WO1986007097A1 - Metal halide reduction with molten sodium/potassium alloy - Google Patents

Metal halide reduction with molten sodium/potassium alloy Download PDF

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Publication number
WO1986007097A1
WO1986007097A1 PCT/AU1985/000113 AU8500113W WO8607097A1 WO 1986007097 A1 WO1986007097 A1 WO 1986007097A1 AU 8500113 W AU8500113 W AU 8500113W WO 8607097 A1 WO8607097 A1 WO 8607097A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
reducing agent
reaction
halide
liquid
Prior art date
Application number
PCT/AU1985/000113
Other languages
English (en)
French (fr)
Inventor
William Reginald Bulmer Martin
Original Assignee
The University Of Melbourne
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by The University Of Melbourne filed Critical The University Of Melbourne
Priority to DE19853590793 priority Critical patent/DE3590793T1/de
Priority to JP60502313A priority patent/JPH06104869B2/ja
Priority to GB8701633A priority patent/GB2185493B/en
Priority to PCT/AU1985/000113 priority patent/WO1986007097A1/en
Publication of WO1986007097A1 publication Critical patent/WO1986007097A1/en

Links

Classifications

    • 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
    • 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
    • C22B21/00—Obtaining aluminium
    • C22B21/04—Obtaining aluminium with alkali metals earth alkali metals included
    • 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
    • C22B34/14—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
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • 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
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/24—Obtaining niobium or tantalum
    • 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
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/36—Obtaining tungsten
    • 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
    • C22B47/00—Obtaining manganese
    • 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
    • C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02—Obtaining thorium, uranium, or other actinides
    • C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
    • C22B60/0213—Obtaining thorium, uranium, or other actinides obtaining uranium by dry processes

Definitions

  • this invention relates to chemical processes.
  • this invention relates to chemical processes invol ing reactive metal(s) in the liquid state at temperatures and pressures such that the other reactants, generally covalent halides, are present in compact phase, i.e. not in the gaseous phase.
  • one of the reactants is a suitable metal or is a suitable metal mixture, in the liquid state, substantial and unexpected advantages accrue from employment of the liquid metal in considerable stoichiometric excess.
  • the invention takes advantage of the extrao dinarily high capability to transfer heat which is exhibited by metals in the liquid state.
  • the excess liquid metal also functions as a materials transfer agent.
  • the present invention provides a method of obtaining a desired metal selected from the group consisting of metals capable of existing in the form of a compound capable of being reduced with a liquid metal reducing agent which comprises a reaction comprising contacting such a compound of said desired metal in substantially compact form with a liquid metal reducing agent whereby to obtain said desired metal.
  • a desired metal selected from the group consisting of metals capable of existing in the form of a compound capable of being reduced with a liquid metal reducing agent which comprises a reaction comprising contacting such a compound of said desired metal in substantially compact form with a liquid metal reducing agent whereby to obtain said desired metal.
  • said compound is a covalent halide.
  • said desired metal is selected from the group consisting of titanium, aluminium, iron, manganese, hafnium, zirconium, tantalum, vanadium, uranium and tungsten.
  • the present invention provides a method of obtaining a desired metal selected from the group consisting of titanium, aluminium, iron, manganese hafnium, zirconium, tantalum, vanadium, uranium and tungsten which comprises a reaction comprising contacting a halide of said desired metal in substantially compact form with a liquid metal reducing agent whereby to obtain said desired metal.
  • a desired metal selected from the group consisting of titanium, aluminium, iron, manganese hafnium, zirconium, tantalum, vanadium, uranium and tungsten which comprises a reaction comprising contacting a halide of said desired metal in substantially compact form with a liquid metal reducing agent whereby to obtain said desired metal.
  • a liquid metal reducing agent whereby to obtain said desired metal.
  • a development of the invention envisages the preparation of al loys which are required to be free to impurities, particularly oxygen, such as iron titanium and titanium iron manganese alloys. Alloys such as these can be used to store hydrogen in the form of hydrides and the amount of hydrogen which can be stored is inversely dependant on the amount of oxygen conta ination.
  • the alloys referred to above as hydrogen stores may provide a satisfactory source of hydrogen for use as a fuel for internal combustion engines and for storage of energy via the fully reversible heat of 'reaction.
  • said liquid metal reducing agent comprises a metal selected from the group consisting of Group I metals or a mixture containing a Group I metal.
  • said liquid metal reducing agent is a mixture of sodium and potassium alloy.
  • Said liquid metal reducing agent may contain at least one of calcium and magnesium. It is desirable that said reaction is conducted at a temperature not greater than the boi l ing point or subl imation point of the halide under the pressure pertaining. It is desirable that said reaction is conducted at a temperature such that solid by-product halides of said liquid metal reducing agent are formed.
  • the reaction is greatly exothermic. When using NaK alloy in the presence of approximately equivalent amounts of reactants without cool ing, the evoked heat caused the reaction to "run away" with a resultant explosion. This is avoided, in accordance with the present invention, by employment of the liquid metal reducing agent in considerable excess to transfer the heat to an external sink.
  • the excess liquid metal reducing agent not only displaces the equilibrium in favour of the reaction; while part of the liquid metal reducing agent reacts and ceases to be metal lic, the excess continues to act as a potent reductant but also acts as a highly efficient heat transfer medium, in situ, at the actual reactive zone where the heat is produced.
  • a high yield of fully reduced desired metal is obtained by operating under these conditions, at a suitable reactor temperature. Partially this is because the strongly electro positive liquid metal reducing agent not only acts as a carrier and heat transfer medium but also as an unrestricted source of electrons by electronic conduction, once the covalent bonds of the halide of the desired metal are split. Substantial ly full reduct on to desired metal occurs.
  • liquid metal reducing agent is present in stoichiometric excess.
  • desired metal that is produced is removed from said reaction with the liquid metal reducing agent and is thereafter separated from by-product halides of said liquid metal reducing agent and from the liquid metal reducing agent.
  • the operating pressure of the process should preferably be maintained by rare gas, e.g. argon, the current economic choice.
  • the process according to the invention may be carried out continuously and in such case excess liquid metal may be employed as a carrier to remove the reaction products at low temperature from the reaction vessel to suitable filters, screens, decantation vessels and/or centri fuges or vacuum distil lation stages.
  • the product salts sodium chloride and/or potassium chlori de
  • the product salts may be separated from the much heavier desired metal powder in a centrifuge, and the excess sodium, potassium or NaK alloy may then be centrifuged or filtered from these separately.
  • the residual NaK metal may be evaporated under high vacuum from the titanium powder after particle modification if desired, in a higher temperature loop.
  • complete removal of liquid metal reducing agent halides from liquid metal reducing agent which is to be reused is not considered essential as such halides probably act as seeds for reaction initiation.
  • Anhydrous ammonia wi ll be found useful in removing traces of liquid metal reducing agent from desired metal.
  • said reaction is initiated by l iquefying said halide and, if necessary, a precursor material in solid form of said liquid metal reducing agent. It i s poss ib le to pass l iqui d sodi um meta l co un te re urre nt to by-product halides of said l iquid metal reducing agent wherbey to regenerate potassi um metal from potassium chloride.
  • powder produced by the process of the present invention is preferably directly melted by the electron beam technique, which avoids the contamination experienced in the use of electric arcs on water washed metal powder or that which has been exposed to the air.
  • An electric arc must have a mini um amount of gas present to ionise, and wi ll not operate in an ultra high vacuum that would strip all gases off hot surfaces.
  • argon or helium atmospheres are employed but the absolute pressure necessary prevents good stri pping of air and water vapour form the washed metal powder.
  • Electron beam melti ng is general ly becomi ng the preferred compacting means in rare and contami natable metal technology, for example that of titanium, hafni um, zirconium, tantalum and tunsten.
  • metal powder from which the residual NaK al loy has been evaporated is fed directly into the melting electron beam without ever having been exposed to air or water.
  • small particle si ze is advantageous.
  • electroslag melting may be applicable.
  • powder suitably conditioned., in a, hot l oop may be re leased to ambi ent and hand led conventionally for use in powder metallurgy or for hydrogen storage as hydride.
  • TiCl ⁇ and Na metal and the products be Ti metal and NaCl which latter could be recycled directly to an electrolytic cel l from which in turn C 1 would be available either to an integrated TiCl ⁇ production plant or for sale according to economics of procurement of Ti C 14 and titanium source materials, e.g. ruti le plus carbon, at the plant site.
  • site melted Na brought into the site may be better than recycle to an integrated electrolytic cell , without affecting the generality of the principle of captive K, which essentially removes its cost from the economics of production, this being essentially tied to T i C 1 and Na in and Ti + NaCl out of the essential process.
  • Si i l ar considerations apply to other desired metals.
  • Titani um metal was recovered from T i C 1 by reaction with a large excess of NaK alloy.
  • the apparatus incorporated means for evacuating the system to below 10 microns of mercury; a supply of inert gas; the means for external heating and cooling a reactor, with a heat transfer medium inert to NaK.
  • the reactor was made of pyrex glass so that the reaction mixture was clearly visible.
  • a stirrer totally isolated from ambient was built into the reactor, and means for sampling ' whi le stir ing while under inert gas or vacuum were provided. Safety of operation was a paramount consideration.
  • the stirrer was adjustable and made of nickel tubing, as it is known that nickel is an inert reaction vessel material for the preparation of titanium from its chlorides.
  • the reactor was made of pyrex glass, surrounded by a pyrex glass jacket through which high flash point, low viscosity oi l was pumped to either heat or cool the reactants.
  • the jacket in particular the base, was designed to maintain high heat transfer rates at the vessel wal ls.
  • the stirred liquid NaK al loy itself constituted an excellent heat transfer medium.
  • On one side of the vessel was provided a connection to a burette containing Ti C 1 , and on the other side a vent to a mercury lute.
  • a sampling probe was also provided.
  • thermocouple was connected into the cooling systm at the point where the oil leaves the glass jacket surrounding the reactor.
  • the lute provided was adapted to vent to atmosphere any pressure surge which may occur in the system, yet al low a high vacuum to be applied to the system.
  • Argon gas was used as the protective gas, as is customary the preparation of titanium, but facil ities fo using nitrogen were also bui lt i nto the system.
  • the argon used was a commercially pure grade, and was purified of any traces of water vapour and oxygen before admission following evacuation.
  • the titanium tetrachlori de used was laboratory reagent grade, which was disti lled in an atmosphere of nitrogen before use, the boi ling range 133°C to 136°C being col lected.
  • 60/40 mole % NaK sodium- potassium alloy was prpared.
  • 30 g (1020 mi ll imoles) of the al loy was charged into the reactor via a No. 3 porous filter disc, u-nder the cover of argon gas, and the tet ra ch 1 o ri de was placed in a burette which had a fitting to connect it to the reactor.
  • the stirrer was set running and 2.00 m l. ( 18 mi llimoles) of T i C 14 was added to the al loy.
  • the reaction mixture was stirred vigorously.
  • the top layer of al loy became darker and went through a wide range of colours; gold, blue, pink and green all being noticeable.
  • Example II The- procedure of Example I was repeated excepting that AICI3 was used in lieu of Ti Cl 4. Aluminium metal was produced although yields were low and reaction times long probably due to the fact that the A 1 C 13 remained in sol id state throughout the process; the apparatus used being incapable of holding the pressure necessary to liquefy A 1 C 13 under the temperatures that were practical.
  • EXAMPLE III While the process exemplified in Example II proved the process of this invention as applicable to aluminium, further experiment was made to improve yields by conducting the process inside a sealed bomb so as to ensure liquefaction of A 1 C 13.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)
PCT/AU1985/000113 1985-05-27 1985-05-27 Metal halide reduction with molten sodium/potassium alloy WO1986007097A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE19853590793 DE3590793T1 (enrdf_load_stackoverflow) 1985-05-27 1985-05-27
JP60502313A JPH06104869B2 (ja) 1985-05-27 1985-05-27 化学的方法
GB8701633A GB2185493B (en) 1985-05-27 1985-05-27 Metal production
PCT/AU1985/000113 WO1986007097A1 (en) 1985-05-27 1985-05-27 Metal halide reduction with molten sodium/potassium alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/AU1985/000113 WO1986007097A1 (en) 1985-05-27 1985-05-27 Metal halide reduction with molten sodium/potassium alloy

Publications (1)

Publication Number Publication Date
WO1986007097A1 true WO1986007097A1 (en) 1986-12-04

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ID=3762115

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1985/000113 WO1986007097A1 (en) 1985-05-27 1985-05-27 Metal halide reduction with molten sodium/potassium alloy

Country Status (4)

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JP (1) JPH06104869B2 (enrdf_load_stackoverflow)
DE (1) DE3590793T1 (enrdf_load_stackoverflow)
GB (1) GB2185493B (enrdf_load_stackoverflow)
WO (1) WO1986007097A1 (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4865644A (en) * 1987-07-23 1989-09-12 Westinghouse Electric Corporation Superconducting niobium alloys
EP0521608A1 (en) * 1991-05-31 1993-01-07 British Nuclear Fuels PLC A method of producing uranium metal
RU2152449C1 (ru) * 1994-08-01 2000-07-10 Интернэшнл Титаниум Паудер Л.Л.С. Способ получения металлов и других элементов
RU2163936C2 (ru) * 1999-05-19 2001-03-10 Евдокимов Владимир Иванович Непрерывный магниетермический способ получения титана
WO2005035806A1 (ja) * 2003-10-10 2005-04-21 Sumitomo Titanium Corporation Ｃａ還元によるＴｉ又はＴｉ合金の製造方法
WO2005035805A1 (ja) * 2003-10-10 2005-04-21 Sumitomo Titanium Corporation Ca還元によるTi又はTi合金の製造方法
WO2005083135A1 (ja) * 2004-03-01 2005-09-09 Sumitomo Titanium Corporation Ｃａ還元によるＴｉ又はＴｉ合金の製造方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4923531A (en) * 1988-09-23 1990-05-08 Rmi Company Deoxidation of titanium and similar metals using a deoxidant in a molten metal carrier
US20080011124A1 (en) * 2004-09-08 2008-01-17 H.C. Starck Gmbh & Co. Kg Deoxidation of Valve Metal Powders

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951647A (en) * 1971-10-26 1976-04-20 Deepsea Ventures, Inc. Reduction method for producing manganese metal
US4105192A (en) * 1975-02-13 1978-08-08 Nippon Mining Company Process and apparatus for producing zirconium sponge

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB479014A (en) * 1936-09-10 1938-01-28 Degussa A process for the production of metallic tiatnium
GB697530A (en) * 1951-04-17 1953-09-23 Ici Ltd Production of titanium
GB899406A (en) * 1959-01-15 1962-06-20 Atomic Energy Authority Uk Improvements in or relating to the production of metals
GB863428A (en) * 1959-09-21 1961-03-22 Dow Chemical Co Production of titanium metal
JPS4863914A (enrdf_load_stackoverflow) * 1971-12-07 1973-09-05
JPS491370A (enrdf_load_stackoverflow) * 1972-04-18 1974-01-08
AU514181B2 (en) * 1976-11-26 1981-01-29 Westinghouse Electric Corporation High temperature reactor
LU81469A1 (fr) * 1979-07-05 1981-02-03 Luniversite Libre Bruxelles Procede et installation pour la production de metaux reactifs par reduction de leurs halogenures
EP0134643A3 (en) * 1983-07-08 1986-12-30 Solex Research Corporation of Japan Preparing metallic zirconium, hafnium or titanium

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951647A (en) * 1971-10-26 1976-04-20 Deepsea Ventures, Inc. Reduction method for producing manganese metal
US4105192A (en) * 1975-02-13 1978-08-08 Nippon Mining Company Process and apparatus for producing zirconium sponge

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4865644A (en) * 1987-07-23 1989-09-12 Westinghouse Electric Corporation Superconducting niobium alloys
EP0521608A1 (en) * 1991-05-31 1993-01-07 British Nuclear Fuels PLC A method of producing uranium metal
US5322545A (en) * 1991-05-31 1994-06-21 British Nuclear Fuels, Plc Method of producing uranium metal
RU2152449C1 (ru) * 1994-08-01 2000-07-10 Интернэшнл Титаниум Паудер Л.Л.С. Способ получения металлов и других элементов
RU2163936C2 (ru) * 1999-05-19 2001-03-10 Евдокимов Владимир Иванович Непрерывный магниетермический способ получения титана
WO2005035806A1 (ja) * 2003-10-10 2005-04-21 Sumitomo Titanium Corporation Ｃａ還元によるＴｉ又はＴｉ合金の製造方法
WO2005035805A1 (ja) * 2003-10-10 2005-04-21 Sumitomo Titanium Corporation Ca還元によるTi又はTi合金の製造方法
US7648560B2 (en) 2003-10-10 2010-01-19 Osaka Titanium Technologies Co., Ltd. Method for producing Ti or Ti alloy through reduction by Ca
WO2005083135A1 (ja) * 2004-03-01 2005-09-09 Sumitomo Titanium Corporation Ｃａ還元によるＴｉ又はＴｉ合金の製造方法

Also Published As

Publication number Publication date
DE3590793T1 (enrdf_load_stackoverflow) 1987-09-17
GB2185493B (en) 1990-02-14
GB8701633D0 (en) 1987-03-04
GB2185493A (en) 1987-07-22
JPH06104869B2 (ja) 1994-12-21
JPS63500389A (ja) 1988-02-12

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