WO1993018193A1 - Lavage a l'acide de solides ayant subi une lixiviation et provenant de l'enrichissement de minerais titaniferes - Google Patents

Lavage a l'acide de solides ayant subi une lixiviation et provenant de l'enrichissement de minerais titaniferes Download PDF

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Publication number
WO1993018193A1
WO1993018193A1 PCT/AU1993/000097 AU9300097W WO9318193A1 WO 1993018193 A1 WO1993018193 A1 WO 1993018193A1 AU 9300097 W AU9300097 W AU 9300097W WO 9318193 A1 WO9318193 A1 WO 9318193A1
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WO
WIPO (PCT)
Prior art keywords
acid
leach
wash
process according
beneficiation
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/AU1993/000097
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English (en)
Inventor
Edgar George Newman
Graham Francis Balderson
Charles Alexander Macdonald
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
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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 AU36238/93A priority Critical patent/AU3623893A/en
Publication of WO1993018193A1 publication Critical patent/WO1993018193A1/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 acid washing of leached solids obtained from the beneficiation of titaniferous ores.
  • 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.
  • an aim of the present invention is to overcome, or at least partly alleviate, some of the difficulties with the acid regeneration stage.
  • solutions to the problems with the leaching step have been described in our copending applications titled “Continuous Leaching of Treated Titaniferous Ores With Alcohol Solutions” and “Continuous Leaching of Treated Titaniferous Ores with Inter-Stage Evaporation” .
  • the present invention provides a process for treating leached solids obtained from the beneficiation of titaniferous ores, the process comprising subjecting a treated titaniferous ore to an acid leach and subsequently washing the solids obtained with an acid.
  • the present invention provides a process comprising subjecting synthetic ilmenite, to an acid leach, the synthetic ilmenite being produced by oxidising substantially all of the 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 the solids obtained are subsequently washed with an acid.
  • the acid wash is conducted as a counter current acid washing stage immediately after the completion of the leach cycle, and in vessels similar to the leach vessel.
  • the wash acid from this stage may become the feed acid to the leach circuit, and the solids may be separated from the wash acid by filtration and the filtrate returned to the wash acid stage.
  • the acid wash as for the acid leach, may be conducted as a co-current stage or indeed may be conducted utilising any suitable techniques.
  • the acid leach for instance may be conducted counter-currently or co-currently or a mechanically agitated vessel may be used.
  • the acid could not be used as a feed to an acid absorber section without firstly being concentrated by evaporation. Only then could the acid be used as regeneration feed.
  • the fresh acid is only marginally diluted with residual ferrous chloride from the leached solids and may thus then be used as the feed acid to the last stage of leaching.
  • an alcohol species is added to the leach solution prior to the acid wash of the invention.
  • 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. For example, if ethanol is substituted for the water component in the leach, 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.
  • 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 are located between 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 use of the inter-stage evaporators and the addition of the alcohol species are not essential features of this invention.
  • 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.
  • 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 atmosphieric 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 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. This is of course further assisted by conducting the acid wash of the invention rather than usual water wash.
  • 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.
  • Two small inter-stage evaporators 22 are located between various of the leaching stages 26 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. These evaporators and their associated condensers enable 14% acid to be evaporated to 16% acid with little loss of acid to the condensate. The size of the evaporators will of course be dependent upon plant capacity and solution throughput.
  • An alcohol species is preferably added to the 31% HC1 solution 18 to allow for lower temperatures to be used during leaching and to enhance the process economics as less energy is required to achieve the inter-stage evaporation required for chloride balance throughout the leach cycle.
  • an alcohol species and the use of inter-stage evaporators are not essential for this invention.
  • the alcohol species added is 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.
  • the acid washing stage of the invention is preferably a counter current- acid washing stage 24 in a vessel similar to the leach vessels 26. In this way, the wash acid from this stage becomes the feed acid to the leach circuit (via stream 28). It will again be appreciated that the acid leach and the acid wash may be conducted using any appropriate process and apparatus.
  • 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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  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention permet le lavage à l'acide de solides ayant subi une lixiviation et provenant de l'enrichissement de minerais titanifères. 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/AU1993/000097 1992-03-09 1993-03-09 Lavage a l'acide de solides ayant subi une lixiviation et provenant de l'enrichissement de minerais titaniferes Ceased WO1993018193A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU36238/93A AU3623893A (en) 1992-03-09 1993-03-09 Acid washing of leached solids from the beneficiation of titaniferous ores

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPL129492 1992-03-09
AUPL1294 1992-03-09

Publications (1)

Publication Number Publication Date
WO1993018193A1 true WO1993018193A1 (fr) 1993-09-16

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PCT/AU1993/000097 Ceased WO1993018193A1 (fr) 1992-03-09 1993-03-09 Lavage a l'acide de solides ayant subi une lixiviation et provenant de l'enrichissement de minerais titaniferes

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WO (1) WO1993018193A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2315742B (en) * 1996-07-26 2000-08-30 Tiomin Resources Inc Method for the production of synthetic rutile
CN104437851A (zh) * 2014-10-31 2015-03-25 天津市凯特隆焊接材料有限公司 一种钛铁矿的选矿方法
CN113846230A (zh) * 2021-10-26 2021-12-28 中国科学院过程工程研究所 一种改善钛渣酸浸处理后固液分离效果的处理方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1225826A (fr) * 1967-05-01 1971-03-24
US3649243A (en) * 1969-07-31 1972-03-14 British Titan Products Beneficiating iron-containing titaniferous material
GB1316195A (en) * 1971-04-02 1973-05-09 British Titan Ltd Beneficiation process for ilmenite
US4663131A (en) * 1983-11-30 1987-05-05 Bayer Aktiengesellschaft Process for the preparation of titanium dioxide
AU5316590A (en) * 1989-04-17 1990-10-18 Bayer Aktiengesellschaft A process for the production of titanium dioxide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1225826A (fr) * 1967-05-01 1971-03-24
US3649243A (en) * 1969-07-31 1972-03-14 British Titan Products Beneficiating iron-containing titaniferous material
GB1316195A (en) * 1971-04-02 1973-05-09 British Titan Ltd Beneficiation process for ilmenite
US4663131A (en) * 1983-11-30 1987-05-05 Bayer Aktiengesellschaft Process for the preparation of titanium dioxide
AU5316590A (en) * 1989-04-17 1990-10-18 Bayer Aktiengesellschaft A process for the production of titanium dioxide

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2315742B (en) * 1996-07-26 2000-08-30 Tiomin Resources Inc Method for the production of synthetic rutile
CN104437851A (zh) * 2014-10-31 2015-03-25 天津市凯特隆焊接材料有限公司 一种钛铁矿的选矿方法
CN113846230A (zh) * 2021-10-26 2021-12-28 中国科学院过程工程研究所 一种改善钛渣酸浸处理后固液分离效果的处理方法

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