EP0132073A2 - Verfahren zur Herstellung von metallischem Niob oder Tantal - Google Patents

Verfahren zur Herstellung von metallischem Niob oder Tantal Download PDF

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Publication number
EP0132073A2
EP0132073A2 EP84304461A EP84304461A EP0132073A2 EP 0132073 A2 EP0132073 A2 EP 0132073A2 EP 84304461 A EP84304461 A EP 84304461A EP 84304461 A EP84304461 A EP 84304461A EP 0132073 A2 EP0132073 A2 EP 0132073A2
Authority
EP
European Patent Office
Prior art keywords
metallic
tantalum
niobium
gaseous
nbf
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Withdrawn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
EP84304461A
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English (en)
French (fr)
Other versions
EP0132073A3 (de
Inventor
Morio Watanabe
Sanji Nishimura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solex Research Corp
Original Assignee
Solex Research Corp
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 Solex Research Corp filed Critical Solex Research Corp
Publication of EP0132073A2 publication Critical patent/EP0132073A2/de
Publication of EP0132073A3 publication Critical patent/EP0132073A3/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Withdrawn legal-status Critical Current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
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/24—Obtaining niobium or tantalum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/28—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from gaseous metal compounds
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases

Definitions

  • the present invention relates to a process for producing metallic niobium or metallic tantalum.
  • the present invention provides a new, improved, process.
  • a fluorine containing compound of niobium or tantalum is reacted with hydrogen gas, metallic magnesium, metallic aluminium or metallic lead, to produce metallic niobium or metallic tantalum.
  • the invention provides a process for producing metallic niobium or metallic tantalum, which process comprises bringing a fluorine containing compound of niobium or tantalum:
  • 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 in (B) 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, magnesium or lead.
  • the fluorine containing compound in the present reaction is gaseous.
  • the compound may contact initially as a solid with the aluminium, magnesium or lead 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 present reaction is preferably between gaseous NbF 5 or gaseous TaF 5 and the hydrogen, aluminium, magnesium or lead, the gaseous NbF 5 or gaseous TaF 5 being comprised in the gaseous fluorine containing compound of niobium or tantalum.
  • the gaseous NbF 5 or gaseous TaF 5 in (B) is preferably employed in the inert gas or reducing gas mentioned above.
  • Gaseous fluorine containing compound is generally produced by heating solid fluorine containing compound.
  • the fluorine containing compound of niobium or tantalum can be produced by extracting a niobium or tantalum compound into an organic solvent, and bringing the solution into contact with an aqueous solution containing NH 4 + (and preferably also F - ) to extract into the aqueous phase niobium or tantalum in the form of a fluorine containing compound of niobium or tantalum.
  • 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 organic solvent comprises at least one extracting agent (for example one or two) selected from the group consisting of (a) alkylphosphoric acids, (b) neutral phosphoric esters, (c) alkylamines and (d) ketones.
  • the organic solvent comprises (i) at least one extracting agent selected from (a), (b), (c) and (d), and (ii) a diluent which is a petroleum hydrocarbon.
  • Fig. 1 illustrates the production of Nb or Ta.
  • Fluorine containing compounds (A) of Nb or Ta are supplied to the vaporization stage (B) to produce gaseous NbF 5 or TaF 5 .
  • the gaseous NbF 5 or TaFS is transferred to a reactor which is full of hydrogen gas (C) and the temperature is maintained at above 400°C (Reaction stage (D) ).
  • metallic Nb or metallic Ta can be produced according to the following equations:
  • Fig. 2 illustrates the production using as reducing agent metallic aluminium, metallic magnesium or metallic lead, instead of hydrogen gas.
  • Gaseous TaF 5 or NbF 5 is prepared by supplying fluorine containing compounds of Ta or Nb (A), such as crystals of ( N H 4 ) 2 TaF 7 or (NH 4 ) 2 NbF 7 , respectively, to the vaporization stage (B) and heating them at a temperature above 150°C, as expressed by the following equations:
  • reaction stage (D) an inert gas or a reducing gas fills the reactor and metallic aluminium, metallic magnesium or metallic lead heated to above 300°C is supplied to the reactor.
  • the NbF 5 or TaF 5 supplied from the vaporization stage (B) to the reaction stage (D) produces metallic Nb or Ta, respectively, by reduction.
  • This reaction stage (D) may be carried out in vacuum.
  • Fig. 3 illustrates the process of the invention including the preparation of fluorine containing compounds (A) of Nb or Ta and also the recovery of HF produced as by-product in the reaction stage.
  • the organic solution (H) containing extracted Nb or Ta is delivered to the stripping stage (J) and allowed to contact with the aqueous solution (K) containing F and NH 4 + .
  • the Nb or Ta is transferred to the aqueous phase, and the organic solvent (P) is transferred to the circulation route to the extraction stage.
  • TBP represents tributyl phosphate
  • R is such that RH represents an extracting agent having an H-type exchanging group.
  • the crystals formed are separated by filtration in the separation stage (L), and the subsequent operations to obtain metallic Nb or Ta are as shown in Fig.1.
  • the by-product HF gas (F) in the reaction stage (D) is absorbed for recovery in the gas absorbing stage (M) where a solution containing NH 4 + and F - circulates.
  • reducing agent (C) there is used metallic aluminium, metallic magnesium or metallic lead, and by-product gases produced in the reaction stage (D) are AlF 3 , MgF 2 or PbF 2 as illustrated in equations (5) to (10) above.
  • the oxides produced Al 2 O 3 , MgO or PbO, contain as little fluorine as is permissible for commercial material.
  • the HF gas is recovered in the gas absorbing stage (M).
  • the fluoride content of the by-product produced in the present basic reaction i.e. of the HF, AlF 3 , MgF 2 or PbF 2
  • the fluoride content of the by-product produced in the present basic reaction i.e. of the HF, AlF 3 , MgF 2 or PbF 2
  • the fluoride content of the by-product produced in the present basic reaction i.e. of the HF, AlF 3 , MgF 2 or PbF 2
  • the fluoride content of the by-product produced in the present basic reaction i.e. of the HF, AlF 3 , MgF 2 or PbF 2
  • gaseous TaF S or NbF 5 can be produced by vaporization of fluorine containing compounds of Nb or Ta such as (NH 4 ) 2 NbF 7 or (NH 4 ) 2 TaF 7 .
  • the vaporization can be carried out using an external heating furnace, an external heating type rotary furnace or naturally a flow type external heating furnace.
  • the gaseous NbF 5 or gaseous TaF S is preferably prepared by heating (NH 4 ) 2 NbF 7 or (NH 4 ) 2 TaF 7 at a temperature above 150°C.
  • furnaces of various known types can be employed such as the closed type of electric furnace, shaft furnace, rotary or static type of external heating furnace.
  • Metallic aluminium, magnesium or lead used as reducing agent may be employed in the form of a gas or liquid or mixture thereof.
  • the metallic Nb or Ta can be produced by bringing the gaseous fluoride in a stream of an inert gas or a reducing gas or in vacuum into contact with the metallic reducing agent.
  • the inert gas which can be employed to maintain the reaction condition of the reactor can be selected for example from the group consisting of argon, helium and nitrogen.
  • Reducing gases which can be employed in the invention include H 2 , CO and various gaseous hydrocarbons C H .
  • alkylphosphoric acids which can be employed as extracting agents in the invention, to produce fluorine containing compounds of Nb or Ta, are selected from the group consisting of the following compounds: where R represents an alkyl group, generally of 4 to 22 carbon atoms.
  • the neutral phosphoric esters which can be employed as extracting agents are selected from the following compounds: R is as defined above.
  • TBP tributyl phosphate
  • R C 4 H 9 R C 4 H 9 .
  • alkylamines which can be employed as extracting agents are selected from the following group of compounds:
  • cyclohexanone(C 6 H 12 O) is also often employed.
  • the diluents which can be employed are mostly petroleum hydrocarbons, but aromatic and aliphatic hydrocarbons and mixtures thereof may also be used.
  • aromatic and aliphatic hydrocarbons and mixtures thereof may also be used.
  • kerosene a mixture of many kinds of hydrocarbon, is commonly used.
  • the concentration of extracting agent should be chosen according to the character of the treated solution, the concentration of metal ions, the concentration and nature of impurities, and the nature of the chemical species to be extracted, but generally is 2 to 100% by volume.
  • 20 g of these crystals were introduced into a vaporization furnace and heated to 220°C under a stream of H 2 gas.
  • Gaseous TaF 5 formed in the vaporization furnace and was transferred to a reactor which was maintained at a temperature of 600°C. The reaction was continued for an hour, and then the reactor was cooled. A substance had adhered to the inner wall of the reactor, and this substance proved to be Ta, as confirmed by X-ray diffraction analysis. The substance amounted to10g.
  • H 2 NbF 7 extracted by 100% MIBK (methyl isobutyl ketone) was stripped with an aqueous solution containing 250 g/1 of NH 4 HF 2 , to obtain crystals of (NH 4 ) 2 NbF 7 , of which 180 g was heated in an atmosphere of helium to produce NbF S .
  • the NbF 5 gas was continuously treated in a reactor in which the NbF 5 containing gas just obtained was blown onto an aluminium metal surface heated at 950°C in a helium stream. After 6 hours of continuous treatment, the reactor was cooled and disassembled. A substance was found on the aluminium surface in an amount of 62 g and this substance proved to be metallic Nb, as confirmed by X-ray diffraction analysis and chemical analysis.
  • H 2 NbF 5 extracted by a solvent consisting of 80% by volume cyclohexanone and 20% by volume Shellsol AB was stripped with an aqueous solution containing 200 g/1 of NH4HF2, to obtain crystals of (NH 4 ) 2 NbF 7 .
  • These crystals and metallic lead were heated separately in an external heating furnace. Gases of metallic Pb and NbF 5 were led to a reactor and held for 2 hours at a reactor temperature of 750°C. The reactor was then cooled and disassembled. Powder adhering to the inner wall of the reactor proved to be metallic Nb by X-ray diffraction measurement and chemical analysis.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
EP84304461A 1983-07-14 1984-06-29 Verfahren zur Herstellung von metallischem Niob oder Tantal Withdrawn EP0132073A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP126995/83 1983-07-14
JP12699583A JPS6021343A (ja) 1983-07-14 1983-07-14 金属ニオブ又は金属タンタルの製造方法

Publications (2)

Publication Number Publication Date
EP0132073A2 true EP0132073A2 (de) 1985-01-23
EP0132073A3 EP0132073A3 (de) 1986-12-30

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EP84304461A Withdrawn EP0132073A3 (de) 1983-07-14 1984-06-29 Verfahren zur Herstellung von metallischem Niob oder Tantal

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EP (1) EP0132073A3 (de)
JP (1) JPS6021343A (de)
AU (1) AU3049684A (de)
BR (1) BR8403514A (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4663130A (en) * 1983-11-14 1987-05-05 Cabot Corporation Process for dissolving tantalum/columbium materials containing alkali metal impurities
JPS62185841A (ja) * 1986-02-10 1987-08-14 Nishimura Watanabe Chiyuushiyutsu Kenkyusho:Kk 金属ニオブまたは金属タンタルの製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2905548A (en) * 1957-09-06 1959-09-22 Fansteel Metallurgical Corp Method of recovering tantalum and columbium
GB955832A (en) * 1959-10-21 1964-04-22 Ciba Ltd Process for the manufacture of metallic niobium or tantalum or alloys thereof
US3341320A (en) * 1966-04-05 1967-09-12 Seymour H Smiley Production of low particle size-high surface area metal powders
EP0052354A2 (de) * 1980-11-18 1982-05-26 Solex Research Corporation of Japan Verfahren zur Herstellung von Metallen aus Fluor enthaltenden Verbindungen

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5237866B2 (de) * 1973-07-20 1977-09-26
JPS609575B2 (ja) * 1981-04-09 1985-03-11 古河鉱業株式会社 溶煉炉

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2905548A (en) * 1957-09-06 1959-09-22 Fansteel Metallurgical Corp Method of recovering tantalum and columbium
GB955832A (en) * 1959-10-21 1964-04-22 Ciba Ltd Process for the manufacture of metallic niobium or tantalum or alloys thereof
US3341320A (en) * 1966-04-05 1967-09-12 Seymour H Smiley Production of low particle size-high surface area metal powders
EP0052354A2 (de) * 1980-11-18 1982-05-26 Solex Research Corporation of Japan Verfahren zur Herstellung von Metallen aus Fluor enthaltenden Verbindungen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
G.L. MILLER: "Tantalum and Niobium", Butterworths, Scientific Publications, 1959, pages 196-207; page 240, London, GB; *

Also Published As

Publication number Publication date
BR8403514A (pt) 1985-06-25
AU3049684A (en) 1985-01-17
JPS6021343A (ja) 1985-02-02
EP0132073A3 (de) 1986-12-30

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