WO1997012071A1 - Recuperation de vanadium - Google Patents

Recuperation de vanadium Download PDF

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Publication number
WO1997012071A1
WO1997012071A1 PCT/AU1996/000614 AU9600614W WO9712071A1 WO 1997012071 A1 WO1997012071 A1 WO 1997012071A1 AU 9600614 W AU9600614 W AU 9600614W WO 9712071 A1 WO9712071 A1 WO 9712071A1
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WO
WIPO (PCT)
Prior art keywords
vanadium
acid
process according
leaching
bearing material
Prior art date
Application number
PCT/AU1996/000614
Other languages
English (en)
Inventor
John Sydney Hall
Roy Randall Lovel
Ronald Miles Anthony
Original Assignee
Commonwealth Scientific And Industrial Research Organisation
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 Commonwealth Scientific And Industrial Research Organisation filed Critical Commonwealth Scientific And Industrial Research Organisation
Priority to AU70791/96A priority Critical patent/AU7079196A/en
Publication of WO1997012071A1 publication Critical patent/WO1997012071A1/fr

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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
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • C22B34/225—Obtaining vanadium from spent catalysts
    • 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
    • C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
    • C22B3/1608—Leaching with acyclic or carbocyclic agents
    • C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
    • C22B3/165—Leaching with acyclic or carbocyclic agents of a single type with organic acids
    • 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
    • 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

  • This invention relates to the recovery of vanadium from a variety of sources.
  • the invention provides a process for the recovery of vanadium from vanadium-bearing materials by leaching with one or more polycarboxylic organic acids.
  • the invention relates to processes for recovery of vanadium values from vanadium-bearing minerals, mineral slags, and from industrial wastes such as spent vanadium pentoxide catalyst used in preparation of sulphuric acid.
  • Citric acid is the preferred leaching agent.
  • Citric acid may be produced by many different bacteria and fungi, including organisms naturally occurring in soils, and the pre ⁇ ent invention i ⁇ ideally suited to a biological heap leach process.
  • Vanadium i ⁇ a valuable metal u ⁇ ed inter alia in production of catalysts, for use for example in sulphuric acid manufacture, and in the production of special metals.
  • vanadium pentoxide is u ⁇ ed as catalyst in sulphuric acid production, and in dyes, inks and glasses; vanadium trichloride and vanadium oxytrichloride are used as mordants for dye ⁇ , and in the manufacture of alloy steels and vanadium-aluminium alloys.
  • Vanadium is an abundant element in the earth's crust, and is more abundant than many of the familiar metals, such as lead, zinc, nickel, copper and tin. It is found in patronite (V 2 S 5 +S), carnotite (KV0 2 V0 4 1.5H 2 0) , vanadinite (Pb 5 (V0 4 ) 3 Cl), roscoelite, and certain phosphate rocks and crude oils. Nearly 50% of the total known vanad.um
  • Vanadium grade wt% V 2 0 5
  • vanadium is usually extracted either as a co-product or a by-product of other processes.
  • mineral processing slags may contain over 8% vanadium, a ⁇ well a ⁇ iron and exotic and precious metals. In many cases, these slags are discarded rather than reprocessed, resulting in the lose of metal values.
  • Vanadium recovery processes vary, due to the range of chemistry and mineralogy of the resources used.
  • Examples of Vanadium recovery from industrial wastes include a) calcium reduction of vanadium pentoxide, which is able to yield 19.8% pure ductile vanadium; reduction with aluminium, cerium, or other metals can be u ⁇ ed, but the product is of low purity.
  • vanadium extraction is the formation of soluble or volatile vanadium salts.
  • This is generally achieved by roasting the vanadium (eg v 2 0 3 ) with a sodium source to produce a pentavalent vanadium salt, a ⁇ tep referred to as "fluxing".
  • Water leaching of the vanadium salt is most commonly used, although acid leaching with H 2 S0 4 is used in some operations to attack insoluble vanadates, ⁇ uch a ⁇ calcium, iron and magnesium vanadates.
  • Alkali leaches are u ⁇ ed in other processes to extract vanadium together with uranium, for example from camotite.
  • Direct acid leaching has been used in commercial leaching procedures, but the non-selective nature of the acid and the high consumption of H 2 S0 4 (100 kg per tonne of ore) results in a large volume of low grade solution, high cost, and problems associated with disposal of acid waste.
  • Organic substances are part of the natural system involved in mineral solubilization. They are pre ⁇ ent in ⁇ oil ⁇ , sediments and water and although the nature of the organic compounds making up this material is not completely understood it has been divided into two categories.
  • Nonhumic substances those with recognisable physical and chemical characteristics (eg. sharp melting, definite Infra-Red Spectrum) ; and ii. Humic substances; those that no longer exhibit specific physical and chemical characteristics.
  • solubility in acid and alkali Schnitzer M and Su (in "Soil Organic Matter", Developments in Soil Science, 1978, New York,
  • Humic acid which i ⁇ soluble in dilute alkali but is precipitated on acidification of the alkaline extract
  • Fulvic acid which is soluble in dilute alkali and remains in solution after acidification of the alkaline extract (i.e. it i ⁇ soluble in both dilute alkali or acid)
  • Humin which is the humic fraction that cannot be extracted from the Humic substance.
  • citric acid and tartaric acid are both low molecular weight, naturally occurring polycarboxylic acid. They are commercially available and both can be produced via fermentation processes.
  • citric acid is produced commercially by fermentation of Aspergillus niger in aerated submerged culture, or by growing Candida lipolytica on long-chain n-alkanes.
  • humic acids and fulvic acids in which acids, particularly polycarboxylic acids, similar too and including citric acid and tartaric acid, are active components.
  • the invention provides a process for recovery of vanadium values and optionally other metal values from a vanadium-bearing material, comprising the step of leaching the vanadium-bearing material with one or more polycarboxylic organic acids.
  • the polycarboxylic organic acid is present in a humic sub ⁇ tance.
  • the polycarboxylic organic i ⁇ citric acid.
  • another polycarboxylic organic acid produced during metabolism of soil microorganisms for example in the tricarboxylic cycle in metabolism of an aerobic soil microorganism may be used. Citric acid and tartaric acid have both been demonstrated as effective leachant ⁇ .
  • the vanadium-bearing material may be a naturally-occurring vanadium ore, preferably a titaniferous magnetite; a mineral slag, such as an iron ore ⁇ lag re ⁇ ulting from the refining of iron ore; or may be a by product of industrial processes, such as spent catalyst resulting from sulphuric acid production.
  • a titaniferous magnetite such as an iron ore ⁇ lag re ⁇ ulting from the refining of iron ore
  • a by product of industrial processes such as spent catalyst resulting from sulphuric acid production.
  • the vanadium-bearing material may also comprise many different ⁇ pecie ⁇ including ⁇ pecie ⁇ which do not comprise vanadium and ⁇ pecie ⁇ which compri ⁇ e other metal values such as main group metals, transition metals, Lanthanides or Actinides.
  • vanadium-bearing material it may be necessary to subject the material to pretreatment before the leaching step.
  • iron ore slag is oxidised prior to leaching, usually by roasting in air at temperatures between 550°C and 1100°C, conveniently for 24 hours.
  • Magnetite may be roasted (fluxed) in the presence of a sodium source to convert hexavalent V 2 0 3 to a pentavalent vanadium salt.
  • the material is fluxed at 750°C with sodium borate.
  • Spent vanadium pentoxide catalyst from sulphuric acid processes does not require pretreatment.
  • the leaching step may most conveniently be performed by heap leaching, which provides a very low cost process.
  • vanadium values may be recovered as vanadium pentoxide from solution using standard chemical procedures.
  • the leachate is subjected to solvent extraction, ion exchange, or carbon adsorption and desorption followed by recovery of a vanadium salt.
  • vanadium is precipitated as an ammonium salt by the addition of ammonium hydroxide, and then the_ precipitate is heated to decompose the precipitate to vanadium pentoxide * .
  • vanadium may be recovered from vanadium-bearing slags which contain oxides of iron. We have found that oxidising the spinel mineral structures enables over 80% of the vanadium to be extracted with either dilute citric acid or dilute tartaric acid leaving the iron oxide ⁇ essentially untouched.
  • vanadium may be recovered from spent cataly ⁇ t by the process of the present invention. More preferably the catalyst is vanadium pentoxide. As vanadium waste i ⁇ highly toxic, recycling of ⁇ pent cataly ⁇ t in thi ⁇ manner will provide reduction of the total amount of toxic vanadium metal in circulation in the environment.
  • Feedstock Fe (wt%) V (wt%) Mn (wt%) Ti (wt%)
  • metals other than vanadium may be complexed by citric acid and feedstock may be manipulated to prevent leaching of other metals such a ⁇ iron.
  • FIG. 1 is a graph depicting the major mineral specie ⁇ ⁇ olubilized by hot (90°C) 0.4 M citric acid in a 5 hr leach.
  • vanadium solubilization was observed to be related to oxidation of the iron, vanadium, manganese and titanium spinel, to haematite, vanadium oxide (in which the valency of vanadium i ⁇ 3+ or greater) , and the other metal oxide ⁇ .
  • haematite vanadium oxide (in which the valency of vanadium i ⁇ 3+ or greater)
  • vanadium oxide in which the valency of vanadium i ⁇ 3+ or greater
  • Iron solubilization is initially high, but decreases with the formation of haematite.
  • a practical embodiment of the process of the pre ⁇ ent invention for solubilizing vanadium from iron slag wastes using citric acid leaching is a ⁇ follows. After crushing, iron metal (up to 10% by weight) is separated from the powder using magnetic or density separation techniques. Oxidation is achieved by fluid bed roasting at temperatures between 750°C and 1100°C. To minimise processing steps it may be possible to remove iron metal during fluid bed roasting. The oxidised ⁇ lag i ⁇ then heap leached by biologically produced citric acid.
  • Titaniferous magnetites are a major source of vanadium, and citric acid leaching procedures offer considerable promise.
  • This example u ⁇ ed ⁇ ample ⁇ of titaniferous magnetite from Chong Qing.
  • Test work on ⁇ ample ⁇ fluxed at 750°C with sodium borate indicate that citric acid is an ideal leachant.
  • the results, summarised in Table 2, show that hot O.I M citric acid i ⁇ a more aggressive leachant than either distilled water (hot or cold) or hot nitric acid (pH 2)
  • the ⁇ e re ⁇ ult ⁇ confirm that citric acid ⁇ olution ⁇ ⁇ olubilize vanadium from oxidised slags without the need for sodium fluxing, and that citric acid is a more aggressive leachant than those currently used for vanadium extraction.
  • the re ⁇ ult ⁇ demon ⁇ trate that citric acid can be u ⁇ ed to recover vanadium from ⁇ pent cataly ⁇ t.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

Procédés de récupération de vanadium et éventuellement d'autres métaux dans des matériaux contenant du vanadium, en particulier des minerais tels que des magnétites titanifères, et des déchets industriels tels que des scories de minerai de fer et des catalyseurs d'acide sulfurique épuisés. Lesdits procédés utilisent la lixiviation avec de l'acide organique polycarboxylique. Dans un mode de réalisation préféré, ledit acide organique est de l'acide citrique ou tartrique. Ledit procédé peut être appliqué à la lixiviation en tas.
PCT/AU1996/000614 1995-09-27 1996-09-26 Recuperation de vanadium WO1997012071A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU70791/96A AU7079196A (en) 1995-09-27 1996-09-26 Recovery of vanadium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPN5644 1995-09-27
AUPN5644A AUPN564495A0 (en) 1995-09-27 1995-09-27 Recovery of vanadium

Publications (1)

Publication Number Publication Date
WO1997012071A1 true WO1997012071A1 (fr) 1997-04-03

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ID=3789971

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Application Number Title Priority Date Filing Date
PCT/AU1996/000614 WO1997012071A1 (fr) 1995-09-27 1996-09-26 Recuperation de vanadium

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AU (1) AUPN564495A0 (fr)
WO (1) WO1997012071A1 (fr)
ZA (1) ZA968141B (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014140700A1 (fr) * 2013-03-14 2014-09-18 University Of Calcutta Procédés de production de borure de vanadium et utilisations associées
RU2561554C2 (ru) * 2010-05-19 2015-08-27 ТиЭнДжи Лимитед Способ извлечения и восстановления ванадия
CN106673061A (zh) * 2017-03-17 2017-05-17 攀枝花学院 TiCl4除钒尾渣提取氧化钒的方法
RU2628586C2 (ru) * 2013-05-17 2017-08-21 Инститьют Оф Проусес Энжиниринг, Чайниз Экэдеми Оф Сайенсиз Способ переработки ванадиево-титано-магнетитового концентрата с применением мокрого процесса
CN112410542A (zh) * 2020-11-20 2021-02-26 攀枝花钢城集团有限公司 一种降低转炉钢渣中磷含量的方法
CN115354156A (zh) * 2022-07-18 2022-11-18 承德燕北冶金材料有限公司 一种钙化焙烧-浸出脱除提钒尾渣中碱金属的方法
CN115710646A (zh) * 2022-11-07 2023-02-24 山西大学 利用无机-有机混合酸浸出报废脱硝催化剂中钒的方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1183612A (en) * 1966-03-08 1970-03-11 Rech S Geol Et Minieres Bureau Improvements in or relating to processes for Extracting Elements from Rocks or Ores
US3511645A (en) * 1967-06-08 1970-05-12 Rech Geolog Miniere Processes for extracting metals from rocks or ores
JPS5295501A (en) * 1976-02-09 1977-08-11 Nittan Co Ltd Process for separation and recovery of heavy metal from aqueous suspension of fine carbon particles containing heavy metal
JPS5440213A (en) * 1977-09-06 1979-03-29 Sakai Chem Ind Co Ltd Separation method
US4677085A (en) * 1985-09-30 1987-06-30 Amoco Corporation Process for removing metals from spent catalyst
FR2611745A1 (fr) * 1987-02-27 1988-09-09 Inst Francais Du Petrole Procede pour recuperer selectivement un melange de vanadium, de molybdene et/ou de tungstene d'un catalyseur desactive, provenant du traitement d'une charge d'hydrocarbures de petrole
AU3741993A (en) * 1992-04-02 1993-11-08 Commonwealth Scientific And Industrial Research Organisation Mineral processing

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1183612A (en) * 1966-03-08 1970-03-11 Rech S Geol Et Minieres Bureau Improvements in or relating to processes for Extracting Elements from Rocks or Ores
US3511645A (en) * 1967-06-08 1970-05-12 Rech Geolog Miniere Processes for extracting metals from rocks or ores
JPS5295501A (en) * 1976-02-09 1977-08-11 Nittan Co Ltd Process for separation and recovery of heavy metal from aqueous suspension of fine carbon particles containing heavy metal
JPS5440213A (en) * 1977-09-06 1979-03-29 Sakai Chem Ind Co Ltd Separation method
US4677085A (en) * 1985-09-30 1987-06-30 Amoco Corporation Process for removing metals from spent catalyst
FR2611745A1 (fr) * 1987-02-27 1988-09-09 Inst Francais Du Petrole Procede pour recuperer selectivement un melange de vanadium, de molybdene et/ou de tungstene d'un catalyseur desactive, provenant du traitement d'une charge d'hydrocarbures de petrole
AU3741993A (en) * 1992-04-02 1993-11-08 Commonwealth Scientific And Industrial Research Organisation Mineral processing

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2561554C2 (ru) * 2010-05-19 2015-08-27 ТиЭнДжи Лимитед Способ извлечения и восстановления ванадия
WO2014140700A1 (fr) * 2013-03-14 2014-09-18 University Of Calcutta Procédés de production de borure de vanadium et utilisations associées
RU2628586C2 (ru) * 2013-05-17 2017-08-21 Инститьют Оф Проусес Энжиниринг, Чайниз Экэдеми Оф Сайенсиз Способ переработки ванадиево-титано-магнетитового концентрата с применением мокрого процесса
CN106673061A (zh) * 2017-03-17 2017-05-17 攀枝花学院 TiCl4除钒尾渣提取氧化钒的方法
CN112410542A (zh) * 2020-11-20 2021-02-26 攀枝花钢城集团有限公司 一种降低转炉钢渣中磷含量的方法
CN112410542B (zh) * 2020-11-20 2022-12-27 攀枝花钢城集团有限公司 一种降低转炉钢渣中磷含量的方法
CN115354156A (zh) * 2022-07-18 2022-11-18 承德燕北冶金材料有限公司 一种钙化焙烧-浸出脱除提钒尾渣中碱金属的方法
CN115710646A (zh) * 2022-11-07 2023-02-24 山西大学 利用无机-有机混合酸浸出报废脱硝催化剂中钒的方法

Also Published As

Publication number Publication date
ZA968141B (en) 1997-05-27
AUPN564495A0 (en) 1995-10-19

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