EP0134643A2 - Verfahren zur Herstellung von metallischem Zirkon, Hafnium oder Titan - Google Patents

Verfahren zur Herstellung von metallischem Zirkon, Hafnium oder Titan Download PDF

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Publication number
EP0134643A2
EP0134643A2 EP84304460A EP84304460A EP0134643A2 EP 0134643 A2 EP0134643 A2 EP 0134643A2 EP 84304460 A EP84304460 A EP 84304460A EP 84304460 A EP84304460 A EP 84304460A EP 0134643 A2 EP0134643 A2 EP 0134643A2
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EP
European Patent Office
Prior art keywords
titanium
metallic
fluorine
hafnium
zirconium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP84304460A
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English (en)
French (fr)
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EP0134643A3 (de
Inventor
Morio Watanabe
Sanji Nishimura
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Solex Research Corp
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Solex Research Corp
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Filing date
Publication date
Priority claimed from JP58123193A external-priority patent/JPS6017026A/ja
Priority claimed from JP12319483A external-priority patent/JPS6017027A/ja
Application filed by Solex Research Corp filed Critical Solex Research Corp
Publication of EP0134643A2 publication Critical patent/EP0134643A2/de
Publication of EP0134643A3 publication Critical patent/EP0134643A3/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
    • C22B34/1272—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams reduction of titanium halides, e.g. Kroll process
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C22B34/1277—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using other metals, e.g. Al, Si, Mn
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/14—Obtaining zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon

Definitions

  • the present invention relates to the preparation of metallic zirconium, metallio hafnium and metallic titanium.
  • metallic zirconium (Zr) and metallic hafnium (Hf) have been produced by reducing their chlorides with metallic magnesium or sodium in a stream of an inert gas. Since metallic sodium is hazardous, metallic magnesium has been used more often as the reducing agent.
  • Metallic titanium has generally been produced from TiO 2 , by chlorinating it in the presence of carbon to produce TiC1 4 as an intermediate, and reducing this intermediate by contact with metallic magnesium or sodium to obtain metallic titanium.
  • the present invention provides a new, improved, process which is intended to overcome such drawbacks of the previous processes.
  • the invention provides a process for preparing metallic zirconium, hafnium or titanium, which process comprises bringing a fluorine--containing compound of zirconium, hafnium or titanium into contact with heated metallic aluminium or magnesium, to convert the fluorine-containing compound into the corresponding metal.
  • metallic Zr, Hf and Ti are prepared from fluorine-containing compounds of the metals, instead of from their chlorides.
  • the fluorine-containing compounds are better starting materials. Crystals of them are prepared more easily.
  • the fluorine-containing compounds provide more easily purifiable crystals than do the corresponding chlorides.
  • metallic aluminium can be used as the reducing agent in the present invention.
  • the fluorine necessary for preparing the fluorine-containing compounds as intermediates can be recirculated in the process.
  • a fluorine-containing compound of zirconium, hafnium or titanium reacts with heated metallic aluminium or magnesium to convert the fluorine--containing compound into the corresponding metal.
  • the reaction should naturally not be conducted in the presence of material which mars the reaction. Oxygen, for example air, mars the reaction and hence should be avoided.
  • the reaction can be conducted in the presence of an inert gas or a reducing gas.
  • the reaction can be conducted "in vacuum", i.e. with no other gas being present besides any from the fluorine--containing compound and the aluminium or magnesium.
  • the fluorine-containing compound in the reaction is gaseous.
  • the compound may contact initially as a solid with the aluminium or magnesium and then be heated to make it gaseous.
  • the reaction is conducted with the compound being gaseous and being in an inert gas or a reducing gas.
  • the aluminium or magnesium is generally heated to a temperature above 400°C.
  • the aluminium or magnesium is generally heated to a temperature above 220°C.
  • the fluorine-containing compound can be for instance (NH 4 ) 2 ZrF 6 , (NH 4 ) 2 TiF 6 , (NH 4 ) 2 TiF 6 , TiF 4 , ZrF 4 , HfF 4 or K 2 TiF 6 .
  • Gaseous fluorine-containing compound is generally produced by heating solid fluorine-containing compound.
  • the fluorine-containing compound is preferably produced by extracting a zirconium, hafnium or titanium compound into an organic solvent, and bringing the solution into contact with an aqueous solution containing at least one of F - , NH 4 + and K + to extract into the aqueous phase zirconium, hafnium or titanium in the form of a fluorine-containing compound thereof.
  • the fluorine-containing compound can then be crystallized from the aqueous solution.
  • the organic solvent can be regarded as comprising an extracting agent, which can be in admixture with a diluent.
  • the fluorine-containing compound is produced by extracting a zirconium, hafnium ortitanium compound into a solvent comprising at least one extracting agent selected from the group consisting of (a) alkylphosphoric acids, (b) alkylarylphosphoric acids, (c) alkylamines, (d) neutral phosphoric acid esters and (e) ketones, and bringing the solution into contact with an aqueous solution containing at least one of F , NH 4 + and K + to extract into the aqueous phase zirconium, hafnium or titanium in the form of a fluorine-containing compound thereof.
  • the solvent can comprise the extracting agent, i.e.
  • the solvent comprises the extracting agent diluted with petroleum hydrocarbon
  • the aqueous solution contains NH 4 +
  • metallic zirconium or hafnium is prepared.
  • metallic titanium is prepared and the fluorine-containing compound of titanium is produced by extracting a titanium compound into a solvent comprising (1) at least one extracting agent selected from the group consisting of (A) alkylphosphoric acids, (B) alkylarylphosphoric acids, (C) carboxylic acids, (D) oximes and (E) neutral phosphoric acid esters, and (2) petroleum hydrocarbon as diluent, and bringing the solution into contact with an aqueous solution containing at least one of F - , NH 4 + and K + to extract Into the aqueous phase titanium in the form of a fluorine--containing compound thereof.
  • a solvent comprising (1) at least one extracting agent selected from the group consisting of (A) alkylphosphoric acids, (B) alkylarylphosphoric acids, (C) carboxylic acids, (D) oximes and (E) neutral phosphoric acid esters, and (2) petroleum hydrocarbon as diluent, and bringing the solution into contact with an aqueous solution
  • alkylphosphoric acids which can be employed as extracting agent in the present invention are preferably selected from the group consisting of the following compounds:
  • R represents an alkyl group generally containing 4 to 22 carbon atoms.
  • the compound D 2 EHPA (di-2-ethylhexylphosphorio acid) referred to in the Examples below is the compound of group (a) where R represents C 8 H 17 .
  • alkylarylphosphoric acids which can be employed in the present invention are preferably selected from the compounds of the following general formula:
  • R represents an alkyl group containing generally 4 to 14 carbon atoms and A represents an aryl group, for instance a phenyl, tolyl, or xylyl group).
  • carboxylic acids which can be employed as extracting agent in this invention are preferably selected from the group consisting of the compounds of the following general formulae:
  • R represents an alkyl group having 4 to 18 carbon atoms.
  • R represents H-, CH 3 -, or and X represents a halogen atom such as Cl or an H atom).
  • neutral phosphoric acid esters which can be employed in the present invention are preferably selected from the following compounds:
  • TBP tributyl phosphate
  • alkylamines which can be employed in this invention are preferably selected from the following groups of compounds:
  • TOA trioctylamine
  • ketone which can be employed in this invention has the formula: Cyclohexanone, (C 6 H 10 )0, is also a preferred compound.
  • the most frequently used diluents in this invention are petroleum hydrocarbons, but aromatic and aliphatic hydrocarbons and mixtures thereof can also be used with success. Further, a mixture of various hydrocarbons such as kerosene is often used.
  • a higher alcohol generally containing an alkyl group of 4 to 24 carbon atoms can be employed to improve the quality of the products.
  • the higher alcohol is generally present in a proportion ranging from 0 to 30% (by volume).
  • the concentration of the extracting agent should be chosen according to the nature of the solution to be treated as well as of the suspected impurities, the concentration of the metal of interest and of impurities, and also according to the chemical species to be extracted.
  • the concentration of the extracting agent is generally, however, in the range 2 to 100% (by volume).
  • the metallic aluminium and metallic magnesium for use as reducing agents may be in the form of a liquid or gas.
  • the metallic Zr, Hf or Ti can be produced by bringing gaseous fluorine-containing compound thereof into contact with the metallic aluminium or magnesium in a stream of an inert gas or a reducing gas or in vacuum.
  • the inert gas which can be used to maintain the reaction conditions in the present process may be for example argon, helium or nitrogen, and the reducing gas for the same purpose may be for example H 2 , CO or a number of hydrocarbons whose molecular formula is C BM.
  • the fluoride in the aluminium fluoride or magnesium fluoride produced as by-product in the present process can be recovered and reused. Thus, it can be recycled for use inthe aqueous solution discussed above for producing the fluorine-containing compound of zirconium, hafnium or titanium.
  • the aluminium fluoride or magnesium fluoride can be reacted for instance with steam to produce HF which can be recycled for use in the aqueous solution.
  • the flow sheet of Fig. 1 shows the basic process for producing Zr, Hf or Ti.
  • the fluorine-containing compound (A) of Zr, Hf or Ti is introduced into a reactor (C) where metallic aluminium or magnesium is heated, preferably above 400°C for zirconium and hafnium, and preferably above 220°C for titanium, in a stream of an inert or reducing gas or in vacuum.
  • metallic zirconium, metallic hafnium or metallic titanium is prepared according to reactions such as are expressed by the following equations:
  • the fluorine-containing compounds of Zr and Hf are not limited to those shown in equations (1) to (4).
  • A1F 3 , MgF 2 , HF and NH 4 F (D) are produced as by-products in addition to the metallic zirconium or metallic hafnium.
  • the former compounds can be led outside the system in a gaseous form, depending on the operating conditions of the reactor (C). If they are retained in the reactor, they can be removed by washing with water or dilute aqueous acids or by heating in a vacuum furnace.
  • Metallic titanium can be prepared by the reaction with metallic aluminium according to the following equations: By-products such as AlF 3 , KF and NH 4 F (D) are led outside the reactor (C) in gaseous form to separate them from Ti. Alternatively, depending on the operating conditions, the metallic titanium is washed with water or dilute aqueous acid to remove the by-products.
  • By-products such as AlF 3 , KF and NH 4 F (D) are led outside the reactor (C) in gaseous form to separate them from Ti.
  • the metallic titanium is washed with water or dilute aqueous acid to remove the by-products.
  • Metallic titanium (E) can be obtained from fluorine--containing compounds of titanium (A) by the reaction with metallic magnesium (B). usually heated at a temperature above 220°C, as shown in the following equations:
  • the flow sheet of Fig. 2 illustrates the process in which the fluorine-containing compound of Zr, Hf or Ti is produced as starting material.
  • An organic solvent (F) extracting and containing Zr, Hf or Ti is led to a stripping stage (G), where Zr, Hf or Ti in the organic phase is transferred to an aqueous phase (H) by being contacted with an aqueous solution (E) which contains one or more of NH 4 + and F - for Zr and Hf and of NH 4 + , F - and K + for Ti, to obtain fluorine-containing compounds of these metals.
  • R.H is an extracting agent having an H-type exchanging group
  • TBP represents tributyl phosphate.
  • Regenerated organic solvent (K) is circulated again to the extraction stage.
  • the Zr, Hf or Ti transferred to the aqueous medium is deposited as crystals such as (NH 4 ) 2 ZrF 6 , (NH 4 ) 2 HfF 6 , TiF 4 , (NH 4 ) 2 TiF 6 or K2TiF6, and is removed from the aqueous medium by filtration (J).
  • the fluorine-containing compound of Zr, Hf or Ti obtained (A) is treated as shown in Fig. 1 to produce metallic zirconium, hafnium or titanium.
  • Fig. 3 is a flow-sheet of the present invention which includes a procedure for treating AlF 3 , MgF 2 and NH 4 F (D) by-products from the reduction of the fluorine-compounds of Zr, Hf and Ti by means of metallic magnesium and aluminium.
  • the route from the organic solvent (F) which contains Zr, Hf or Ti as a result of extraction to the reactor (C) is as shown in Fig. 2.
  • AlF 3 or MgF 2 (D) from the reactor (C) is transferred to the decomposition stage (M), where it is converted into A1203 or Mg0 (N) by the action of steam or air, as illustrated by the following equations:
  • the HF (Q) produced in the oxidation reactions is introduced for recovery into the absorption stage (P) where a NH 4 F- and NH4HF2-containing solution circulates, the solution acting as stripper for Zr, Hf or Ti.
  • reactor (C) of the present invention those of various forms can be used including conventional closed type electric furnaces or external heating furnaces having a double structure (upright, horizontal or rotational).
  • Crystals of (NH 4 ) 2 ZrF 6 were obtained by a process in which zirconium extracted with a mixed organic solvent consisting of 10% TOA and 90% kerosene was stripped with a solution containing 250 g/l of NH 4 HF 2 .
  • the white crystals (20 g) of (NH 4 ) 2 ZrF 6 were heated in a stream of argon and the resulting gas passed into a reactor, where it was contacted with metallic aluminium preheated at 660°C for an hour. Then the reactor was cooled. Analysis of the material lying at the bottom of the reactor revealed that metallic zirconium was present at the deep bottom, being covered by the metallic aluminium thereon. The substance at the deep bottom was collected, crushed and analyzed, revealing that it was 7.5 g of Zr.
  • Crystals of (NH 4 ) 2 HfF 6 were obtained by a process in which hafnium extracted with 100% MIBK (methyl isobutyl ketone) was stripped with a solution containing 200 g/l of NH 4 HF 2 .
  • the crystals in an amount of 20 g, were heated in a stream of argon to vaporize them. Meanwhile, metallic aluminium was heated at 660 o C in a stream of argon to vaporize it. Both vapours were introduced into a reactor for reaction. When the reactor had cooled, the material deposited on its wall was analyzed, revealing that the material was 10.8 g of metallic hafnium.
  • Crystals of (NH 4 ) 2 ZrF 6 were obtained by a process in which zirconium extracted with a mixed organic solvent consisting of 60% TBP and 40% aromatic hydrocarbon was stripped with an aqueous solution containing 180 g/l of NH 4 F. 20 Grams of the crystals were placed together with metallic magnesium at the bottom of a reactor. The temperature of the reactor was then raised rapidly in a stream of argon, and maintained at 800°C for an hour. Then the reactor was cooled. Analysis of the residue found revealed it to be 7.5 g of metallic zirconium.
  • a total of 10 g of white crystals of TiF 4 was converted into a gas by heating at 600°C in a stream of argon, and this gas was blown into a reactor which was filled up with argon gas and contained metallic aluminium in the molten state.
  • argon gas contained metallic aluminium in the molten state.
  • a black reaction product found on the inside wall and at the bottom proved to be 3.8 g of metallic titanium.
  • Crystals of (NH 4 ) 2 TiF 6 were obtained by contacting this solvent with an aqueous solution containing 150 g/1 of NH 4 HF 2 .
  • 20 Grams of the white crystals (NH 4 ) 2T iF 6 were heated to vaporize them in a stream of argon and the vapour passed to a reactor which was preheated and maintained at 1000°C. Meanwhile, aluminium was vaporized by heating in a stream of argon. The two vapours were brought into contact in a separate reactor. When the latter reactor was cooled, analysis of a black reaction product deposited on the inside wall and at the bottom of the reactor revealed that-it was 4.8 g of metallic titanium.
  • a mixed organic solvent consisting of 60% of TBP and 40% of isoparaffin (commercially available under the name "Isoparaffin”) which extracted and contained H 2 TiF 6 was brought into contact with an aqueous solution containing 200 g/1 of KHF 2 to produce orystals of X 2 TiF 6 , 20 Grams of the crystals were packed together with 50 g of metallic aluminium at the bottom of a reactor.
  • the reactor was filled up with H 2 gas and the temperature was rapidly raised to 1000°C and maintained there for 2 hours. Then the reactor was cooled. All the residue found on the inside wall and at the bottom of the reactor was collected, washed with 5% HCl, and analysed as 4 g of metallic titanium.
  • Gaseous TiF 4 which was produced by heating 20 g of crystalline TiF 4 at a sufficient temperature in a stream of hydrogen, was transferred to a reactor in which metallic magnesium was preheated at 800°C. The reactor was cooled after an hour. Then black powders deposited on the inside wall and at the bottom of the reactor were oolleoted. They amounted to 7.6 g, and were shown to be of metallic titanium by X-ray diffraction analysis.
  • a gaseous material produced by heating 20 g of (NH 4 ) 2 TiF 6 crystals in a stream of argon was blown into a reactor inwhich metallic magnesium was heated at a temperature above 800°C in a stream or argon.
  • the reactor was cooled after an hour.
  • the powders deposited in its inside were found to amount to 4.8 g. They were shown to be of metallic titanium by X-ray diffraction analysis.

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EP84304460A 1983-07-08 1984-06-29 Verfahren zur Herstellung von metallischem Zirkon, Hafnium oder Titan Withdrawn EP0134643A3 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP58123193A JPS6017026A (ja) 1983-07-08 1983-07-08 金属チタンの製造方法
JP123194/83 1983-07-08
JP123193/83 1983-07-08
JP12319483A JPS6017027A (ja) 1983-07-08 1983-07-08 金属ジルコニウム及び金属ハフニウムの製造方法

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EP0134643A2 true EP0134643A2 (de) 1985-03-20
EP0134643A3 EP0134643A3 (de) 1986-12-30

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2185493B (en) * 1985-05-27 1990-02-14 Univ Melbourne Metal production
WO2005002766A1 (en) * 2003-07-04 2005-01-13 Commonwealth Scientific And Industrial Research Organisation A method and apparatus for the production of metal compounds
US7670407B2 (en) * 2005-01-27 2010-03-02 Peruke (Proprietary) Limited Method of producing titanium
US7674441B2 (en) 2003-07-25 2010-03-09 Nippon Mining & Metals Co., Ltd Highly pure hafnium material, target and thin film comprising the same and method for producing highly pure hafnium
US8277723B2 (en) 2005-07-07 2012-10-02 Jx Nippon Mining & Metals Corporation High-purity hafnium, target and thin film comprising high-purity hafnium, and process for producing high-purity hafnium
GB2498606A (en) * 2012-01-18 2013-07-24 Shenzhen Sunxing Light Alloys Materials Co Ltd Making sponge titanium by reducing potassium fluotitanate using aluminium and/or magnesium
GB2498607A (en) * 2012-01-18 2013-07-24 Shenzhen Sunxing Light Alloys Materials Co Ltd Making sponge titanium by reducing sodium fluotitanate using auminium and/or magnesium
EP2669393A1 (de) * 2012-05-30 2013-12-04 Shenzhen Sunxing Light Alloys Materials Co., Ltd Verfahren zur industriellen Herstellung von Zirkoniummetall und zur Herstellung eines Niedrigtemperaturaluminiumelektrolyts als Nebenprodukt
US8632724B2 (en) 2008-04-21 2014-01-21 Commonwealth Sci. and Ind. Res. Org. Method and apparatus for forming titanium-aluminium based alloys
CN103862059A (zh) * 2012-12-07 2014-06-18 北京有色金属研究总院 一种以铪氟酸钾为原料制备高纯度铪的方法
US8821612B2 (en) 2006-03-27 2014-09-02 Commonwealth Scientific And Industrial Research Organisation Apparatus and methods for the production of metal compounds
US8834601B2 (en) 2009-12-18 2014-09-16 Commonwealth Scientific And Industrial Research Organisation Method for producing low aluminium titanium-aluminium alloys

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB173236A (en) * 1920-12-21 1922-10-19 Westinghouse Lamp Co Improved process for the preparation of rare metals
US4127409A (en) * 1975-10-17 1978-11-28 Teledyne Industries, Inc. Method of reducing zirconium
JPS57169029A (en) * 1981-04-08 1982-10-18 Nishimura Watanabe Chiyuushiyutsu Kenkyusho:Kk Method for obtaining metallic titanium or titanium hydride from compound containing titanium and fluorine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB173236A (en) * 1920-12-21 1922-10-19 Westinghouse Lamp Co Improved process for the preparation of rare metals
US4127409A (en) * 1975-10-17 1978-11-28 Teledyne Industries, Inc. Method of reducing zirconium
JPS57169029A (en) * 1981-04-08 1982-10-18 Nishimura Watanabe Chiyuushiyutsu Kenkyusho:Kk Method for obtaining metallic titanium or titanium hydride from compound containing titanium and fluorine

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GMELINS HANDBUCH DER ORGANISCHEN CHEMIE, "Titan", 8th edition, 1951, pages 287-288, Verlag Chemie, Weinheim; *
PATENT ABSTRACTS OF JAPAN, vol. 7, no. 11 (C-145)[1156], 18th January 1983; & JP - A - 57 169 029 (WATANABE) 18-10-1982 *

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2185493B (en) * 1985-05-27 1990-02-14 Univ Melbourne Metal production
US8562712B2 (en) 2003-07-04 2013-10-22 Commonwealth Sci. and Ind. Res. Org. Method and apparatus for the production of metal compounds
WO2005002766A1 (en) * 2003-07-04 2005-01-13 Commonwealth Scientific And Industrial Research Organisation A method and apparatus for the production of metal compounds
EA010932B1 (ru) * 2003-07-04 2008-12-30 Коммонвелт Сайентифик Энд Индастриал Рисерч Организейшн Способ и устройство для получения металлических соединений
CN1812859B (zh) * 2003-07-04 2011-03-23 联邦科学和工业研究组织 生产金属化合物的方法和设备
US7674441B2 (en) 2003-07-25 2010-03-09 Nippon Mining & Metals Co., Ltd Highly pure hafnium material, target and thin film comprising the same and method for producing highly pure hafnium
US7964070B2 (en) 2003-07-25 2011-06-21 Jx Nippon Mining & Metals Corporation Highly pure hafnium material, target thin film comprising the same and method for producing highly pure hafnium
US7670407B2 (en) * 2005-01-27 2010-03-02 Peruke (Proprietary) Limited Method of producing titanium
AU2005325906B2 (en) * 2005-01-27 2010-03-11 Peruke (Proprietary) Limited A method of producing titanium
AU2005325906C1 (en) * 2005-01-27 2010-07-29 Peruke (Proprietary) Limited A method of producing titanium
US7846232B2 (en) * 2005-01-27 2010-12-07 Adams & Adams Method of producing titanium
US8277723B2 (en) 2005-07-07 2012-10-02 Jx Nippon Mining & Metals Corporation High-purity hafnium, target and thin film comprising high-purity hafnium, and process for producing high-purity hafnium
US8821612B2 (en) 2006-03-27 2014-09-02 Commonwealth Scientific And Industrial Research Organisation Apparatus and methods for the production of metal compounds
US8632724B2 (en) 2008-04-21 2014-01-21 Commonwealth Sci. and Ind. Res. Org. Method and apparatus for forming titanium-aluminium based alloys
US9080224B2 (en) 2008-04-21 2015-07-14 Commonwealth Science And Industrial Research Organization Method and apparatus for forming titanium-aluminium based alloys
US8834601B2 (en) 2009-12-18 2014-09-16 Commonwealth Scientific And Industrial Research Organisation Method for producing low aluminium titanium-aluminium alloys
GB2498607A (en) * 2012-01-18 2013-07-24 Shenzhen Sunxing Light Alloys Materials Co Ltd Making sponge titanium by reducing sodium fluotitanate using auminium and/or magnesium
GB2498606A (en) * 2012-01-18 2013-07-24 Shenzhen Sunxing Light Alloys Materials Co Ltd Making sponge titanium by reducing potassium fluotitanate using aluminium and/or magnesium
GB2498606B (en) * 2012-01-18 2015-03-11 Shenzhen Sunxing Light Alloys Materials Co Ltd Process for producing sponge titanium
GB2498607B (en) * 2012-01-18 2015-06-03 Shenzhen Sunxing Light Alloys Materials Co Ltd Method for preparing sponge titanium from sodium fluotitanate raw material
EP2669393A1 (de) * 2012-05-30 2013-12-04 Shenzhen Sunxing Light Alloys Materials Co., Ltd Verfahren zur industriellen Herstellung von Zirkoniummetall und zur Herstellung eines Niedrigtemperaturaluminiumelektrolyts als Nebenprodukt
CN103862059A (zh) * 2012-12-07 2014-06-18 北京有色金属研究总院 一种以铪氟酸钾为原料制备高纯度铪的方法
CN103862059B (zh) * 2012-12-07 2016-07-06 北京有色金属研究总院 一种以铪氟酸钾为原料制备高纯度铪的方法

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