EP0475953B1 - Production of acid soluble titania - Google Patents

Production of acid soluble titania Download PDF

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Publication number
EP0475953B1
EP0475953B1 EP90906758A EP90906758A EP0475953B1 EP 0475953 B1 EP0475953 B1 EP 0475953B1 EP 90906758 A EP90906758 A EP 90906758A EP 90906758 A EP90906758 A EP 90906758A EP 0475953 B1 EP0475953 B1 EP 0475953B1
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EP
European Patent Office
Prior art keywords
mineral
iron
process according
titania
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.)
Expired - Lifetime
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EP90906758A
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German (de)
English (en)
French (fr)
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EP0475953A4 (en
EP0475953A1 (en
Inventor
Michael John Wimmera Industrial Hollitt
Brian Anthony Chemistry Centre Of O'brien
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Wimmera Industrial Minerals Pty Ltd
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Wimmera Industrial Minerals Pty Ltd
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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

Definitions

  • the present invention relates to a process for the formation of acid digestible titania products.
  • the major application of titania bearing minerals is feed to processes for the formation of white titania pigments.
  • chloride and sulphate processing are two types of alternative pigment production operations, viz. chloride and sulphate processing.
  • sulphate method of pigment production for which specifications on mineral feed, both in composition and particle size distribution, are generally less stringent than for the chloride method.
  • a particular requirement of the sulphate process for pigment production is that the mineral feed should be substantially digestible in strong sulphuric acid.
  • ilmenite mineral FeO. TiO2
  • its weathered products with strictly limited degrees of alteration to rutile and ferric titanate.
  • synthetic sources of acid digestible titania are available in the form of slag products formed in the smelting of ilmenite. Slag products (75 - 85% TiO2) are considerably upgraded in comparison with acid digestible ilmenite (up to 58% TiO2) and are preferred where acid consumption or waste disposal are problems for sulphate pigment producers.
  • ilmenite feed has the disadvantage of low titania content while slag feed has the coupled disadvantages of requiring dangerous and unpredictable digestion conditions and providing incomplete titania recovery in digestion and subsequent dissolution.
  • ilmenites are suitable for pigment production via the sulphate process or upgrading to slag.
  • ilmenites with greater than about 0.15% Cr2O3 have not found direct or indirect application in sulphate pigment production, as chromium causes severe problems with pigment product colouration.
  • Ilmenites with relatively high iron contents (especially in excess of the composition "FeO. TiO2”) and with high gangue contents (eg. about 5% total contained alumina and silica) are unlikely to be suited for upgrading to a valuable slag product, and may also not compete economically with other feeds for the production of sulphate process pigments.
  • the present invention provides a process for producing acid soluble titania which process comprises the steps of:-
  • the titania product may contain greater than 90% TiO2 (on the basis of contained titanium), yet it will normally have higher solubility in sulphuric acid and exhibit higher recoveries of titania in sulphate process pigment than slag products, which typically only contain up to 85% TiO2.
  • the product properties will depend on the particular feed used.
  • the flowsheet illustrating a preferred embodiment of the invention is depicted diagrammatically in Figure 1.
  • the flowsheet consists of an (optional) grinding step followed by an optional mixing/agglomeration step, a thermal reduction and cooling step and an iron metal removal step.
  • Optional mineral separations step may follow iron removal.
  • a particular preferred step is agglomeration prior to the heating step.
  • agglomeration prior to the heating step.
  • the present invention allows for the use of mineral in fine grained form (typically 100% passing a 100 ⁇ m aperture screen but 95% coarser than 5 ⁇ m diameter).
  • the agglomerates are capable of being treated in the reduction systems of the present invention.
  • titaniferous minerals it will be necessary to grind the feed, using any suitable technique prior to the agglomeration step. Since the titania product derived from a mineral feed which is finer than 20 ⁇ m in diameter is not be easily separable from fine iron oxide products in subsequent processing steps the grinding step should seek to minimise the proportion of the mineral reporting to the minus 20 ⁇ m fraction.
  • the weight average particle size of the ground product would ideally lie between 50 ⁇ m and 100 ⁇ m.
  • the agglomeration step will typically include the addition of binder to a moistened (eg. 5 - 12% moisture) fine mineral feed in a suitable agglomerating device.
  • a moistened (eg. 5 - 12% moisture) fine mineral feed in a suitable agglomerating device.
  • Either low intensity disk or drum type or high intensity mixing type agglomerators are preferably used, although briquetting or any other suitable technique may be applied.
  • a range of suitable agglomeration techniques has been described in International Patent Application No. PCT/AU89/00314. There are few limitations on agglomerate size, although advantageously only a few percent of the agglomerated product should pass a screen with 50 ⁇ m aperture and agglomerates of less than 4mm particle size will be more readily treated in subsequent steps of the present invention. A narrow particle size distribution is not required.
  • additives may be incorporated in either the agglomeration or grinding steps. Even distribution of additives within the agglomerates is advantageous.
  • Additives may be included in powdered or slurry form or in solution with the moisture input to the agglomeration step.
  • additives may include compounds of magnesium, as disclosed in prior art.
  • compounds of manganese may be used to achieve special advantages under some circumstances.
  • any suitable organic or inorganic binder may be used in the agglomeration step.
  • inorganic binder eg. sodium silicate, bentonite and other clay minerals, magnesium salts, lime, soda, etc
  • organic binder eg. lignosulphonate, PVA, molasses etc.
  • Binders which hydrolyse in-situ eg. tetraethyl orthosilicate, aluminium sulphate/urea mixtures
  • Binder additions in the range 0.5 - 5.0% on a water free basis have been found to be suitable. In the case of inorganic binders it is beneficial to limit binder addition to less than 1% on a water free basis.
  • agglomerates having an open st2ructure and little closed porosity.
  • the surface which is available for reduction and for inward diffusion of additives will only be slightly lower than that of the mineral prior to agglomeration.
  • the formation of densely packed agglomerates which shrink and sinter significantly upon heating is consequently to be avoided.
  • the desired open structure is more readily achievable where the mineral to be agglomerated contains only small quantities of material of smaller particle diameter than 20 ⁇ m and where the average size of agglomerates is less than 1mm (although larger particle size can be used).
  • Additional steps may be incorporated between grinding and agglomeration, for example where grinding has resulted in the liberation of gangue or impurity bearing grains.
  • a separation step of any type but especially including separations based on particle size and density, magnetic or electrostatic response or on surface properties, or on any combination of these properties, may be included. If necessary the liberated and upgraded mineral may then be dried prior to agglomeration, using any suitable drying device.
  • While reduction may be carried out in any suitable device, eg. packed bed, fluidised bed or circulating fluidised bed reactors, the most suitable device for continuous, long residence time (greater than 30 minutes), high temperature reduction with metallisation is an inclined rotary kiln, using coal or coke as fuel and reductant.
  • Rotary kilns for iron ore reduction and ilmenite metallisation in the production of synthetic rutile have been in operation for almost two decades and their operation is well documented.
  • Kiln operation according to the present invention is similar to that for synthetic rutile production.
  • Additives may also be incorporated in order to assist in removal of impurity grains in operations subsequent to reduction.
  • chromite metallisation is encouraged by addition of manganese into agglomerates, enhancing chromium removal from the acid soluble titania product by magnetic separation after aqueous aeration in which the magnetic ferrochrome alloy remains passive. Separations based on chromite metallisation are the subject of International Patent Application No. PCT/AU89/00461.
  • the char may be separated from the minerals by a combination of sizing and magnetic separation. Where the mineral has been agglomerated prior to reduction the reduced agglomerates may be crushed to liberate gangue which has not been metallised, allowing upgrading by magnetic separation.
  • An important aspect of the present invention is an improvement to prior art processes for removal of metallic iron from reduced mineral.
  • Prior art methods of aqueous aeration for metallic iron removal have been applied to removal of iron only from non acid soluble titania matrices. It has been found that the prior art methods are not always effective in the removal of metallic iron from acid soluble matrices without in-situ precipitation of contaminating iron oxides within titania grains. Difficulties are especially observed where the desired iron oxide product for subsequent separation purposes is a granular magnetite.
  • the improvement resides in the definition of the necessary conditions for the effective removal of iron metal from an acid soluble titania matrix with control of the nature of the separable iron oxide product.
  • it is the definition of specific reagents which are effective in assisting iron removal by aqueous aeration which is the basis of the improvement.
  • aqueous aeration involves the agitated suspension of metallised acid soluble titania in a solution of reagents formulated in a particular manner into which finely divided air bubbles are introduced.
  • aqueous aeration is conducted in the temperature range 60 - 80°C and will continue for from 8 to 24 hours.
  • the improvement comprises adding reagents to the aeration step which form complexes with iron in order to stabilise iron in aqueous solution and also have the effect of locally buffering pH in such a manner that iron oxides form only at higher oxidation potentials, i.e. at sites away from metal bearing grains.
  • the reagents should also ideally act to stabilise a particular iron oxide (eg. magnetite, haematite, lepidocrocite or goethite). Further, despite prior art references to the use of alkali salts it has been found that such additions are to be avoided, as they interact with the iron oxide product in such a manner as to encourage in-situ iron oxide formation.
  • aqueous systems which provide for chelation or complexing of iron i.e. sequestering agents for iron, and therefore have the effect of stabilising iron temporarily in aqueous solution in pores in and around the titanate grains are highly effective as aeration systems.
  • the stability of iron in solution must not be such as to prevent its precipitation as iron oxide under the strongly oxidising conditions which exist in the general aeration liquor. Strong stabilisation of iron in solution will result in consumption of complexing reagents and sharp increase in pH. As a consequence further transport of iron out of titanate grains will be retarded and in-situ iron oxide precipitation may result.
  • citric acid is a particularly preferred additive for assisting aeration of reduced titania minerals, especially where the titania matrix is acid soluble.
  • Useful additions have been made in the range 0.06 to 1.0% by weight to aerating solutions.
  • Citric acid may be added by itself or in adjunct to other previously disclosed aeration chemicals, such as ammonium chloride.
  • the addition of chloride irons by way of ferric chloride even at high levels (eg. 5% ferric chloride addition) has been found to be effective. Many other complexing systems are similarly expected to be effective in a manner not previously foreseen.
  • Agglomerate disintegration during aeration allows removal of the thus liberated gangue or impurity bearing grains by any suitable means after aeration.
  • Iron oxides are first removed from the predominantly titaniferous granular product of aeration by wet cycloning, gravity based separation, wet screening or any other effective means.
  • Subsequent separation of non titaniferous grains eg. by flotation, magnetic separation, electrostatic separation or gravity based separation
  • Such an upgrading step is particularly useful for impurity grains whose properties are similar to the process feed properties prior to the disclosed treatments but where a property difference exists between product grains (eg. where the feed is contaminated by chromite).
  • a particular feature of the acid soluble titania product formed according to the disclosed procedures is that a small amount of metallic iron, at 0.1 - 2% by weight of the product, remains in a form which is totally inaccessible to aeration or acid leaching. It has been found that this residual iron metal typically is distributed in metal particles of diameter less than 3 ⁇ m which are totally encapsulated by dense acid soluble titania. This residual iron metal allows an effective magnetic separation of the product from non magnetic contaminants, eg. quartz and silicate gangue, while not interfering with the removal of highly magnetic material at lower magnetic field strengths and field strength gradients.
  • non magnetic contaminants eg. quartz and silicate gangue
  • titaniferous product washing with dilute acid for example 5 - 20% sulphuric acid
  • dilute acid for example 5 - 20% sulphuric acid
  • chromite grains remaining in the titaniferous products of the processes described herein may not be apprecially soluble in acid digestion of the contained titania.
  • the chromite grains are rendered inert to acid digestion during thermal reduction in the presence of ilmenite. This disclosure has important implications for the usefulness of the product in the sulphate process for pigment manufacture.

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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)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Compounds Of Iron (AREA)
  • Glass Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
EP90906758A 1989-05-11 1990-05-10 Production of acid soluble titania Expired - Lifetime EP0475953B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AUPJ412289 1989-05-11
AU4122/89 1989-05-11
PCT/AU1990/000190 WO1990013614A1 (en) 1989-05-11 1990-05-10 Production of acid soluble titania

Publications (3)

Publication Number Publication Date
EP0475953A1 EP0475953A1 (en) 1992-03-25
EP0475953A4 EP0475953A4 (en) 1992-12-02
EP0475953B1 true EP0475953B1 (en) 1994-08-31

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EP90906758A Expired - Lifetime EP0475953B1 (en) 1989-05-11 1990-05-10 Production of acid soluble titania

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EP (1) EP0475953B1 (da)
AT (1) ATE110698T1 (da)
AU (1) AU626682B2 (da)
BR (1) BR9007364A (da)
CA (1) CA2055428C (da)
DE (1) DE69012117T2 (da)
DK (1) DK0475953T3 (da)
ES (1) ES2061032T3 (da)
WO (1) WO1990013614A1 (da)
ZA (1) ZA903563B (da)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7611588B2 (en) 2004-11-30 2009-11-03 Ecolab Inc. Methods and compositions for removing metal oxides

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI104965B (fi) * 1997-04-03 2000-05-15 Kemira Pigments Oy Menetelmä titaanidioksidin valmistamiseksi

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU416432B1 (en) * 1966-04-29 1971-08-20 WESTERN TITANIUN M. L. and COMMONWEALTH SCIENTIFIC AND INDUSTRIAL RESEARCH ORGANIZATION Production of anosovite from titaniferous minerals

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7611588B2 (en) 2004-11-30 2009-11-03 Ecolab Inc. Methods and compositions for removing metal oxides

Also Published As

Publication number Publication date
EP0475953A4 (en) 1992-12-02
AU5644890A (en) 1990-11-29
ES2061032T3 (es) 1994-12-01
DE69012117T2 (de) 1995-05-18
DK0475953T3 (da) 1995-01-09
DE69012117D1 (de) 1994-10-06
CA2055428C (en) 2001-01-23
ATE110698T1 (de) 1994-09-15
ZA903563B (en) 1991-02-27
CA2055428A1 (en) 1990-11-12
AU626682B2 (en) 1992-08-06
BR9007364A (pt) 1992-05-12
WO1990013614A1 (en) 1990-11-15
EP0475953A1 (en) 1992-03-25

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