WO2005090640A1 - Electrochemical reduction of metal oxides - Google Patents

Electrochemical reduction of metal oxides Download PDF

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Publication number
WO2005090640A1
WO2005090640A1 PCT/AU2005/000409 AU2005000409W WO2005090640A1 WO 2005090640 A1 WO2005090640 A1 WO 2005090640A1 AU 2005000409 W AU2005000409 W AU 2005000409W WO 2005090640 A1 WO2005090640 A1 WO 2005090640A1
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WO
WIPO (PCT)
Prior art keywords
electrolyte
powders
process defined
cathode
metal oxide
Prior art date
Application number
PCT/AU2005/000409
Other languages
French (fr)
Inventor
Ivan Ratchev
René Ignacio OLIVARES
Andrew Arthur Shook
Gregory David Rigby
Original Assignee
Bhp Billiton Innovation Pty Ltd
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
Priority claimed from AU2004901524A external-priority patent/AU2004901524A0/en
Application filed by Bhp Billiton Innovation Pty Ltd filed Critical Bhp Billiton Innovation Pty Ltd
Priority to JP2007504212A priority Critical patent/JP2007529631A/en
Priority to AU2005224292A priority patent/AU2005224292A1/en
Publication of WO2005090640A1 publication Critical patent/WO2005090640A1/en
Priority to US11/522,761 priority patent/US20070131560A1/en

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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
    • 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
    • C22B34/129—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 by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts
    • 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
    • C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C22B4/08—Apparatus

Definitions

  • the present invention relates to electrochemical reduction of metal oxides .
  • the present invention relates particularly to electrochemical reduction of metal oxides in the form of powder to produce metal having a low oxygen concentration, typically no more than 0.2% by weight.
  • the present invention was made during the course of an on-going research project on electrochemical reduction of metal oxides being carried out by the applicant.
  • the research project has focussed on the reduction of titanium oxide, more specifically titania (Ti0 2 ) .
  • the CaCl 2 -based electrolyte used in the experiments was a commercially available source of CaCl 2 , namely calcium chloride dihydrate, which decomposed on heating and produced a very small amount of CaO.
  • the applicant operated the electrolytic cells at a potential above the decomposition potential of CaO and below the decomposition potential of CaCl 2 .
  • the present invention was made unexpectedly in two experiments on sub-micron powders of pigment grade titania.
  • the powders were mixed with molten CaCl 2 -based electrolyte containing CaO in electrolytic cells comprising anodes and cathodes in contact with the electrolyte/powder baths .
  • the applicant found unexpectedly that the titania powders were successfully reduced in the molten electrolyte baths .
  • the applicant also found unexpectedly that there was very little carbon produced in the experiments that was retained in the cells - this is a potentially important finding given that carbon contamination can be significant. The applicant had not expected to achieve these results .
  • a process for electrochemically reducing metal oxide feed material in a solid state which includes the steps of: agitating an electrolyte and metal oxide powders in the electrolyte and applying an electrical potential across (a) a cathode in contact with the electrolyte and (b) an anode and electrochemically reducing the metal oxides.
  • the agitation caused intermittent contact between the powder particles and the cathode that was sufficient to enable reduction of titania powders and restrict sintering of the powder particles together that could adversely affect the reduction of unreduced or partially reduced powders .
  • the particle size of the powders is selected so that the electrolyte and the powders form a slurry, ie a two phase mixture, in which the powder particles are suspended in the electrolyte .
  • the electrolyte and the metal oxide powders may be agitated by any suitable means .
  • the electrolyte and the metal oxide powders may be agitated by physical means , such as a stirrer .
  • the electrolyte and the metal oxides powders may be agitated by gas injection.
  • the applicant has found in the two experiments described above that gas injection enabled segregation of carbon contaminant formed in the experiments to the surface of the bath and titanium to the bottom of the bath. This is an important feature in terms of separating carbon and titanium in the process .
  • the metal oxide powders may be any suitable metal oxide.
  • the present invention has particular application to solid state reduction of titanium oxide particles, specially titania particles.
  • the electrolyte is a CaCl 2 -based electrolyte containing CaO.
  • the powders are sub-micron size.
  • the process comprises applying a potential across the anode and the cathode that is above the decomposition potential of CaO and below the decomposition of CaCl 2 .
  • the process may be carried out on a batch basis, a semi-continuous basis, and a continuous basis.
  • the process may be carried out by positioning a member such as bar or plate or sheet in contact with the electrolyte so that reduced powders can deposit on the member.
  • the process comprises removing the member from the electrolyte and stripping deposited reduced powders from the members .
  • the process may be carried out in a cell that contains a bath of electrolyte and metal oxide powders , an anode, and a cathode.
  • the anode may be made from any suitable material .
  • the anode may be a consumable or a non-consumable anode .
  • the anode is a consumable anode.
  • the cathode may be made from any suitable material .
  • the process may be carried out as a multi-stage process with electrolyte and partially reduced and unreduced powders in a slurry form being transferred from a first stage to one or more than one successive stage in the process and being reduced in each stage.
  • the multi-stage process may be carried out in the above-described cell , with discharge and recycling of the slurry to the cell .
  • the multi-stage process may be carried out in a series of the above-described cells . The process is not confined to being carried out in the above-described cell.
  • the process may be carried out on a continuous basis by passing a slurry of the electrolyte and metal oxide powders through a reactor, such as a pipe reactor, that defines a pathway for flow of the slurry between an inlet and an outlet and includes one or more than one anode and one or more than one cathode along the length of the pathway.
  • a reactor such as a pipe reactor
  • the reactor may include agitating the slurry by a means, such as baffles or the like in the pathway, that causes the slurry to flow in a turbulent flow pattern along the pathway.
  • a means such as baffles or the like in the pathway
  • the process may include agitating the slurry by introducing the slurry in a turbulent flow into the reactor .
  • the process comprises separating reduced powders from the electrolyte downstream of the outlet of the pathway and processing the reduced powders as required.
  • an apparatus for electrochemically reducing metal oxide powders such as titanium oxide powders , which includes (a) a means for containing a bath of a molten electrolyte and metal oxide particles in the electrolyte, (b) a cathode in contact with the electrolyte, (c) an anode, (d) a means for applying a potential across the anode and the cathode, and (e) a means for agitating the electrolyte .
  • the apparatus may be adapted to operate on a batch basis, a semi-continuous basis, or a continuous basis.
  • the means for applying a potential across the anodes and the cathode includes (a) a power source and (b) an electrical circuit that electrically interconnects the power source , the anodes , and the cathode .
  • the basic cell configuration of (a) a means for containing a bath of a molten electrolyte and metal oxide particles in the electrolyte, (b) a cathode in contact with the electrolyte, (c) an anode, (d) a means for applying a potential across the anode and the cathode is as described by way of example in other patent families of the applicant such as WO2003/01659 , WO2003/076690 , WO2004/035873 and WO2004/053201.
  • the present invention was made unexpectedly in two experiments in which sub-micron powders of pigment grade titania were reduced in electrolytic cells containing baths of molten CaCl 2 -based electroly e containing CaO, anodes and cathodes .
  • the anode and the cathode were arranged to extend into the cell and the cathode had a relatively large surface area compared to the size of the cell.
  • the titania powders were 10% by weight of the total weight of the powders and the electrolyte.
  • the titanium powders were sub-micron sized.
  • the cell was operated at a constant potential of 3 V for a period of 7 hours. The cell achieved currents of up to 8 A during the experiment .
  • the second experiment which was run after the success of the first experiment, the wall of the cell formed the cathode and the anode was arranged to extend into the cell.
  • the solids loading was 5% in this experiment.
  • the titania powders were 5% by weight of the total weight of the powders and the electrolyte.
  • the titania powders were sub-micron size.
  • the cell was operated at a constant potential of 3 V for a period of 7 hours.
  • the cell achieved currents of up to 30 A during the experiment.
  • the operating potential of 3 V is a potential above the decomposition potential of CaO in the electrolyte and below the decomposition potential of CaCl 2 ;
  • the titania powders were reduced up to 95% by the end of the second experiment.
  • the applicant allowed the cell to cool to room temperature and then sectioned the cell.
  • the applicant found that the cell comprised a layer of titanium metal powders on the bottom wall of the cell and a layer of substantially "clean" electrolyte on the metal layer .
  • the side walls of the cell had a layer of titanium carbide .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Geology (AREA)
  • Mechanical Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

A process for electrochemically reducing metal oxide feed material in a solid state is disclosed. The process includes the steps of agitating an electrolyte and metal oxide powders in the electrolyte and applying an electrical potential across a cathode in contact with the electrolyte and an anode and electrochemically reducing the metal oxides.

Description

ELECTROCHEMICAL REDUCTION OF METAL OXIDES
The present invention relates to electrochemical reduction of metal oxides .
The present invention relates particularly to electrochemical reduction of metal oxides in the form of powder to produce metal having a low oxygen concentration, typically no more than 0.2% by weight.
The present invention was made during the course of an on-going research project on electrochemical reduction of metal oxides being carried out by the applicant. The research project has focussed on the reduction of titanium oxide, more specifically titania (Ti02) .
During the course of the research project the applicant has carried out a series of experiments investigating the reduction of titania in electrolytic cells comprising a pool of molten CaCl2-based electrolyte, an anode formed from graphite , and a range of cathodes .
The CaCl2-based electrolyte used in the experiments was a commercially available source of CaCl2, namely calcium chloride dihydrate, which decomposed on heating and produced a very small amount of CaO.
The applicant operated the electrolytic cells at a potential above the decomposition potential of CaO and below the decomposition potential of CaCl2.
The applicant found that the cells electrochemically reduced titania to titanium with low concentrations of oxygen, ie concentrations less than 0.2 w . % , at these potentials . The applicant operated the cells under a wide range of different operating set-ups and conditions .
The present invention was made unexpectedly in two experiments on sub-micron powders of pigment grade titania. The powders were mixed with molten CaCl2-based electrolyte containing CaO in electrolytic cells comprising anodes and cathodes in contact with the electrolyte/powder baths . The applicant found unexpectedly that the titania powders were successfully reduced in the molten electrolyte baths . The applicant also found unexpectedly that there was very little carbon produced in the experiments that was retained in the cells - this is a potentially important finding given that carbon contamination can be significant. The applicant had not expected to achieve these results .
The unexpected success of the experiments opens up the possibility of commercial production of metals from metal oxides such as titania on a far more straightforward basis than was hitherto thought to be possible.
According to the present invention there is provided a process for electrochemically reducing metal oxide feed material in a solid state which includes the steps of: agitating an electrolyte and metal oxide powders in the electrolyte and applying an electrical potential across (a) a cathode in contact with the electrolyte and (b) an anode and electrochemically reducing the metal oxides.
The applicant speculates that the agitation caused intermittent contact between the powder particles and the cathode that was sufficient to enable reduction of titania powders and restrict sintering of the powder particles together that could adversely affect the reduction of unreduced or partially reduced powders . Preferably the particle size of the powders is selected so that the electrolyte and the powders form a slurry, ie a two phase mixture, in which the powder particles are suspended in the electrolyte .
The electrolyte and the metal oxide powders may be agitated by any suitable means . By way of example, the electrolyte and the metal oxide powders may be agitated by physical means , such as a stirrer .
Alternatively, or in addition, the electrolyte and the metal oxides powders may be agitated by gas injection.
The applicant has found in the two experiments described above that gas injection enabled segregation of carbon contaminant formed in the experiments to the surface of the bath and titanium to the bottom of the bath. This is an important feature in terms of separating carbon and titanium in the process . The metal oxide powders may be any suitable metal oxide. As is indicated above, the present invention has particular application to solid state reduction of titanium oxide particles, specially titania particles. Preferably the electrolyte is a CaCl2-based electrolyte containing CaO.
In the case of a CaCl2~based electrolyte containing CaO, preferably the powders are sub-micron size.
In the case of a CaCl2-based electrolyte containing CaO preferably the process comprises applying a potential across the anode and the cathode that is above the decomposition potential of CaO and below the decomposition of CaCl2.
The process may be carried out on a batch basis, a semi-continuous basis, and a continuous basis.
The process may be carried out by positioning a member such as bar or plate or sheet in contact with the electrolyte so that reduced powders can deposit on the member.
With this arrangement the process comprises removing the member from the electrolyte and stripping deposited reduced powders from the members .
The process may be carried out in a cell that contains a bath of electrolyte and metal oxide powders , an anode, and a cathode.
The anode may be made from any suitable material . The anode may be a consumable or a non-consumable anode . Typically, the anode is a consumable anode.
The cathode may be made from any suitable material .
The process may be carried out as a multi-stage process with electrolyte and partially reduced and unreduced powders in a slurry form being transferred from a first stage to one or more than one successive stage in the process and being reduced in each stage. The multi-stage process may be carried out in the above-described cell , with discharge and recycling of the slurry to the cell . The multi-stage process may be carried out in a series of the above-described cells . The process is not confined to being carried out in the above-described cell.
By way of example, the process may be carried out on a continuous basis by passing a slurry of the electrolyte and metal oxide powders through a reactor, such as a pipe reactor, that defines a pathway for flow of the slurry between an inlet and an outlet and includes one or more than one anode and one or more than one cathode along the length of the pathway.
The reactor may include agitating the slurry by a means, such as baffles or the like in the pathway, that causes the slurry to flow in a turbulent flow pattern along the pathway.
Alternatively, or in addition, the process may include agitating the slurry by introducing the slurry in a turbulent flow into the reactor . When operated on a continuous basis preferably the process comprises separating reduced powders from the electrolyte downstream of the outlet of the pathway and processing the reduced powders as required. According to the present invention there is also provided an apparatus for electrochemically reducing metal oxide powders , such as titanium oxide powders , which includes (a) a means for containing a bath of a molten electrolyte and metal oxide particles in the electrolyte, (b) a cathode in contact with the electrolyte, (c) an anode, (d) a means for applying a potential across the anode and the cathode, and (e) a means for agitating the electrolyte .
The apparatus may be adapted to operate on a batch basis, a semi-continuous basis, or a continuous basis.
Preferably the means for applying a potential across the anodes and the cathode includes (a) a power source and (b) an electrical circuit that electrically interconnects the power source , the anodes , and the cathode .
The basic cell configuration of (a) a means for containing a bath of a molten electrolyte and metal oxide particles in the electrolyte, (b) a cathode in contact with the electrolyte, (c) an anode, (d) a means for applying a potential across the anode and the cathode is as described by way of example in other patent families of the applicant such as WO2003/01659 , WO2003/076690 , WO2004/035873 and WO2004/053201.
As is indicated above , the present invention was made unexpectedly in two experiments in which sub-micron powders of pigment grade titania were reduced in electrolytic cells containing baths of molten CaCl2-based electroly e containing CaO, anodes and cathodes .
In the first experiment the anode and the cathode were arranged to extend into the cell and the cathode had a relatively large surface area compared to the size of the cell. The titania powders were 10% by weight of the total weight of the powders and the electrolyte. The titanium powders were sub-micron sized. The cell was operated at a constant potential of 3 V for a period of 7 hours. The cell achieved currents of up to 8 A during the experiment . In the second experiment, which was run after the success of the first experiment, the wall of the cell formed the cathode and the anode was arranged to extend into the cell. The solids loading was 5% in this experiment. In other words, the titania powders were 5% by weight of the total weight of the powders and the electrolyte. The titania powders were sub-micron size. The cell was operated at a constant potential of 3 V for a period of 7 hours. The cell achieved currents of up to 30 A during the experiment.
In both experiments :
• the bath was agitated during the course of the experiments by inert gas injection to ensure movement of the powders within the bath;
• the operating potential of 3 V is a potential above the decomposition potential of CaO in the electrolyte and below the decomposition potential of CaCl2 ; and
• there was a build-up of reduced powders on the cathode, although without any apparent sintering of reduced powders that restricted reaction rates or otherwise adversely affected the experiments .
Some regions of the titania powders were reduced by up to 50% by the end of the first experiment.
The titania powders were reduced up to 95% by the end of the second experiment.
At the end of the second experiment, the applicant allowed the cell to cool to room temperature and then sectioned the cell. The applicant found that the cell comprised a layer of titanium metal powders on the bottom wall of the cell and a layer of substantially "clean" electrolyte on the metal layer .
The applicant also found that the side walls of the cell had a layer of titanium carbide .
Many modifications may be made to the present invention described above without departing from the spirit and scope of the invention.

Claims

Claims
1. A process for electrochemically reducing metal oxide feed material in a solid state which includes the steps of: agitating an electrolyte and metal oxide powders in the electrolyte and applying an electrical potential across (a) a cathode in contact with the electrolyte and (b) an anode and electrochemically reducing the metal oxides .
2. The process defined in claim 1 includes agitating an electrolyte and metal oxide powders to an extent required to cause intermittent contact between the powder particles and the cathode that is sufficient to enable reduction of titania powders and restrict sintering of the powder particles together that could adversely affect the reduction of unreduced or partially reduced powders .
3. The process defined in claim 1 or claim 2 includes selecting the particle size of the powders so that the electrolyte and the powders form a slurry, i.e. a two phase mixture, in which the powder particles are suspended in the electrolyte .
4. The process defined in any one of the preceding claims includes agitating the electrolyte and the metal oxide powders by physical means, such as a stirrer, and/or by gas injection.
5. The process defined in any one of the preceding claims wherein the powders are sub-micron size.
6. The process defined in any one of the preceding claims wherein the electrolyte is a CaCl2-based electrolyte containing CaO.
7. The process defined in claim 6 includes applying a potential across the anode and the cathode that is above the decomposition potential of CaO and below the decomposition of CaCl2.
8. The process defined in any one of the preceding claims includes positioning a member such as bar or plate or sheet in contact with the electrolyte so that reduced powders can deposit on the member.
9. The process defined in claim 8 includes removing the member from the electrolyte and stripping deposited reduced powders from the members .
10. The process defined in any one of the preceding claims wherein the process is a multi-stage process with electrolyte and partially reduced and unreduced powders in a slurry form being transferred from a first stage to one or more than one successive stage in the process and being reduced in each stage.
11. The process defined in any one of claims 1 to 9 wherein the process is a continuous process that includes passing a slurry of the electrolyte and metal oxide powders through a reactor, such as a pipe reactor, that defines a pathway for flow of the slurry between an inlet and an outlet and includes one or more than one anode and one or more than one cathode along the length of the pathway .
12. The process defined in claim 11 includes agitating the slurry by a means , such as baffles or the like in the pathway, that causes the slurry to flow in a turbulent flow pattern along the pathway.
13. The process defined in claim 11 or claim 12 includes agitating the slurry by introducing the slurry in a turbulent flow into the reactor.
1 . The process defined in any one of claims 11 to 13, when operated on a continuous basis, includes separating reduced powders from the electrolyte downstream of the outlet of the pathway and processing the reduced powders as required.
15. The process defined in any one of the preceding claims wherein the metal oxide particles are titanium oxide particles, such as titania particles.
16 An apparatus for electrochemically reducing metal oxide powders which includes (a) a means for containing a bath of a molten electrolyte and metal oxide particles in the electrolyte, (b) a cathode in contact with the electrolyte, (c) an anode, (d) a means for applying a potential across the anode and the cathode, and (e) a means for agitating the electrolyte .
17. The apparatus defined in claim 16 wherein the means for applying the potential across the anodes and the cathode includes (a) a power source and (b) an electrical circuit that electrically interconnects the power source, the anodes , and the cathode .
PCT/AU2005/000409 2004-03-22 2005-03-22 Electrochemical reduction of metal oxides WO2005090640A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2007504212A JP2007529631A (en) 2004-03-22 2005-03-22 Electrochemical reduction of metal oxides
AU2005224292A AU2005224292A1 (en) 2004-03-22 2005-03-22 Electrochemical reduction of metal oxides
US11/522,761 US20070131560A1 (en) 2004-03-22 2006-09-18 Electrochemical reduction of metal oxides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2004901524A AU2004901524A0 (en) 2004-03-22 Electrochemical reduction of metal oxides
AU2004901524 2004-03-22

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US (1) US20070131560A1 (en)
JP (1) JP2007529631A (en)
CN (1) CN1961098A (en)
RU (1) RU2006137273A (en)
WO (1) WO2005090640A1 (en)

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US20110114509A1 (en) * 2009-11-19 2011-05-19 Water Vision Incorporated Method and Apparatus for Removing Impurities from a Liquid
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