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WO1995007366A1 - Ennoblissement de materiaux titaniferes - Google Patents

Ennoblissement de materiaux titaniferes Download PDF

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Publication number
WO1995007366A1
WO1995007366A1 PCT/AU1994/000528 AU9400528W WO9507366A1 WO 1995007366 A1 WO1995007366 A1 WO 1995007366A1 AU 9400528 W AU9400528 W AU 9400528W WO 9507366 A1 WO9507366 A1 WO 9507366A1
Authority
WO
WIPO (PCT)
Prior art keywords
leach
caustic
leaching
caustic leach
titaniferous
Prior art date
Application number
PCT/AU1994/000528
Other languages
English (en)
Inventor
Ross Alexander Mcclelland
Michael John Hollitt
Original Assignee
Technological Resources 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
Application filed by Technological Resources Pty Ltd. filed Critical Technological Resources Pty Ltd.
Priority to AU76475/94A priority Critical patent/AU697952B2/en
Priority to JP7508358A priority patent/JPH09504828A/ja
Priority to EP94926722A priority patent/EP0717783A4/fr
Publication of WO1995007366A1 publication Critical patent/WO1995007366A1/fr
Priority to NO19960917A priority patent/NO317932B1/no

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
    • C22B34/10—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
    • C22B34/1236—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 titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
    • C22B34/1254—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 titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using basic solutions or liquors
    • 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
    • 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
    • C22B34/1236—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 titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
    • C22B34/124—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 titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
    • C22B34/125—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 titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors containing a sulfur ion as active agent
    • 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 removal of impurities from naturally occurring and synthetic titaniferous materials.
  • the invention is particularly suited to the enhancement of titaniferous materials used in the production of titanium metal and titanium dioxide pigments by means of industrial chlorination systems.
  • Embodiments of the present invention have the common features of the use of caustic leaching and pressure sulphuric acid leaching for the upgrading of titaniferous materials, e.g. titaniferous slags, derived from hard rock ilmenites. Additional steps may be employed as will be described below.
  • titanium dioxide bearing feedstocks are fed with coke to chlorinators of various designs (fluidised bed, shaft, molten salt), operated to a maximum temperature in the range 700 - 1200°C.
  • chlorinators of various designs (fluidised bed, shaft, molten salt), operated to a maximum temperature in the range 700 - 1200°C.
  • the most common type of industrial chlorinator is of the fluidised bed design.
  • Gaseous chlorine is passed through the titania and carbon bearing charge, converting titanium dioxide to titanium tetrachloride gas, which is then removed in the exit gas stream and condensed to liquid titanium tetrachloride for further purification and processing.
  • the chlorination process as conducted in industrial chlorinators is well suited to the conversion of pure titanium dioxide feedstocks to titanium tetrachloride.
  • most other inputs i.e. impurities in feedstocks
  • the attached table provides an indication of the types of problems encountered.
  • each unit of inputs which does not enter products contributes substantially to the generation of wastes for treatment and disposal.
  • Some inputs e.g. particular metals, radioactives
  • Preferred inputs to chlorination are therefore high grade materials, with the mineral rutile (at 95-96% Ti0 2 ) the most suitable of present feeds. Shortages of rutile have led to the development of other feedstocks formed by upgrading naturally occurring ilmenite (at 40-60% Ti0 2 ), such as titaniferous slag (approximately 86% Ti0 2 ) and synthetic rutile (variously 92-95% Ti0 2 ) . These upgrading processes have had iron removal as a primary focus, but have extended to removal of magnesium, manganese and alkali earth impurities, as well as some aluminium.
  • Si Accumulates Can May require i ne ncourage distillat ion chlorinator, d u c t from product r e d u c i n gb lockage . c a m p a i g n Condenses in life. part with
  • titaniferous minerals e.g. ilmenite
  • the titaniferous mineral is reduced with coal or char in a rotary kiln, at temperatures in excess of 1100°C.
  • the iron content of the mineral is substantially metallised.
  • Sulphur additions are also made to convert manganese impurities partially to sulphides.
  • the metallised product is cooled, separated from associated char, and then subjected to aqueous aeration for removal of virtually all contained metallic iron as a separable fine iron oxide.
  • the titaniferous product of separation is treated with 2-5% aqueous sulphuric acid for dissolution of manganese and some residual iron.
  • aqueous sulphuric acid for dissolution of manganese and some residual iron.
  • Recent disclosures have provided a process which operates reduction at lower temperatures and provides for hydrochloric acid leaching after the aqueous aeration and iron oxide separation steps. According to these disclosures the process is effective in removing iron, manganese, alkali and alkaline earth impurities, a substantial proportion of aluminium inputs and some vanadium as well as thorium.
  • the process may be operated as a retrofit on existing kiln based installations. However, the process is ineffective in full vanadium removal and has little chemical impact on silicon.
  • ilmenite is first thermally reduced to substantially complete reduction of its ferric oxide content (i.e. without substantial metallisation), normally in a rotary kiln.
  • the cooled, reduced product is then leached under 35 psi pressure at 140-150°C with excess 20% hydrochloric acid for removal of iron, magnesium, aluminium and manganese.
  • the leach liquors are spray roasted for regeneration of hydrogen chloride, which is recirculated to the leaching step.
  • the ilmenite undergoes grain refinement by thermal oxidation followed by thermal reduction (either in a fluidised bed or a rotary kiln) .
  • the cooled, reduced product is then subjected to atmospheric leaching with excess 20% hydrochloric acid, for removal of the deleterious impurities. Acid regeneration is also performed by spray roasting in this process.
  • ilmenite is thermally reduced (without metallisation) with carbon in a rotary kiln, followed by cooling in a non-oxidising atmosphere.
  • the cooled, reduced product is leached under 20 - 30 psi gauge pressure at 130°C with 10 - 60% (typically 18 - 25%) sulphuric acid, in the presence of a seed material which assists hydrolysis of dissolved titania, and consequently assists leaching of impurities.
  • Hydrochloric acid usage in place of sulphuric acid has been claimed for this process. Under such circumstances similar impurity removal to that achieved with other hydrochloric acid based systems is to be expected. Where sulphuric acid is used radioactivity removal will not be complete.
  • a commonly adopted method for upgrading of ilmenite to higher grade products is to smelt ilmenite at temperatures in excess of 1500°C with coke addition in an electric furnace, producing a molten titaniferous slag (for casting and crushing) and a pig iron product.
  • molten titaniferous slag for casting and crushing
  • pig iron product Of the problem impurities only iron is removed in this manner, and then only incompletely as a result of compositional limitations of the process.
  • a titaniferous ore is treated by alternate leaching with an aqueous solution of alkali metal compound and an aqueous solution of a non-sulphuric mineral acid (US Patent No. 5,085,837).
  • the process is specifically limited to ores and concentrates and does not contemplate prior processing aimed at artificially altering phase structures. Consequently the process requires the application of excessive reagent and harsh processing conditions to be even partially effective and is unlikely to be economically implemented to produce a feedstock for the chloride pigment process.
  • a wide range of potential feedstocks is available for upgrading to high titania content materials suited to chlorination.
  • Examples of primary titania sources which cannot be satisfactorily upgraded by prior art processes for the purposes of production of a material suited to chlorination include hard rock (non detrital) ilmenites, siliceous leucoxenes, many primary (unweathered) ilmenites and large anatase resources.
  • Many such secondary sources e.g. titania bearing slags also exist.
  • titania reserves A large portion of the world's identified titania reserves is in the form of hard rock ilmenites.
  • the residue of the caustic leach was subjected to a leach with refluxing 20% hydrochloric acid at 30% slurry density for 6 hours. After filtration and washing the solid residue had the composition which is also indicated in Table 2.
  • Example 1 The treatment indicated in Example 1 was repeated with the exception that the caustic leach was conducted under pressure at 165°C.
  • the residue of the caustic leach was subjected to a pressure leach at 150°C with 20% sulphuric acid at 5% slurry density for 6 hours. After filtration and washing the solid residue had the composition which is also indicated in Table 4.
  • titaniferous slag having the composition shown in Table 1 was subjected to roasting for two hours in an atmosphere of 1:19 (volumetric basis) of hydrogen to carbon dioxide at 1000°C. After cooling in the roasting atmosphere the roasted slag was pressure leached at 135°C in 20% sulphuric acid at 25% w/w slurry density for six hours.
  • Example 5 A sample of slag to which no addition of additive had been made and which was not subjected to any thermal treatment was treated by the same leaching steps as indicated in Example 3.

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

Abstract

L'invention concerne un procédé d'ennoblissement d'un matériau titanifère par enlèvement des impuretés dudit matériau. Ce procédé comprend un affinage alternatif du matériau titanifère dans un bain caustique et dans un bain d'acide sulfurique sous pression.
PCT/AU1994/000528 1993-09-07 1994-09-07 Ennoblissement de materiaux titaniferes WO1995007366A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU76475/94A AU697952B2 (en) 1993-09-07 1994-09-07 Upgrading titaniferous materials
JP7508358A JPH09504828A (ja) 1993-09-07 1994-09-07 チタン含有原料の品質改良
EP94926722A EP0717783A4 (fr) 1993-09-07 1994-09-07 Ennoblissement de materiaux titaniferes
NO19960917A NO317932B1 (no) 1993-09-07 1996-03-06 Kvalitetsforbedring av titanholdige materialer

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPM1051 1993-09-07
AUPM105193 1993-09-07

Publications (1)

Publication Number Publication Date
WO1995007366A1 true WO1995007366A1 (fr) 1995-03-16

Family

ID=3777178

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1994/000528 WO1995007366A1 (fr) 1993-09-07 1994-09-07 Ennoblissement de materiaux titaniferes

Country Status (7)

Country Link
EP (1) EP0717783A4 (fr)
JP (1) JPH09504828A (fr)
CN (1) CN1042349C (fr)
CA (1) CA2171185A1 (fr)
NO (1) NO317932B1 (fr)
WO (1) WO1995007366A1 (fr)
ZA (1) ZA946864B (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995028502A1 (fr) * 1994-04-15 1995-10-26 Technological Resources Pty. Ltd. Lessivage d'un materiau titanifere
WO1995028503A1 (fr) * 1994-04-15 1995-10-26 Technological Resources Pty Ltd Traitement de liqueurs de lessivage pour la valorisation de materiaux titaniferes.
US6627165B2 (en) * 1994-04-15 2003-09-30 Technological Resources Pty Ltd Process for upgrading a titaniferous material containing silica
WO2005024074A1 (fr) * 2003-09-05 2005-03-17 Promet Engineers Pty Ltd Procede destine a extraire des oxydes de titane cristallins
RU2336348C1 (ru) * 2007-03-07 2008-10-20 Николай Васильевич Туляков Способ переработки титан-кремнийсодержащих концентратов с получением искусственного рутила

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1060817C (zh) * 1997-08-08 2001-01-17 杨道光 钛铁矿电解渗析分离法
RU2264478C1 (ru) * 2004-05-26 2005-11-20 Федун Марина Петровна Способ переработки титан-кремнийсодержащих концентратов
WO2007052801A1 (fr) * 2005-11-07 2007-05-10 Tohoku University Procede d’extraction du rutile
RU2377332C2 (ru) * 2008-02-19 2009-12-27 Государственное образовательное учреждение высшего профессионального образования Томский политехнический университет Способ переработки титан-кремнийсодержащего сырья
RU2390572C1 (ru) * 2008-11-19 2010-05-27 ООО "Гирмет" Способ переработки кварц-лейкоксеновых концентратов
CN103834798B (zh) * 2012-11-26 2015-11-18 贵阳铝镁设计研究院有限公司 由低品位TiO2炉渣制备富钛料的方法
CN103966423B (zh) * 2014-04-23 2016-02-03 鞍钢集团矿业公司 利用碱浸、酸洗及重选再选钒钛磁铁精矿的方法
CN103952533B (zh) * 2014-04-23 2016-01-20 鞍钢集团矿业公司 利用煅烧、碱浸及脱泥再选钒钛磁铁精矿的方法
RU2592655C2 (ru) * 2014-12-24 2016-07-27 Федеральное государственное бюджетное учреждение науки Объединенный институт высоких температур Российской академии наук (ОИВТ РАН) Способ термохимической переработки редкометального сырья
CN104828864B (zh) * 2015-05-26 2017-07-21 昆明冶金研究院 一种钛铁矿盐酸浸出制备人造金红石的工艺
RU2623564C1 (ru) * 2016-04-25 2017-06-27 Федеральное государственное бюджетное учреждение науки Институт металлургии и материаловедения им. А.А. Байкова Российской академии наук (ИМЕТ РАН) Способ переработки лейкоксенового концентрата

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021533A (en) * 1974-10-04 1977-05-03 Societa' Italiana Resine S.I.R. S.P.A. Manufacture of titanium dioxide by the sulphate process using nuclei formed by steam hydrolysis of TiCl4
AU3403478A (en) * 1977-03-09 1979-09-13 Mineracao Vale Do Paranaiba S.A.-Valep Obtaining higher grade anatase concentrate from lower grade anatase concentrate
US4176159A (en) * 1976-11-15 1979-11-27 Mendonca Paulo Ayres Falcao De Process for concentration of titanium containing anatase ore
AU3900289A (en) * 1988-07-28 1990-02-01 E.I. Du Pont De Nemours And Company Method for purifying tio2 ore
AU5316590A (en) * 1989-04-17 1990-10-18 Bayer Aktiengesellschaft A process for the production of titanium dioxide
AU1498192A (en) * 1991-04-19 1992-10-22 Rgc Mineral Sands Limited Removal of radionuclides from titaniferous material
AU1498092A (en) * 1991-04-19 1992-10-22 Rgc Mineral Sands Limited Removal of radionuclides from titaniferous material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE276025C (fr) *
GB711833A (en) * 1949-03-03 1954-07-14 Nat Titanium Pigments Ltd Improved manufacture of titanium compounds
JPH01301518A (ja) * 1988-05-28 1989-12-05 Sakai Chem Ind Co Ltd 酸化チタンの製造方法
BR9106105A (pt) * 1990-03-02 1993-02-24 Wimmera Ind Minerals Pty Ltd Processo para beneficiar o teor de titania de um minerio ou concentrado titanifero
US5063032A (en) * 1990-03-27 1991-11-05 Qit-Fer Et Titane, Inc. Method of preparing a synthetic rutile from a titaniferous slag containing magnesium values

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021533A (en) * 1974-10-04 1977-05-03 Societa' Italiana Resine S.I.R. S.P.A. Manufacture of titanium dioxide by the sulphate process using nuclei formed by steam hydrolysis of TiCl4
US4176159A (en) * 1976-11-15 1979-11-27 Mendonca Paulo Ayres Falcao De Process for concentration of titanium containing anatase ore
AU3403478A (en) * 1977-03-09 1979-09-13 Mineracao Vale Do Paranaiba S.A.-Valep Obtaining higher grade anatase concentrate from lower grade anatase concentrate
AU3900289A (en) * 1988-07-28 1990-02-01 E.I. Du Pont De Nemours And Company Method for purifying tio2 ore
AU5316590A (en) * 1989-04-17 1990-10-18 Bayer Aktiengesellschaft A process for the production of titanium dioxide
AU1498192A (en) * 1991-04-19 1992-10-22 Rgc Mineral Sands Limited Removal of radionuclides from titaniferous material
AU1498092A (en) * 1991-04-19 1992-10-22 Rgc Mineral Sands Limited Removal of radionuclides from titaniferous material

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DERWENT ABSTRACT; Accession No. 84-181664/29, Class E32; & SU,A,1 054 296 (KHAKONOV), 15 November 1983 (15.11.83). *
Derwent Soviet Inventions Illustrated, Section 1, Chemical, issued November 1969, General Inorganic, p. 3; & SU,A,235 883 (BORODINA et al.), 12 June 1969 (12.06.69). *
PATENT ABSTRACTS OF JAPAN, C-17, page 691; & JP,A,1 301 518 (SAKAI CHEM IND CO LTD), 5 December 1989 (05.12.89). *
See also references of EP0717783A4 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995028502A1 (fr) * 1994-04-15 1995-10-26 Technological Resources Pty. Ltd. Lessivage d'un materiau titanifere
WO1995028503A1 (fr) * 1994-04-15 1995-10-26 Technological Resources Pty Ltd Traitement de liqueurs de lessivage pour la valorisation de materiaux titaniferes.
US5885536A (en) * 1994-04-15 1999-03-23 Technological Resources Pty Ltd Process for alkaline leaching a titaniferous material
US6627165B2 (en) * 1994-04-15 2003-09-30 Technological Resources Pty Ltd Process for upgrading a titaniferous material containing silica
WO2005024074A1 (fr) * 2003-09-05 2005-03-17 Promet Engineers Pty Ltd Procede destine a extraire des oxydes de titane cristallins
RU2336348C1 (ru) * 2007-03-07 2008-10-20 Николай Васильевич Туляков Способ переработки титан-кремнийсодержащих концентратов с получением искусственного рутила

Also Published As

Publication number Publication date
NO960917L (no) 1996-04-25
NO317932B1 (no) 2005-01-10
EP0717783A1 (fr) 1996-06-26
ZA946864B (en) 1995-09-04
NO960917D0 (no) 1996-03-06
EP0717783A4 (fr) 1997-04-23
CA2171185A1 (fr) 1995-03-16
CN1042349C (zh) 1999-03-03
CN1134730A (zh) 1996-10-30
JPH09504828A (ja) 1997-05-13

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