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WO1993018192A1 - Lixiviation en continu par des solutions a base d'alcool de minerais titaniferes traites - Google Patents

Lixiviation en continu par des solutions a base d'alcool de minerais titaniferes traites Download PDF

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Publication number
WO1993018192A1
WO1993018192A1 PCT/AU1993/000096 AU9300096W WO9318192A1 WO 1993018192 A1 WO1993018192 A1 WO 1993018192A1 AU 9300096 W AU9300096 W AU 9300096W WO 9318192 A1 WO9318192 A1 WO 9318192A1
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WO
WIPO (PCT)
Prior art keywords
acid
leach
leaching
ilmenite
treated
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/AU1993/000096
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English (en)
Inventor
Edgar George Newman
Graham Francis Balderson
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.)
PIVOT MINING NL
Original Assignee
PIVOT MINING NL
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 PIVOT MINING NL filed Critical PIVOT MINING NL
Priority to AU36237/93A priority Critical patent/AU3623793A/en
Publication of WO1993018192A1 publication Critical patent/WO1993018192A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C22B34/10—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

Definitions

  • THIS INVENTION relates to the continuous leaching of treated titaniferous ores with alcohol solutions.
  • the invention forms a part of a process for the beneficiation of titaniferous ores to produce a product high in titanium dioxide, and low in other metal oxides, which is suitable for use as a pigment, or is suitable for the subsequent production by chlorination of titanium dioxide pigments, or for the production of titanium metal.
  • ilmenite Commercial grades of ilmenite generally contain about 46 to 65% titanium dioxide combined with 30 to 45% iron oxides.
  • iron oxides and oxides of manganese and magnesium which substitute for iron oxides in the ilmenite lattice
  • the Murso process achieves this desired quality in six major steps:
  • titaniferous ores such as ilmenite contain a mixture of ferrous and ferric oxide.
  • the oxidation stage heats the material in a fluid bed or rotary kiln in the presence of excess atmospheric air. This treatment was required to ensure that all the ferrous oxide was converted to the ferric oxide form. There is then a crystal structure change that is beneficial to the following reduction stage.
  • the oxidised ore is reduced using either a solid or gaseous reducing agent to convert the ferric iron to the ferrous stage without continuing to the formation of metallic iron.
  • This conversion reaction makes the ore more amenable to the following leaching process which utilises hydrochloric acid.
  • the ore is preferably leached using a hydrochloric acid solution.
  • various improvements to the Murso process have resulted in (amongst other things) the addition to the leachate of metal chlorides, such as ferrous chloride, to facilitate the leach process.
  • the solids are filtered from the spent acid liquors and are washed with water and refiltered to remove the excess water.
  • the final step of recovering hydrochloric acid from ferrous chloride liquors is then undertaken to produce fresh hydrochloric acid which is recycled to the leach step, together with solid iron oxide which may be used as a feed material in the iron industry.
  • the present invention provides a process for the continuous leaching of treated titaniferous ores, said process comprising subjecting a treated titaniferous ore to an acid leach wherein an alcohol species is added to the leachate.
  • the present invention provides a process comprising subjecting synthetic ilmenite to an acid leach, the synthetic ilmenite having been produced by oxidising substantially all iron values associated with titanium in a titaniferous ore to the ferric state and by then reducing substantially all of the iron values to the ferrous state, wherein an alcohol species is added to the leachate.
  • the addition of the alcohol species allows for lower temperatures to be used during leaching due to the leach operating at a lower boiling point.
  • the boiling point will be about 94°C compared with a 20% hydrochloric acid/water mixture which boils at 108°C.
  • plastic materials may be used in equipment construction.
  • ethanol is here used as an example of a suitable acid, and indeed ethanol is the preferred alcohol, other alcohols such as methanol and ethylene glycol may be used. Ethanol is the preferred alcohol as it has been found to be particularly effective in lowering the reaction temperature.
  • an alcohol/acid solution allows for the economic multiple re-crystallisation of the ferrous chloride liquors to produce an iron oxide product after acid regeneration that is of sufficient high purity as to possibly command a market premium.
  • the addition of an alcohol species is most preferably used in conjunction with the use of small inter-stage evaporators located between the leach stages.
  • the combination of the alcohol species and the inter-stage evaporators assists in providing an optimum balance between acid strength and ion concentration over several stages of leaching with only the water component produced by the reaction being removed.
  • the use of more than one evaporator and only removing a small portion of the water at each stage is also the most energy efficient method of evaporation.
  • the purpose of the leaching in the overall process is to dissolve selectively iron and other metal oxides from the ilmenite lattice with a minimum loss of titanium values. However, some titanium does go into solution and a certain amount of it is subsequently precipitated from the solution as a fine material.
  • the main factors which affect the rate of leaching, production of fines, titanium dissolution and its hydrolysis are acid concentration, mixing velocity and leaching temperature. Both high acid concentration and high temperature favour higher rate of leaching.
  • other factors such as titanium loss in solution, reduction of fines, materials of construction for leaching vessels, and economic recovery of hydrochloric acid influence the choice of acid strength, temperature of leaching and the method of mixing.
  • the original Murso process found the optimum conditions for leaching to be 20% hydrochloric acid and a temperature of 108 to 110°C at atmospheric pressure in a fluid bed contactor. Subsequent variations to the Murso process discuss the merits of using a leachate with an increased chloride ion concentration over a hydrochloric acid solution but fail to describe a mechanism for maintaining constant chloride concentrations in a continuous operation.
  • the substitution of the water component with an alcohol species and the removal of water produced during the reaction assists in maintaining the high level of chloride ion concentration even towards the completion of the leach cycle when most of the acid has been depleted.
  • weak acid solutions extend the leach period and promote the formation of fine material, both of which are undesirable.
  • a further advantage of maintaining a high level of chloride ion concentration in the leach liquor is gained in the improved energy efficiency of the acid regeneration stage where a lower concentration of water requires less energy in the evaporation stages.
  • a low grade titaniferous ore such as ilmenite containing a mixture of ferrous and ferric oxide is subjected to temperatures in the order of 850 to 1000°C in the presence of excess air in a fluid bed or rotary kiln (oxidation reactor 10) for periods of one or more hours. Substantially all of the ferrous oxide is converted to the ferric oxide form and the ilmenite undergoes a crystal structure change that is beneficial to the following reduction stage.
  • the oxidised ore is then reduced (at reduction reactor 12) using either a solid reducing agent such as carbon or a gaseous reducing agent such as carbon monoxide, hydrocarbon gases, hydrogen or mixtures of these, to convert the ferric iron to the ferrous state without continuing to the formation of metallic iron.
  • Conversion of the oxidised product to the synthetic ilmenite is relatively rapid and efficient when carried out by hydrogen at 850 to 900°C.
  • the reduction step makes the synthetic ilmenite more amenable to the leaching process to be conducted with hydrochloric acid.
  • the synthetic ilmenite is then preferably leached in a counter current fluid bed system (indicated at 14 in Figure 1 and in detail in Figure 2) using a 15 to 20% hydrochloric acid solution containing 15 to 25% ferrous chloride at temperatures between 90 and 110°C.
  • This solution is made up by a combination of the fresh acid 16, the alcohol containing acid 18 and the ferrous chloride solution 20, and enters the system primarily through the acid wash 24.
  • alcohol species is added to allow for lower temperatures to be used during leaching and to enhance the process economics as less energy is required to achieve the required chloride balance throughout the leach cycle.
  • the alcohol species preferably ethanol, is added to the fresh 31% hydrochloric acid 18 as a dilutant to form the 20% hydrochloric acid solution required.
  • the alcohol species added is preferably substantially removed from the leachate by evaporation prior to the leachate being processed in the following acid regeneration stage. In this preferred form, allowance is made for a leachate nearly saturated in ferrous chloride to be regenerated again.
  • Two small inter-stage evaporators 22 are also preferably located between various leaching stages to assist in maintaining an optimum balance between acid strength and ion concentration and to thus give an improvement in leach- kinetics.
  • the removal of water in this way is also advantageous in later stages of the process due to a lower amount of energy being needed to. evaporate the remaining water.
  • Vacuum flash evaporators are preferably used to ensure an acceptable efficiency of separation of water and acid between leaching stages.
  • An acid washing stage 24 preferably concludes the leach cycle and is preferably a counter current acid washing stage in a vessel similar to the leach vessels 26.
  • the wash acid from this stage advantageously becomes the feed acid to the leach circuit (via stream 28).
  • this acid wash, and also the acid leach may be conducted in any known manner that is appropriate, using any type of process and apparatus.
  • counter-current or co-current operations may . be used, or mechanical agitation or the like may be adapted.
  • the solids exiting from the acid wash 24 in stream 30 are then separated from the wash acid by filtration 32 and the filtrate is returned to the wash acid stage.
  • the now semi dried solids are dried 34 at controlled temperatures up to 400°C either in a fluid bed or rotary kiln to remove any contained acid, while the acid vapour is passed through recovery scrubbers 36.
  • the calcination process 38 for the dried solids is then conducted at 800 to 850°C for a period of 30 to 60 minutes to stabilise the crystal structure and to remove any final traces of moisture, iron chloride and hydrochloric acid.
  • the solid material can be passed through a magnetic field 40 to remove any incompletely leached material or any other magnetic material not effected by the acid leach.
  • the non magnetic fraction is recovered as the synthetic ilmenite product.

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

Abstract

L'invention permet la lixiviation en continu par des solutions à base d'alcool des minerais titanifères traités. Elle s'intègre notamment dans un procédé d'enrichissement des minerais titanifères destinés à fournir un produit à forte teneur en dioxyde de titane et à faible teneur en autres oxydes métalliques, produit susceptible d'être utilisé comme pigment ou pour la fabrication ultérieure, par chloration, de pigments au dioxyde de titane, ou pour celle du titane métal.
PCT/AU1993/000096 1992-03-09 1993-03-09 Lixiviation en continu par des solutions a base d'alcool de minerais titaniferes traites Ceased WO1993018192A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU36237/93A AU3623793A (en) 1992-03-09 1993-03-09 Continuous leaching of treated titaniferous ores with alcohol solutions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPL129592 1992-03-09
AUPL1295 1992-03-09

Publications (1)

Publication Number Publication Date
WO1993018192A1 true WO1993018192A1 (fr) 1993-09-16

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1993/000096 Ceased WO1993018192A1 (fr) 1992-03-09 1993-03-09 Lixiviation en continu par des solutions a base d'alcool de minerais titaniferes traites

Country Status (1)

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WO (1) WO1993018192A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7008602B2 (en) 2002-04-19 2006-03-07 Millennium Inorganic Chemicals, Inc. Beneficiation of titaniferous ore with sulfuric acid

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1225826A (fr) * 1967-05-01 1971-03-24
WO1990010721A1 (fr) * 1989-03-07 1990-09-20 Dean Robert Butler Recuperation de metaux du groupe comprenant l'or, l'argent et le platine a l'aide d'agents de lessivage a des basses densites de pulpe

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1225826A (fr) * 1967-05-01 1971-03-24
WO1990010721A1 (fr) * 1989-03-07 1990-09-20 Dean Robert Butler Recuperation de metaux du groupe comprenant l'or, l'argent et le platine a l'aide d'agents de lessivage a des basses densites de pulpe

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
INTERNATIONAL JOURNAL OF MINERAL PROCESSING, Vol. 24, issued 1988, (Elsevier, Amsterdam), I. GIRGIN, L. TURKER, D. GOODALL, "The Dissolution of Ilmenite in HCl-H2O, HCl-CH3OH and HCl-C2H5OH Systems - A Theoretical Approach", pages 173-184. *
THE AUS IMM BULLETIN AND PROCEEDINGS, Volume 291, No. 5, issued July 1986, I. GIRGIN AND L. TURKER, "Hydrochloric Acid Leaching of Ilmenite - Effect of Alcohol Species", pages 61-64. *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7008602B2 (en) 2002-04-19 2006-03-07 Millennium Inorganic Chemicals, Inc. Beneficiation of titaniferous ore with sulfuric acid

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