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WO2000056662A1 - Procede d'oxydation de vanadium - Google Patents

Procede d'oxydation de vanadium Download PDF

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Publication number
WO2000056662A1
WO2000056662A1 PCT/AT2000/000062 AT0000062W WO0056662A1 WO 2000056662 A1 WO2000056662 A1 WO 2000056662A1 AT 0000062 W AT0000062 W AT 0000062W WO 0056662 A1 WO0056662 A1 WO 0056662A1
Authority
WO
WIPO (PCT)
Prior art keywords
vanadium
oxidation
solution
sodium chloride
mother liquor
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/AT2000/000062
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 AU34076/00A priority Critical patent/AU3407600A/en
Publication of WO2000056662A1 publication Critical patent/WO2000056662A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • 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
    • C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
    • 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 pH of the solution is then changed to a range which is favorable for the precipitation of vanadium pentoxide.
  • the mother liquor is cleaned.
  • cationically dissolved heavy metals are separated from the mother liquor by precipitation.
  • a method is to be provided with which it is possible to minimize the waste and waste water problem which arises from the oxidizing leaching of vanadium from feedstocks containing vanadium.
  • the object is achieved in that the oxidation is carried out at least partially with elemental chlorine as the oxidizing agent, whereby vanadium compounds of the oxidation state IV and / or V are formed.
  • the vanadium to be oxidized is expediently present in a solid which is dispersed or dissolved in a liquid.
  • Residues from combustion oil ash
  • petroleum processing gasification residues
  • vanadium-containing catalysts are predominantly used as the vanadium-containing solid which is used as the starting material in the process according to the invention.
  • the solid is preferably dissolved or dispersed in an aqueous solution.
  • the solution can be presented as a deionized product.
  • electrolyte-containing aqueous solutions for example a sodium chloride, sodium sulfate or HCl solution
  • a particularly preferred embodiment of the process according to the invention is characterized in that a solution containing sodium chloride is used as the liquid for dispersing or dissolving the solid.
  • chlorine gas is introduced into the solution or dispersion (both physical states can also occur simultaneously), the temperature being not essential.
  • V 2 0 3 + 4 H + + CIO " > 2 V0 2+ + Cl " + 2 H 2 0
  • the dissolving or oxidizing step can take place either in one pass or in several sub-steps.
  • the choice of procedure is primarily determined by the matrix of the feed material.
  • the oxidation is carried out in one stage and with elemental chlorine as the oxidizing agent.
  • the method according to the invention can, however expediently also be carried out in such a way that the oxidation is carried out in two stages, elemental chlorine being used as the oxidizing agent in at least one stage.
  • soluble vanadium of oxidation stage IV into soluble vanadium (V) using chlorine gas as the oxidizing agent in a one-step process.
  • soluble vanadium (IV) in a material dispersed or dissolved in a suitable liquid containing vanadium by oxidation with chlorine gas in a one-step process to soluble vanadium (V).
  • vanadium (III) in a material dispersed or dissolved in a suitable liquid containing vanadium by oxidation with chlorine gas in a one-step process to soluble vanadium (V).
  • soluble vanadium (IV) there is also the possibility of carrying out the oxidation of the above-mentioned starting material in a two-stage process, treatment with chlorine gas in a first stage until the vanadium is present quantitatively as soluble vanadium (IV).
  • the solution is separated from the solid residue and can be oxidized to vanadium (V) in a further oxidation step using chlorine gas.
  • this two-stage process can also be carried out in such a way that an oxidizing agent other than chlorine gas is used in one of the two stages.
  • the chlorine gas used as the oxidizing agent can also be combined with other oxidizing agents in each of the stages described above.
  • the transition between the different oxidation levels of the dissolved vanadium is shown optically by the color transition and can be followed spectrophotometrically.
  • the vanadium-containing starting material is preferably dispersed or dissolved in a sodium chloride-containing solution and the oxidation of the vanadium up to oxidation level V of the vanadium is carried out with formation of an aqueous solution of vanadiu (V) and then at least a part of the oxidized vanadium is separated from the solution by precipitation , whereby what is liked Polyvanadat and a sodium chloride-containing mother liquor can be obtained.
  • the polyvanadate is usually precipitated by setting an optimal pH value for the precipitation with neutralizing agent, e.g. Sodium hydroxide solution and setting an optimal precipitation temperature.
  • the polyvanadate can be separated from the mother liquor by filtration. Depending on the precipitation conditions, residual levels of vanadium in the mother liquor of ⁇ 0.5 g / l are achieved in this separation operation. After this separation operation, the mother liquor has a NaCl content of approx. 120 g / 1.
  • the elemental chlorine used as the oxidizing agent in the process according to the invention is advantageously produced by electrolysis of a solution containing sodium chloride, free chlorine gas and an anolyte containing CIO " or C10 3 " being formed on the anode and a catholyte containing sodium hydroxide solution on the cathode.
  • a solution containing sodium chloride, free chlorine gas and an anolyte containing CIO " or C10 3 " being formed on the anode and a catholyte containing sodium hydroxide solution on the cathode.
  • part of the chlorine formed is converted to CIO " or C10 3 " during electrolysis in the anolyte. The proportion depends on which sodium chloride-containing feed solution is used.
  • the sodium chloride-containing mother liquor obtained after removal of the precipitated polyvanadate is advantageously used as the sodium chloride-containing feed solution for the electrolysis.
  • the chlorine gas required for the oxidation process can thus be produced from the mother liquor containing sodium chloride.
  • the mother liquor therefore does not have to be subjected to the complex processes for separating heavy metals and reducing the chloride load by evaporation and crystallization, which are necessary for disposal as waste water.
  • the anolyte from the electrolysis is therefore used as a liquid for dispersing or dissolving the vanadium-containing solid which is provided as the starting material for the oxidation.
  • C10 " -containing and C10 3 " -containing anolyte can also be returned to the dissolving stage, since both substances are suitable for the oxidizing solution V (III) -containing products.
  • the anolyte which is circulated in this way can also contain iron and nickel, the iron being present in iron-containing anolyte as Fe (III), for example as dissolved FeCl 3 .
  • Fe (III) iron-containing anolyte
  • Both ionogenic metals (Fe and Ni) can be deposited from the mother liquor both before and after the electrolysis, the deposition of Fe (III) by hydroxide formation being complete at a pH of 5.
  • Nickel which is chemically neutral in the cycle, can be separated, for example by hydroxide precipitation or carbonate precipitation, to the desired final contents.
  • the mother liquor from the polyvanadate precipitation can also be used as catholyte both before and after a partial or complete separation of iron and nickel, the sodium chloride-containing sodium hydroxide solution also being able to be recycled without restriction into the precipitation stage for the polyvanadate precipitation.
  • the electrolyzed catholyte is used to precipitate the polyvanadate from the aqueous solution containing vanadium (V) oxidized.
  • the process according to the invention thus enables a circuit to be closed with regard to the recycling and recycling of the process water obtained in the process and thereby a practically wastewater-free overall process.
  • Electrolytic chlorine production from the mother liquor can also be used for heavy metal precipitation in the cathode compartment by hydroxide formation if required. If necessary, matrix elements of the feed material can be separated from the mother liquor by precipitation with hydroxide formers. Residual vanadium does not interfere in the electrolyte, since the chlorine-saturated anolyte can also be returned to the dissolution and oxidation stages.
  • Anodic chlorine gas and cathodic sodium hydroxide solution were produced in a membrane electrolysis cell using a known method.
  • the chlorine gas was introduced at room temperature into an absorption vessel in which a suspension containing V2 ⁇ 3 had been placed.
  • the suspension was composed as follows: 40 g NaCl, 30 g Na 2 S0 4 , 14.9 g V 2 0 3 , 330 ml water.
  • the stoichiometric amount of chlorine gas based on the amount of V 2 0 3 presented, was introduced.
  • the suspension was filtered and examined for dissolved vanadium. A total of 4.9 g V (IV) was measured.
  • V 2 0 3 + 4 H + + CIO " > 2 V0 2+ + Cl " + 2 H 2 0
  • Anodic chlorine gas and cathodic sodium hydroxide solution were produced in a membrane electrolysis cell using a known method.
  • the chlorine gas was introduced at room temperature into an absorption vessel in which a suspension containing V 2 0 3 had been placed.
  • the suspension was composed as follows: 60 g NaCl, 45 g Na 2 SO 4 , 22.35 g V 2 0 3 , 500 ml water. It was initiated twice the stoichiometric amount of chlorine gas, based on the amount of V 2 0 3 presented for the oxidation of V 2 0 3 to V0 2 + . After the end of the experiment, polyvanadate precipitation was carried out.
  • the vanadium could be precipitated quantitatively as V 2 0 5 except for a residual content of 0.14 g / 1 in the reaction solution.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne un procédé d'oxydation de vanadium dans des matériaux contenant du vanadium à un degré d'oxydation inférieur à V. Selon ce procédé, l'oxydation est réalisée au moins en partie avec du chlore élémentaire comme agent d'oxydation, ce qui donne lieu à la formation de composés de vanadium présentant un degré d'oxydation s'élevant à IV et/ou V.
PCT/AT2000/000062 1999-03-18 2000-03-17 Procede d'oxydation de vanadium Ceased WO2000056662A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU34076/00A AU3407600A (en) 1999-03-18 2000-03-17 Vanadium oxidation method

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA493/99 1999-03-18
AT0049399A AT408454B (de) 1999-03-18 1999-03-18 Verfahren zur oxidation von vanadium

Publications (1)

Publication Number Publication Date
WO2000056662A1 true WO2000056662A1 (fr) 2000-09-28

Family

ID=3492078

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AT2000/000062 Ceased WO2000056662A1 (fr) 1999-03-18 2000-03-17 Procede d'oxydation de vanadium

Country Status (3)

Country Link
AT (1) AT408454B (fr)
AU (1) AU3407600A (fr)
WO (1) WO2000056662A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2266343C2 (ru) * 2003-02-03 2005-12-20 НПО "Ванадий-катализатор" Способ переработки конверторных ванадийсодержащих шлаков
RU2437946C2 (ru) * 2010-03-05 2011-12-27 Владиллен Александрович Козлов Способ переработки ванадийсодержащего сырья
RU2607292C2 (ru) * 2014-05-21 2017-01-10 ПанГан Груп Панжихуа Айрон энд Стил Рисёрч Инститьют Со., Лтд. Способ двухстадийного кальцинирующего обжига ванадийсодержащего материала
RU2607290C2 (ru) * 2014-05-21 2017-01-10 ПанГан Груп Панжихуа Айрон энд Стил Рисёрч Инститьют Со., Лтд. Способ кальцинирующего обжига ванадийсодержащего материала

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111733337B (zh) * 2020-07-06 2022-05-24 攀钢集团研究院有限公司 钒溶液还原制备氧化钒的方法
CN114134346B (zh) * 2021-11-30 2022-08-12 大连理工大学 一种连续离子膜脱钠-沉钒的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1474152A (en) * 1976-04-09 1977-05-18 British Aluminium Co Ltd Leaching process for separation of calcium and vanadium oxides
JPS53117602A (en) * 1977-03-24 1978-10-14 Toyo Soda Mfg Co Ltd Separating and recovering method for valuable metals from waste catalyst containing molybdenum
US4579721A (en) * 1984-08-03 1986-04-01 Getty Oil Company Process for recovering metals from waste
US4788044A (en) * 1986-07-17 1988-11-29 Ente Minerario Siciliano Method for recovering vanadium from residues from the combustion of petroleum fractions
US4851199A (en) * 1985-01-03 1989-07-25 Union Oil Company Of California Methods for recovering vanadium from phosphoric acid and vanadium sources

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1474152A (en) * 1976-04-09 1977-05-18 British Aluminium Co Ltd Leaching process for separation of calcium and vanadium oxides
JPS53117602A (en) * 1977-03-24 1978-10-14 Toyo Soda Mfg Co Ltd Separating and recovering method for valuable metals from waste catalyst containing molybdenum
US4579721A (en) * 1984-08-03 1986-04-01 Getty Oil Company Process for recovering metals from waste
US4851199A (en) * 1985-01-03 1989-07-25 Union Oil Company Of California Methods for recovering vanadium from phosphoric acid and vanadium sources
US4788044A (en) * 1986-07-17 1988-11-29 Ente Minerario Siciliano Method for recovering vanadium from residues from the combustion of petroleum fractions

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 84, no. 24, 14 June 1976, Columbus, Ohio, US; abstract no. 170201, CORNELIUS, RICHARD D. ET AL: "Kinetics and mechanism of the oxidation of vanadium (III) by chlorine in aqueous solution" XP002142186 *
DATABASE WPI Section Ch Week 197846, Derwent World Patents Index; Class H04, AN 1978-83164A, XP002142187 *
INORG. CHEM. (1976), 15(5), 997-1002 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2266343C2 (ru) * 2003-02-03 2005-12-20 НПО "Ванадий-катализатор" Способ переработки конверторных ванадийсодержащих шлаков
RU2437946C2 (ru) * 2010-03-05 2011-12-27 Владиллен Александрович Козлов Способ переработки ванадийсодержащего сырья
RU2607292C2 (ru) * 2014-05-21 2017-01-10 ПанГан Груп Панжихуа Айрон энд Стил Рисёрч Инститьют Со., Лтд. Способ двухстадийного кальцинирующего обжига ванадийсодержащего материала
RU2607290C2 (ru) * 2014-05-21 2017-01-10 ПанГан Груп Панжихуа Айрон энд Стил Рисёрч Инститьют Со., Лтд. Способ кальцинирующего обжига ванадийсодержащего материала

Also Published As

Publication number Publication date
AU3407600A (en) 2000-10-09
AT408454B (de) 2001-12-27
ATA49399A (de) 2001-04-15

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