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WO1999045160A1 - Procede d'oxydation electrochimique du vanadium en solution aqueuse et procede d'obtention du pentoxyde de vanadium - Google Patents

Procede d'oxydation electrochimique du vanadium en solution aqueuse et procede d'obtention du pentoxyde de vanadium Download PDF

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Publication number
WO1999045160A1
WO1999045160A1 PCT/AT1999/000047 AT9900047W WO9945160A1 WO 1999045160 A1 WO1999045160 A1 WO 1999045160A1 AT 9900047 W AT9900047 W AT 9900047W WO 9945160 A1 WO9945160 A1 WO 9945160A1
Authority
WO
WIPO (PCT)
Prior art keywords
vanadium
oxidation
carried out
solution
oxidation state
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.)
Ceased
Application number
PCT/AT1999/000047
Other languages
German (de)
English (en)
Inventor
Matthaeus Siebenhofer
Peter Janz
Herwig Krassnitzer
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.)
Treibacher Industrie AG
Original Assignee
Treibacher Industrie AG
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 Treibacher Industrie AG filed Critical Treibacher Industrie AG
Priority to AU25029/99A priority Critical patent/AU2502999A/en
Publication of WO1999045160A1 publication Critical patent/WO1999045160A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • C22B34/225—Obtaining vanadium from spent catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/045—Leaching using electrochemical processes
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to a method for the oxidation of vanadium in materials which contain vanadium in an oxidation state less than V.
  • the invention further relates to a process for the production of vanadium pentoxide (V 2 O 5 ).
  • the pH of the solution is then changed to a range which is favorable for the precipitation of vanadium pentoxide.
  • the sulfuric acid mother liquor is cleaned.
  • cationically dissolved heavy metals are separated from the mother liquor by precipitation.
  • the object of the present invention is therefore to provide a process for the oxidation of vanadium in materials which contain vanadium in an oxidation state less than V, and a process for the production of vanadium pentoxide which avoids these difficulties and problems.
  • the object is achieved in that the oxidation is at least partially carried out electrochemically as an anodic oxidation.
  • the anodic oxidation of the vanadium can either be carried out with the suspension of a material containing vanadium in an oxidation state less than V in a suitable solvent or with a solution of a vanadium compound in a suitable solvent.
  • Suitable solvents are basically those that form soluble compounds with vanadium of oxidation levels IV and V, but are not incorporated into the redox process even under the selected operating conditions, so that the aqueous electrolyte solution carries the redox processes through anodic formation of oxygen and cathodic formation of hydrogen.
  • Sulfuric acid is preferably used as the solvent.
  • the suspension or solution containing vanadium is introduced into the anode compartment of an electrolysis system and the oxidation process is initiated by applying a favorable working voltage.
  • the setting of the favorable working voltage and the optimal anode current strength is preferably carried out so that only a minimal formation of oxygen gas bubbles can be observed at the anode. It has been shown that a high current yield can be achieved in this way with the method according to the invention.
  • Platinum mesh electrodes for example, can be used as electrodes for carrying out the electrolysis.
  • the oxidation to the desired oxidation state of the vanadium can either be carried out in one step as anodic oxidation or can be carried out in two steps. With two-stage guidance, at least one stage is carried out as anodic oxidation. In a preferred embodiment of the method, both stages are carried out as anodic oxidation.
  • vanadium (IV) soluble vanadium of the oxidation state TV
  • vanadium (III) in a suspended vanadium-containing material can be oxidized through to anodic oxidation in a one-step process to soluble vanadium (V).
  • oxidation is carried out in a first stage by chemical oxidizing agents to form soluble vanadium (IV), which in a second stage is converted to soluble by anodic oxidation Vanadium (V) is oxidized.
  • the two oxidation methods can also be used in the two-step process in the reverse order, or an anodic oxidation can be used in both steps, for example.
  • the transition between the different oxidation levels of the dissolved vanadium is shown optically by the color transition and can be followed spectrophotometrically.
  • the anodic oxidation be carried out in an electrolysis bath with separate electrode spaces for the anode and cathode.
  • the anode compartment can be separated from the cathode compartment either by a sintered membrane or pore membrane or by a membrane with a low voltage drop.
  • the cathode compartment can be made with the same electrolyte as the anode compartment, e.g. Sulfuric acid, be filled.
  • a sulfate salt for example, can also be used as the electrolyte in the cathode compartment.
  • the cation of the sulfate salt is electrolytically deposited on the cathode instead of hydrogen and the sulfate is converted into free sulfuric acid.
  • heavy metals such as e.g. Nickel.
  • the free sulfuric acid can be removed from the cathode compartment by the continuous supply of salt electrolyte and used, for example, to produce the suspension of the vanadium-containing material used as the starting material for the oxidation, since the residual heavy metal content does not impair the oxidizing solution of the vanadium from the suspended material.
  • the anodic oxidation can also be carried out in an electrolysis bath with a common electrode space for the anode and cathode, the oxidation being carried out up to an oxidation state of the vanadium of less than V.
  • the separation of the anode and cathode spaces can also be omitted, since vanadium is not deposited on the cathode under these conditions.
  • the oxidation according to the process of the invention is carried out up to oxidation level V of the vanadium with formation of an aqueous solution of vanadium (V) and then at least part of this solution for the oxidation of vanadium in materials which have vanadium in an oxidation level less than IV included, used, wherein an aqueous solution of vanadium (IV) is formed.
  • the material containing vanadium in an oxidation state less than IV can be present, for example, as a solid and in the aqueous solution of vanadium (V) are dispersed, the vanadium present in the dispersed material in an oxidation state less than IV being oxidized to a soluble vanadium (IN) while simultaneously reducing the vanadium (V) present in the aqueous solution.
  • Any inert solid residue which may be present can then be mechanically separated off and the aqueous solution of vanadium (IN) thus obtained can be subjected, for example, to a further oxidation step by chemical or anodic oxidation.
  • the process according to the invention can preferably also be carried out in such a way that the oxidation up to the oxidation state V of the vanadium is carried out with formation of an aqueous solution of vanadium (V) and at least a part of the oxidized vanadium is separated from the solution by precipitation and the solution is then regenerated .
  • V vanadium
  • oxidized vanadium in oxidation state V its solubility can be reduced by setting suitable conditions to such an extent that it is completely or partially precipitated from the solution as a crystalline precipitate, for example in the form of the water-containing vanadium pentoxide (V 2 O 5 ) .
  • This change in solubility can be achieved by adding a neutralizing additive.
  • the pH of the solution is adjusted in a range that is optimal for the precipitation, approximately 1.8 to 2.0. Basically reacting oxides and / or hydroxides, for example, can be used as neutralizing additives.
  • the precipitated water-containing V 2 O 5 is filtered off and calcined to remove the water.
  • the solution is regenerated and can be used again for the oxidation of material containing vanadium in accordance with the process according to the invention.
  • the solution can be regenerated in a known manner using chemical methods or preferably electrochemically.
  • the present invention also relates to a process for the oxidation of vanadium in materials which contain vanadium in an oxidation state less than IV, characterized in that vanadium (V) is used as the oxidizing agent.
  • the vanadium (V) used as the oxidizing agent can be produced by oxidizing vanadium with a lower oxidation state by any known method. However, it is preferred that the vanadium (V) is produced by a process in which the oxidation of the starting material is carried out at least partially electrochemically as an anodic oxidation.
  • the present invention further relates to a process for the production of vanadium pentoxide (V 2 O 5 ) by oxidation of vanadium in materials which contain vanadium in an oxidation state less than V, in an aqueous solution, in which process the vanadium pentoxide formed is separated from the solution and the solution is regenerated, characterized in that the regeneration is carried out electrochemically.
  • V 2 O 5 vanadium pentoxide
  • the oxidation of vanadium in materials which contain vanadium in an oxidation state less than V in an aqueous solution can be carried out by any known method. However, it is preferred that the oxidation is carried out in such a way that it is at least partially carried out electrochemically as anodic oxidation or that vanadium (V) is used as the oxidizing agent.
  • the regenerated solution can be used again for the oxidation of vanadium-containing material according to the method according to the invention.
  • the invention is explained in more detail in the following examples.
  • test results confirm that vanadium can be converted from a solid, in which vanadium is present in an oxidation state smaller than TV, by anodic oxidation in dissolved vanadium of oxidation states IV and V.
  • Example 2 50 ml of the vanadium pentoxide solution prepared in Example 1 were placed in a beaker. Then 2 g of powdered V 2 O 3 were metered in. A prompt reaction of the vanadium pentoxide of the solution with the divanadium trioxide started, releasing the heat of reaction of this exothermic redox reaction and forming intensely blue-colored vanadium of the oxidation state TV.
  • the test result shows that vanadium from a solid, in which vanadium is present in an oxidation state less than IV, can also be converted into dissolved vanadium of oxidation state IV if dissolved vanadium of oxidation state V is used as the oxidizing agent.

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

Abstract

L'invention concerne un procédé d'oxydation du vanadium dans des matériaux renfermant du vanadium à un degré d'oxydation inférieur à V, caractérisé en ce que l'oxydation électrochimique s'effectue au moins partiellement sous forme d'oxydation anodique. L'invention concerne en outre un procédé d'obtention du pentoxyde de vanadium par anodisation anodique d'une solution aqueuse renfermant du vanadium, obtenue par exemple par lixiviation de résidus renfermant du vanadium (cendres de pétrole, catalyseurs, etc.), procédé dans lequel le V2O5 formé est séparé de la solution par précipitation et la solution est régénérée principalement électrochimiquement.
PCT/AT1999/000047 1998-03-06 1999-02-25 Procede d'oxydation electrochimique du vanadium en solution aqueuse et procede d'obtention du pentoxyde de vanadium Ceased WO1999045160A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU25029/99A AU2502999A (en) 1998-03-06 1999-02-25 Method for electrochemical oxidation of vanadium in aqueous solutions and methodto obtain vanadium pentoxide

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT0039598A AT409764B (de) 1998-03-06 1998-03-06 Verfahren zur oxidation von vanadium
ATA395/98 1998-03-06

Publications (1)

Publication Number Publication Date
WO1999045160A1 true WO1999045160A1 (fr) 1999-09-10

Family

ID=3489473

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AT1999/000047 Ceased WO1999045160A1 (fr) 1998-03-06 1999-02-25 Procede d'oxydation electrochimique du vanadium en solution aqueuse et procede d'obtention du pentoxyde de vanadium

Country Status (4)

Country Link
AT (1) AT409764B (fr)
AU (1) AU2502999A (fr)
WO (1) WO1999045160A1 (fr)
ZA (1) ZA991705B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2169203C1 (ru) * 2000-06-19 2001-06-20 Открытое акционерное общество "Ванадий-Тулачермет" Способ извлечения ванадия
CN100422357C (zh) * 2007-01-29 2008-10-01 中经九丰（北京）投资有限公司 电场分解钒矿浆隔膜萃取生产五氧化二钒的方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4987513A (fr) * 1972-12-25 1974-08-21
US4222826A (en) * 1978-10-10 1980-09-16 Kerr-Mcgee Corporation Process for oxidizing vanadium and/or uranium
US4539186A (en) * 1984-03-15 1985-09-03 Intevep, S.A. Method for leaching and recovering vanadium from vanadium bearing by-product materials
EP0225674A2 (fr) * 1985-12-11 1987-06-16 Shell Internationale Researchmaatschappij B.V. Procédé de récupération de vanadium
DE3940978A1 (de) * 1989-12-12 1991-06-13 Hoechst Ag Verfahren zur elektrochemischen regenerierung von chromschwefelsaeure
DE4134109A1 (de) * 1990-10-15 1992-04-16 Agency Ind Science Techn Verfahren zur herstellung einer elektrolytischen vanadiumloesung
US5171548A (en) * 1990-06-06 1992-12-15 Advanced Separation Technologies Incorporated Process for the removal of vanadium from wet process phosphoric acid

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD239348A5 (de) * 1985-07-19 1986-09-24 ��������@�����������@�@������������@���������@����@����������@���k�� Verfahren zur verarbeitung von vanadinhaltigen altkatalysatoren
SU1691424A1 (ru) * 1988-07-26 1991-11-15 Дагестанский Государственный Университет Им.В.И.Ленина Способ получени оксида ванади (У)

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4987513A (fr) * 1972-12-25 1974-08-21
US4222826A (en) * 1978-10-10 1980-09-16 Kerr-Mcgee Corporation Process for oxidizing vanadium and/or uranium
US4539186A (en) * 1984-03-15 1985-09-03 Intevep, S.A. Method for leaching and recovering vanadium from vanadium bearing by-product materials
EP0225674A2 (fr) * 1985-12-11 1987-06-16 Shell Internationale Researchmaatschappij B.V. Procédé de récupération de vanadium
DE3940978A1 (de) * 1989-12-12 1991-06-13 Hoechst Ag Verfahren zur elektrochemischen regenerierung von chromschwefelsaeure
US5171548A (en) * 1990-06-06 1992-12-15 Advanced Separation Technologies Incorporated Process for the removal of vanadium from wet process phosphoric acid
DE4134109A1 (de) * 1990-10-15 1992-04-16 Agency Ind Science Techn Verfahren zur herstellung einer elektrolytischen vanadiumloesung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 7522, Derwent World Patents Index; Class J01, AN 75-36477W, XP002103993 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2169203C1 (ru) * 2000-06-19 2001-06-20 Открытое акционерное общество "Ванадий-Тулачермет" Способ извлечения ванадия
CN100422357C (zh) * 2007-01-29 2008-10-01 中经九丰（北京）投资有限公司 电场分解钒矿浆隔膜萃取生产五氧化二钒的方法

Also Published As

Publication number Publication date
ATA39598A (de) 2002-03-15
ZA991705B (en) 1999-09-06
AT409764B (de) 2002-11-25
AU2502999A (en) 1999-09-20

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