WO1994005600A1 - Production de fluorotitanates - Google Patents

Production de fluorotitanates Download PDF

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Publication number
WO1994005600A1
WO1994005600A1 PCT/GB1993/001654 GB9301654W WO9405600A1 WO 1994005600 A1 WO1994005600 A1 WO 1994005600A1 GB 9301654 W GB9301654 W GB 9301654W WO 9405600 A1 WO9405600 A1 WO 9405600A1
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WO
WIPO (PCT)
Prior art keywords
fluorotitanate
titanium source
hydrofluoric acid
titanium
dissolution
Prior art date
Application number
PCT/GB1993/001654
Other languages
English (en)
Inventor
Philip John Brockerton
Sean Paul Lynch
Iain Stewart Mackirdy
David Barry Mobbs
Original Assignee
Laporte Industries Limited
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 Laporte Industries Limited filed Critical Laporte Industries Limited
Publication of WO1994005600A1 publication Critical patent/WO1994005600A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/002—Compounds containing, besides titanium, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • C22B34/1245—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 halogen ion as active agent
    • 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
    • C22B34/1259—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 treatment or purification of titanium containing solutions or liquors or slurries
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • This invention relates to the production of fluorotitanates.
  • Fluorotitanic acid is understood to be the compound H2 iF 6 and the products envisaged in this invention are the corresponding alkali metal salts and the ammonium salts.
  • Fluorotitanates find use in the metallurgical industries, for example as a constituent of aluminium master alloys or as a source of highly pure titanium metal. Potassium fluorotitanate is in common use for such purposes and is currently subject to stringent industry requirements in respect of purity, for example l- ⁇ TiFg at least 97.5%, elemental composition vanadium ⁇ 0.25%, silicon ⁇ 0.2%, zirconium, calcium or magnesium ⁇ 0.05% any other metal compound ⁇ 0.1% by weight. Fluorotitanates have been produced by processes involving the dissolution of the titanium content of titanium bearing minerals in hydrofluoric or hydrofluorosilicic acid followed by precipitation of the required fluorotitanate. European Patent Specification No.
  • alkali metal fluorotitanates by treating rutile ore with a 36% hydrofluorosilicate solution, evaporating to dryness over 6 hours, extracting the residue in demineralised water and precipitating potassium fluorotitanate by neutralising to a pH of 3 to 4 with potassium carbonate or potassium hydroxide. If this process is implemented with other than a highly pure ore the product may be contaminated with metallic hydrous oxides or carbonates. To counter this the use of a sodium compound as the base is taught where impure ores are treated so that the relatively soluble sodium fluorotitanate may be separated from precipitated impurities.
  • United States Patent Specification No. 2568341 discloses the production of potassium fluorotitanate by adding pulverised ilmenite ore containing 38% of iron calculated as FeO to a quantity of 28.6% hydrofluoric acid the addition being conducted at a rate sufficiently low to avoid, aided by the addition of increments of water, more than a gentle boiling of the reacting mass.
  • the quantity of hydrofluoric acid is taught to be 10% to 20% in excess of that required to convert the titanium and iron components of the titaniferrous material to titanium tetrafluoride and iron fluoride.
  • the iron content of the reacted mass is then reduced to the ferrous state by the addition of iron powder and, preferably, sulphuric acid, the insolubles are separated and potassium fluorotitanate precipitated at a temperature of about 70°C by the addition of potassium chloride.
  • potassium chloride or as an alternative, potassium nitrate, is intended to form soluble compounds of iron and thereby reduce the contamination of the fluoro itanate product but the large quantity of iron present would make it difficult to attain the degree of purity now required.
  • This process is adapted for the treatment of any titaniferous raw material containing significant quantities of elements other than titanium.
  • US Patent Specification No. 4497779 also discloses the use of potassium chloride to precipitate potassium fluorotitanate from a solution of fluorotitanic acid.
  • the solution of fluorotitanic acid is obtained by the dissolution of the highly pure titanium mineral anatase using 6.3% hydrofluoric acid solution over a contact period of 6 hours at a temperature of 190°F.
  • the potassium fluorotitanate so produced is acceptably pure. If the process is to be applied to a titanium source which contains impurities such as iron or silicon, such as ilmenite, the recovery of titanium is considerably reduced due to incomplete dissolution and if any ferric iron is present in the liquor it must be reduced to the ferrous state by the addition of iron or other reductant.
  • the present invention provides a process for the production of salts of fluorotitanic acid by the dissolution of a source of titanium in hydrofluoric acid to form a solution containing fluorotitanic acid, or precursor thereof such as titanium tetrafluoride, treating the solution with an ammonium or alkali metal halide or nitrate to precipitate the ammonium or alkali metal fluorotitanate and recovering the said fluorotitanate, the process being characterised by the use of mineral rutile or synthetic rutile as a source of titanium and the dissolution of the source of titanium directly in concentrated hydrofluoric acid.
  • the process of this invention can be made to produce salts of fluorotitanic acid meeting the industry requirement without an intervening reduction stage and/or using a relatively short dissolution time and/or a relatively small excess of fluorine.
  • mineral or native rutile as a source of titanium is not excluded from the present invention although it is relatively unreactive with hydrofluoric acid and may require a long period of digestion. It is found that the product of a titaniferous ore, including particularly suitably weathered il enites such as beach sands, alluvial deposits or leucoxene ⁇ , which have been subjected to beneficiation to remove a proportion of their iron content and to convert a majority or substantially all of their titanium dioxide content into the rutile form, a product hereafter referred to as synthetic rutile, is particularly suitable for use in the practice of this invention.
  • An example of a beneficiation process which may be used to produce a synthetic rutile may involve treating a suitable titaniferous ore such as an ilmenite to form a pseudobrokite phase therein, for example by means of an oxidising roast. Thereafter the excess iron is reduced, for example by heating in the presence of a carbonaceous reductant, to metallic iron or to reduced iron oxide which is selectively leached from the ore to leave a residual rutile titanium dioxide product.
  • the synthetic rutile so produced may typically contain over 90% of titanium dioxide together with a significant quantity of iron oxides, for example ferric oxide, and other impurities.
  • Synthetic rutiles such as have been described above are particularly reactive with hydrofluoric acid in comparison with native rutile.
  • the synthetic rutile utilised according to the invention may suitably contain about 0.5% to about 15% of iron calculated as F ⁇ 2 ⁇ 3 although it is preferred that it contain not more than about 10% and particularly preferred that it contain not more than about 6% of iron on the same basis. All percentages are by weight.
  • the synthetic rutile in finely divided form is suitably added to the hydrofluoric acid at a rate such that boiling does not occur, preferably so that 100°C is not exceeded, the. reaction mixture being agitated to suspend the synthetic rutile.
  • the temperature is maintained at at least 80°C by the input of heat if necessary, for example, very suitably at about 90°C + 5°C until at least 80% very suitably at least 90% of the synthetic rutile has been dissolved.
  • reaction times of the order of only about one hour may be attained.
  • the concentrated hydrofluoric acid preferably has a concentration of at least 40% by weight.
  • hydrofluoric acid should preferably be used in at least the stoichiometric quantity to react with the titanium present to form H 2 TiFg, e.g. a 6:1 molar ratio but particularly preferably an excess is used. Since the use of an undue excess is wasteful we prefer not to use more than 7.5 moles of HF per atom of Ti and a very suitable quantity is 6.2 to 7.2 moles.
  • the temperature at which the dissolution is conducted is preferably at least 60°C and may be up to the boiling point although it has been found that excellent dissolution can be obtained using a temperature of 90°C.
  • the time taken to dissolve the ore given suitable selection of the other parameters may preferably be from 0.5 to 2 hours, a very suitable direction being from 0.5 to 1 hour assuming that the ore is in a particulate form with not more than 1.0% wt being above 20 mesh USS (841 microns).
  • At least 90% wt of the ore is in t e size range of 200 to 20 mesh USS (74 to 841 microns) .
  • the solution produced by the dissolution of the source of titanium may suitably be separated from the solid residue by any suitable means such as decantation, filtration or centrifugation.
  • the solid residue generally contains a substantial proportion of the silicon, aluminium, zirconium and chromium values present in the original source of titanium as well as proportion of the iron values. It is a feature o_ the present invention that the use of a combination of a limited excess of concentrated hydrofluoric acid in the dissolution stage and the use of a halide or nitrate in the fluorotitanate precipitation stage results in a lower precipitation pH than that applying in the prior art where precipitation is conducted by means of strong bases.
  • the precipitation pH is below 2 for example from 0 to 1.
  • the precipitation of fluorotitanate is preferably conducted by forming an aqueous solution of the halide or nitrate, preferably the chloride, suitably at a concentration below 50% wt and above 10% wt, for example from 10% wt to 30% wt and adding the solution to that obtained by dissolution of the source of titanium.
  • the quantity of the precipitating salt is preferably in stoichiometric excess. This excess is preferably at least 5% and for example up to 50% on a molar basis.
  • the precipitation is conducted at a preferred temperature of below 40°C and preferably at a temperature of from 10°C to 35°C.
  • the slurry of fluorotitanate salt so produced is preferably washed, separated and dried by normal means.
  • the product so obtained may have a purity considerably exceeding the industry requirements stated above.
  • the synthetic rutile had a particle size of 98.8% wt greater than 200 mesh USS (74 microns) and 0.0% greater than 20 mesh USS (841 microns) .
  • Samples of the synthetic rutile were dissolved in hydrofluoric acid under varying conditions of acid concentration and excess, and treatment time, temperature and the degree of dissolution of the ore was noted.
  • the treatment of the synthetic rutile with the acid was conducted as follows. The synthetic rutile was added to the hydrofluoric acid with stirring so as to attain full addition in less than 1 minute. Once the addition had been completed the reaction vessel was heated to maintain a temperature of 90°C + 5°C and maintained under agitation for the specified reaction duration.
  • the residue was found to amount to 10% of the weight of the ore.
  • the supernatant solution was separated by filtration and treated with a 50% molar excess of potassium chloride added as a 20% aqueous solution.
  • the temperature was maintained at 25°C and the pH of the solution during crystallisation was 0.5.
  • the crystals of potassium fluorotitanate so formed were separated by filtration, washed and dried, and were then analysed to give the following elemental composition.

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

Abstract

L'invention concerne un procédé de production de sels sensiblement purs de l'acide fluorotitanique à partir d'une source de titane impur, qui consiste à dissoudre la source de titane dans de l'acide fluorhydrique, à traiter la solution ainsi formée avec un halogénure ou un nitrate de métal alcalin ou d'ammonium en une quantité suffisante pour précipiter le fluorotitanate d'ammonium ou de métal alcalin et à récupérer ledit fluorotitanate. On utilise un rutile naturel ou synthétique comme source de titane et cette source est dissoute directement dans de l'acide fluorhydrique concentré.
PCT/GB1993/001654 1992-08-26 1993-08-05 Production de fluorotitanates WO1994005600A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9218170.0 1992-08-26
GB929218170A GB9218170D0 (en) 1992-08-26 1992-08-26 The production of fluorotitanates

Publications (1)

Publication Number Publication Date
WO1994005600A1 true WO1994005600A1 (fr) 1994-03-17

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1993/001654 WO1994005600A1 (fr) 1992-08-26 1993-08-05 Production de fluorotitanates

Country Status (3)

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CN (1) CN1083795A (fr)
GB (1) GB9218170D0 (fr)
WO (1) WO1994005600A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5788948A (en) * 1993-10-22 1998-08-04 The University Of Melbourne Process for the production of fluorometallate salts useful in the processing of mineral sands and related materials
WO2006079887A2 (fr) * 2005-01-27 2006-08-03 Peruke (Proprietary) Limited Procede de production de titane

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102586628A (zh) * 2012-02-22 2012-07-18 深圳市新星轻合金材料股份有限公司 以氟钛酸钠为中间原料生产海绵钛并同步产出钠冰晶石的循环制备方法
CN110697767B (zh) * 2019-11-07 2022-08-05 河钢股份有限公司承德分公司 一种利用碱金属钛酸盐制备碱金属氟钛酸盐的方法
CN110760683A (zh) * 2019-11-07 2020-02-07 河钢股份有限公司承德分公司 一种废弃scr催化剂提钒并制备碱金属氟钛酸盐的方法及其产品和用途

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2568341A (en) * 1951-02-03 1951-09-18 Beryllium Corp Production of potassium titanium fluoride
GB2185248A (en) * 1986-01-09 1987-07-15 Allied Corp Recovery of titanium dioxide from ilmenite-type ores

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2568341A (en) * 1951-02-03 1951-09-18 Beryllium Corp Production of potassium titanium fluoride
GB2185248A (en) * 1986-01-09 1987-07-15 Allied Corp Recovery of titanium dioxide from ilmenite-type ores

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5788948A (en) * 1993-10-22 1998-08-04 The University Of Melbourne Process for the production of fluorometallate salts useful in the processing of mineral sands and related materials
WO2006079887A2 (fr) * 2005-01-27 2006-08-03 Peruke (Proprietary) Limited Procede de production de titane
WO2006079887A3 (fr) * 2005-01-27 2006-10-05 Peruke Invest Holdings Pty Ltd Procede de production de titane
US7670407B2 (en) 2005-01-27 2010-03-02 Peruke (Proprietary) Limited Method of producing titanium
AU2005325906B2 (en) * 2005-01-27 2010-03-11 Peruke (Proprietary) Limited A method of producing titanium
EA013432B1 (ru) * 2005-01-27 2010-04-30 Перук (Проприетари) Лимитед Способ получения титана
AU2005325906C1 (en) * 2005-01-27 2010-07-29 Peruke (Proprietary) Limited A method of producing titanium
US7846232B2 (en) 2005-01-27 2010-12-07 Adams & Adams Method of producing titanium
EA015885B1 (ru) * 2005-01-27 2011-12-30 Перук (Проприетари) Лимитед Способ получения титана

Also Published As

Publication number Publication date
GB9218170D0 (en) 1992-10-14
CN1083795A (zh) 1994-03-16

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