vertical





shafts as deep as 600 feet are  currently used to reach deposits





in the Colorado  Plateau.







Many of the mines are small and mining methods vary.  How-




ever, drilling and blasting are usually required to  loosen the





ore before it is  loaded on a conveyance for transport to the sur-





face.  Next comes another loading operation as the ore is  trans-





ferred to trucks for the journey to the mill.







Since there is a low vanadium  content in surface-mined ores




from the Colorado Plateau, there has been little open-pit min-




ing.  However,  where surface  mining is used the overburden is




loosened with explosives and then removed.  Ore is then loaded




into trucks or train cars for the trip to the mill.  This same




type  of operation is employed in open-pit mines in  New Mexico




and Arkansas.

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                           -22-
In the most widely used vanadium extraction processes, the





ores are put through dry grinding, mixed with lime and salt,





and roasted.  The resulting product from the roaster,  sodium





vanadate, is leached with water, acid,  or a basic solution.  The





vanadium is precipitated from this solution in a form known as





"red cake", a sodium polyvanadate.  By redissolving the "red





cake" ammonium metavanadate is precipitated, which is then





fused to yield vanadium pentoxide.  This technical-grade vana-





dium pentoxide contains a minimum of 86 percent vanadium





pentoxide and 6 to 10 percent sodium oxide.







While this study was in progress several of the larger  companies





were contacted concerning mining and processing methods, as




well as vanadium emissions to the atmosphere.  Records of





vanadium emissions were not available, but estimates  obtained





indicated  average atmospheric emissions are about 25  pounds





per ton of vanadium  handled.







Vanadium emissions to the atmosphere during 1968 from sources




of mining and processing totaled 81  short tons.  This estimate





includes  emissions during the production of vanadium pentoxide.

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                           -23-
              METALLURGICAL,  PROCESSING







During 1968 nearly all of the vanadium produced in the United





States was recovered as vanadium pentoxide (V^O,-), which was





further processed into ferrovanadium for use principally by the





steel industry.  The vanadium consumption was 5,495 tons,  in-





cluding 4,712 tons in the form of ferrovanadium.  The vanadium





used as an alloy in steel was 4-, 350 tons.







Ferrovanadium is produced by the reduction of vanadium ore,





slag,  or  a technical-grade oxide with carbon, ferrosilicon, or




aluminum.  Carbon is a cheaper raw material for reducing vana-





dium, but there is a problem with carbon control in the  finished




product.   Electric reduction furnaces are used for smelting ores




to produce ferrovanadium.  Furnace production is continuous




with charges placed in the  furnace at the top and the molten prod-




uct  tapped near the bottom.







Low carbon grades of ferrovanadium are produced by reducing




technical-grade vanadium pentoxide with ferrosilicon.  Since





silicon is not a powerful reducer of  vanadium oxides,  a  two-step




process is required.  A charge of 90 percent grade  ferrosilicon,





Lime, vanadium pentoxide, and some fluorspar is smelted in  an





electric furnace lined with magnesite.  This yields an iron alloy

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                           -24-
containing about 30 percent vanadium,  but undesirable amounts





of silicon.  In the second step the silicon is decreased by adding





more vanadium pentoxide and lime so that most of the silicon





goes into  the slag phase.  This slag contains  some vanadium and





is returned  to the first step for vanadium recovery.







The preparation of ferrovanadium using a silicon process is be-





ing used commercially to produce tonnage quantities.  A reaction





between vanadium-bearing slags, silica, flux,  and a carbonace-




ous reducer takes place in a submerged-arc electric  furnace to





produce a vanadium silicide alloy.   This alloy is  refined with





vanadium  oxide so that the alloy  contains less than 20 percent





silicon.  This is  then reacted with a molten vanadiferous  slag




in the presence of lime.  This produces a ferrovanadium  alloy




called Solvan of approximately 28 percent vanadium,  11 percent





other metals,  and the  remainder iron.







Aluminum is a more expensive reducing agent; however, the




product is relatively pure and the recovery of vanadium is high.





A charge  of technical-grade vanadium oxide,  aluminum,  iron





scrap, and a flux  is put into an electric arc furnace.  Since this




is an  exothermic  reaction, no carbon is required in the charge.





The reaction between the vanadium pentoxide and aluminum is

-------
                           -25-
initiated by the arc.  Ferrovanadium containing as much as 80




percent vanadium is produced in this manner.







Another process  is the thermite  reaction in which vanadium and




iron oxides are both reduced by aluminum granules in a magne-




site lined steel vessel or a copper crucible cooled by water.





The reaction is produced by a barium per oxide-aluminum igni-




tion charge.







In each of these methods the vanadium pentoxide is melted be-





fore it is used in alloying.  During this melting process, there




is a vapor  of the  pentoxide produced that becomes an aerosol.





Then during the actual reduction process in the furnaces, the





vanadium pentoxide goes to tetroxide, trioxide, oxide,  and fin-





ally vanadium metal.







In addition to its  use in the production of ferrovanadium, vana-




dium pentoxide is reduced with calcium  to. produce vanadium




metal of about 99. 5 percent purity.  An  exothermic reaction  is




carried out in a sealed vessel and it is initiated either  by pre-




heating the vessel or internal heating  with a fuse  wire embedded




in the charge.  Iodine has been added  to the calcium  and vana-





dium pentoxide charge.  Calcium iodide  is produced  by the re-




action  and  serves as both a flux and thermal booster.  Two

-------
                            -26-
problems with this process are that metal yields amount to only





75 to 80 percent,  and there is a high amount of calcium required.








Most of the vanadium metal of 99 percent purity used for alloy-





ing purposes is produced commercially by the alumino-thermic





process. In this process vanadium pentoxide in powder form is





reacted with high-purity aluminum in a "bomb", or sealed ves-





sel,  to form a vanadium-aluminum alloy.  The reaction is ini-





tiated by a vanadium fuse wire. A molten alloy of vanadium and





aluminum separates  from a fused  aluminum  oxide slag and set-





tles  to the bottom of  the vessel.  The vanadium alloy is then puri-




fied  by crushing the brittle alloy and heating plus electron beam




melting, or two steps of direct electron beam melting of the




vanadium-aluminum  alloy.







Vanadium can be even further purified by one of three methods:





iodide refining, electrolytic refining in a fused  salt,  or electro-




transport.   In iodide  refining an impure grade of vanadium metal





is reacted with iodine at 800 to 900 C to form vanadium diodide




in volatilized form which is thermally  decomposed and deposited





on a hot filament.  This process is carried out  in an evacuated





and sealed tube.   The electrolytic  refining process involves the





cathodic deposition of vanadium from an electrolyte in solution.

-------
                           -27-
Electrotransport has been reported as producing the highest





purity vanadium,  A high-density current is passed through a





rod of electrolytically refined metal, heating  it to  1,700 to





1, 850  C.  Atoms of carbon, oxygen, and nitrogen migrate to





the negative end of the bar, resulting in a high degree of puri-




fication along the remainder of the bar.







Vanadium carbide is a product which may be used  as a replace-




ment for ferrovanadium in steel making, and  there are two





methods of manufacturing.  In one  method a powdered vanadium





metal, or hydride and carbon,  is heated in  a vacuum furnace as





high as 2, 000 C without an excessive loss of vanadium.  When a





low carbon content product is needed,  low temperatures must be





used or there will be an excessive  loss of vanadium to oxygen.







Vanadium emissions to the atmosphere from electric furnaces




producing ferrovanadium  have been determined to  be 49 pounds




per ton of vanadium processed.   The particle size generally




ranges from  0. 1 to 1  micron and the total particulate emission





is 240 pounds per  ton of charge   /.   This data is based on un-




controlled emissions,  stack samples,  and chemical analysis  of




the particulate matter.
1- Private communication with industrial source.

-------
                           -28-
In addition to furnace operations,  other emissions occur during




materials handling.  These emissions are estimated at 12




pounds per ton of vanadium.







In the United States during 1968 vanadium emissions to the at-




mosphere resulting from the production of ferrovanadium totaled




144 short tons.

-------
                           -29-
                      REPROCESSING


Vanadium is an important alloying element in steelmaking.  It

is used in the form of ferrovanadium in relatively small quan-

tities and is usually added to the melt near the end of the refin-

ing period or after the steel is in the ladle.


From the standpoint of air pollution, the vanadium added to the

melt is not as important as the vanadium that is contained in the

raw materials, the steel  scrap and the iron ore.


Certain types of iron ore contain vanadium from a trace to more

than one percent V^O    In  titaniferous magnetites, the content

ranges from about 0. 2 to more than one percent and probably

averages about 0.  5 percent. In nontitaniferous magnetites vana-

dium is reported in only a few of the deposits, and these contain

0. 1 to  about 0. 3 percent V2O5   ^J.


In some  instances vanadium has been recovered from iron ore.

During World War II this source was taken up actively in Ger-

many.   The iron ore was melted in the blast furnace in the nor-

mal manner, 80 to 90 percent of the vanadium remaining with
1- Busch, P.  M. ;  "Vanadium - A Materials Survey";  U. S.
   Bureau of Mines;  Information  Circular 8060;  p.  27; 1961.

-------
                           -30-
the pig iron.  On transferring to an acid-lined Bessemer con-

verter and blowing for 3 to 5 minutes, 80 percent of the vana-

dium was recovered in the slag as  vanadium pentoxide  /.


During this study information was obtained from several indus-

trial sources regarding the vanadium content of iron ore pro-

cessed in the United States.  Actual data was not available and

estimates varied considerably;  however,  all agreed the average

would not be more than 0. 1 percent and  likely not less than 0. 01

percent.   In this report an average figure  used is 0. 03 percent.


STEEL

The basic steps in the production of steel include  the partial re-

moval of impurities when the iron ore is reduced  to pig iron in

the blast furnace.   Further purification  takes place as pig iron

and scrap are converted to steel in an open-hearth, a basic oxy-

gen, or an electric furnace. Other associated operations include

ore crushing,  materials handling,  sintering,  pelletizing and

scarfing.


Blast Furnace  - The blast furnace is a  large refractory lined

vessel into which iron ore,  coke, and limestone are charged and
1- Dennis, W.  M. ;   Metallurgy of the Nonferrous Metals; Sir
   Issac Pitman and Sons, Ltd.;  London;  1961.

-------
                           -31-
reacted with large amounts of hot air to produce molten iron.

Slag and blast furnace gases are byproducts from this reaction.

As the gas leaves the top of the furnace it contains large quan-

tities of particulates averaging about 150 pounds per ton of pig

iron _/;   however, it is subsequently  cleaned and used as fuel.

The gas cleaning is usually accomplished in three stages and

the annual overall efficiency of cleaning is estimated at 97 per-

cent.


During 1968,  140 million tons of net ores and agglomerates

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

estimated vanadium content of the ore was 0.03 percent and the

vanadium leaving the blast furnace was about 5 percent of the a-

mount contained in the charge.  Vanadium emissions to the atmos-

phere during the year were 1.4 pounds per thousand tons of pig

iron produced;  a total of 63 tons.


Open-Hearth Furnace  -  Three types of furnaces are commonly

used in  steelmaking:  the open-hearth,  the basic oxygen, and the

electric furnace.   In all  instances, regardless of the type of fur-

nace, the  primary object of the operation is to reduce the
1- "Air Pollutant Emission Factors";  Environmental Protection
   Agency;  Preliminary Document; April 1971.

2- Minerals Yearbook;  Bureau of Mines;  1968.

-------
                           -32-
impurities present in the charge to the limits specified for the

different melts.  In the open-hearth furnace,  steel is made from

a mixture of scrap (about 45 percent) and pig iron (about 55 per-

cent) in a shallow basin or hearth.   Oil, coke-oven gas, natural

gas, tar,  or producer gas provides  the required heat.


The open-hearth process consists of several steps or stages:

               Tap to start         Ore and lime boil
               Charging             Working
               Meltdown            Tapping
               Hot-metal addition   Delay

The melting  step begins  when the first  scrap has  been charged

and continues as the solid material is added.  After the  charge

has melted,  molten pig iron is delivered and poured  into the  fur-

nace.  The next step is the ore and lime boil, which  is a bubbling

action  caused by the oxidized gases  rising to the surface.   The

purpose of the working period is to: (1) lower the phosphorus and

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

(3)  increase  the heat for final deoxidation or for tapping.  At the

end of  the working period the temperature of the melt is approxi-

mately 3,000 F.


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

ten hours and fumes or metal oxides are discharged  continuously

at varying  rates.  In spite of  the variations, average  emission

-------
                           -33-
factors have been established for operation both with and without

oxygen lancing.  With oxygen lancing,  the  factor for uncontrolled

emissions is 21  pounds of particulate per ton of steel;  without

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

control is estimated at 40 percent, and the average emission

factor (controlled) for  all open-hearth furnace operations is 10.2

pounds of particulate per ton of steel produced  /.


During 1968 the  steel produced in open-hearth furnaces was 65

million short tons   / and the vanadium content of the particulate

matter emitted was about 0.05 percent  /.   Vanadium emissions

to the atmosphere were 5. 1 pounds per thousand tons  of steel

produced; a total of 166 tons.


Basic Oxygen  Furnace  - The basic oxygen furnace, in many re-

spects,  is similar to the well known Bessemer converter.  The

principal difference  is in the means for supplying oxygen to the

molten metal.  The converter is a  refractory-lined,  cylindrical
1- "Emissions,  Effluents,  and Control Practices'1;  Environmental
   Protection Agency; Study in progress (unpublished); 1970.

2- Minerals Yearbook;  Bureau of Mines;  1968.

3- "Air Pollution Engineering Manual"; Public Health Service
   Publication No.  999-AP-40;  p.  243; 1967.

-------
                           -34-
vessel mounted on trunions.  It can be rotated to a horizontal or


a vertical position as required during operation.  When charged


and in the vertical position, a stream of oxygen is supplied from


overhead downward  into the converter.  The oxygen impinges on


the liquid metal surface causing violent agitation and intimate


mixing with the pig iron.  The overall operating cycle is about


one hour.




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


mated at 46 pounds of particulate per ton of steel */  and the de-


gree of emission control at 97 percent.




During 1968 the steel produced in basic oxygen furnaces was 48

                  2
million short tons  / and  the estimated vanadium content of the


particulate emissions was  0. 02  percent.  Vanadium emissions


to the atmosphere were  0.3 pound per thousand tons of steel pro-


duced; a total  of 7 tons  during the  year.




Electric Furnace -  Electric arc furnaces are well suited to


the production  of alloy steels and are used extensively for that


purpose.  They are refractory-lined, cylindrical vessels with
1- "Air Pollution Emission Factors";  Environmental Protection

   Agency;  Preliminary Document; April 1971.


2- Minerals Yearbook;  Bureau of Mines;  1968.

-------
                           -35-
large carbon electrodes passing through the furnace roof.


Emissions generated during steelmaking consist of fume and

dust emitted from the furnace during charging and refining.

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

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

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

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

throughout the operation  reaching a peak as the pour tempera-

ture is approached.


Particulate emissions  from electric arc furnaces have been es-

timated at 11 pounds per ton of steel with oxygen lancing, and 7

pounds per ton  without _/.   The degree of control is estimated

at 78 percent, and the  average emission factor (controlled) at

2. 5 pounds per ton of steel produced.


During 1968 the steel produced in electric arc furnaces was 16

million short tons  /,  and the estimated vanadium content  of

the particulate  emissions was 0.003 percent.  Vanadium emis-

sions to the atmosphere during the  year were negligible;  less
1- "Air Pollution Emission Factors";  Environmental Protection
   Agency;  Preliminary Document; April 1971.

2- Minerals Yearbook;  Bureau of Mines;  1968.

-------
                           -36-
than one ton.








CAST IRON





During this study spectrographic analyses of dust samples from





foundries have been examined;  they all indicated vanadium and





many other elements are contained in the dust.







The cupola is the most used method for producing cast iron.





The rate of particulate emissions from gray iron cupolas  has





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





including emissions from handling, charging,  or other non-




melting operations.







Based on the information obtained from industry the particulate





emission factor is estimated at 22 pounds per  ton of process





weight, including melting and non-melting operations.  The vana-





dium content of the particulate is about 0.001 percent  /   and the





degree of emission control approximately 25 percent.







During 1968 the pig iron and scrap used by iron foundries  totaled




16, 788, 000  short tons * (.   Vanadium emissions to the
1- Private communication with industrial source.




2- Minerals Yearbook;  Bureau of Mines;  1968.

-------
                           -37-
atmosphere due to the production of cast iron were one ton.







NONFERROUS ALLOYS





Vanadium is employed as an alloying agent to control grain size,





thermal expansion, and electrical resistivity and to improve





high temperature strength.   It is used mostly with aluminum and





titanium;  production methods are generally the  same as those





used with other alloys.







Based on information obtained from two industrial sources, vana-





dium emissions to the atmosphere are estimated at 12 pounds per





ton of vanadium processed.  During 1968 the emissions were  3





tons.







CHEMICALS AND  CERAMICS




Catalysts  -  Compounds of vanadium are important to the chem-





ical industry as catalysts for many industrial processes including




the synthesis of sulfuric acid,  the oxidation of hydrocarbons,  and




the polymerization of mono- and di-olefins. However,  the quan-




tity used by the chemical and related industries  is small compared




with metallurgical applications.







Catalyst manufacturers use either ammonium metavanadate or





vanadium pentoxide as a starting material.  In one process

-------
                           -38-
vanadic acid is produced first, then caustic potash, dilute sul-





furic acid, and water are added;   they are all mixed to damp





earth consistency.   The mass is  then dumped on a drying band





heated by exit gases from the calcining furnace.  The band goes





into  the furnace for about 25 minutes at 800 C.  Upon exit,  the





dried granules are cooled and sieved.   Sieve residue is ground





and used again.







Manufacturers of catalysts contacted during this study stated





their atmospheric emissions are about 20 pounds  of vanadium





per ton of vanadium  processed.   During 1968 vanadium emis-





sions to the atmosphere resulting from the manufacture of cata-




lysts totaled 2 tons.







Glass and Ceramics -  The use of vanadium in glass and cer-





amics  is limited and shows little promise of potential growth.





About 2 tons per year are consumed in the production of a yel-




low stain for coloring pottery and glass.







The  main steps  in glassmaking are: (1) compounding the mix-




tures or "charge";  (2)  heating in a fire-clay pot to about 2, 800




F; (3) heat purification or cooking;  (4) shaping the glass objects




by blowing, pressing, or casting; and, (5) gradual cooling in an





oven.

-------
                           -39-
In the manufacture of glazes the dry ingredients are usually mixed





in the presence of an excess of water although it may  be desirable





to mix them dry.  Glaze materials are measured  dry  before pour-





ing into a mixer.  After thorough mixing,  there is a grinding stage





generally with a ball mill.







Dry mixing is usually done with a frit batch.  Measuring,  pouring,





mixing, and grinding are  carried on in a way very similar to wet





mixing.  There is, however, one additional  step;   the dry mixture





goes through a crushing stage.  This is to keep the batch from





clogging the ball mill.







Emissions due to making  glass and ceramics were negligible.







MISCELLANEOUS




Permanent magnetic alloys consist of iron,  cobalt, and about 15




percent vanadium.  They  are made in a manner similar to cast




iron and vanadium is added in the ladle before pouring into molds.







Welding rods and wires are usually made from steel produced in




an open-hearth furnace.  Any vanadium used in these  products





is added to the steel in  the ladle.  The steel billets are heated





and formed into  rods in the rolling mill.  These rods  are  then





drawn into wire.

-------
                           -40-
Compounds of certain metals  soluble in paint oils are used as





driers.  They may be prepared separately and added in the damp





paint mixing process, or they may be an incorporated part of the





paint oil through chemical reaction.  Liquid paint drier is pre-





pared especially for addition to paint. Driers may be added to





varnishes during the cooking period or later.  Varnish cooking




temperatures usually vary from 450 to 600  F.







A vanadium compound,  vanadium chloride,  is used for toning





silver  bromide in  the development of color  film.  This develop-




ment process involving  vanadium occurs in solution.  The vana-





dium chloride used is made first by heating vanadium pentoxide




with sulfur monochloride to produce vanadium trichloride.  Dis-





proportionation of the trichloride at 800 C in a stream of nitrogen




produces vanadium chloride.







Information obtained during this study varies considerably re-





garding vanadium  emissions from reprocessing operations.   Es-





timates have ranged from less than 0.25 to  5 percent.  Average




emissions are estimated at 10 pounds per ton of vanadium pro-




cessed.







During 1968 vanadium used in miscellaneous reprocessing opera-




tions totaled 460 tons, and atmospheric emissions were 2 tons.

-------
                           -41-
                   CONSUMPTIVE  USES







The largest vanadium emissions to the atmosphere are those





that are due to the combustion of coal and oil.   Those that oc-





cur during other  consumptive uses are mostly of such a nature




that atmospheric emissions are negligible.







COAL





During the combustion of coal vanadium is discharged with the




ash;  part with the bottom ash and part with the fly ash.   On the





average about 65 percent of the total ash is fly ash.







With respect to fly ash,  a study has been made  regarding emis-




sions from coal fired power plants and the emissions of vana-





dium have been recorded. Six power boilers  were tested, each





a different type,  and  each value reported was the average of at





least two tests.  Two of the boilers  were fired with Illinois coal;





two burned Pennsylvania coal;  one used s'ome coal from Ohio and




some from West  Virginia; one burned part Kentucky and part




West Virginia coal.   The coal burned during the tests represented




only a small portion of the coal mined in the various regions  of




the United States. Vanadium concentrations in  the fly ash samples




taken after fly  ash collection ranged from  0. 88  to 6. 6 grains  per

-------
                           -42-
scf x 10"     /.   The average was 2. 91 grains per scf x 10.

Based on  508, 990, 000 tons of coal consumed in the United States

during 1968   /,  90 percent application of control, a vanadium

concentration of 2. 91 grains per scf x 10" ,  and 160 scf of flue

gas per pound of coal, the vanadium emissions due to  the com-

bustion of coal are calculated at 3, 760 tons.
   508,990,000  x 160 x 2. 91 x  10'4 x 2,000
       —•                                     ~  3.760
             7,000 x 2, 000 x 0.9
Many samples of coal have been analyzed and the vanadium con-

tent reported is shown in Table I.  Based on a vanadium concen-

tration in coal averaging 22. 5 ppm,  90 percent application of con-

trol and 85 percent efficiency of control,  the vanadium emissions

calculated in this manner totaled 1, 750 tons.


  508,990,000 x 22. 5 x  10'6 x 0.65  [l  -  (0.85 x 0.90)]  = 1,750


In this report the figure of 1, 750 tons  is used as the vanadium

emissions to the atmosphere during 1968 due  to the combustion

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

2- Minerals Yearbook;  Bureau of Mines;  1968.

-------
                          -43-
                       TABLE  I

    AVERAGE MINOR  ELEMENT CONTENTS OF  COALS
FROM VARIOUS REGIONS OF THE UNITED  STATES - PPM
Region
Northern Great Plains
Eastern Interior
Appalachian
Western and Southwestern
Average Vanadium Content
Ash Content
of Coal - %
13.42
6. 16
6. 11
NR*
in Coal
V Content
of Coal - ppm
16.0
35.0
21.0
18.0
22. 5
*Not reported
NOTE - The above table based on Geological Survey Bulletins
        1117-C and 1117-D.

-------
                           -44-
OIL





In order to estimate vanadium emissions to the atmosphere due





to the combustion of fuel oil,  it was necessary to determine the





vanadium content, as well as  the quantity,  of oil. received from





numerous foreign and domestic, sources.  Analyses of more than





400 samples  of crude and residual oils were obtained from the





major oil companies and the utilities along the east coast of the




United States.







The data show that nearly all  crude oil contains some vanadium;




the concentrations ranging from nearly  zero to more  than 1,000




ppm.  It also shows that residual  oil contains a higher percentage




of vanadium  than the crude.   When oil is refined the vanadium




and other trace metals  tend to concentrate in the heavy fractions;




the residual  oil,  the road oil, and the asphalt.  According to the





information obtained from oil companies,  the residual fuel oils





may  be  expected  to contain 30 to 90 percent more vanadium than




the crude oils.







Unfortunately, most of  the analyses available were of crude oil.





They  show oil from California contains  more vanadium than that





from Kansas, Oklahoma, and Texas (Table II).  Crude  from





western Venezuela has  a much higher concentration than crude





from the eastern part of the country (Table III) or that from

-------
                           -45-
                        TABLE II

   VANADIUM  CONTENT  OF DOMESTIC CRUDE OILS
        c                                Vanadium
        Source
                                       Content - ppm
      Arkansas                               9.3
      California                             50. 0
      Colorado                               0.44
      Kansas                                15. 1
      Louisiana                              0. 5
      Montana                               78.0
      New Mexico                            0. 1
      Oklahoma                              4. 0
      Texas                                  2. 6
      Utah                                    4.6
      Wyoming                              49. 7
NOTE  -  The above table is based on private communication
         with industrial sources.

-------
                           -46-
                        TABLE  III

    VANADIUM  CONTENT  OF  VENEZUELAN CRUDE OILS
Crude
Western Venezuela
Bachaquero Heavy
Bachaquero
Bachaquero Light
Barinas
Boscan
Cumarebo
Lagunillas Heavy
La Rosa Medium
Mara
Mototan #7
Taparito
Tia Juana Light
Tia Juana Medium
Tia Juana Heavy
Urdaneta
Eastern Venezuela
Cachipo
Guanipa
Jusepin
Oficina Light
Oficina Heavy
Pedernales
Pilon
Quiriquire
San Joaquin
Temblador
Tigre
Tucupita
Gravity
API

13.2
16.6
35.4
25.9
10.6
47. 8
17.6
23.9
29. 5
19.7
17.2
31.9
25.6
18.2
11.3

34. 3
32. 7
31.9
35.3
31. 5
21.7
9.7
16.5
45.9
20. 6
26.5
15.7
Vanadium
Content - ppm

390
370
49
165
1,400
0.7
300
230
220
390
450
100
200
300
430

14
110
26
57
62
230
510
95
0.6
56
160
84
NOTE  -  The above table is based on private communication
         with industrial sources.

-------
                           -47-
other foreign sources (Table IV).  Residual oil from South

America contains about 280 ppm vanadium;  from the Middle

East about 50 ppm; and from the United States 30 ppm.


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

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

and the remainder were principally from domestic production  /.

Imports were about 92 percent from South America and the West

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

countries ^/.
              VANADIUM IN RESIDUAL OIL
       CONSUMED IN  THE  UNITED STATES -  1968

United
Source
States
South America
Middle
East and Other
TOTAL
Quantity
Barrels
258,311,000
376,000,000
33, 928, 000
668,239,000
V Content
ppm
30
280
50
V Content
Tons
1,280
17,350
280
18,910
1- "Crude Petroleum,  Petroleum Products, and Natural-Gas-
   Liquids: 1968";  Petroleum Statement, Annual;  Mineral
   Industry Surveys;  Bureau of Mines;   Washington,  D. C.

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

-------
                           -48-
                       TABLE  IV

   VANADIUM  CONTENT OF MIDDLE EAST  CRUDE  OILS
Crude
Agha Jari (Iranian)
Ain Dar (Arabian)
Ain Zalah (Iraqi)
Bai Hassan (Iraqi)
Gach Saran (Iranian)
Jambur (Iraqi)
Kirkuk (Iraqi)
Kuwait
Qatar
Safaniya (Arabian)
Shedgum (Arabian)
Uthmaniyah (Arabian)
Wafra (Neutral Zone)
Zubair (Iraqi)
Gravity
API
33.9
33.9
32. 1
33.3
31.0
39.2
36.3
32.3
42.2
27. 1
34.3
30. 0
24. 1
36.4
Vanadium
Content - pprn
36
51
95
19
114
6
30
30
3
80
18
51
52
20
NOTE  -  The above table is based on private communication
         with industrial sources.

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                            -49-
In the past power boilers designed to burn fuel oil were not us-





ually equipped with air pollution control apparatus.  It was only





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





mechanical collectors and/or electrostatic precipitators.   When




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




late matter becomes an atmospheric emission.







The records show that 669 million barrels of residual oil were





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





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





were the only users with any significant degree  of air pollution





control.  A survey was conducted and it was determined that





the electric utility percent of control when burning fuel oil  was




about 32 percent.







Based  on 10 percent overall control, the vanadium emissions




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




totaled 17, 000 tons.

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                           -50-


                    APPENDIX  A

          COMPANIES DEALING IN VANADIUM
               AND VANADIUM PRODUCTS
ALABAMA
LOCATION
   S.  Bornstein Metals,  Inc.
Birmingham
CALIFORNIA
   Centrifugal Products, Inc.
   Electronic Space Products, Inc.
   Fred H. Lenway and Company, Inc.
   Reactor Experiments, Inc.
   Research Inorganic Chemical Corp.
   Rolla Sitkin Metals,  Inc.
Long Beach
Los Angeles
San Francisco
San Carlos
Sun Valley
Los Angeles
COLORADO
   Climax Uranium Company
Grand Junction
ILLINOIS
   L. H. Hedger and Sons Metal Co.
   Steel Sales Corporation
Collinsville
Chicago
INDIANA
   Mefco, A Teledyne Company
   Union Carbide Corporation
Elkhart
Kokomo
MARYLAND
   Chicago Development Corporation
   Max  Zuckerman and  Sons, Inc.
Riverdale
Owing Mills

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                           -51-
MASSACHUSETTS

   Benton Corporation
   Whittaker Corporation
Beverly
West Concord
MICHIGAN

   Frankel Company, Inc.
   Wolverine Metal Company
Detroit
Detroit
MISSOURI
   Metal Goods Corporation
   Whitehead Metals, Inc.
St.  Louis
St.  Louis
NEW  JERSEY
   J.  T.  Baker Chemical Company
   Hyperrefiners, Inc.
   M  & R Refractory Metals,  Inc.
   E.  L. Payer Company
   Schiavone-Bonomo Corporation
   Shieldalloy Corporation
   Var-Lac-Oid Chemical Company
Phillipsburg
Clifton
Springfield
Wenoah
Jersey City
Newfield
Elizabeth
NEW  YORK

   Advanced Alloys, Inc.
   Alloychem, Inc.
   American Metal Climax, Inc.
   American Nickel Alloy Manufacturing
     Corporation
   Anglo-American Metal & Ferro
     Alloy Corporation
   Associated Metals and Minerals Corp.
   Atomergic Chemetals Company
   Baird Chemical Industries,  Inc.
   Belmont Smelting &: Refining Works, Inc.
   Paul Blum Company
   Brandeis, Goldschmidt and  Company
College Point
New York City
New York City

New York City

New York City
New York City
Carle Place, L.
New York City
Brooklyn
Buffalo
New York City

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                           -52-
   City Chemical Corporation
   Cometals, Inc.
   Continental Ore Corporation
   Diesel Chemical & Metal Company, Inc.
   Duro-Dyne Corporation
   Elgen Manufacturing Corporation
   Henning Bros. & Smith, Inc.
   Kolon Trading Company, Inc.
   Materials Research Corporation
   Mercer Alloys Corporation
   Metal Trading, Inc.
   Morgan Chemicals, Inc.
   Niagara Falls Metals & Minerals,  Inc.
   Overseas Metal and Ore Corporation
   Pancoast International Corporation
   Philipp Brothers
   Progressive Alloys Corporation
   Samincorp
   J.  A. Samuel & Company, Inc.
   Skandia Metals Corporation
   Stalco International
   Stevens Metallurgical Corporation
   C.  Tennant Sons and Company
   Union Carbide Corporation
   United Mineral and Chemical Corp.
   Vanadium Corporation of America
   Samuel J. Zuckerman,  Inc.
New York City
New York City
New York City
Brooklyn
Farmingdale,  L.
Long Island City
Brooklyn
New York City
Orangeburg
New York City
New York City
Buffalo
Buffalo
New York City
New York City
New York City
Brooklyn
New York City
New York City
New York City
New York City
New York City
New York City
New York City
New York City
New York City
Floral Park
OHIO
   Cleveland-Cliffs Iron Company
   Metal Powder Products,  Inc.
Cleveland
Logan
OREGON
   Oregon Metallurgical Corporation
Albany
PENNSYLVANIA

   Bram Metallurgical-Chemical Company  Philadelphia
   Chemalloy Company, Inc.               Philadelphia

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                           -53-
   Derby and Company, Inc.                Pittsburgh
   Foote Mineral Company                 Exton
   Mercer Alloys Corporation              Greenville
   Reading Alloys,  Inc.                    Robesonia
   Semi-Elements,  Inc.                    Saxonburg
   Joseph Tyson and Company              Cheltenham
   Vitro Manufacturing Company           Pittsburgh
TEXAS
   Lloyd M. Parkans Company             Houston
   Robinson Orifice  Fittings Company       Houston
WASHINGTON
   Stoker Engineering Company             Tacoma
(American Metals Market,   Jan.  13, 1970;  Thomas Register,
Dec. 1968 Ed. )

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 BIBLIOGRAPHIC DATA
 SHEET
1. Report No.
  APTD-1511
                                                                      3. Recipient's Accession No.
  Title and Subtitle
  National  Inventory of  Sources and  Emissions:  Vanadium -  1968
                                                 5- Report Date
                                                   June 1971
                                                                      6.
7. Auihor(s)
                                                 8- Performing Organization Rept.
                                                   No.
9. Performing Organization Name and Address
 W.  E. Davis  & Associates
 9726 Sagamore Road
 Leawood,  Kansas
                                                 10. Project/Task/Work Unit No.
                                                 11. Contract/Grant No.

                                                    CPA  70-128
12. Sponsoring Organization Name and Address

  ENVIRONMENTAL PROTECTION AGENCY
  Office of  Air Programs
  Durham,  North Carolina
                                                 13. Type of Report & Period
                                                    Covered
                                                 14.
15. Supplementary Notes
16. Abstracts

 An  emission  inventory has  been prepared to determine the  nature, magnitude, and  extent
 of  the emissions of vanadium in the  United States  for the year 1968.   The production
 and use  of  vanadium in  the U. S.  has  been traced  and charted.  The  consumption  was
 5,495 tons,  exports 741  tons, and  imports 652  tons.   About 80% was used in the produc-
 tion of steel.   Emissions  to the atmosphere during the year totaled  19,231 tons.
 Emissions  due to the combustion of fuel oil and coal were 17,000 tons  and 1,750  tons
 respectively.   Emissions resulting from the production of ferrovanadium were  144 tons
 and those  from the production of steel were 236 tons.
17. Key Words and Documem. Analysis.  17o. Descriptors
 Air pollution             Utilization
 Vanadium                  Consumption
 Emission
 Inventories
 Sources
 Mining
 International  trade
 Reprocessing
 Metallurgical  furnaces

17b. Identifiers/Open-Ended Terms

 Year 1968
 United States
17c. COSATI Field/Group    ] 35
18. Availability Statement
FORM NTIS-35 (REV. 3-72»
                     Unlimited
                                      19. Security Class (This
                                        Report)
                                                           20. Security Class (This
                                                             Papc
                                                                UNCLASSIFIED
21. No. of Pages
        60
                                                            22. Price
                                                                                 USCOMM-DC 14Q52-P72

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FORM NTIS-33 (REV. 3-721                                                                                  USCOMM-DC  14032-P72
                                                 S G. P. O.  1973 — 746-77O / 4IB1

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