US20090188348A1 - Continuous process - Google Patents

Continuous process Download PDF

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Publication number
US20090188348A1
US20090188348A1 US11/658,754 US65875405A US2009188348A1 US 20090188348 A1 US20090188348 A1 US 20090188348A1 US 65875405 A US65875405 A US 65875405A US 2009188348 A1 US2009188348 A1 US 2009188348A1
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United States
Prior art keywords
metal
particles
seed particles
fluidised bed
process according
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Abandoned
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US11/658,754
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English (en)
Inventor
Christopher Geoffrey Goodes
Grant Ashley Wellwood
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Commonwealth Scientific and Industrial Research Organization CSIRO
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Commonwealth Scientific and Industrial Research Organization CSIRO
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Filing date
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Priority claimed from AU2004904306A external-priority patent/AU2004904306A0/en
Application filed by Commonwealth Scientific and Industrial Research Organization CSIRO filed Critical Commonwealth Scientific and Industrial Research Organization CSIRO
Assigned to COMMONWEALTH SCIENTIFIC AND INDUSTRIAL RESEARCH ORGANISATION reassignment COMMONWEALTH SCIENTIFIC AND INDUSTRIAL RESEARCH ORGANISATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GOODES, CHRISTOPHER GEOFFREY, WELLWOOD, GRANT ASHLEY
Publication of US20090188348A1 publication Critical patent/US20090188348A1/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/32—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with introduction into the fluidised bed of more than one kind of moving particles
    • 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
    • C22B21/02—Obtaining aluminium with reducing
    • 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
    • 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
    • C22B5/14—Dry methods smelting of sulfides or formation of mattes by gases fluidised material

Definitions

  • the present invention relates to a process for producing a metal by the reduction of the corresponding metal halide. More specifically, the present invention relates to a process for producing a metal in a fluidised bed reactor that offers operational advantages when compared with conventional techniques.
  • titanium tetrachloride can be reduced by reaction with a reductant such as magnesium, sodium or hydrogen under suitable reaction conditions.
  • a reductant such as magnesium, sodium or hydrogen
  • One way in which this reaction is typically carried out involves a fluidised bed of seed particles of the metal it is desired to produce.
  • the reactants are delivered into the fluidised bed with the intention that metal formed by the reduction reaction is deposited on the surface of the seed particles. In turn this results in growth/coarsening of the seed particles. Seed particles that have grown to a suitable extent may be removed continuously and replenished with fresh seed particles.
  • the present invention provides a process for producing a metal from the corresponding metal halide by reaction of the metal halide at elevated temperature in a reactor comprising a fluidised bed, the fluidised bed comprising seed particles of an inert material that has a melting point higher than that of the metal.
  • a reactor comprising a fluidised bed, the fluidised bed comprising seed particles of an inert material that has a melting point higher than that of the metal.
  • the term “inert” means that the material does not undergo any chemical reaction with any species present in the reactor under the prevailing conditions that are encountered.
  • the inert material is selected so that the seed particles remain solid and as discrete particles under the prevailing conditions that will be encountered in the reactor. It is also a requirement that the inert material has a melting point that is higher than the metal it is desired to produce. Typically, the melting point of the inert material is at least 30° C. higher than the melting point of the metal to be produced. The maximum temperature encountered in the fluidised bed during operation of the process of the invention will be below the melting point of the inert material.
  • the weight ratio of inert material to metal will be from 20:80 to 80:20, and one skilled in the art would have no difficulty in manipulating the relative proportions of the seed particles to achieve the desired technical effect in accordance with the present invention.
  • the fluidised bed consists solely of seed particles of the inert material.
  • the fluidised bed is agitated and brought up to a suitably elevated temperature. This may be achieved by injection into the fluidised bed of a heated inert gas such as argon.
  • the inert material that is used in practice of the invention may vary between reaction systems and operating conditions. Taking into account the requirements already mentioned, the inert material may be selected from metallic or non-metallic materials. Examples of such include metal oxides, nitrides and silicates, metals or metal alloys. Particles of coke may also be used. Preferably, the inert material is silica. This is a cheap and abundant material. Mixtures of different types of inert materials may make up the fluidised bed.
  • the particle size of the inert seed particles is usually within the range 500-1000 ⁇ m, for example from 500-750 ⁇ m.
  • the reactants are introduced.
  • metal may be deposited on the surface of the inert seed particles.
  • the inert seed particles grow as fresh metal is deposited on the outer surface of the particles.
  • composite particles are much less prone to sintering and agglomeration when compared with particles formed from the metal only. The exact reason for this is not clearly understood, although it is believed to be associated with the structure of the metal formed at the surface of the inert seed particles.
  • composite particles comprising a core of inert material and a coating of deposited metal will be continuously discharged from the reactor. Uncoated seed particles may also be discharged. Sampling of the discharged particles may be used to determine when no further seed particles and composite particles are present in the fluidised bed. At that point it can be assumed that particles discharged subsequently will be of the metal per se. These particles may then be isolated after discharge from the bed for subsequent processing as necessary.
  • the sintering and agglomeration problem may be most prevalent on start up of the fluidised bed.
  • the use of seed particles formed from an inert high melting point material allows start up to be effected with minimal or no sintering and agglomeration.
  • the fluidised bed may be run continuously.
  • the fluidised bed may be replenished with seed particles formed from the metal it is desired to produce.
  • the fluidised bed would be operated in conventional manner. If during operation of the fluidised bed sintering and agglomeration are observed, it may be appropriate to introduce into the bed seed particles of the inert material to overcome the problem. In this case there will also be a period of time before the inert seed particles are discharged again.
  • the process is operated so that inert seed particles are always present in the bed. This will involve continuous addition of fresh inert seed particles as coated seed particles are discharged from the bed. In this case it will be necessary to separate composite particles from pure metal particles that have been discharged. This may be done on a density basis.
  • the fluidised bed (and reactor) are operated such that the fluidised particles are at a higher temperature than the reactor walls. This may help to reduce incidence of sintering when the particles come into contact with the reactor walls. The same effect may be achieved by varying the material from which the walls of the reactor (and other parts of the rector that come into contact with fluidised particles) are constructed.
  • the method of the invention may be applied in the manufacture of a variety of metals as might usually be produced by the kind of reduction reaction described herein.
  • metals include titanium, hafnium, zirconium, vanadium and aluminium.
  • the metal halide is typically the chloride.
  • Suitable reductants include magnesium, zinc, hydrogen and sodium.
  • the bed of seed particles is usually fluidised using an inert gas such as argon.
  • the rate at which the gas is injected into the bed may vary depending upon such things as particle size and density, volume occupied by the particles, and reactor design.
  • a cylindrical reaction vessel with a conical base having an internal diameter of 200 mm and an aspect ratio of 10 was charged with 40 grams of 500-1000 ⁇ m titanium sponge particles.
  • High purity argon was then passed through the bed of starter particles at a rate of 65 standard litres of argon per minute to promote vigorous fluidisation.
  • the bed sintered into a solid mass before the reactants could be admitted. This solid mass is shown in FIG. 1 .
  • Example 1 was repeated except the starter bed of 500-1000 ⁇ m titanium particles was replaced with sand particles having a particle size between 500 and 600 ⁇ m. To achieve vigorous fluidisation, the high purity argon flowrate was increased to 83 standard litres per minute. Once the temperature measured 50 mm above the upper bed surface reached 900° C. the two reactant feeds were applied. Titanium tetrachloride was supplied at a rate of 80 millilitres per hour as a vapour at a temperature of around 700° C. In this example, the reductant phase was magnesium metal, which was supplied at a rate of 36 grams per hour as a vapour in conjunction with a low volume argon gas carrier stream at a temperature of around 700° C.
  • Both reactant inlets were located at the base of the fluidising zone.
  • the temperature of the gas leaving the bed increased by around 22° C. consistent with the exothermic nature of the reaction.
  • the level of external heating was increased such that the temperature of the gas leaving the bed increased to 1037° C. Even at this elevated temperature the bed remained fluidised with indications that sinter free operation at even higher temperatures was possible.
  • Particles removed from the reactor were found to consist of the original sand particle totally encapsulated in a 10 ⁇ m shell of titanium. This is shown in FIG. 2 , with the cross-section of the particle being shown in FIG. 3 .
  • Example 1 was repeated except the starter bed of 600-500 ⁇ m sand particles was replaced with low volatile content coke particles having a particle size between 600 and 500 ⁇ m. High purity argon was then passed through the bed of starter particles at a rate of 42.4 standard litres of argon per minute to promote fluidisation. Once the temperature measured 5 cm above the upper bed surface reached 990° C. the two reactant feeds were applied. Titanium tetrachloride was supplied at a rate of 86.35 millilitres per hour in a vapour form at a temperature of around 700° C.
  • the reductant phase was magnesium metal, which was supplied at a rate of 40.16 grams per hour as a vapour in conjunction with a low volume argon gas carrier stream at a temperature of around 700° C.
  • the temperature of the gas leaving the bed increased by around 18° C. due to the exothermic nature of the reaction.
  • the level of external heating was increased such that the temperature of the gas leaving the bed increased to 1010° C. Particles removed from the reactor were found to consist of the original coke particle completely encapsulated in a titanium based shell.
  • a cylindrical reaction vessel with a conical base having an internal diameter of 200 mm and an aspect ratio of 10 was charged with 200 grams of graded (600-500 ⁇ m) sand particles.
  • High purity argon was then passed through the bed of starter particles at a rate of 23 standard litres of Argon per minute to promote fluidisation. Once the temperature measured 5 cm above the upper bed surface reached 970° C. the two reactant feeds were applied. Titanium tetrachloride was supplied at a rate of 220 millilitres per hour in a vapour form at a temperature of around 700° C.
  • the reductant phase was zinc metal, which was supplied at a rate of 262 grams per hour as a vapour in conjunction with a low volume argon gas carrier stream at a temperature of around 700° C. Both reactant inlets were located at the base of the fluidising zone.
  • the temperature of the gas leaving the bed decreased by around 12° C. consistent with thermodynamic expectations.
  • the level of external heating was maintained such that the temperature of the gas leaving the bed increased was around 960° C. Even at this elevated temperature, where titanium has been observed to sinter, the bed remained fluidised with indications that higher temperatures were possible. Particles removed from the reactor were found to consist of the original sand particle encapsulated in a 10 ⁇ m shell of titanium.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
US11/658,754 2004-07-30 2005-07-29 Continuous process Abandoned US20090188348A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AU2004904306A AU2004904306A0 (en) 2004-07-30 Continuous Process
AU2004904306 2004-07-30
PCT/AU2005/001127 WO2006010224A1 (en) 2004-07-30 2005-07-29 Continuous process

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CN (1) CN100554447C (zh)
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2827371A (en) * 1951-11-01 1958-03-18 Ici Ltd Method of producing titanium in an agitated solids bed
US3252823A (en) * 1961-10-17 1966-05-24 Du Pont Process for aluminum reduction of metal halides in preparing alloys and coatings
US4039324A (en) * 1975-11-14 1977-08-02 Cyprus Metallurgical Processes Corporation Fluidized hydrogen reduction process for the recovery of copper
US4877445A (en) * 1987-07-09 1989-10-31 Toho Titanium Co., Ltd. Method for producing a metal from its halide
US6475462B1 (en) * 1997-09-30 2002-11-05 Mortimer Technology Holdings Limited Process and apparatus for treating particulate matter
US20040005028A1 (en) * 2002-07-03 2004-01-08 Burckhardt Darrell D. Adaptive opto-emission imaging device and method thereof
US20080307925A1 (en) * 2004-10-20 2008-12-18 Commonwealth Scientific And Industrial Research Or Organization Low Temperature Industrial Process

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03150327A (ja) * 1989-11-06 1991-06-26 Osaka Titanium Co Ltd 金属Ｔｉの製造方法
US6902601B2 (en) * 2002-09-12 2005-06-07 Millennium Inorganic Chemicals, Inc. Method of making elemental materials and alloys
US6955703B2 (en) * 2002-12-26 2005-10-18 Millennium Inorganic Chemicals, Inc. Process for the production of elemental material and alloys

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2827371A (en) * 1951-11-01 1958-03-18 Ici Ltd Method of producing titanium in an agitated solids bed
US3252823A (en) * 1961-10-17 1966-05-24 Du Pont Process for aluminum reduction of metal halides in preparing alloys and coatings
US4039324A (en) * 1975-11-14 1977-08-02 Cyprus Metallurgical Processes Corporation Fluidized hydrogen reduction process for the recovery of copper
US4877445A (en) * 1987-07-09 1989-10-31 Toho Titanium Co., Ltd. Method for producing a metal from its halide
US6475462B1 (en) * 1997-09-30 2002-11-05 Mortimer Technology Holdings Limited Process and apparatus for treating particulate matter
US20040005028A1 (en) * 2002-07-03 2004-01-08 Burckhardt Darrell D. Adaptive opto-emission imaging device and method thereof
US20080307925A1 (en) * 2004-10-20 2008-12-18 Commonwealth Scientific And Industrial Research Or Organization Low Temperature Industrial Process

Also Published As

Publication number Publication date
CN101014722A (zh) 2007-08-08
CN100554447C (zh) 2009-10-28
WO2006010224A1 (en) 2006-02-02

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Owner name: COMMONWEALTH SCIENTIFIC AND INDUSTRIAL RESEARCH OR

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:GOODES, CHRISTOPHER GEOFFREY;WELLWOOD, GRANT ASHLEY;REEL/FRAME:022528/0014

Effective date: 20090225

STCB Information on status: application discontinuation

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