`·EPA-56/2-15-D05A
`
`PRELIMINARY INVESTIGATION OF
`EFFECTS ON THE ENVIRONMENT OF BORON,.
`INDIUM NICKEL, SELENIUM, TIN, VANADIUM
`AND THEIR COMPOUNDS
`
`'
`
`VOLUME I
`
`BORON
`
`. .
`
`OFFICE OF TOXIC 11/aTAMCEI
`f/ROII.EMTAL PROTECT/OM ASSCY
`WASNIMSTDM, D.C. 11411
`
`AUSUST, 1116
`
`CFAD v. Anacor, IPR2015-01776 ANACOR EX. 2043 - 1/118
`
`
`
`EPA-560/2-75-00Sa
`
`PRELIMINARY INVESTIGATION OF
`INDIUM
`EFFE:T~ ON THE ENVIRONMENT OF BORON,
`NICKEL, SELENIUM, TIN, VANADIUM AND THEIR COMPOUNDS
`
`Volume I
`
`Boron
`
`Contract No. 68-01-2215
`
`Project Officer
`
`Farley Fisher
`
`Prepared for
`
`Office of Toxic Substances
`Environmental Protection Agency
`Washington. D.C.
`20460
`
`August 1975
`
`CFAD v. Anacor, IPR2015-01776 ANACOR EX. 2043 - 2/118
`
`
`
`BOIDN
`TABLE OF CX>NTENTS
`
`I.
`
`ro~OID . . . . • • . .
`. . . . . •
`OOIDN INDUSTRY IN THE UNITED STATES
`A. Producers and Sites
`• • • • • • • • • • • • • • •
`B. Costs a."ld Physical Prqerties of Irrportant Boron
`Compounds • • • • • • • •
`rr . ProrucrroN . . • . • . • . • • .
`A. Natural Souroes of Berates •
`B. Manufacturing Proresses.
`1. Elenental Boron
`• • •
`2 . B<Jr ax • • • • • o
`a. The Mining Process •
`b. Trona Process. • • •
`3. Anhydrous Borax
`• • . •
`4. Boric Acid .
`.
`.
`.
`.
`.
`.
`.
`.
`. .
`.
`5. Boric Oxide (Bz03, boron trioxide)
`6. Boron Trifluoride (BF3)
`• • • • • • • • • • •
`7. Boron Trichloride
`• • . • . • • • • . • • . •
`8. Diborane and Higrer Boranes (Pentaborane, etc.)
`9. Refracto.cy boron c::x::rrp:mnds (rretal borides, boron
`carbide, and boron nitride)
`III. USES OF OORCN CCMPOUNDS. • • • •
`A. Uses of Boron Catpounds
`• •
`B. Future and Potential Uses
`
`• • •
`
`• • •
`
`•
`
`•
`
`•
`
`•
`
`•
`
`. • • •
`• • • • •
`.
`.
`.
`.
`
`IV.
`v.
`
`aJRRENT PRACI'ICES • • • • • •
`
`ENVIRONMENTAL CCNTAMINATION
`
`.. .
`
`A. From Uses. • • • • • • • • •
`1. Emissions to the At::nosphere (including fran
`production) • • • • • • • • • • • • • • •
`2. Arrount Enrering Warers and Earth .
`. • • •
`B. Frc:J!l Prcduction
`. • .
`.
`· 1. Mining . • .
`. • . •
`. • .
`2. Processing •
`c.
`. • . • • •
`. • • .
`Inadvertent
`•
`. • .
`D. Total Anounts Entering Envi.rarurent per Year
`
`.
`.
`
`i.
`
`Page
`I-1
`I-2
`I-2
`
`I-12
`r -16
`I-16
`I-16
`I-16
`I -19
`I-19
`I-21
`I-21
`I-21
`I-24
`I-24
`I-24
`I-24
`
`I-27
`I-28
`I-28
`I-34
`I-35
`I-37
`I-37
`
`I-39
`I-40
`I-40
`I-40
`I-40
`I -41
`I-41
`
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`
`
`
`OORON
`TABLE OF OONl'EN'IS
`(Con 't)
`
`VI.
`
`. . . .
`
`MCNI'IORLNG AND ANALYSIS •
`• • • • •
`A. Monitoring
`• • • • •
`• • • • •
`B. Analysis. • • • • •
`1. Deternti.natian of Boron in Water • • • • • • • •
`2. Detenninaticn of Boron in Plants and Biological
`Materials • • • • • • • • • • • • • • • •
`3. Analysis of Available Boron in Soil • • • •
`4. Detection of Boron in Airborne Contaminants
`COllected in Air Filters
`• • • • • • • • • •
`5. Analysis of Boron in Air by COlorinetry • • . • •
`VII. ~CAL REACriVI'I"i • • • • • • • • • • • • • •
`A. Environmental and Use Associated :Reactions
`B. Aspects with Biological Inplication ••••
`VIII. BIOIOOY
`A. Absorption, Excretion, Grcwth, and Nutrition. •
`1. Hllllli3l1S • • • • • • •
`• • • • • • • • • • •
`2 • Nonhuman Manlnals
`• • • • • • •
`3. PlarltS
`•
`. • .
`.
`.
`.
`.
`. • .
`.
`4 . Microorganisms
`• • • •
`B • BiocheJni.stry. • • •
`• • • •
`1. Humans. • • • •
`2. Nonhuman Mammals ••••••.
`3 • Ncnrnarnmalian Vertebrates
`4. Plants
`. • • • • . • • • •
`5. MicroorganiS!l\'3
`'nlerar.eutic Uses . •
`1. Humans . . . • •
`2. Nonhuman Mamnals
`3. Plants
`• . • • •
`ENVIRONMENTAL EF.FECI'S • • •
`A. Enviranrrental Content, Transport, Contamination
`B. Bioaccunulation and Content •
`1. Human ••
`2 • Man'lrlals •
`3. Plants
`
`.
`
`.
`
`.
`
`.
`
`.
`
`.
`
`. .
`
`c.
`
`IX.
`
`ii.
`
`Page
`I-43
`I-43
`I-43
`I-43
`
`I-43
`I-44
`
`I-44
`I-44
`I-45
`I-45
`I-45
`
`I-48
`I-48
`I-48
`I-49
`I-51
`I-51
`I-51
`I-53
`I-56
`I-56
`I-58
`I-59
`I-59
`I-60
`I-60
`I-62
`I-62
`I-64
`I-64
`I-65
`I-65
`
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`
`
`
`-.{RjAR [NC.
`
`BORON
`
`TABLE OF CON'IENI'S
`(Coo. 't)
`
`X.
`
`'roXICITY . .
`A. Htlllal1S . .
`
`. . . .
`. .
`. .
`. . . .
`. . .
`1. Acute Toxicity
`. . . . .
`. . .
`2. Chrcari.cToxicity
`B. Manmal.s . . . . . . . . . .
`
`. . . . .
`. . .
`. .
`1. Acute Toxicity •
`2. Olronic'lbxicity .
`3.
`'Ieratogenicity •
`4. Allergic Reactions and Sensitization
`5. Behavioral Effects . .
`. . . . .
`6. carcinbgenici ty
`c. Naunanmalian Vertebrates
`D.
`Invertebrates
`E. Plants . . . . . . . . .
`. . . .
`. .
`F. Microorganisms . . . . . . . . . .
`Iesults of Personal Contacts with M:rlical Personnel
`G.
`aJRRENT REGULATIONS AND EFFECI'S LEVELS . . . .
`A. Toxicity levels . . . . . . • . . . . .
`. . •
`c. Foreign Iegulaticns . . . . . .
`. .
`srANOAIDS. . . . . . • . . . . . • . . . • .
`XII.
`XIII. St:Jf.MARY AND CONCLUSIONS
`A. Sumnary . . . .
`B. Ccnclusicns . . . .
`c.
`Iecxmrendations
`
`. . . . .
`
`XI.
`
`B. Transportation and Handling Pegulaticns
`
`. . . .
`
`. . . .
`
`iii.
`
`Page
`I-66
`I-66
`I-66
`I-67
`I-68
`I-68
`I-69
`I-72
`I-73
`I-73
`I-73
`I-73
`I-74
`I-77
`I-84
`I-84
`I-86
`I-86
`I-86
`I-87
`I-88
`I-89
`I-89
`I-90
`I-90
`
`CFAD v. Anacor, IPR2015-01776 ANACOR EX. 2043 - 5/118
`
`
`
`BORON
`
`I.JSI' OF TABLES
`
`1.
`· • • •
`Products and P:rcxluccrs • • • ·
`2.
`Pria=s of Boron Minerals and Chemicals •
`3.
`Physical Properties
`.
`. • • . • .
`.
`.
`Production of Berates in the United States as of 1972
`4.
`5. Uses .
`.
`.
`.
`. .
`.
`Emission Factors .
`6.
`7.
`Bon1n Emissions by Sourre, 19 72
`8. Rclotivc Stabilities of Boron Hydrides
`9. DL:tqnostic Criteria for Boron Nutrition of Field and Vegetable
`Crops Based upon Hot Water Extraction of Soil Boron
`Toxic !bran Ccnrentrations of Saturation Extracts for
`Se.nsi ti 'I.e, Sr.>Jn.i.tolerant Crop Sp:=cies .
`Plant GrCMth as Affected by Boron • • • • • • .
`Syrnptorrs of Boron 'I'oxici ty • .
`.
`.
`
`10.
`
`11.
`12.
`
`. . .
`
`Page
`I-2
`I-13
`I-14
`I-18
`I-30
`I-38
`I-38
`I-46
`
`I-:)0
`
`I-78
`I-79
`I-82
`
`iv.
`
`CFAD v. Anacor, IPR2015-01776 ANACOR EX. 2043 - 6/118
`
`
`
`BORON
`Lisr OF FIGURES
`
`Location of Bo:r.ate de!;X)sits m California, Nevada and Oregon .
`1.
`2.
`Borax production from ore . . . . . • • . • • . . • • • • • • .
`3.
`Borax manufacture fi:On Searles Lake brine
`4.
`Anhydrous Borax process
`5. Boric ucid manufacture
`G.
`Boric acid manufacture
`Distribution of Boron uses . .
`7.
`8.
`Boron conmntr<J.tion in plant tissues related to concentration
`in soil solution .
`.
`.
`.
`. • .
`.
`. • . • • .
`.
`. . •
`Effect of Boron concentration an plant growth
`
`9.
`
`~
`I-17
`I-20
`I-22
`I-23
`I-25
`I-26
`I-29
`
`I-52
`I-76
`
`v.
`
`CFAD v. Anacor, IPR2015-01776 ANACOR EX. 2043 - 7/118
`
`
`
`Vol1..1100 I
`
`Preliminary Investigation of Effects
`on Envirol'liTent of Boron and Its eonpounds
`
`This is Velure I of a series of six reports on the environrrental
`effects of lx>ron, indiun, nickel, selenium, tin, and vanadium and their
`oonpounds. The information is based on literature reviews, direct ron(cid:173)
`tact with representatives of companies involved in the production or
`usc of the materials, and consultation with knowledgeable individuals
`from industry r academic institutions and the Federal Governrrent.
`
`CFAD v. Anacor, IPR2015-01776 ANACOR EX. 2043 - 8/118
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`
`
`1-2
`
`I.
`
`BORJN INDUSTRY IN THE UNITED STATES
`
`A. Prcrlurers and sites
`Table I li!3ts CXJI'llrercially significant chemical products and the
`o::mpanies involved. For this study significant is defined as production
`exreeding 1/2 rretri~ ton or $1,000 value. Other reterials rey also re included
`in the discussion because of treir tmusual properties, such as toxicity, or
`their anticipated future significance.
`Table 1
`f3oron PrOO.uct.s and PrOO.ucers (l)
`
`Che.m:i.. cal
`
`Producer
`Company, subordination
`
`Location
`
`Beverly, Mass.
`Wilmington, Del.·
`
`Marcus Hook, Pa.
`Boyertown, Pa.
`
`Cle~land, Ohio
`
`Marcus Hook, Pa.
`Brooklyn, N.Y.
`Jersey City, N.J.
`
`Marcus Hook, Pa.
`
`Trona, Calif.
`
`San Francisco, calif.
`Wilmington, Calif.
`
`Boron, Calif.
`Brooklyn, N.Y.
`
`Newark, N.J.
`Boyertown, Pa.
`
`Annonium fluolx>rate
`(Ammonium lx>roflooride}
`
`Antirrony fluoborate
`
`Barium borotunqstate.
`Boric acid (Boracic
`acid)
`
`Ventran Corp. , Alfa Prcrlucts Di v.
`Aluminum diboridc
`U.S. ~rax & Chern. Corp.
`Amronium lx>rate
`(Ammonium acid tetraborate)
`Allied Chern. Corp.
`Specialty Chems • Di v.
`Kawecki Beryloc Indust., Inc.
`Kewanee Oil Co., Harshaw Chern. Co.,
`Indust. Chems. Dept.
`Allied Chern. Corp.
`Specialty Chems • Di v.
`Harstan Chern. Corp.
`City Chern. Corp.
`Allied Chern. Corp.
`Specialty Olems • Di v.
`Kerr-McGee Corp.
`Kerr-McGee Chern. Corp. , subsid.
`Stauffer Chern. Co.
`Indust. Olern. Div.
`U.s. ~rax & Chern. Corp.
`u.s. Borax & Chern. Corp.
`Belrront Srrelting & Refining
`Works, Inc.
`Fairnotmt Chern. Co., Inc.
`Kawecki Pcryloo Indust., Inc.
`
`Ibric acid es tcrs
`
`Boron
`
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`
`
`
`. y{ u}i R I Nl:.
`
`ili~mical
`
`noron (Con' t)
`
`1-3
`
`IDeation
`
`Henderson, Nev.
`
`Callery, Pa.
`
`Wood Ridge, N.J.
`Rockford, Ill.
`Newark, N.J.
`Boyertown, Pa.
`Worcester, Mass.
`
`(l)
`~ral>le 1 (Con' t)
`Boron Products and Producers
`Producer
`Conpany, subordination
`Kerr-Mc!",ee Corp.
`Kerr-McGee.Chern. Corp., subsid.
`Mine Safety Appliances Co.
`Callery Chern. Co., di.v.
`u.s. Borax & Chern. Corp.
`U.S. Borax Iesearch Corp., subsid. Anaheim, Calif.
`Ventron Corp.
`Chems. Div.
`
`Ibron cat"bide
`
`!bran fluoridc(cid:173)
`cthylamli1e complex
`(Ethyl amine boron
`triflmridc)
`
`Boron fluoride
`orthophosphoric acid
`
`Po ron ni tridc
`
`no ron oxi< 1c
`
`Boron phosphate
`
`Boron phosl,)h.i.dc
`
`Apache Chems • , Inc.
`Fairnount Ch:!m. Co. , Inc.
`~cki Beryloo Indust., Inc.
`
`Norton Co.
`
`Ven tron Corp.
`Alfa Products Div.
`Kewanee Oil Co.
`Harshaw Olein. Co., div.
`Indust. Chems. I:ept.
`Ozark-Mahoning co.
`Kewanee Oil Co.
`Harshaw Chern. Co., di.v.
`Indus t. Chems • Dept.
`The carborundum Co.
`Refractories and Electronics Div.
`Fairrrotmt Chern. Co., Inc.
`Ka~cki Be:ry loo · Indust. , Inc.
`Ventron Corp.
`Alfa.Products Div.
`Allied Chern. Co:rp.
`Specialty Chems • Di v.
`Eagle-Picher Indust., Inc.
`Electronics Div.
`Stauffer Chern. Co.
`Indust. Chern. Div.
`Ventron Corp.
`Alfa Products Div.
`
`Ventron Corp.
`Alfa Products Div.
`
`Beverly, Mass.
`
`Cleveland, Ohio
`'I\llsa, Okla.
`
`Cleveland, Ohio
`
`Ia t.rol::e , P a .
`Newark, N.J.
`Boyertown, Pa.
`
`Beverly, Mass.
`
`Marcus Hook, Pa.
`Miami, Okla.
`Quapaw, Okla.
`
`San Francisco, calif.
`
`Beverly, Mass.
`
`Beverly 1 Mass.
`
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`
`
`Olemical
`
`Boron tribrcrnide
`
`Boron trichloride
`
`Boron trifluoride
`
`(l)
`Table 1 (can't)
`·
`Boron Products and Producers
`· Producer
`canpany 1 SuOOrdinatial
`Eagle-Picher Indust., Inc.
`Electronics Div.
`Kerr-McGee Corp.
`Kerr-McGee Chern. Corp.,
`Allied Chern. Corp.
`Specialty Chems. Div.
`Kerr-McGee Corp.
`Kerr-McGee Chern. Corp.,
`Allied Chern. Corp.
`Specialty Chems • Di v.
`Kewanee Oil Co.
`Harshaw Olern. Co., div.
`Indust. Chems. rept.
`
`subsid.
`
`subsid.
`
`Boron trifluoride ethyl
`ether complex
`·
`
`Allied Chern. Corp.
`Sp:!cial ty Chems • Di v.
`
`Boron trifluoride(cid:173)
`phenol oonplex
`
`Allied Chern. Corp.
`Sp:!cialty Cherns. Di v.
`
`Boron triiodide
`
`Ventron Corp.
`Alfa Products Div.
`
`Boroxines (unspecified)
`
`Calcitnn borire
`(calciwn hexaboride)
`
`Ch:ronri.wn boride (mono)
`
`Chromium fluoboratc
`
`CObalt oorate
`(Oobaltous borate)
`Cobalt fluoborate
`(Cobaltous fluobor<lte)
`
`Mine Safety Appliances Co.
`Callery Chern. Co"¥ div.
`'.nmne<X> Inc.
`Termeoo Oil Co., Div.
`U.S. Borax & Chern. Corp.
`u.s. Borax Ieseardl. Co:rp., subbid.
`fulybcenum Oo:rp. of Arrerica
`Cherre • and Rare Earth Di v.
`Ventron Corp.
`Alfa Products Di v.
`U.S. Borax & Chem. CO:rp.
`U.S. Borax Research Co:rp.
`Ventran Co:rp. , Alfa
`Products Di v.
`Allied Chern. Corp.
`Sp:!cialty Chems. Div.
`The Shepherd Chern. Co.
`
`Harstan Clem. Co:rp.
`Ventran Chern. Corp.
`Alfa Products Div.
`
`1-4
`
`IDeation
`Miami, Okla.
`Quapaw, Okla.
`
`Henderson, Nev.
`
`Marcus Hook, Pa.
`
`Henderson, Nev.
`
`Marcus Hook, Pa.
`
`Cleveland, Ohio
`
`Cleveland, Ohio
`
`Marcus Hook, Pa.
`
`Marcus Hook, Pa.
`
`Beverly, Mass.
`
`Callecy·, Pa.
`J::eath Valley
`Jmction, Calif.
`
`Anaheim, Calif.
`
`Washington, Pa.
`
`Beverly, Mass.
`.
`Anaheim, Calif.
`
`Beverly, Mass.
`
`Marcus Hook, Pa.
`
`Cincinnati, Ohio
`
`Brooklyn, N.Y.
`
`Beverly, Mass.
`
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`
`
`V:u;;, u I xr:.
`
`Cllemi.cal
`Copt:er borate
`(Cupric l:x>rate)
`
`Copp:!r fluaborate
`(Cupric fluoborate)
`
`Indium fluoborate
`
`Iron borate
`(Ferric borate)
`Iron fluoborate
`(Ferrous fluaborate)
`
`· lead borate
`
`Lead fluaborate
`(Plumbous fluoborate)
`
`Lithium borohydridc
`
`Lithium fluoroborate
`
`M.ilgnesium borate
`
`Magnesium fluoborate
`
`(l)
`Table 1 (Con' t)
`Boron Products and Producers
`Producer
`
`1-5
`
`Cbrrpany, subordination
`
`IDeation
`
`City Chern. Co:r:p.
`The Shepherd Chern. Co.
`Allied Chern. Corp.
`Specialty . 01ems • Di v.
`Iiarstan Chern. Corp.
`Kewanee Oil Co.
`Harshaw Chern. Co.
`Indust. Chems. ll!pt.
`Allied Chern. Corp.
`Specialty Chems • Di v.
`Harstan Chern. Corp.
`The Indium Corp. of Anerica
`City Chern. Corp.
`
`Allied Chern. Corp.
`Specialty 01ems. Div.
`Harstan Chern. Corp.
`
`Hunphrey Chern. Corp.
`The Srepherd Chern. Co.
`Allied Chern. Corp.
`Specialty Chems. Div.
`Harstan Olem. Corp.
`Kewanee Clem. Co.
`Harshaw Chern. Co.
`Indust. Chems • Dept.
`Mine Safety Appliances Co.
`callery Chern. Co.
`Ventran Corp.
`Alfa Products Di v.
`Chems. Div.
`Foote Mineral Co.
`Ozark-Mahoning Co.
`Ventron Corp.
`Alfa Products Div.
`The Srepherd Clem. co.
`Allied Chern. Corp.
`Specialty Chems. Di v.
`Kewanee Oil Co.
`Harshaw ~. Co.
`Indust. Chems. ~pt.
`
`Jersey City, N.J.
`Cincinnati, Ohio
`
`Marcus Hook, Pa.
`Brooklyn, N.Y.
`Cleveland, Ohio
`
`Cleveland, Ohio
`
`Marcus Hook, Pa.
`
`Brooklyn, N.Y.
`Utica, N.Y.
`Jersey City, N.J.
`
`Marcus Hook, Pa.
`Brooklyn, N.Y.
`Edgewood Arsenal, Md.
`Cincinnati, Ohio
`
`Marcus Hock, Pa.
`Brooklyn, N.Y.
`
`Cleveland, Ohio
`
`Callery, Pa.
`
`Beverly u Mass.
`Exton, Pa.
`Tulsa, Okla.
`
`Beverly, Mass.
`Cincinnati, Ohio
`
`Marcus Hook, Pa.
`
`Cleveland, Ohio
`
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`
`
`v::J~jA R /.Nr:.
`
`Chemical
`Manqancse borate
`(Manqanous borate)
`
`Manganese boride
`
`Manganese flooborate
`(Manganous fluol::orate)
`J.l.blybdenum boride', nono
`, di-:
`
`Nickel flooborate
`(Ni<"'..kelous flooborate)
`
`Niobiwn boride
`(Niobium dibbride)
`
`Phosphine borancs
`
`Potassium borohydride
`
`Potassium fluoboriltc
`
`(l)
`Table 1 (Con' t)
`Boron Products and Producers
`
`1-6
`
`Producer
`Conpany, subordination
`CheiTe tron Corp. , Cherng.
`Group, Inorganic Cherrs • Di v.
`Gen. Metallic Oxides Co.
`The Sh:;!pherd Chern. Co.
`
`J.l.blybdenum Corp. of 1\merica
`Chems. and Rare Earth Di v.
`City Chern. Corp.
`
`U.s. Borax & Chern. Corp.
`U.s. Borax Pesearch Corp.
`Allied Chern. Corp.
`Specialty Chems. Div.
`Arrerican Can Co.
`M&T Olems. Inc.
`Hars tan Chern. Corp.
`Kewanee Oil Co.
`Harshaw Chern. Co.
`Indust. Cherns • Dept.
`
`Ozark-Mahaning Cb.
`Ventrc:rn Corp. , Alfa
`Products Div.
`Kawecki Beryloo Indust., Inc.
`u.s. Borax & Chern. Corp.
`U.S. Borax Research Corp.
`Ventron Corp.
`Alfa Products Div.
`Mine Safety Appliances Co.
`Callery Chern. Co.
`Mine Safety Appliances Co.
`Callery Chern.· Co., div.
`Ventran Corp.
`Chems. Div.
`Allied Chern. Corp.
`Specialty Cherns. Di v.
`Borden Inc.
`Borden Chems • Di v.
`Smith-Douglass
`Kawecki Beryloo Indust., Inc.
`Kewanee Oil Co.
`Harshaw Chern. Cb. di v.
`Indust. Cherns. Dept.
`
`Location
`
`Cleveland, Chio
`Jersey City, N.J.
`Cincirmati, Ohio
`
`Washington, Pa.
`Jersey City, N.J.
`
`Anaheim, calif.
`
`Marcus Hook, Pa.
`
`East Chicago, Ind.
`Brooklyn, N.Y.
`
`Cleveland, Ohio
`
`Tulsa, Okla.
`
`Beverly, Mass.
`Boyerta.vn, Pa.
`
`Anaheim, Calif.
`
`Beverly, Mass.
`
`call.e:ry, P a.
`
`callery, Pa.
`
`Beverly, Mass.
`
`Marcus Hook, Pa.
`
`Plant City, Fla.
`Boyertown, Pa.
`
`Cleveland, Ohio
`
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`
`
`
`'l'able l (Con' t)
`1
`Boron Prcducts and Producers ( )
`
`1-7
`
`~1nical
`
`Potassiwn fluoborate
`(o:n 't)
`
`Rubidium borohydride
`
`Silicon hexaboride
`(Hexaboron silicide)
`
`Silicon tetraboride
`
`Sil~r fluo:r.borate
`
`Sodium borodeuteric"b
`
`Sodium borohydride
`
`Sodium flt.nborate
`(Sodium borofloori~)
`
`Sodium Octa}_x)rate
`Sodi urn Pen tilboratc
`
`Sodium ~rboratc,
`rronohydratc
`
`Prcxlucer
`Conpany, subordination
`
`Ozark-Mahoning Co.
`Ventron Corp.
`Alfa Products Di v.
`Vent..ral Corp.
`Alfa Products Div.
`Ventron Corp.
`Alfa Products Div.
`Mallinck.rcx:lt Chern. W:n:ks
`Indust. Chems. Div.
`Ventron Corp.
`Alfa Products Div.
`Allied Cllem. Corp.
`Specialty Cherns • Di v.
`Harstan Cl'lern. Corp.
`Ozark-Ma.honing Co.
`
`Ventron Corp.
`Alfa Chems. Div.
`Ventron Corp.
`Alfa Products Di v. ,
`Chems. Div.
`
`Mine Safety Appliances, Co.
`callery Chern. co. , di v.
`Ventron Corp.
`Alfa Products Div.
`Cl'lerns • Di v.
`Allied OJem. Corp.
`Specialty ~. Div.
`Kawecki Beryloo Indust., Inc.
`Kewanee Oil Co.
`Harshavv Olein. Co. , di v.
`Indust. Chems. Dept.
`Ozark-Mahoning Co.
`Ventran Corp.
`·Alfa Products Div.
`U.S • Borax & Chern. Corp.
`Kerr-McGee Corp.
`Kerr~ Chern. Corp., subsid.
`
`Location
`
`Tulsa, Okla.
`
`Bever 1 y, Mass •
`
`Beverly 1 Mass.
`
`Beverly 1 Mass.
`
`St. Louis, Mo.
`
`Beverly, Mass •
`
`Marcus Hook, Pa.
`Brooklyn, N.Y.
`
`Tulsa, Okla.
`
`Beverly, Mass.
`
`Beverly I Mass.
`Beverly, Mass.
`
`callery, Pa.
`
`Bever 1 y 1 M:l.ss •
`Beverly 1 Mass.
`
`Marcus Hook 1 Pa.
`Boyert:c:fNn 1 P a.
`
`Cleveland, Ohio
`'I\llsa, Okla.
`
`Beverly, Mass.
`Wilmington, calif.
`
`Trona, calif.
`
`FM:: Coxp.
`Inorganic Cherns • Di v.
`
`Buffalo, N.Y.
`
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`
`
`
`(Con' t)
`'I'<Jblc l
`Boron Products and Producers (l)
`
`1-8
`
`Olemical
`
`Scx1itm1 perborate
`tetrahydrate (Sodium
`rretaborate peroxyhydrate)
`
`Soditm1 tetraborate (:Borax)
`(Produood as Anhydroun
`Borax, Borax decahydrate,
`and Borax pentahydrare)
`
`Sodium tetraphenylboror
`(Sodium tetraphenylborate)
`
`Tantalum diboride
`Tin fluoborate
`(Stannous fluoborate)
`
`Titanitun diboridc
`('I'itaniurn boride)
`
`'I\.lnqsten rronoboride
`
`Vanadium diboride
`
`Zinc borate
`
`Producer
`Cbnpany, subordination
`
`E. I. duPont re Nerrours & Co., Inc.
`Indust. Chems. ~pt.
`Filo Color & Chern. <l:>rp •
`FMC Corp.
`Inorganic Chems. Div.
`Kerr-McGee Corp.
`Kerr-McGee Chern. Corp. , subsid.
`Occidental Petroleum Corp.
`Searles Lake Olern. Co., subsid. *
`Stauffer Chern. Co.
`Indust. Chem. Di v.
`U.s. Borax & Chern. Corp.
`Allied ChP.rn. Corp.
`Specialty ChenlS. Di v.
`Richardson-!Jerrell, Inc.
`J .T. Baker Chern. Co., subsid.
`Kawecki Beryl co Indust., Inc.
`Allied Chern. Q:>rp.
`Specialty Chems. Div.
`Harstan Olern. Corp.
`Kewanee Chern. <l:>rp.
`Harshaw Chern. Co.
`Indust. Cherns. Dept.
`Kawecki Beryloo Indust., Inc.
`U.s. Borax & Chern. Co1:p.
`U.S. Borax ~search Corp.
`Ventron Corp.
`Al.fa Products Di v.
`U.S. Borax & Chern. Corp.
`u.s. Borax Ieseard1 Corp.
`U.S . Borax & Chern. Corp.
`u.s . Borax :research Corp .
`Ventran Corp.,
`Alfa Products Div.
`Hunphrey Chern. Corp •
`Maryland Zinc & Research Co.
`U . S . Borax & Chern. Corp.
`ven t..ran Corp.
`Alfa Products Div.
`
`IDeation
`
`~his, Tenn.
`Newa.rl<., N .J •
`
`Buffalo, N.Y.
`
`Trona, Calif.
`
`Searles Lake, Calif.
`
`West End, Calif.
`Boron, Calif.
`
`Marcus Hook, Pa.
`
`Phillipsburg, N.J.
`Boyertor,.m, Pa.
`
`Marcus Hook, Pa.
`Brooklyn, N.Y.
`
`Cleveland, Ohio
`Boyertown, Pa.
`
`Anaheim, Calif.
`
`Beverly, Mass.
`
`l.nahe:i.m, Calif.
`
`Anaheim, Calif.
`
`Beverly, Mass.
`Edgewood Arsenal, Md.
`Cockeysville, Md.
`Wilmington, Calif.
`
`Beverly, Mass.
`
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`
`
`Olemical
`
`Zinc fluaborate
`
`<::.i. rconiwn diboridc
`(Zirconium boride)
`
`Decaborane
`
`Diborane
`
`'rable 1 (Con't)
`(1)
`Boron Products and Producers
`Producer
`Canpany, subordination
`
`Allied Chern. Corp.
`Specialty Chems. Di v.
`Harstan Chern. Corp.
`Kewanee Oil Co.
`Harshaw Chern. Co.
`Indust. Chems. Oept.
`Mineral Ibsearch and Oev. Corp.
`VGntron Corp.
`Alfa Products Div.
`Kawecki Beryloo Indust. Inc.
`U.S. Borax & Chern. Corp.
`u.S • Borax Fesearch Corp •
`
`OO:AANES (Inorganic)
`
`Mine Safety Appliances Co.
`Callery Chern. Co., div.
`Mine Safety Appliances co.
`Callery Chern. Co., div.
`G. D. Searle & CO.
`Will Ross, Inc., subsid.
`Matheson Gas Products, div.
`
`Octadccaborune
`
`Pcntabor<mc
`
`Ventron Corp.
`Alfa Products Div.
`Mine Safety Appliances Co.
`Callery Chern. Co. , di v.
`
`OffiANIC IPRON COMPOUNDS
`
`1-9
`
`Location
`
`Marcus Hook, Pa.
`
`Brooklyn, N.Y.
`
`Cleveland, Ohio
`Conoord, N.c.
`
`Beverly, Mass.
`Boyertown, Pa.
`
`Anaheim, calif.
`
`Callery, Pa.
`
`Callery, Pa.
`
`CUcamonga, Calif.
`East Rutherford, N.J.
`Gloucester, Mass •
`Joliet, Ill.
`I.a Porte , 'Iex.
`M::>rr<JW', Ga.
`Newaxk , Calif.
`
`Beverly, Mass.
`
`Callery, Pa.
`
`Dirrcthylmninc bor<me
`
`Diox.:lbor in ;:me s
`
`Mine Safety Appliances Co.
`callery Chern. eo. , di v.
`u.s. Borax & <l1ern. Corp.
`
`Callery, Pa.
`Boron, Calif.
`
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`
`
`
`Olemical
`Hexylene borate
`Morpholine borane
`
`Sodium tetrapheny ll: ::n::on
`(Sodium tetraphenyll~rate)
`
`wrt-Butylamine borane ·
`
`(l)
`'rable 1 (Con't)
`Boron Products and Producers
`Proquc:er
`Company, subordination
`Kipers Labs.
`Ventron Corp.
`Alfa Products Div.
`Chems. Div.
`Allied Chern. Corp.
`Specialty Cherns • Di v.
`Richa.rdson-.tJ.en:ell, Inc.
`J. T. Baker <llem. Co • , subsid.
`Mine Safety Appliances Co.
`Callery Chern. eo., div.
`Ventran Corp.
`Alfa Products Di v.
`Stauffer Chern. Co.
`Specialty Chern. Div.
`Anderson Dev. Co.
`
`1-10
`
`Location
`Santa Ana, calif.
`
`Beverly, Mass.
`Beverly, Mass.
`
`Marcus Hook, Pa.
`
`Phillipsburg, N.J.
`
`callery I Pa.
`
`Beverly 1 Mass.
`
`W:!stan, Mich.
`Adrian, Mich.
`
`U.S • Borax & Chern. Corp.
`U.S. Borax Peseardl Corp., subsid. Anaheim, Calif.
`Anderson Dev. Co.
`Adrian, Mich.
`U.S. Borax & Chern. Corp.
`u.s. Borax :Research Corp. 1 subsid. Anaheim, calif.
`Mine Safety Appliances Co.
`Callery Chern. Co. 1 di v.
`Texas Alkyls, Inc.
`Ventron Corp.
`Alfa Products Div.
`Anderson r:ev. Co.
`U.s. Borax & Chern. Corp. /
`u.s. Borax Research Corp. , subsid. Anaheim, calif.
`
`callery, Pa.
`rear Park, Tex.
`
`Beverly, Mass.
`Adrian, Mich.
`
`Ventron Corp.
`Alfa Products Di v.
`
`· Beverly, Mass.
`
`U.S . Borax & Chern. Corp.
`u.s. Borax IEsearch Corp., subsid. Anaheim, Calif.
`Texas Alky ls , Inc.
`Leer Park v
`'lex.
`Anrerson r:ev. Co.
`Adrian, Mich.
`Stauffer Chern., Co.
`Specialty Chern. Div.
`Ventron Corp.
`Alfa Products Div.
`
`Beverly, Mass.
`
`Weston, Mich.
`
`Trialkyl ooranes
`
`Tributyl oorate
`(Butyl borate)
`Tri-m, p-cresyl borate
`
`Tricyclohexyl borate
`TriethanolanQne borate
`
`Triethy lboranc
`(Tricthy lborinc)
`
`Tricthyl borate
`(Tricthoxy boranc)
`
`Triethyloxonium tetra(cid:173)
`fluoroborate
`
`Tri (hexylcnc glycol)
`biborate
`
`'l'riisobuty lborane
`'I'riisq?!"q)yl borate
`
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`
`
`
`J{,dAu /Nr:.
`
`Olernical
`
`Trirrethoxyboroxine
`(r-ethyl rretaborate)
`
`Tri-2-rrethoxycthyl bora~
`'I'rirrethyl borate
`(M=thyl borate)
`(Tri.Jrethoxyborine)
`
`Trirrcthyl borate(cid:173)
`rrethanol azeot:rq::e
`
`* Scheduled late 1974
`
`(l)
`'l'able l (Cont)
`Boron Products and Producers
`Producer
`carpany, subordination
`
`Mine Safety Appliances Co.
`callery Chern. Co., div.
`Stauffer Chern. Co.
`Specialty Chern. Div.
`Anderson D:!v. Co.
`Anoorson D:!v. Co.
`Mine Safety Appliances Co.
`callery Olein. Co. , di v.
`Stauffer Chern. Co.
`Specialty Chern. Div.
`Ventran Corp.
`Chems. Div.
`
`Ventran Corp.
`Alfa Products Di v.
`
`1-11
`
`Location
`
`callery, Pa.
`
`V€ston, Mich •
`.Adrian, Mich.
`.Adrian, Mich.
`
`Callery, Pa.
`
`Weston, Mich.
`
`Danvers, Mass .
`
`Beverly, Mass.
`
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`
`
`
`1-12
`
`I3.
`
`Costs and Physical Properties of Inportant Boron Corrpounds
`
`Tre prices of selected boron minerals and chemicals are given
`The materials listed are the most oammercially significant
`in Table 2.
`of the bonn family. Another oonnon factor is that their rrost important
`2o3) content.
`applications are basrii on their boron oxide (B
`In many
`instances these mat.?rials are interchangeable.
`In 1970 anhydrous borax
`was the least expensive in B2o3 content, but under 1974 prices borax
`pentahydrat:e is cheapest. Physical properties of the rrost important
`boron oonpounds are presente1 in Tab~e 3.
`
`Many netals form borides of' various carcposi tions. M:>st are
`sr.:ecial.ty rmtcrials only, but a few are used in the aerospace indusb:y.
`general, enviraurental effects are minimal.
`
`In
`
`Many of t."le rretal borides oxidize in air considerably belo.v the
`listed rrelting points. This limits the significance of the high rrelting points
`(c .g. , vanadium and tungsten borides oxidize in air at less than 1200C versus
`listed rrelting points of 2000 - 3000C. As a rule the rrelting point of a parti(cid:173)
`cular boridc c:arpositio:1 increases with the atcmic ~ight in a Group but de(cid:173)
`creases with increasing atomic weight in each period. Hafnium and tantalum
`boridcs therefore have the highest rrelting points - 3250 ± lOOC and 3400 ± SOC.
`
`CFAD v. Anacor, IPR2015-01776 ANACOR EX. 2043 - 19/118
`
`
`
`w
`I
`
`57.2
`
`2.63
`3.01
`
`2.12
`2. 33
`
`1.53
`:1.. 81
`
`1.63
`2.01
`
`573
`
`148
`169
`
`145
`159
`
`73
`86
`
`60
`73
`
`per unit B2o3
`
`1974 Prices {$)
`
`per rretric ton
`
`f.o.b. Plant
`
`Price in Carlots,
`
`PriCES of Boron H.1.nerals and Clemicals
`
`(2)
`Table 2
`
`1.56
`1.67
`3.60
`
`1.83
`2.01
`
`1.26
`1.36
`
`1.26
`1.43
`
`1.24
`1.46
`
`fer unit B203
`
`149
`159
`360
`
`104
`113
`
`84
`93
`
`60
`68
`
`45
`53
`
`per rretric ten
`
`1970 Prices ($)
`
`95-96
`95-96
`99.9
`
`56.24
`56.24
`
`68.5
`68.5
`
`47.56
`47.56
`
`36.3
`36.3
`
`bulk
`bags
`bags
`
`bulk
`bags
`
`bulk
`bags
`
`bulk
`bags
`
`bul.\
`bags
`
`oxide
`Boric
`
`acid
`Boric
`
`oorax
`Anhydrous
`
`pentahydrate
`Borax
`
`recahydrate
`Borax
`
`OJntent, %
`
`B203
`
`CFAD v. Anacor, IPR2015-01776 ANACOR EX. 2043 - 20/118
`
`
`
`**So.Gr. at 11 °C referenced to water at 4°C
`*cazB6o11• 5H2o
`
`...
`
`.Jlo.
`I
`
`avogadrite
`Natural
`
`erni ts hydrogen chloride
`furres in rroist air
`pilllgen t odor
`furres in rroist air
`trioxide
`boron
`Ofth
`H3BOd
`
`fonn
`
`Natural mineral
`
`68.5
`
`% B203-
`
`% B203-
`Natural mineral
`
`47.5
`
`% B
`Natural mineral
`c:x:rrrbined £orm only
`O.OCl% 8~~·s crust
`
`-36.3
`
`2o3
`
`97
`100
`25
`16
`6.27
`0.44100
`
`20
`210100
`108
`
`26
`
`d hot
`d hot
`106 oo1d
`15.7
`1.1 100
`27.6100
`6.3530
`
`8.79 @ 40
`1.05 @ 0
`
`52.3 @ 100
`22.65 @ 65
`
`170 @ 100
`2.01 @ 0
`
`d
`
`d
`
`sub1
`
`d350
`384
`sl d
`
`12.5
`
`-107.3
`
`-99.9
`
`-126.7
`
`0
`
`2
`
`1860
`-1 1/2 H
`300
`
`460
`to HB02
`169
`
`d
`
`1575
`
`0
`
`2
`
`-lOH
`320
`
`741
`2
`-H 0
`120
`
`75
`
`23CO
`
`II1301.
`
`2550 SID
`
`Coiments
`
`g/lOOcc oc
`Solubility
`
`Water
`
`Boiling
`
`oc
`PoL1t
`
`!-Elting
`
`oc
`Point
`
`Physical Properties
`
`Table 3
`
`1.87115
`
`2.49820
`
`20
`
`2.47
`
`1.349 4ll*k
`
`(gas)
`2.99 g/1
`1.812 glass
`2.46 crys
`!Soc
`1.435
`2.43
`2.42-
`
`2.67
`
`1.815
`
`l. 73
`2.37 arror
`2. ~4 crys
`
`Gravity
`Specific
`
`Ammonium fluoborate
`
`Potassium f1uoborate
`
`Sodium f1uoborate
`
`Boron trichioride
`
`Boron trifluoride
`
`Boric oxide
`
`Boric Acid
`
`Co1em:mi te*
`Anhydrous
`Sodium tetraborate
`
`Pe.ntahydrate
`Sodium tetraborate
`
`Decahydrate (Borax)
`Sodium tetraborate
`
`B:lr:m
`
`Chemical
`
`CFAD v. Anacor, IPR2015-01776 ANACOR EX. 2043 - 21/118
`
`
`
`l1l
`
`I
`
`hydride
`Boron
`
`i cold, sl d hot
`i
`cold water
`sl. s, d
`
`Caments
`
`g/lOOcc °C
`
`Solubility
`
`Water
`
`73500
`
`-92.5
`
`oc
`Point
`Boiling
`
`3000
`subl ca
`2350
`
`-165.5
`
`~lting
`
`oc
`Point
`
`Physical Properties
`
`Table 3 (Con't)
`
`2.25
`2.52
`0.447
`Liq. -ll
`
`Gravitv
`Specific
`
`Boron nitride
`Bor'O!"l ( tetra) c...rrbide
`
`Di.l:orane
`
`Olemical
`
`CFAD v. Anacor, IPR2015-01776 ANACOR EX. 2043 - 22/118
`
`
`
`v/.:ujA u I xc.
`
`II . PRODUcriON
`
`1-16
`
`A. Natural Sourres of Borates
`
`The map in Figure 1 (J) shows the location of tbe significant borate
`dep:>si ts in tbe United States. They produre virtual! y all of the raJN materials
`for the boron industry in the U.S. Approximately 20% of tbe present production
`sterns from the utilization of Searles Lake brines. Significar,t colernanite (Table 3)
`mining is also perfonred by Tenneco. Total borate production by c::x:Jrq?any and
`location is presented in Table 4 J
`
`B. Manufacturing Proresses
`
`1. Elerrental Boron
`Although widespread in nature boron occurs naturally only in
`canbined fonn. Elem=>..ntul bo;ron is not one of tbe rrore i.nportant co:rrrrercial
`fonns of boron.
`
`'I'hree general techniques are used to prepare boron from its
`conpounds: (1) Chemical reduction with active elerrents, (2) Non-aqueous electro(cid:173)
`lytic reduction, anll (3) Thermal deCX'liTpOSition. Reduction of boron corrpounds to
`elerrental boron has been carried out with magnesium, hydrogen, and many other
`elerrents. Among the boron corrpounds used are borates, boron oxides, boron
`halides, fluoborates, and borohydrides. The rrost comron rrethod for producing
`lar9e arrounts of elerrental boron is the exotberrni.c reduction (thennit reaction)
`of boric oxide with rnagncsit:nn. The prcrluct of this reaction, a finely-divided
`po.o~der kno..vn as "Moissum' s boron" is arrorphous as is boron produced fran any
`of the Chemical reduction rrethods except for high temperatme reduction by
`hydrogen.
`'1'hc lattP.r rrethod, especially when involving hot filarrent reaction
`of hydrogen with b:m:>n tribromi.de, has becx:Jre a conventional rrearts for obtaining
`boron with puri tics of 99% and higher.
`
`Electrolytic preparation of boron usually involves t:h= passage of
`a current through fused rrel ts of boric oxide in p:>tassium halides or oxides.
`Electrolysis of p:>tassium fluorborate-p:>tassium chloride or potassium chloride(cid:173)
`sodium chloride rrelts is perfomed with a boron carbide anode. The purity of
`the product obtained by these rrethods has been 87-99. 8%. Direct electrolysis
`
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`
`
`
`1-17
`
`OREGON
`
`IN OREGON
`BORATE DEPOSITS
`DISCOVERED AND WORKED DURING
`EARLY PERIOD
`LAIC£
`ALVORDO
`
`NEVADA
`
`CALIFORNIA
`
`(BORAX CRYSTALS
`CLE:AR~N MUD) FIRST
`LAKE DISCOVERY OF
`BORAX 18156
`PRODUCTION 1864"1874
`
`BARTLETT
`(BRINE)
`SMALL
`PRODUCTION
`1929 "1953
`
`FRAZIER MOUNTAIN=-t---=~
`DISTRICT (COLEMANITE)
`PROOUCTION 1899-1907,
`1911"1913
`
`KRAMER DISTRICT( BORON)(cid:173)
`(BORAX AND KERNITE ORE)
`MAIN SOURCE SINCE 1927
`
`....--- TEELS MARSH
`
`RHODES MARSH
`COLUMBUS MARSH
`FISH LAKE VAllEY
`
`DEPOSITS NOW ABANDONED
`BUT WERE
`IMPORTANT
`SOURCES DURING EARLY
`STAGES
`
`NACE CREEK DISTRICT (LAKE
`DEPOSITS AND COL..EMANITE) MAIN
`SOURCE OF PRODUCTION 1915 -1926
`ILA C. MINE (COLEMANITE)
`LARGEST PRODUCER IN 1912
`ESTLEY -SHOSHONE MINE (ULEXITE
`AND COLEMANITE) PRODUCTION
`191!5-1926
`~WHITE BASIN(CCt..EMANITE)
`PRODUCTION 1924-1962
`CALLVILLE WASH
`(COLEMANITE)
`PRODUCTION 1921-1927
`~--~~:---------J~---~URCOR~RS
`(COLEMANITE)
`
`CALICO MOUNTAIN
`DISTRICT (COlEMANITE)
`PRODUCTION 1887 -1907
`
`LANG(COLEMANITE)
`PRODUCTION 1908-1923
`
`Figure i
`Location of Borate deposits
`in California 9 Nevada 01nd Oregon
`
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`
`
`
`V:u;A N INc
`
`1-18
`
`Table 4
`ni
`.
`. (4}
`Productl.on of Borates 1.n the U ted States
`as of 1972
`
`Quantity
`
`IDeation
`
`Products
`
`> 500,000 metric tons
`as B o3 canbined
`annu~ capacity
`
`Boron, california
`
`crude borax
`refined borax
`anhydrous borax
`boric acid
`boric oxide
`
`boron oorrpounds
`
`Searles Lake,
`Trona, california
`
`Searles Lake,
`Trona, california
`
`ooron a:>rtp)unds
`
`Furnace Creek,
`California
`
`oolenani.te ore
`
`calcined cx:>lernanite
`
`approx. 100,000
`rretri? tons a2o3
`capaCl.ty
`
`25-30,000
`ootric;: tons B/.03
`capac1.ty
`
`Oesign-150,000 metric
`tons rOM oolernani te
`Design- 70,000 metric
`tons calcined oolernani te
`Producticn: metric tons
`calcined oolemanite
`6,300 metric tons
`
`Conpany
`u.s. Borax &
`Cllemical Corp.
`
`Ker~McGee
`cremi.cal Corp.
`
`Stauffer
`Chern. Corp.
`
`Tenneoo Oil
`Con;>any
`
`Searles Lake
`Chern. 0).
`subsid. of
`Occidental
`Pet. Corp.
`
`24,JOO rretric tons*
`
`Searles Lake,
`Calif.
`
`borax
`
`*SchL>duled lnte 1974. M"ly be indefinitely postponed.
`
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`
`
`
`1-19
`
`of alkali or alkaline earth berates yields a product of )..<::Mer purity.
`Electrolysis has not been an important CXJIT~Irercial rrethod for the production
`of elerrental lx:>ron.
`
`Boron L.unpounds that can be decomposed to high purl ty fonns of
`boron are limited to the halides and hydrides. Boron tribrorni.de, boron
`triiodide, and ooron hydrides (from diborane to decaborane) have been de(cid:173)
`ccmposed