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WO2016112432A1 - Enrichissement de matériaux porteurs de titane - Google Patents

Enrichissement de matériaux porteurs de titane Download PDF

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Publication number
WO2016112432A1
WO2016112432A1 PCT/AU2016/050012 AU2016050012W WO2016112432A1 WO 2016112432 A1 WO2016112432 A1 WO 2016112432A1 AU 2016050012 W AU2016050012 W AU 2016050012W WO 2016112432 A1 WO2016112432 A1 WO 2016112432A1
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WO
WIPO (PCT)
Prior art keywords
titanium
anatase
bearing material
rutile
sulphuric acid
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/AU2016/050012
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English (en)
Inventor
Nicholas Glen Bernard
Victor Emmanuel HUGO
Sally-Anne Fiona ROWLANDS
Clasina Maria Susanna ROODT
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.)
Iluka Resources Ltd
Original Assignee
Iluka Resources 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
Priority claimed from AU2015900086A external-priority patent/AU2015900086A0/en
Application filed by Iluka Resources Ltd filed Critical Iluka Resources Ltd
Priority to CN201680005801.4A priority Critical patent/CN107531507A/zh
Priority to AU2016206434A priority patent/AU2016206434A1/en
Publication of WO2016112432A1 publication Critical patent/WO2016112432A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/008—Titanium- and titanyl sulfate
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
    • 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
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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 beneficiation of titanium bearing materials having a substantial component of anatase and/or rutile and/or pseudorutile structure.
  • Such materials include anatase ores and minerals and other sources of anatase, as well as blends or mixtures that include traditional sources of titanium and titanium dioxide such as ilmenite and titanium slag.
  • the invention is of particular, though not exclusive, interest in the processing of anatase materials to titanium dioxide of pigment quality.
  • the process is additionally effective in processing materials having a substantial component of anatase or rutile, e.g. leucoxene.
  • the titanium sulphate species are hydrolysed by heating the solution, usually above 80°C, to obtain a precipitate of hydrated titanium dioxide.
  • the earlier reduction of ferric iron was necessary as ferric sulphate has a tendency to co-precipitate with the titanium.
  • the wet pulp product of the hydrolysis step is then calcined in an internally fired, inclined rotary kiln in which the pulp is dried and strongly adsorbed water, SO2 and SO3 are driven off and the amorphous TiO(OH) 2 is converted to anatase or rutile pigments according to the applied conditions. For example, seeding is employed in the hydrolysis step to obtain a downstream rutile product, otherwise anatase will result.
  • the current process for digestion stage involves:
  • the reaction then proceeds exothermically such that the temperature rises to 200-220°C, depending on the ore being reacted, generally forming a cake which can have a consistency from treacle through to solid. Compressed air and/or steam mixing continues during this stage.
  • the reaction mixture is left to "bake” for ⁇ 45 minutes for ilmenite and 5-6 hours for slag.
  • the heat loss at the industrial scale is minimal as the reactors are refractory lined and the external surface area of the reactor compared to the volume of the reactants is low.
  • the peak temperature of 200-220°C is largely retained during the baking stage.
  • the cake After baking is complete, the cake is dissolved with water or dilute (usually recycled) sulphuric acid. The Ti and other sulphates are thereby included in the solution phase.
  • the amount of acid that is recycled is controlled to ensure that the acid to titanium ratio (A:T) is kept 1 .75-1.85 (where the ratio is H2SO4 to Ti0 2 where all the T1OSO4 is converted to T1O2 and H 2 S0 4 ) as higher acid ratios adversely affect the hydrolysis stage.
  • the remaining residue is usually filtered and washed to collect any remaining liquor and then disposed of.
  • the residue contains insoluble mineral phases (e.g. silica and alumino-silicates) and any insoluble Ti phases such as rutile and pseudorutile, insoluble forms of Fe such as magnetite and insoluble sulphate species which can include sulphates of Ba, Sr, Ca and the insoluble a-TiOS0 4 .
  • the digestion stage in the process of WO 92/08816 differs from the conventional Sulphate Process in that a mixture of concentrated sulphuric acid, ore and crystallized titanium sulphates, similar to a fine sand, is maintained in suspension, and in a fluid phase, with a large excess of acid, i.e. A:0 from 2: 1 to 10: 1.
  • the suspension is maintained under boiling conditions in an equilibrium that causes the titanium sulphates to crystallise.
  • European patent publication EP 0475104 discloses a process for working up the digestion residue that remains after titanium dioxide has been produced via the Sulphate Process.
  • the digestion residue is effectively the solids that remain after the step of removing the soluble sulphate species generated by the Sulphate Process.
  • EP 0475104 discloses that the digestion residue can contain from 20 to 60% Ti (as ⁇ 2 ).
  • the Ti is present in insoluble phases, including: rutile, pseudorutile, ilmenomagnetite, leucoxene and insoluble a-TiOS0 4 .
  • the digestion residue is also known to typically contain high proportions of Ca, Mg, Mn, Al, Si, and Fe oxides (such as magnetite), and Ba and Sr sulphates.
  • EP 0475104 further discloses that the Ti0 2 in this digestion residue cannot be extracted under the usual conditions of the Sulphate Process, and is therefore typically rejected or recycled into a pulping process for further extraction albeit at low yield.
  • EP 0475104 proposes a process for recovering Ti0 2 from this digestion residue.
  • EP 0475104 describes a two-stage process for enhanced recovery of Ti0 2 , including a first stage of treating an ore using the conventional Sulphate Process, and a second stage of extracting further Ti0 2 from the resultant digestion residue.
  • EP 0475104 discloses mixing the digestion residue with sulphuric acid in a Ti0 2 :H 2 S0 4 ratio of from 1 :1 to 1 :3.5 and then supplying heat energy to heat this mixture to a temperature of 120°C to 300°C for a period of 15 minutes to 20 hours.
  • EP 0475104 discloses that the energy is supplied by addition of water to the mixture.
  • a process for beneficiating a titanium bearing material having a substantial component of anatase structure comprising: digesting the titanium bearing material in 94 to 98% sulphuric acid or oleum with addition of non-exothermic heat sufficient to raise the temperature to 220°C or above to form a resultant mix;
  • the process further includes the step of hydrolysing the titanium sulphate species to obtain a precipitate of hydrated titanium dioxide.
  • the titanium bearing material is selected from the group consisting of: an anatase ore, an anatase containing ore, an upgraded ore having a higher proportion of anatase than before upgrading, an anatase concentrate, or an anatase containing concentrate.
  • anatase extraction is at least 90%, expressed as oxides, of the anatase structure in the titanium bearing material. That is, at least 90% of the anatase structure in the titanium bearing material is separated out in the liquor.
  • a process for beneficiating a titanium bearing material of having a substantial component of rutile or pseudorutile structure comprising:
  • the process further includes the step of hydrolysing the titanium sulphate species to obtain a precipitate of hydrated titanium dioxide.
  • the titanium bearing material is selected from the group consisting of: a rutile or pseudorutile ore, a rutile or pseudorutile containing ore, an upgraded ore having a higher proportion of rutile or pseudorutile than before upgrading, a rutile or pseudorutile concentrate, or a rutile of pseudorutile containing concentrate.
  • rutile or pseudorutile extraction is at least 65%, expressed as oxides, of the rutile or pseudorutile structure in the titanium bearing material. That is, at least 65% of the rutile or pseudorutile structure in the titanium bearing material is separated out in the liquor.
  • non-exothermic heat refers to heat that is added to the system from an outside source and not generated from a reaction between constituents within the system. Such heat may be supplied by a heating element, heat exchanger, or direct contact between the titanium bearing material and/or 94 to 98% sulphuric acid or oleum with a heated or superheated gas (including steam).
  • a superheated gas is advantageous as it also assists to agitate the mix of the titanium bearing material and the sulphuric acid.
  • sulphuric acid is mixed with the ilmenite and then diluted.
  • the dilution of sulphuric acid is a highly exothermic reaction which generates sufficient exothermic heat to drive the digestion and baking steps of the Sulphate Process.
  • Obtaining heat energy from this exothermic dissolution reaction is generally considered advantageous in the context of the Sulphate Process as it reduces energy costs, i.e. externally applied heat is not required.
  • the inventors have found that providing non-exothermic heat for the digestion and baking steps of the inventive process has a number of advantages in respect of a titanium bearing material having a substantial component of anatase, rutile, or pseudorutile.
  • the titanium bearing material and sulphuric acid or oleum can be heated to temperatures higher than that generally adopted in the Sulphate Process (for example 220°C or above) and the sulphuric acid or oleum can be maintained at high concentration.
  • This allows for efficient recovery of T1O2 from a titanium bearing material having a substantial component of anatase, rutile, or pseudorutile.
  • the step of digesting the titanium bearing material includes agitating the material with the 94 to 98% sulphuric acid or oleum.
  • compressed air and/or steam e.g. superheated steam
  • the titanium bearing material is agitated with the 94 to 98% sulphuric acid or oleum.
  • set off water there is substantially no addition of set off water to dilute the 94 to 98% sulphuric acid or oleum to provide exothermic heat of dilution during the digesting and baking steps.
  • the heat energy added to raise the temperature from a base temperature (such as from ambient) to 220°C or above is predominantly non-exothermic heat.
  • the non-exothermic heat accounts for more than 50% of the total energy required to raise the temperature to 220°C or above, preferably 60%, more preferably 70%, even more preferably 90%, and most preferably 95%.
  • said non-exothermic heat is substantially not supplemented by exothermic heat of reaction from dissolution of the sulphuric acid or oleum.
  • this non-exothermic heat may be provided by different mechanisms.
  • the titanium bearing material and optionally also the sulphuric acid or oleum are preheated with non-exothermic heat e.g. to a temperature of 220°C or above prior to the digesting step.
  • the non-exothermic heat is added with the sulphuric acid feed.
  • the sulphuric acid or oleum feed is preheated so that during the digestion step, the temperature is raised to 220°C or above.
  • the baking temperature is in the range 220 to 275°C.
  • the liquor is treated to remove iron prior to the step of hydrolysing the titanium sulphate species.
  • ferric iron is not present during the step of hydrolysing the titanium sulphate species.
  • the process further includes the step of upgrading the titanium bearing material to separate the titanium bearing material from gangue prior to the step of digesting the titanium bearing material.
  • the process is a continuous process.
  • the continuous process is further defined in that at least the step of digesting the titanium bearing material and the step of baking the resultant mixture are carried out in a continuous reactor.
  • the continuous process is further defined in that the continuous reactor is a screw reactor.
  • the process further includes the step of calcining the precipitated hydrated titanium dioxide to produce anatase ⁇ 2 .
  • the process further includes the step of calcining the precipitated hydrated titanium dioxide to produce rutile ⁇ 2 .
  • Figure 1 is a process flow diagram illustrating an embodiment in which the process of the invention is carried out in a mixed tank reactor.
  • Figure 2 is a process flow diagram illustrating an embodiment in which the process of the invention is carried out in a screw reactor.
  • Figure 3 is a process flow diagram illustrating an embodiment in which the process of the invention is carried out using a mixing tank and a screw reactor.
  • anatase ores and other anatase-containing and rutile or pseudorutile-containing titanium bearing materials can be successfully treated by the Sulphate Process with certain modifications of the conventional digestion and baking steps.
  • the conventional digestion step is modified by providing sufficient non-exothermic heat to reach reaction temperatures of 220°C or above for baking. It has also been found that the higher the bake temperature, the shorter the bake time required, getting as low as 4 hours (which is not dissimilar to the existing process 5-6 hours for slag). It has further been found that the longer the time for the subsequent dissolution stage, the higher the yield of the ⁇ 2 to the TiOS0 4 solution.
  • the invention accordingly provides, in the first aspect, a process for beneficiating a titanium bearing material having a substantial component of anatase structure, comprising:
  • the invention provides a process for beneficiating a titanium bearing material having a substantial component of rutile or pseudorutile structure, comprising:
  • the invention is especially useful when applied to alteration products of ilmenite containing mixtures of two or more of anatase, rutile and pseudorutile.
  • a typical such product is the mineral mixture leucoxene.
  • all of the required heat may be provided externally, i.e. non-exothermically.
  • the first aspect of the invention is especially applicable to a variety of titanium bearing materials of predominately anatase structure.
  • these include anatase in occurrences as a primary mineral and as an alteration product of other titanium bearing minerals such as ilmenite, sphene, perovskite and potentially titaniferous magnetite. These occurrences can be associated with: weathering of alkaline intrusive complexes, hydrothermal alteration or sedimentary (placer) deposits, sedimentary metamorphic deposits and bauxite or laterite hosted minerals.
  • the baking temperature is in the range 220 to 275°C, more preferably at least 230°C and most preferably at least 240°C, more preferably at most 260°C, most preferably at most 250°C.
  • the non-exothermic heat provided during the digestion step is sufficient to maintain the baking temperature within the desired range for the duration of the bake.
  • the baking step converts the mix to a sulphate cake, i.e. a solid mix of sulphates.
  • the proportion of sulphuric acid provided is typically sufficient for the stoichiometric requirements of the acid-consuming reaction(s) plus an excess, typically about 10%.
  • the duration of the baking is preferably in the range 2 to 18 hours, more preferably in the range 4 to 12 hours.
  • the bake is preferably such, for example in relation to A:0 ratio, temperature and duration, that the anatase extraction is at least 90%, more preferably at least 95% (expressed as oxides).
  • the bake is preferably such, for example in relation to A:0 ratio, temperature and duration, that the rutile or pseudorutile extraction is at least 65%, more preferably at least 80%, most preferably at least 90% (expressed as oxides).
  • Rutile extraction can reach a value greater than 80% more preferably at least 85%, most preferably at least 90% (expressed as oxides), but can be tailored according to the desired liquor properties and baking conditions.
  • the titanium bearing material feed for the process may typically be an anatase, or an anatase containing ore such as a leucoxene ore and/or may often be a prepared concentrate.
  • the anatase or anatase containing ore may be treated in a number of different ways prior to the digestion step depending on the form and morphology. Some occurrences, such as those typified by the anatase present in the Murray Basin of Australia, will require some upgrading. Such upgrading may be by conventional mineral sands concentration processes.
  • Weathered alkaline complexes will require some upgrading using conventional techniques such as light crushing, wet magnetic separation, attritioning and desliming, while others such as hydrothermally altered rock deposits would require crushing and grinding and perhaps concentration techniques such as flotation to liberate the anatase from the silica host matrix, or at least to make the anatase accessible to the acid attack in the digestion step.
  • the mixture of feed titanium bearing material in sulphuric acid is preferably agitated, e.g. preferably by means of compressed air, steam (typically superheated) or by physical means, such as through the use of an agitator.
  • ferric iron is preferably not present for the hydrolysis step as this has a tendency to co-precipitate with the titanium and would be reduced to the ferrous form prior to crystallisation.
  • the hydrolysis step may be effected by increasing the temperature of the titanium sulphate solution to cause the precipitation of hydrated titanium dioxide, for example to ⁇ 80°C. Precipitation of hydrated titanium dioxide may be accelerated by introduction of nuclei, in either anatase or rutile form.
  • the hydrolysis step may be substantially according to the conventional Sulphate Process.
  • the precipitated hydrated titanium dioxide once calcined is in the anatase form, but the calcination (see below) may produce either anatase or rutile pigment according to the conditions and according to the nature of the nuclei added in the hydrolysis stage.
  • the precipitated hydrated titanium dioxide is calcined, e.g. in internally fired inclined rotary kilns through which the titanium dioxide pulp travels by gravity.
  • the precipitate may be treated prior to calcination, for example by being filtered and washed and/or being leached under reducing conditions to eliminate any residual ferric iron.
  • the calcination may be substantially according to the conventional Sulphate Process.
  • the hydrated titanium dioxide is initially dried before strongly adsorbed water, SO2 and SO3 are driven off. Conditions in the kiln are controlled to manage crystallite growth, so as to form either anatase or rutile pigment as desired.
  • the temperature is typically in the region of 1000°C.
  • the process may, as required, include treating the liquor to selectively separate one or more impurities from the titanium sulphate species.
  • the selective separation may where appropriate be by solvent extraction and/or ion exchange.
  • the impurities separated in the selective separation treatment of the liquor containing predominantly titanium sulphate species may typically include at least one or more transition metals, e.g. chromium, vanadium and niobium, and/or the elements derived from the rare earth minerals monazite, xenotime, or crandalite in the original ore.
  • transition metals e.g. chromium, vanadium and niobium
  • the selective separation may be of the transition metals. These are expected to be present as soluble sulphates.
  • a suitable solvent extraction system for this purpose would be triazoloquinazolinone or the neutral organophosphorous tri-n- octylphosphine oxide (TOPO).
  • the selective separation is effected by extracting the titanium sulphate species from the liquor, which retains the impurities. Reagents such as the organophosphoric acid di(2octylhexyl)phosphoric acid (D2EHPA) or the neutral organophosphorous tri-n-octylphosphine oxide (TOPO) are known to extract T1OSO4 from acidic (sulphate and chloride) solutions.
  • TOPO will extract a range of transition metals so may not be selective enough for preventing the transition element oxides co- extracting but it is known that Cr(lll) does not extract from acidic solution of TOPO.
  • the titanium sulphate species are stripped for subsequent hydrolysis from the extracting reagent by contacting the pregnant organic solution with a dilute sulphuric acid phase.
  • the step of treating the liquor to selectively separate one or more impurities from the titanium sulphate species would involve a number of stages designed to treat the different impurities or elements separately since in most cases a single extraction system would not cover all of the required elements.
  • the process may be a batch process, such as one conducted in one or more batch reactors; a semi-continuous process; or a continuous process, such as one conducted in one or more continuous stirred tank type reactors, and/or one or more plug flow type reactors.
  • some parts of the process may be batch operations, while others are continuous.
  • it is preferred that the process is a continuous process.
  • a preferred type of continuous reactor is a screw reactor.
  • Screw reactors include a helical rotating blade or two intermeshing blades that drive the mixture along the reaction volume of the reactor. The blade assists with mixing, and advantageously maintains the mixture in a granular form, which granules are typically 20 to 50 mm in diameter.
  • FIG. 1 is a process flow diagram of a batch process 100.
  • Titanium bearing material e.g. an anatase ore or concentrate, or an anatase containing ore or concentrate
  • first inlet 104 e.g. a reactor 102
  • second inlet 106 e.g. a stirrer 108
  • a stirrer 108 is used to mix the titanium bearing material and the sulphuric acid or oleum.
  • different stirring or mixing systems can be used. Once the mixture has been formed it undergoes digestion and baking within the reactor 102.
  • the mixture of feed titanium bearing material in sulphuric acid is preferably agitated by means of compressed air or steam (not shown).
  • the baked mix is withdrawn from the reactor 102 via outlet 110 and thereafter subjected to downstream processing, including hydrolysing the titanium sulphate species to obtain a precipitate of hydrated titanium dioxide.
  • the titanium bearing material and the sulphuric acid or oleum may be heated prior to being fed into the reactor 102, or may be heated within the reactor 102.
  • non-exothermic heat is provided to raise the temperature of the titanium bearing material feed and the sulphuric acid or oleum feed so that on mixing the temperature of the resultant mix is 220°C or above.
  • the heating step raises the temperature of each of the titanium bearing material feed and the sulphuric acid or oleum feed to 220°C or above.
  • the non-exothermic heat is generally provided by a heat exchanger or heating element (see heating elements 1 12 and 1 14 on feed streams 104 and 106).
  • non-exothermic heat is provided to raise the temperature of the mix in the reactor 102.
  • the reactor 102 includes a heat exchanger or heating element.
  • FIG. 2 is a process flow diagram of a continuous process 200.
  • Titanium bearing material e.g. an anatase ore or concentrate, or an anatase containing ore or concentrate
  • a continuous reactor 202 is fed into a continuous reactor 202 via first inlet 204.
  • 94 to 98% sulphuric acid or oleum is fed into the reactor 202 via a second inlet 206.
  • the continuous reactor 202 is a screw reactor, having a central threaded bore 208 for mixing the titanium bearing material and the sulphuric acid or oleum and transporting that mixture from the inlets 204 and 206 within the reactor to the outlet 210.
  • the reactor includes a first zone 212 and a second zone 214.
  • the first zone 212 Mixing of the titanium bearing material and the sulphuric acid or oleum occurs in the first zone 212, with digestion and baking of the resultant mixture occurring within the second zone 214. After digestion and baking, the baked mix is withdrawn from the reactor 202 via outlet 210 and thereafter subjected to downstream processing, including hydrolysing the titanium sulphate species to obtain a precipitate of hydrated titanium dioxide.
  • the titanium bearing material and the sulphuric acid or oleum may be heated using non-exothermic heat prior to being fed into the reactor 202, or within the reactor 202.
  • the reactor 202 includes a heating element 216 in the first zone to heat the mix to the desired temperature prior to the digestion and baking stages.
  • the feed may be pre-heated prior to introduction into reactor 202 or may be heated in the second zone 214 of the reactor 202.
  • FIG. 3 is a process flow diagram of another process 300.
  • the first reactor 302 is a mixing vessel that receives titanium bearing material via a first inlet 304 and 94 to 98% sulphuric acid or oleum via a second inlet 306.
  • This reactor 302 may be operated as a batch reactor or a continuous stirred tank reactor.
  • the resultant mix exits reactor 302 and is fed into screw reactor 308 via line 310 for digestion and baking.
  • the baked mix is withdrawn from the reactor 308 via outlet 312 and thereafter subjected to downstream processing, including hydrolysing the titanium sulphate species to obtain a precipitate of hydrated titanium dioxide.
  • non-exothermic heat may be provided at various stages of the process to provide a titanium bearing material/sulphuric acid or oleum mixture with a temperature of 220°C or above.
  • the individual feeds to vessel 302 may be preheated; or heating of the resultant mixture may take place in vessel 302, line 310, or a first zone of vessel 308.
  • reactor 302 includes a heating element 314 to heat the titanium bearing material and the sulphuric acid or oleum as it is mixed to the desired temperature prior to being fed into reactor 308 for the digestion and baking stages.
  • the feed of titanium bearing material into the reactors may contain residual moisture due to upstream processing.
  • the titanium bearing material stream will have been subjected to an upstream beneficiation processes, such as flotation, filtration, solid-liquid extraction, etc.
  • the titanium bearing material may include some entrained moisture.
  • the quantity of entrained moisture is insufficient to substantially dilute the sulphuric acid and thus unable to generate exothermic heat to raise the temperature of the mix to 220°C or above.
  • Example 1 A rutile and anatase concentrate was milled and mixed with concentrated sulphuric acid at a mass ratio of 1.5 acid to 1 ore. The resulting mixture was baked at 250°C for eight (8) hours to produce a sulphate cake. The cake was dissolved with 10% sulphuric acid to produce a solution of titanyl sulphate. This resulted in a total extraction of 98% of anatase, 92% of rutile and 92.0% of total Ti0 2 . The feed and dissolution residue assays are provided in table 1 .
  • a rutile and anatase concentrate was milled and mixed with concentrated sulphuric acid at a mass ratio of 1.5 acid to 1 ore.
  • the resulting mixture was baked at 250°C for four (4) hours to produce a sulphate cake.
  • the cake was dissolved with 10% sulphuric acid to produce a solution of titanyl sulphate. This resulted in a total extraction of 98% of anatase, 84% of rutile and 86.7% of total Ti0 2 .
  • the feed and dissolution residue assays are provided in table 2.
  • a rutile and anatase concentrate was milled and mixed with concentrated sulphuric acid at a mass ratio of 1.2 acid to 1 ore.
  • the resulting mixture was baked at 220°C for twelve (12) hours to produce a sulphate cake.
  • the cake was dissolved in water to produce a solution of titanyl sulphate. This resulted in a total extraction of 98% of anatase, 85% of rutile and 84.4% of total Ti0 2 .
  • the feed and dissolution residue assays are provided in table 3.
  • a rutile and anatase concentrate was milled and mixed with concentrated sulphuric acid at a mass ratio of 1.5 acid to 1 ore.
  • the resulting mixture was baked at 180°C for twelve (12) hours to produce a sulphate cake.
  • the cake was dissolved with 10% sulphuric acid to produce a solution of titanyl sulphate. This resulted in a total extraction of 38% of anatase, 18% of rutile and 30.7% of total Ti0 2 .
  • the feed and dissolution residue assays are provided in table 4.
  • a rutile and anatase concentrate was milled and mixed with concentrated sulphuric acid at a mass ratio of 1.0 acid to 1 ore.
  • the resulting mixture was baked at 250°C for eight (8) hours to produce a sulphate cake.
  • the cake was dissolved with 10% sulphuric acid to produce a solution of titanyl sulphate. This resulted in a total extraction of 93% of anatase, 74% of rutile and 74.3% of total Ti0 2 .
  • the feed and dissolution residue assays are provided in table 5.
  • this example demonstrates how reduction in acid relative to ore to merely stoichiometric proportions significantly affects both anatase and rutile dissolution and recovery.
  • a rutile and anatase concentrate was milled and mixed with concentrated sulphuric acid at a mass ratio of 1.0 acid to 1 ore.
  • the resulting mixture was baked at 220°C for twelve (12) hours to produce a sulphate cake.
  • the cake was dissolved with 10% sulphuric acid to produce a solution of titanyl sulphate. This resulted in a total extraction of 92%) of anatase, 70% of rutile and 72.0% of total Ti0 2 .
  • the feed and dissolution residue assays are provided in table 6.
  • Example 7 A rutile concentrate was milled and mixed with concentrated sulphuric acid at a mass ratio of 1 .5 acid to 1 ore. The resulting mixture was baked at 250°C for eight (8) hours to produce a sulphate cake. The cake was dissolved with 10% sulphuric acid to produce a solution of titanyl sulphate. This resulted in a total extraction of 73% of rutile and 70.9% of total Ti0 2 . The feed and dissolution residue assays are provided in table 8.
  • This example indicates lower recovery of rutile where anatase is not present than for the mixed ore of example 1.

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Abstract

Cette invention se rapporte à l'enrichissement de matériaux porteurs de titane ayant une constituant substantiel de structure anatase et/ou rutile et/ou pseudorutile. De tels matériaux comprennent des minerais d'anatase et des minéraux et d'autres sources d'anatase, ainsi que des mélanges ou des associations qui comprennent des sources classiques de titane et de dioxyde de titane telles que l'ilménite et les scories de titane. L'invention présente un intérêt particulier, mais pas exclusif, dans la transformation de matériaux d'anatase en dioxyde de titane de qualité pigment. Le procédé est, en outre, efficace pour la transformation de matériaux ayant un constituant substantiel d'anatase ou de rutile, par exemple de leucoxène.
PCT/AU2016/050012 2015-01-13 2016-01-13 Enrichissement de matériaux porteurs de titane Ceased WO2016112432A1 (fr)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
US10287176B2 (en) 2014-07-08 2019-05-14 Avertana Limited Extraction of products from titanium-bearing minerals
WO2022076564A1 (fr) * 2020-10-06 2022-04-14 The Mosaic Company Procédé de production de dioxyde de titane à partir de minerai anatase par digestion à l'acide sulfurique, suivie d'une lixiviation, d'une hydrolyse et d'une calcination
US12172905B2 (en) 2018-12-14 2024-12-24 Avertana Limited Methods of extraction of products from titanium-bearing materials

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CN116209779A (zh) 2020-05-26 2023-06-02 联邦科学和工业研究组织 回收二氧化钛的方法

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DE2855467A1 (de) * 1978-12-19 1980-09-18 Gock Eberhard Verfahren zur herstellung von synthetischem titandioxid ueber den direkten aufschluss von rutil mit schwefelsaeure
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WO1992008816A1 (fr) * 1990-11-20 1992-05-29 Curuá Mineração Ltda Production de blanc de titane a partir de concentres valorises du minerai d'anatase et a l'aide de la sulfatation par acide sulfurique
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BRPI0705592A2 (pt) * 2007-11-06 2009-07-07 Extramil Sa processo para obtenção de óxido de titánio de alta pureza por extração lìquido-lìquido a partir do minério de anatásio

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10287176B2 (en) 2014-07-08 2019-05-14 Avertana Limited Extraction of products from titanium-bearing minerals
US10294117B2 (en) 2014-07-08 2019-05-21 Avertana Limited Extraction of products from titanium-bearing minerals
US10407316B2 (en) 2014-07-08 2019-09-10 Avertana Limited Extraction of products from titanium-bearing minerals
US12172905B2 (en) 2018-12-14 2024-12-24 Avertana Limited Methods of extraction of products from titanium-bearing materials
WO2022076564A1 (fr) * 2020-10-06 2022-04-14 The Mosaic Company Procédé de production de dioxyde de titane à partir de minerai anatase par digestion à l'acide sulfurique, suivie d'une lixiviation, d'une hydrolyse et d'une calcination
US20230373809A1 (en) * 2020-10-06 2023-11-23 The Mosaic Company Process for the production of titanium dioxide from anatase ore through sulphuric acid digestion, followed by leaching, hydrolysis, and calcination
CN117396435A (zh) * 2020-10-06 2024-01-12 美盛公司 由锐钛矿矿石通过硫酸消化并随后浸析、水解和煅烧来生产二氧化钛的方法

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