WO2021002332A1 - Method for producing titanium concentrate - Google Patents
Method for producing titanium concentrate Download PDFInfo
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- WO2021002332A1 WO2021002332A1 PCT/JP2020/025551 JP2020025551W WO2021002332A1 WO 2021002332 A1 WO2021002332 A1 WO 2021002332A1 JP 2020025551 W JP2020025551 W JP 2020025551W WO 2021002332 A1 WO2021002332 A1 WO 2021002332A1
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- 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
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
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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
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- 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
- the present invention relates to a method for producing a high-quality titanium concentrate by removing impurities such as iron and silica from ilmenite-containing iron ore or its analogs.
- Titanium tetrachloride is usually produced by chlorinating a titanium concentrate with chlorine gas by the fluidization method (that is, fluid chlorination), so that it is high-grade, does not contain fine powder, and is easily chlorinated by the fluidization method. A concentrate was needed. This is because if the titanium concentrate contains a large amount of fine powder, the fine powder is scattered outside the fluidized chlorination furnace, so that the yield of titanium tetrachloride is low.
- the fluid chlorination is a method of causing the reaction while maintaining the titanium raw material and the carbonaceous reducing agent in a uniform fluidized state, that is, a suspended dispersion state by using a chlorinated gas.
- a titanium concentrate a high-grade titanium concentrate obtained by removing iron from natural rutile or titanium-containing iron ore such as ilmenite or ilmenite hematite ore has been used.
- These titanium concentrates for example, reduce titanium-containing iron ore or the like to convert iron into ferrous iron, and in the presence of a seed for promoting titanium salt hydrolysis or a titanium (III) salt, the first is ferrous acid. It is known that iron can be leached and then fired to produce it (Patent Documents 1 and 2).
- Patent Documents 3, 4, 5 and 6 have been proposed as a method for producing a high-grade titanium concentrate using titanium-containing iron ore having a low degree of metamorphism produced from a massive deposit.
- ilmenite produced from a massive deposit is pulverized so that 80% by mass or more thereof passes through a sieve of 200 mesh (opening 75 ⁇ m), and then leachate with mineral acid to remove iron, and TiO 2
- Described is a method of obtaining a powdered titanium concentrate having a quality (that is, TiO 2 content) of 90% by mass or more and granulating it into a size of substantially 10 to 150 mesh (opening 1.70 mm to 100 ⁇ m). Has been done.
- titania slag containing at least one selected from the group consisting of iron oxide, manganese oxide, chromium oxide, vanadium oxide, aluminum oxide, silicon oxide and alkaline earth metal oxide is sized to 75 to 850 ⁇ m.
- Patent Document 5 describes a method for producing pigment-grade titanium oxide by a hydrometallurgical method including a production step of leaching high magnesium ilmenite ore with concentrated hydrochloric acid in two steps.
- Patent Document 6 describes a solid substance obtained by leaching low-grade titanium ore with 35 to 40% hydrochloric acid at a reaction temperature of 60 to 70 ° C. again with 35 to 40% hydrochloric acid at 75 to 80 ° C. A method for producing high-quality synthetic rutile by leaching at the reaction temperature of is described.
- Patent Documents 5 and 6 are both manufacturing methods including a two-step leaching step using concentrated hydrochloric acid, there are problems in terms of safety, durability of the reaction vessel, etc., and the manufacturing method is industrially advantageous. I can't say.
- the present inventor crushes ilmenite-containing iron ore or the like more finely than before, and then at a reaction temperature of 80 ° C. or lower at an initial concentration of hydrochloric acid of 1 to 20% by mass. After pre-leaching, if the main leaching is performed at a reaction temperature of 90 ° C. or higher at an initial concentration of 15 to 20% by mass of hydrochloric acid in the presence of a soluble reducing substance, impurities such as iron and silica can be removed by a simple method. The present invention was completed with the finding that a high-quality titanium concentrate could be obtained.
- the titanium concentrate can be given a particle size and hardness suitable for fluid chlorination, and fine powder of the titanium concentrate can be obtained. Based on the finding that fluid chlorination can be efficiently performed without adversely affecting the production equipment because the content can be prevented and the fine powder can be prevented from being scattered outside the furnace, the present invention was developed. completed.
- a pulverized product obtained by pulverizing a titanium-containing iron ore or a similar product to a particle size passing through a 330 mesh sieve is preliminarily leached at a reaction temperature of 80 ° C. or lower at an initial concentration of 1 to 20% by mass of hydrochloric acid.
- a method for producing a titanium concentrate which comprises performing the main leaching at a reaction temperature of 90 ° C. or higher at an initial concentration of hydrochloric acid of 15 to 20% by mass in the presence of a soluble reducing substance.
- [2] The method for producing a titanium concentrate according to [1], wherein preliminary leaching is performed at an initial concentration of hydrochloric acid of 1 to 15% by mass.
- [3] The method for producing a titanium concentrate according to [1] or [2], which comprises washing and drying the leached product obtained by solid-liquid separation after performing the main leaching.
- [4] The method for producing a titanium concentrate according to [3], wherein the drying is granulation drying.
- [5] The method for producing a titanium concentrate according to [3] or [4], which comprises calcining the dried product obtained by drying at a temperature of 600 to 1000 ° C.
- [6] The method for producing a titanium concentrate according to any one of [1] to [5], wherein the main leaching is performed at a temperature equal to or lower than the boiling point of the leachate.
- [9] The method for producing a titanium concentrate according to any one of [1] to [8], wherein a step of adding a fluorine-based additive is performed after the main leaching is performed.
- the method for producing a titanium concentrate of the present invention even when a titanium-containing iron ore containing a large amount of impurities such as iron and silica and having a low degree of alteration is used as a starting material, it is simple and safe, and a reaction vessel is used. Since it is an industrially advantageous method with less load on the iron, it is possible to efficiently produce a high-quality titanium concentrate. Further, by simultaneously granulating and drying the titanium concentrate, the titanium concentrate can have an appropriate particle size and hardness, and the inclusion of fine powder in the titanium concentrate can be avoided, and the fine powder can be fluidized in a chlorination furnace. It is possible to prevent it from scattering to the outside, and it is possible to obtain titanium tetrachloride in a high yield.
- the titanium-containing iron ore or its analogs applicable to the production method of the present invention are ilmenite, ilmenite variants, for example, titanium-containing iron ore such as ilmenite and hematite, pretreated ores, or these. It is a similar product having the same composition and properties as. It can be applied to both ilmenite-containing iron ore with a high degree of metamorphism and ilmenite containing a low degree of denaturation, and is also suitably applied to ilmenite-containing iron ore with a low degree of denaturation containing a large amount of impurities such as silica or similar substances. it can.
- titanium slag which is a by-product in iron smelting.
- the particle size of these ilmenite-containing iron ores or their analogs is usually 50 to 500 ⁇ m, and those larger than this can be used after being appropriately pulverized.
- Al, Ca, Co, Cr, Cu, Ga, Ge, Mg, Mn, Mo, Nb, Ni, Pd, Ru , Sn, Ta, V, W and Zr may contain impurities consisting of oxides of at least one element selected from the group.
- the content of silica in ilmenite iron ore or its analogs is usually 0.5 to 35% by mass in terms of SiO 2 .
- ilmenite-containing iron ore or an analog thereof is pulverized to a particle size capable of passing through a sieve of 330 mesh (opening 45 ⁇ m) and used.
- the pulverization may be dry pulverization or wet pulverization in which pulverization is performed in a solvent, and commonly used pulverizing means such as ball mill, tube mill, vibrating ball mill, sand mill, disc mill, media mill, medialess mill, roller. This can be done using a mill or the like.
- the pulverization is preferably performed by dry pulverization and then wet pulverization. When wet pulverization is performed, the solvent and the pulverized product are separated into solid and liquid after pulverization.
- Solid-liquid separation can be performed by decantation, sedimentation separation, centrifugation, filtration, membrane separation, etc., but it is preferable to perform decantation. If the obtained pulverized product is not pulverized, or if the pulverized product is insufficiently pulverized to a predetermined particle size, impurities such as silica in the titanium concentrate cannot be sufficiently removed, resulting in high TiO 2 High-quality titanium concentrate cannot be obtained. In addition, there is a drawback that the pre-leaching and main leaching steps are not efficiently performed.
- the particle size is such that it can pass through a sieve with an opening of 20 ⁇ m). It is preferable to perform sizing after pulverization, and the ultrafine powder can be removed by utilizing the difference in the sedimentation rate of the particles.
- the obtained pulverized product was preliminarily leached at a reaction temperature of 80 ° C. or lower at an initial concentration of 1 to 20% by mass of hydrochloric acid, and then at an initial concentration of 15 to 20% by mass of hydrochloric acid in the presence of a soluble reducing substance.
- Main leaching is performed at a reaction temperature of 90 ° C. or higher to remove impurities such as iron and silica.
- the hydrochloric acid used is represented by the initial concentration, which is the hydrochloric acid concentration at the start of leaching. In the preliminary leaching, it is desirable that the initial concentration of hydrochloric acid is 1 to 15% by mass in order to remove the silica content more efficiently.
- the leaching container for pre-leaching and the leaching container for main leaching use a leaching container made of a material that is not corroded by hydrochloric acid. May be good.
- the preliminary leaching may be performed a plurality of times, or the main leaching may be performed a plurality of times.
- the amount (V) of hydrochloric acid used in the preliminary leaching is preferably 1.5 to 20 V / W with respect to the mass (W) of the pulverized product, more preferably 5 to 15, and 7 to 12 Is more preferable. Further, the preliminary leaching is preferably performed at a temperature of 80 ° C. or lower, more preferably 60 ° C. or lower. The time can be set as appropriate, and it is preferably performed for 1 to 15 hours. Further, when the preliminary leaching is performed in the presence of a fluorine-based additive, the silica component can be dissolved, which is efficient. As the fluorine-based additive, sodium fluoride, potassium fluoride, calcium fluoride, hydrofluoric acid and the like can be used.
- the amount of the fluorine-based additive added can be appropriately set.
- a soluble reducing substance described later may be present in order to increase the elution rate and the elution amount of iron.
- the leached product after the preliminary leaching may be directly subjected to the next main leaching step, and the main leaching can be continuously performed by adding hydrochloric acid and a soluble reducing substance to the container after the preliminary leaching.
- the pre-leaching exudate is solid-liquid separated by decantation, sedimentation, centrifugation, filtration, membrane separation, etc., concentrated in the form of a wet cake or slurry, and then subjected to the next main leaching step. May be served. Further, the leachate may be solid-liquid separated and then washed with water to desalt the coexisting ions remaining in the leachate. In this case, the leaching material is separated in the form of a wet cake and subjected to the next main leaching step.
- the amount (V) of hydrochloric acid used in the main leaching is preferably 1 to 10 in V / W with respect to the mass (W) of the leachate after the preliminary leaching, and more preferably 2 to 8.
- the main leaching is carried out at a reaction temperature of 90 ° C. or higher, but it is preferably carried out at a temperature equal to or lower than the boiling point of the leachate, and the time can be appropriately set, and is preferably carried out for 2 to 20 hours.
- an open leaching container it is preferable to perform leaching at 90 to 110 ° C. (below the boiling point) for 5 to 20 hours, and when using a closed leaching container, the temperature and time are adjusted depending on the pressurizing conditions. It can be set as appropriate, and leaching is preferably performed at 110 to 160 ° C. for 2 to 18 hours.
- a soluble reducing substance also referred to as “soluble reducing substance” in the present application
- soluble reducing substance in the present application
- Soluble reducing substances include metallic iron and / or soluble titanium salts.
- Metallic iron dissolves into iron ions when placed in a leachate.
- the soluble titanium salt include titanium (III) salt and titanium (IV) salt, and titanium (III) salt is preferable.
- titanium (III) salt As a method for allowing the titanium (III) salt to exist in the system, in addition to the method of adding a titanium (III) salt solution, metal iron powder or the like is added to the leachate to add titanium (IV) salt in the system to titanium (IV).
- metal iron powder or the like is added to the leachate to add titanium (IV) salt in the system to titanium (IV).
- the amount of the soluble titanium salt added can be appropriately set, and is preferably 0.8 to 1.5 times the amount of reducing trivalent iron to divalent (reduction equivalent), and 0.9 to 1 . Double the amount is more preferred.
- a seed for promoting titanium salt hydrolysis may be used in combination.
- This is a seed crystal used when a titanium salt solution is hydrolyzed to precipitate a titanium content in a method for producing a titanium dioxide pigment by a general sulfuric acid method, and this is an acidity of a titanium salt such as titanyl sulfuric acid.
- the solution is neutralized and the precipitated colloidal titanium compound is aged.
- the amount of titanium added in the titanium salt hydrolysis promoting seed to the leached product after the preliminary leaching should be about 0.05 to 2% by mass as TiO 2. Is preferable, and usually 0.1 to 1% by mass is more preferable.
- a fluorine-based additive When a fluorine-based additive is added to the leaching solution after the main leaching, or to a slurry of the leaching solution that has been solid-liquid separated by decantation, sedimentation separation, centrifugation, filtration, membrane separation, etc. It is preferable because it can remove the silica content.
- This step is called de-silica treatment, and as the fluorine-based additive, the above-mentioned sodium fluoride, potassium fluoride, calcium fluoride, hydrofluoric acid and the like can be used.
- the amount of the fluorine-based additive added can be appropriately set.
- the temperature of the desilicaization treatment is preferably a temperature equal to or lower than the boiling point of the leachate, more preferably a temperature of 20 to 90 ° C.
- the time for the desilicaization treatment can be appropriately set, and is preferably 0.5 to 10 hours.
- the leachate (that is, titanium concentrate) from which impurities such as iron and silica have been removed by pre-leaching, main leaching, and desilicaization is solidified by decantation, sedimentation, centrifugation, filtration, membrane separation, etc. Liquid separation. After that, it is preferable to wash and desalinate the coexisting ions remaining in the leachate.
- the desalting treatment is preferably washed until the electric conductivity becomes 0.1 S / m or less.
- the leachate can then be usually dried to form a powder. The drying temperature can be set as appropriate. Further, after drying, it may be crushed and granulated as needed.
- the titanium concentrate produced as described above has an extremely high TiO 2 grade, preferably 95% by mass or more.
- a normal granulation dryer can be used, and a fluidized bed granulation dryer and spray drying are more preferable.
- a spray dryer it is preferable to make the wet cake into a slurry, wet-pulverize it if necessary, and then spray-dry it.
- the titanium concentrate can be sized to a particle size of 30 to 300 ⁇ m by granulation drying, and can have an appropriate hardness.
- a titanium concentrate of the present invention after pre-leaching and main leaching, and further cleaning of the leachate obtained by solid-liquid separation after the main leaching (preferably, the leachate after desilicing treatment). Drying, especially granulation drying, can produce a titanium concentrate containing titanium oxide with a rutile structure.
- a titanium concentrate containing only titanium oxide having a rutile-type structure can be produced by drying without firing at a high temperature. Titanium oxide having a rutile-type structure has good reactivity with chlorine gas, so that chlorination is efficiently performed.
- the resulting titanium concentrate containing titanium oxide having a rutile structure can be calcined at a temperature of 600 to 1000 ° C. to increase hardness and purity, if necessary.
- the main composition of the raw material ilmenite ore used is shown in Table 1, and the particle size distribution is shown in FIG.
- the total TiO 2 in each table is a value obtained by expressing the Ti content in the composition in terms of TiO 2 .
- the composition was analyzed by volumetric analysis (Ti and Fe) and ICP emission spectroscopy.
- the particle size distribution was measured with a laser diffraction / scattering type particle size distribution measuring device LA-950 (manufactured by HORIBA, Ltd.).
- Example 1 It was confirmed that the ilmenite ore was crushed by a ball mill and passed through a 330 mesh (44 ⁇ m) sieve. The particle size distribution of this pulverized product is shown in FIG.
- titanium concentrate Two types of titanium concentrates were obtained by exchanging the nozzles of the spray dryer, a granular dried product having an average particle size of 40 ⁇ m and a granular dried product having an average particle size of 200 ⁇ m.
- the main component compositions of the obtained titanium concentrate are shown in Table 2.
- the total amount of total TiO 2 was titanium oxide having a rutile structure, and did not contain anatas-type structure titanium oxide or amorphous titanium oxide.
- the total Fe in the table represents the total amount of the analyzed FeO and Fe 2 O 3 in terms of Fe.
- Fe (0) metallic iron
- TiO 2 was titanium oxide having a rutile structure, and did not contain titanium oxide having an anatas-type structure or amorphous titanium oxide.
- the total Fe in the table represents the total amount of the analyzed FeO and Fe 2 O 3 in terms of Fe.
- the method for producing a titanium concentrate of the present invention is a simple method and efficiently even when a titanium-containing iron ore having a low degree of alteration containing a large amount of impurities such as iron and silica is used as a starting material. It is an industrially useful technique such as being able to produce a high-quality titanium concentrate and obtaining titanium tetrachloride in a high yield.
Abstract
Provided is a method for removing iron, silica, and other impurities from a titanium-containing iron ore or an analogue thereof by an industrially advantageous method to produce a high-quality titanium concentrate. In the present invention, a ground product obtained by grinding a titanium-containing iron ore or an analogue thereof to a particle diameter that passes through a 330 mesh sieve is subjected to a preliminary leaching at a reaction temperature of 80°C or below at a hydrochloric acid initial concentration of 1-20% by mass, and then subjected to a main leaching at a reaction temperature of 90°C or above at a hydrochloric acid initial concentration of 15-20% by mass in the presence of a soluble reducing substance. After the main leaching, the leachate obtained by solid-liquid separation is then washed and granulated/dried to produce a titanium concentrate including titanium oxide having a rutile structure.
Description
本発明は、含チタン鉄鉱石又はその類似物から鉄分とシリカ分等の不純物を除去して、高品位なチタン濃縮物を製造する方法に関する。
The present invention relates to a method for producing a high-quality titanium concentrate by removing impurities such as iron and silica from ilmenite-containing iron ore or its analogs.
チタン濃縮物は、塩素法による二酸化チタン顔料の製造及び金属チタンの製造等に用いられる四塩化チタンの製造用原料として用いられる。四塩化チタンは、通常、チタン濃縮物を流動化法によって塩素ガスで塩素化（すなわち、流動塩素化）して製造されるため、高品位で微粉を含まず、流動化法において塩素化し易いチタン濃縮物が必要であった。何故なら、チタン濃縮物が多くの微粉を含んでいると、微粉が流動塩素化炉外に飛散するため、四塩化チタンの収率が低くなるからである。また、チタン濃縮物が鉄分等の不純物を多く含んでいると流動塩素化の際に塩化鉄等が製造するため塩素ガスの利用効率が悪くなるからである。
ここで、流動塩素化とは、塩素化ガスによってチタン分原料と炭素質還元剤とを均一な流動化状態つまり浮遊分散状態に保持しながら反応を行わせる方法のことである。 The titanium concentrate is used as a raw material for producing titanium tetrachloride used in the production of titanium dioxide pigments and the production of metallic titanium by the chlorine method. Titanium tetrachloride is usually produced by chlorinating a titanium concentrate with chlorine gas by the fluidization method (that is, fluid chlorination), so that it is high-grade, does not contain fine powder, and is easily chlorinated by the fluidization method. A concentrate was needed. This is because if the titanium concentrate contains a large amount of fine powder, the fine powder is scattered outside the fluidized chlorination furnace, so that the yield of titanium tetrachloride is low. Further, if the titanium concentrate contains a large amount of impurities such as iron, iron chloride or the like is produced at the time of fluid chlorination, so that the utilization efficiency of chlorine gas deteriorates.
Here, the fluid chlorination is a method of causing the reaction while maintaining the titanium raw material and the carbonaceous reducing agent in a uniform fluidized state, that is, a suspended dispersion state by using a chlorinated gas.
ここで、流動塩素化とは、塩素化ガスによってチタン分原料と炭素質還元剤とを均一な流動化状態つまり浮遊分散状態に保持しながら反応を行わせる方法のことである。 The titanium concentrate is used as a raw material for producing titanium tetrachloride used in the production of titanium dioxide pigments and the production of metallic titanium by the chlorine method. Titanium tetrachloride is usually produced by chlorinating a titanium concentrate with chlorine gas by the fluidization method (that is, fluid chlorination), so that it is high-grade, does not contain fine powder, and is easily chlorinated by the fluidization method. A concentrate was needed. This is because if the titanium concentrate contains a large amount of fine powder, the fine powder is scattered outside the fluidized chlorination furnace, so that the yield of titanium tetrachloride is low. Further, if the titanium concentrate contains a large amount of impurities such as iron, iron chloride or the like is produced at the time of fluid chlorination, so that the utilization efficiency of chlorine gas deteriorates.
Here, the fluid chlorination is a method of causing the reaction while maintaining the titanium raw material and the carbonaceous reducing agent in a uniform fluidized state, that is, a suspended dispersion state by using a chlorinated gas.
このようなチタン濃縮物としては、天然ルチル又はイルメナイトやイルメナイト・へマタイト鉱等の含チタン鉄鉱石等から鉄分を除去した高品位なチタン濃縮物が使用されてきた。これらのチタン濃縮物は、例えば、含チタン鉄鉱石等を還元して鉄分を第一鉄の状態とし、チタン塩加水分解促進用シードやチタン（ＩＩＩ）塩の存在下で、硫酸にて第一鉄を浸出後、焼成して製造できることが知られている（特許文献１及び特許文献２）。これらの方法は、含チタン鉄鉱石等が採掘される以前に受けた圧力及び温度によって決まる変成作用の程度（すなわち、変成度）が高い場合はチタン分が簡単に濃縮され易いため、当該含チタン鉄鉱石等を原料として用いることができるが、シリカを始めとする不純物を多量に含有している塊状鉱床から産出されるような変成度の低い含チタン鉄鉱石等を原料として用いた場合には、特許文献１及び２の方法では高品位なチタン濃縮物が製造できなかった。
As such a titanium concentrate, a high-grade titanium concentrate obtained by removing iron from natural rutile or titanium-containing iron ore such as ilmenite or ilmenite hematite ore has been used. These titanium concentrates, for example, reduce titanium-containing iron ore or the like to convert iron into ferrous iron, and in the presence of a seed for promoting titanium salt hydrolysis or a titanium (III) salt, the first is ferrous acid. It is known that iron can be leached and then fired to produce it (Patent Documents 1 and 2). In these methods, when the degree of transformation (that is, the degree of transformation) determined by the pressure and temperature received before the ilmenite iron ore is mined is high, the titanium content is easily concentrated, so that the titanium-containing iron ore is easily concentrated. Iron ore or the like can be used as a raw material, but when titanium-containing iron ore or the like having a low degree of alteration such as that produced from a massive deposit containing a large amount of impurities such as silica is used as a raw material, , Patent Documents 1 and 2 could not produce a high-quality titanium concentrate.
そこで、塊状鉱床から産出される変成度の低い含チタン鉄鉱石等を用いて、高品位なチタン濃縮物を製造する方法として特許文献３、４、５及び６が提案されている。特許文献３には塊状鉱床から産出するイルメナイトをその８０質量％以上が２００メッシュ（目開き７５μｍ）の篩を通過するように粉砕した後、鉱酸で浸出処理して鉄分を除去し、ＴｉＯ２品位（すなわち、ＴｉＯ２含有量）９０質量％以上の粉状チタン濃縮物を得、これを実質的に１０～１５０メッシュ（目開き１．７０ｍｍ～１００μｍ）の大きさに造粒する方法が記載されている。
Therefore, Patent Documents 3, 4, 5 and 6 have been proposed as a method for producing a high-grade titanium concentrate using titanium-containing iron ore having a low degree of metamorphism produced from a massive deposit. According to Patent Document 3, ilmenite produced from a massive deposit is pulverized so that 80% by mass or more thereof passes through a sieve of 200 mesh (opening 75 μm), and then leachate with mineral acid to remove iron, and TiO 2 Described is a method of obtaining a powdered titanium concentrate having a quality (that is, TiO 2 content) of 90% by mass or more and granulating it into a size of substantially 10 to 150 mesh (opening 1.70 mm to 100 μm). Has been done.
特許文献４には酸化鉄、酸化マンガン、酸化クロム、酸化バナジウム、酸化アルミニウム、酸化ケイ素及びアルカリ土類金属酸化物からなる群から選択される少なくとも一種を含むチタニアスラグを７５～８５０μｍに整粒し、酸化、還元、塩酸浸出、洗浄、焼成の各工程を経て、高品位なチタン濃縮物を製造する方法が記載されている。
In Patent Document 4, titania slag containing at least one selected from the group consisting of iron oxide, manganese oxide, chromium oxide, vanadium oxide, aluminum oxide, silicon oxide and alkaline earth metal oxide is sized to 75 to 850 μm. , A method for producing a high-quality titanium concentrate through each step of oxidation, reduction, hydrochloric acid leaching, washing, and firing is described.
特許文献５には、高マグネシウムイルメナイト鉱石を濃塩酸で２段階浸出する製造工程を含む湿式冶金法によって、顔料級酸化チタンを製造する方法が記載されている。
Patent Document 5 describes a method for producing pigment-grade titanium oxide by a hydrometallurgical method including a production step of leaching high magnesium ilmenite ore with concentrated hydrochloric acid in two steps.
特許文献６には、低品位のチタン鉱石を３５～４０％の塩酸で６０～７０℃の反応温度にて浸出して得られた固形物を、再度３５～４０％の塩酸で７５～８０℃の反応温度にて浸出することにより、高品位な合成ルチルを製造する方法が記載されている。
Patent Document 6 describes a solid substance obtained by leaching low-grade titanium ore with 35 to 40% hydrochloric acid at a reaction temperature of 60 to 70 ° C. again with 35 to 40% hydrochloric acid at 75 to 80 ° C. A method for producing high-quality synthetic rutile by leaching at the reaction temperature of is described.
前記の特許文献３に記載の方法では、造粒による、チタン濃縮物の流動塩素化炉外への飛散は防止されているが、チタン濃縮物にはシリカ分が多く残留しているため、流動塩素化時にシリカ分が微細な反応残渣として塩素化炉外にキャリーオーバーされ、配管に付着することから、その除去のために頻繁な清掃を要するという問題がある。
一方、特許文献４に記載の方法では、７５～８５０μｍのチタニアスラグを出発原料とすることによって、チタン濃縮物の微粉化を防止し、酸化、還元、塩酸浸出、洗浄、焼成の各工程を経て、シリカ分等の不純物を除去しているが、工程が非常に長く煩雑であるという問題がある。このようなことから、簡便な方法で、流動塩素化時に生産設備に悪影響を与えない高品位なチタン濃縮物を製造する方法が課題となっている。
前記特許文献５及び６に記載の方法は、共に濃塩酸を使用した２段階浸出工程を含む製法であるため、安全面、反応容器の耐久性等に課題があり、工業的に有利な製法とはいえない。 In the method described in Patent Document 3 above, scattering of the titanium concentrate to the outside of the fluidized chlorination furnace due to granulation is prevented, but since a large amount of silica remains in the titanium concentrate, it flows. During chlorination, silica is carried over to the outside of the chlorination furnace as a fine reaction residue and adheres to the piping, so there is a problem that frequent cleaning is required to remove it.
On the other hand, in the method described in Patent Document 4, by using titanium slag of 75 to 850 μm as a starting material, the titanium concentrate is prevented from being atomized, and the steps of oxidation, reduction, hydrochloric acid leaching, washing, and firing are performed. Although impurities such as silica are removed, there is a problem that the process is very long and complicated. For this reason, a method for producing a high-quality titanium concentrate that does not adversely affect the production equipment during liquid chlorination by a simple method has become an issue.
Since the methods described in Patent Documents 5 and 6 are both manufacturing methods including a two-step leaching step using concentrated hydrochloric acid, there are problems in terms of safety, durability of the reaction vessel, etc., and the manufacturing method is industrially advantageous. I can't say.
一方、特許文献４に記載の方法では、７５～８５０μｍのチタニアスラグを出発原料とすることによって、チタン濃縮物の微粉化を防止し、酸化、還元、塩酸浸出、洗浄、焼成の各工程を経て、シリカ分等の不純物を除去しているが、工程が非常に長く煩雑であるという問題がある。このようなことから、簡便な方法で、流動塩素化時に生産設備に悪影響を与えない高品位なチタン濃縮物を製造する方法が課題となっている。
前記特許文献５及び６に記載の方法は、共に濃塩酸を使用した２段階浸出工程を含む製法であるため、安全面、反応容器の耐久性等に課題があり、工業的に有利な製法とはいえない。 In the method described in Patent Document 3 above, scattering of the titanium concentrate to the outside of the fluidized chlorination furnace due to granulation is prevented, but since a large amount of silica remains in the titanium concentrate, it flows. During chlorination, silica is carried over to the outside of the chlorination furnace as a fine reaction residue and adheres to the piping, so there is a problem that frequent cleaning is required to remove it.
On the other hand, in the method described in Patent Document 4, by using titanium slag of 75 to 850 μm as a starting material, the titanium concentrate is prevented from being atomized, and the steps of oxidation, reduction, hydrochloric acid leaching, washing, and firing are performed. Although impurities such as silica are removed, there is a problem that the process is very long and complicated. For this reason, a method for producing a high-quality titanium concentrate that does not adversely affect the production equipment during liquid chlorination by a simple method has become an issue.
Since the methods described in Patent Documents 5 and 6 are both manufacturing methods including a two-step leaching step using concentrated hydrochloric acid, there are problems in terms of safety, durability of the reaction vessel, etc., and the manufacturing method is industrially advantageous. I can't say.
本発明者は、上記課題を解決するため、鋭意工夫した結果、含チタン鉄鉱石等を従来よりも細かく粉砕してから、１～２０質量％の塩酸初期濃度で８０℃以下の反応温度にて予備浸出した後、可溶性還元性物質の存在下、１５～２０質量％の塩酸初期濃度で９０℃以上の反応温度にて本浸出すると、簡便な方法で鉄分とシリカ分等の不純物を除去することができ、高品位なチタン濃縮物が得られるとの知見を得て、本発明を完成した。
また、得られたチタン濃縮物の造粒と乾燥を同時に行う造粒乾燥を経ると、チタン濃縮物に流動塩素化に適した粒度と硬度を持たせることができ、また、チタン濃縮物の微粉含有を防止でき、微粉が炉外に飛散されないようにすることができるため、生産設備に悪影響を与えることなく、流動塩素化を効率的に行うことができるとの知見を得て、本発明を完成した。 As a result of diligent efforts to solve the above problems, the present inventor crushes ilmenite-containing iron ore or the like more finely than before, and then at a reaction temperature of 80 ° C. or lower at an initial concentration of hydrochloric acid of 1 to 20% by mass. After pre-leaching, if the main leaching is performed at a reaction temperature of 90 ° C. or higher at an initial concentration of 15 to 20% by mass of hydrochloric acid in the presence of a soluble reducing substance, impurities such as iron and silica can be removed by a simple method. The present invention was completed with the finding that a high-quality titanium concentrate could be obtained.
Further, after the obtained titanium concentrate is granulated and dried at the same time, the titanium concentrate can be given a particle size and hardness suitable for fluid chlorination, and fine powder of the titanium concentrate can be obtained. Based on the finding that fluid chlorination can be efficiently performed without adversely affecting the production equipment because the content can be prevented and the fine powder can be prevented from being scattered outside the furnace, the present invention was developed. completed.
また、得られたチタン濃縮物の造粒と乾燥を同時に行う造粒乾燥を経ると、チタン濃縮物に流動塩素化に適した粒度と硬度を持たせることができ、また、チタン濃縮物の微粉含有を防止でき、微粉が炉外に飛散されないようにすることができるため、生産設備に悪影響を与えることなく、流動塩素化を効率的に行うことができるとの知見を得て、本発明を完成した。 As a result of diligent efforts to solve the above problems, the present inventor crushes ilmenite-containing iron ore or the like more finely than before, and then at a reaction temperature of 80 ° C. or lower at an initial concentration of hydrochloric acid of 1 to 20% by mass. After pre-leaching, if the main leaching is performed at a reaction temperature of 90 ° C. or higher at an initial concentration of 15 to 20% by mass of hydrochloric acid in the presence of a soluble reducing substance, impurities such as iron and silica can be removed by a simple method. The present invention was completed with the finding that a high-quality titanium concentrate could be obtained.
Further, after the obtained titanium concentrate is granulated and dried at the same time, the titanium concentrate can be given a particle size and hardness suitable for fluid chlorination, and fine powder of the titanium concentrate can be obtained. Based on the finding that fluid chlorination can be efficiently performed without adversely affecting the production equipment because the content can be prevented and the fine powder can be prevented from being scattered outside the furnace, the present invention was developed. completed.
即ち、上記課題を解決するための本発明は、以下の通りである。
［１］ 含チタン鉄鉱石又はその類似物を３３０メッシュの篩を通過する粒度に粉砕して得た粉砕物を、１～２０質量％の塩酸初期濃度で８０℃以下の反応温度にて予備浸出を行った後、可溶性還元性物質の存在下、１５～２０質量％の塩酸初期濃度で９０℃以上の反応温度にて本浸出を行うことを含むチタン濃縮物の製造方法。
［２］ １～１５質量％の塩酸初期濃度で予備浸出を行う［１］に記載のチタン濃縮物の製造方法。
［３］ 前記の本浸出を行った後、固液分離して得られた浸出物を洗浄し、乾燥することを含む［１］又は［２］に記載のチタン濃縮物の製造方法。
［４］ 乾燥が造粒乾燥である［３］に記載のチタン濃縮物の製造方法。
［５］ 乾燥して得られた乾燥物を６００～１０００℃の温度で焼成することを含む［３］又は［４］に記載のチタン濃縮物の製造方法。
［６］ 本浸出を浸出液の沸点以下の温度で行う［１］～［５］の何れか一項に記載のチタン濃縮物の製造方法。
［７］ 予備浸出をフッ素系添加剤の存在下で行う［１］～［６］の何れか一項に記載のチタン濃縮物の製造方法。
［８］ 予備浸出を可溶性還元物質の存在下で行うことを含む［１］～［７］の何れか一項に記載のチタン濃縮物の製造方法。
［９］ 前記の本浸出を行った後、フッ素系添加剤を添加する工程を行う［１］～［８］の何れか一項に記載のチタン濃縮物の製造方法。
［１０］ チタン濃縮物がルチル構造を有する酸化チタンを含む［１］～［９］の何れか一項に記載のチタン濃縮物の製造方法。
［１１］ 前記の乾燥を行って、ルチル構造を有する酸化チタンを含むチタン濃縮物を製造する［３］又は［４］に記載のチタン濃縮物の製造方法。
［１２］ 可溶性還元性物質が、金属鉄及び／又は可溶性チタン塩である［１］～［１１］の何れか一項に記載のチタン濃縮物の製造方法。
［１３］ 可溶性還元性物質が、チタン（ＩＩＩ）塩である［１２］に記載のチタン濃縮物の製造方法。 That is, the present invention for solving the above problems is as follows.
[1] A pulverized product obtained by pulverizing a titanium-containing iron ore or a similar product to a particle size passing through a 330 mesh sieve is preliminarily leached at a reaction temperature of 80 ° C. or lower at an initial concentration of 1 to 20% by mass of hydrochloric acid. A method for producing a titanium concentrate, which comprises performing the main leaching at a reaction temperature of 90 ° C. or higher at an initial concentration of hydrochloric acid of 15 to 20% by mass in the presence of a soluble reducing substance.
[2] The method for producing a titanium concentrate according to [1], wherein preliminary leaching is performed at an initial concentration of hydrochloric acid of 1 to 15% by mass.
[3] The method for producing a titanium concentrate according to [1] or [2], which comprises washing and drying the leached product obtained by solid-liquid separation after performing the main leaching.
[4] The method for producing a titanium concentrate according to [3], wherein the drying is granulation drying.
[5] The method for producing a titanium concentrate according to [3] or [4], which comprises calcining the dried product obtained by drying at a temperature of 600 to 1000 ° C.
[6] The method for producing a titanium concentrate according to any one of [1] to [5], wherein the main leaching is performed at a temperature equal to or lower than the boiling point of the leachate.
[7] The method for producing a titanium concentrate according to any one of [1] to [6], wherein the preliminary leaching is performed in the presence of a fluorine-based additive.
[8] The method for producing a titanium concentrate according to any one of [1] to [7], which comprises performing preliminary leaching in the presence of a soluble reducing substance.
[9] The method for producing a titanium concentrate according to any one of [1] to [8], wherein a step of adding a fluorine-based additive is performed after the main leaching is performed.
[10] The method for producing a titanium concentrate according to any one of [1] to [9], wherein the titanium concentrate contains titanium oxide having a rutile structure.
[11] The method for producing a titanium concentrate according to [3] or [4], wherein the drying is performed to produce a titanium concentrate containing titanium oxide having a rutile structure.
[12] The method for producing a titanium concentrate according to any one of [1] to [11], wherein the soluble reducing substance is metallic iron and / or a soluble titanium salt.
[13] The method for producing a titanium concentrate according to [12], wherein the soluble reducing substance is a titanium (III) salt.
［１］ 含チタン鉄鉱石又はその類似物を３３０メッシュの篩を通過する粒度に粉砕して得た粉砕物を、１～２０質量％の塩酸初期濃度で８０℃以下の反応温度にて予備浸出を行った後、可溶性還元性物質の存在下、１５～２０質量％の塩酸初期濃度で９０℃以上の反応温度にて本浸出を行うことを含むチタン濃縮物の製造方法。
［２］ １～１５質量％の塩酸初期濃度で予備浸出を行う［１］に記載のチタン濃縮物の製造方法。
［３］ 前記の本浸出を行った後、固液分離して得られた浸出物を洗浄し、乾燥することを含む［１］又は［２］に記載のチタン濃縮物の製造方法。
［４］ 乾燥が造粒乾燥である［３］に記載のチタン濃縮物の製造方法。
［５］ 乾燥して得られた乾燥物を６００～１０００℃の温度で焼成することを含む［３］又は［４］に記載のチタン濃縮物の製造方法。
［６］ 本浸出を浸出液の沸点以下の温度で行う［１］～［５］の何れか一項に記載のチタン濃縮物の製造方法。
［７］ 予備浸出をフッ素系添加剤の存在下で行う［１］～［６］の何れか一項に記載のチタン濃縮物の製造方法。
［８］ 予備浸出を可溶性還元物質の存在下で行うことを含む［１］～［７］の何れか一項に記載のチタン濃縮物の製造方法。
［９］ 前記の本浸出を行った後、フッ素系添加剤を添加する工程を行う［１］～［８］の何れか一項に記載のチタン濃縮物の製造方法。
［１０］ チタン濃縮物がルチル構造を有する酸化チタンを含む［１］～［９］の何れか一項に記載のチタン濃縮物の製造方法。
［１１］ 前記の乾燥を行って、ルチル構造を有する酸化チタンを含むチタン濃縮物を製造する［３］又は［４］に記載のチタン濃縮物の製造方法。
［１２］ 可溶性還元性物質が、金属鉄及び／又は可溶性チタン塩である［１］～［１１］の何れか一項に記載のチタン濃縮物の製造方法。
［１３］ 可溶性還元性物質が、チタン（ＩＩＩ）塩である［１２］に記載のチタン濃縮物の製造方法。 That is, the present invention for solving the above problems is as follows.
[1] A pulverized product obtained by pulverizing a titanium-containing iron ore or a similar product to a particle size passing through a 330 mesh sieve is preliminarily leached at a reaction temperature of 80 ° C. or lower at an initial concentration of 1 to 20% by mass of hydrochloric acid. A method for producing a titanium concentrate, which comprises performing the main leaching at a reaction temperature of 90 ° C. or higher at an initial concentration of hydrochloric acid of 15 to 20% by mass in the presence of a soluble reducing substance.
[2] The method for producing a titanium concentrate according to [1], wherein preliminary leaching is performed at an initial concentration of hydrochloric acid of 1 to 15% by mass.
[3] The method for producing a titanium concentrate according to [1] or [2], which comprises washing and drying the leached product obtained by solid-liquid separation after performing the main leaching.
[4] The method for producing a titanium concentrate according to [3], wherein the drying is granulation drying.
[5] The method for producing a titanium concentrate according to [3] or [4], which comprises calcining the dried product obtained by drying at a temperature of 600 to 1000 ° C.
[6] The method for producing a titanium concentrate according to any one of [1] to [5], wherein the main leaching is performed at a temperature equal to or lower than the boiling point of the leachate.
[7] The method for producing a titanium concentrate according to any one of [1] to [6], wherein the preliminary leaching is performed in the presence of a fluorine-based additive.
[8] The method for producing a titanium concentrate according to any one of [1] to [7], which comprises performing preliminary leaching in the presence of a soluble reducing substance.
[9] The method for producing a titanium concentrate according to any one of [1] to [8], wherein a step of adding a fluorine-based additive is performed after the main leaching is performed.
[10] The method for producing a titanium concentrate according to any one of [1] to [9], wherein the titanium concentrate contains titanium oxide having a rutile structure.
[11] The method for producing a titanium concentrate according to [3] or [4], wherein the drying is performed to produce a titanium concentrate containing titanium oxide having a rutile structure.
[12] The method for producing a titanium concentrate according to any one of [1] to [11], wherein the soluble reducing substance is metallic iron and / or a soluble titanium salt.
[13] The method for producing a titanium concentrate according to [12], wherein the soluble reducing substance is a titanium (III) salt.
本発明のチタン濃縮物の製造方法では、鉄分とシリカ分等の不純物を大量に含有している変成度の低い含チタン鉄鉱石等を出発原料にした場合でも、簡便で安全な上、反応容器に対する負荷が少ない工業的に有利な方法であるため、効率的に高品位なチタン濃縮物を製造することができる。また、このチタン濃縮物の造粒と乾燥を同時に行うことにより、チタン濃縮物を適度な粒度、硬度とすることができ、また、チタン濃縮物の微粉含有を回避し、微粉が流動塩素化炉外に飛散することを防止でき、高い収率で四塩化チタンを得ることができる。
In the method for producing a titanium concentrate of the present invention, even when a titanium-containing iron ore containing a large amount of impurities such as iron and silica and having a low degree of alteration is used as a starting material, it is simple and safe, and a reaction vessel is used. Since it is an industrially advantageous method with less load on the iron, it is possible to efficiently produce a high-quality titanium concentrate. Further, by simultaneously granulating and drying the titanium concentrate, the titanium concentrate can have an appropriate particle size and hardness, and the inclusion of fine powder in the titanium concentrate can be avoided, and the fine powder can be fluidized in a chlorination furnace. It is possible to prevent it from scattering to the outside, and it is possible to obtain titanium tetrachloride in a high yield.
以下、本発明の実施の形態について詳細に説明する。但し、本発明はこれらに限定されるものではなく、記述した範囲内で種々の変更が可能であり、異なる実施の形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施の形態についても、本発明の技術的範囲に含まれる。
Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to these, and various modifications can be made within the scope described, and the embodiments obtained by appropriately combining the technical means disclosed in the different embodiments are also defined. , Included in the technical scope of the present invention.
本発明の製造方法に適用できる含チタン鉄鉱石又はその類似物とは、イルメナイト、イルメナイトの変成物、例えばイルメナイト・ヘマタイト鉱等の含チタン鉄鉱石、これらの鉱石に予備処理を施したもの又はこれらと類似の組成、性質を有する類似物等である。変成度の高い含チタン鉄鉱石でも、変成度の低いものでも適用することができ、シリカ分等の不純物を多く含有している変成度の低い含チタン鉄鉱石又はその類似物にも好適に適用できる。また、鉄製錬における副生物であるいわゆるチタンスラグを使用することもできる。これらの含チタン鉄鉱石又はその類似物の粒度は通常５０～５００μｍであり、これ以上のものは適宜予備粉砕して使用することができる。そのような含チタン鉄鉱石又はその類似物中には、鉄分、シリカ分の他に、Ａｌ、Ｃａ、Ｃｏ、Ｃｒ、Ｃｕ、Ｇａ、Ｇｅ、Ｍｇ、Ｍｎ、Ｍｏ、Ｎｂ、Ｎｉ、Ｐｄ、Ｒｕ、Ｓｎ、Ｔａ、Ｖ、Ｗ及びＺｒからなる群から選択される少なくとも一種の元素の酸化物から成る不純物が含有されていてもよい。含チタン鉄鉱石又はその類似物中のシリカ分の含有量は、ＳｉＯ２換算で通常、０．５～３５質量％である。
The titanium-containing iron ore or its analogs applicable to the production method of the present invention are ilmenite, ilmenite variants, for example, titanium-containing iron ore such as ilmenite and hematite, pretreated ores, or these. It is a similar product having the same composition and properties as. It can be applied to both ilmenite-containing iron ore with a high degree of metamorphism and ilmenite containing a low degree of denaturation, and is also suitably applied to ilmenite-containing iron ore with a low degree of denaturation containing a large amount of impurities such as silica or similar substances. it can. It is also possible to use so-called titanium slag, which is a by-product in iron smelting. The particle size of these ilmenite-containing iron ores or their analogs is usually 50 to 500 μm, and those larger than this can be used after being appropriately pulverized. In such titanium-containing iron ore or its analogs, in addition to iron and silica, Al, Ca, Co, Cr, Cu, Ga, Ge, Mg, Mn, Mo, Nb, Ni, Pd, Ru , Sn, Ta, V, W and Zr may contain impurities consisting of oxides of at least one element selected from the group. The content of silica in ilmenite iron ore or its analogs is usually 0.5 to 35% by mass in terms of SiO 2 .
本発明の製造方法においては、含チタン鉄鉱石又はその類似物を、３３０メッシュ（目開き４５μｍ）の篩を通過できる粒度に粉砕して用いる。粉砕は、乾式粉砕であっても溶媒中で粉砕を行う湿式粉砕であってもよく、普通に用いる粉砕手段、例えばボールミル、チューブミル、振動ボールミル、サンドミル、ディスクミル、メディアミル、メディアレスミル、ローラーミル等を用いて行うことができる。粉砕は乾式粉砕を行った後、湿式粉砕を行うのが好ましい。湿式粉砕を行った場合には、粉砕後、溶媒と粉砕物を固液分離する。固液分離は、デカンテーション、沈降分離、遠心分離、濾過、膜分離等により行うことができるが、デカンテーションにて行うのが望ましい。得られた粉砕物が粉砕されていなかったり、粉砕が不十分で所定の粒度まで粉砕されていなかったりする場合は、チタン濃縮物中のシリカ分等の不純物が十分に除去できなくなり、高ＴｉＯ２品位のチタン濃縮物が得られなくなる。また、予備浸出や本浸出の工程が効率的に行われないという欠点も生じる。このため、３３０メッシュ（目開き４５μｍ）の篩を通過できる粒度に粉砕するのが重要であり、好ましくは４４０メッシュ（目開き３２μｍ）の篩を通過できる粒度であり、更に好ましくは６３５メッシュ（目開き２０μｍ）の篩を通過できる粒度である。粉砕後、整粒を行うのが好ましく、粒子の沈降速度の差を利用して極微細粉を除去することができる。
In the production method of the present invention, ilmenite-containing iron ore or an analog thereof is pulverized to a particle size capable of passing through a sieve of 330 mesh (opening 45 μm) and used. The pulverization may be dry pulverization or wet pulverization in which pulverization is performed in a solvent, and commonly used pulverizing means such as ball mill, tube mill, vibrating ball mill, sand mill, disc mill, media mill, medialess mill, roller. This can be done using a mill or the like. The pulverization is preferably performed by dry pulverization and then wet pulverization. When wet pulverization is performed, the solvent and the pulverized product are separated into solid and liquid after pulverization. Solid-liquid separation can be performed by decantation, sedimentation separation, centrifugation, filtration, membrane separation, etc., but it is preferable to perform decantation. If the obtained pulverized product is not pulverized, or if the pulverized product is insufficiently pulverized to a predetermined particle size, impurities such as silica in the titanium concentrate cannot be sufficiently removed, resulting in high TiO 2 High-quality titanium concentrate cannot be obtained. In addition, there is a drawback that the pre-leaching and main leaching steps are not efficiently performed. For this reason, it is important to pulverize to a particle size that can pass through a sieve of 330 mesh (opening 45 μm), preferably a particle size that can pass through a sieve of 440 mesh (opening 32 μm), and more preferably 635 mesh (opening 32 μm). The particle size is such that it can pass through a sieve with an opening of 20 μm). It is preferable to perform sizing after pulverization, and the ultrafine powder can be removed by utilizing the difference in the sedimentation rate of the particles.
得られた粉砕物は、１～２０質量％の塩酸初期濃度で８０℃以下の反応温度にて予備浸出を行った後、可溶性還元性物質の存在下、１５～２０質量％の塩酸初期濃度で９０℃以上の反応温度にて本浸出し、鉄分とシリカ分等の不純物を除去する。使用する塩酸は初期濃度で表しており、浸出開始の際の塩酸濃度である。予備浸出において、シリカ分をより効率的に除去するには塩酸初期濃度を１～１５質量％とするのが望ましい。一方、塩酸初期濃度を１５～２０質量％とすると、鉄分のより効率的な除去が可能になる。予備浸出を行う浸出用容器も、本浸出を行う浸出用容器も、共に塩酸によって腐蝕されない材質の浸出用容器を用いるが、開放型容器であっても、オートクレーブのような密閉型容器であってもよい。なお、鉄分とシリカ分を十分除去するためには、前記の予備浸出を複数回行ってもよく、本浸出を複数回行ってもよい。
The obtained pulverized product was preliminarily leached at a reaction temperature of 80 ° C. or lower at an initial concentration of 1 to 20% by mass of hydrochloric acid, and then at an initial concentration of 15 to 20% by mass of hydrochloric acid in the presence of a soluble reducing substance. Main leaching is performed at a reaction temperature of 90 ° C. or higher to remove impurities such as iron and silica. The hydrochloric acid used is represented by the initial concentration, which is the hydrochloric acid concentration at the start of leaching. In the preliminary leaching, it is desirable that the initial concentration of hydrochloric acid is 1 to 15% by mass in order to remove the silica content more efficiently. On the other hand, when the initial concentration of hydrochloric acid is 15 to 20% by mass, more efficient removal of iron becomes possible. Both the leaching container for pre-leaching and the leaching container for main leaching use a leaching container made of a material that is not corroded by hydrochloric acid. May be good. In order to sufficiently remove iron and silica, the preliminary leaching may be performed a plurality of times, or the main leaching may be performed a plurality of times.
予備浸出における塩酸の使用量（Ｖ）は、粉砕物の質量（Ｗ）に対してＶ／Ｗが１．５～２０とするのが好ましく、５～１５とするのがより好ましく、７～１２とするのが更に好ましい。また、予備浸出は８０℃以下の温度で行うのが好ましく、６０℃以下の温度がより好ましい。時間は適宜設定することができ、１～１５時間行うのが好ましい。
更に、予備浸出はフッ素系添加剤の存在下で行うと、シリカ分を溶解できるので、効率的である。フッ素系添加剤としては、フッ化ナトリウム、フッ化カリウム、フッ化カルシウム、フッ化水素酸等が使用できる。フッ素系添加剤の添加量は適宜設定することができる。
予備浸出においても本浸出と同様に、鉄分の溶出速度、溶出量を高めるために後述の可溶性還元性物質を存在させてもよい。予備浸出後の浸出物は、そのまま次の本浸出工程に供してもよく、予備浸出後の容器に塩酸と可溶性還元性物質を添加して連続的に本浸出を行うことができる。
一方、予備浸出した後デカンテーション、沈降分離、遠心分離、濾過、膜分離等により予備浸出の浸出物を固液分離した後、湿ケーキ又はスラリーの形で濃縮した後、次の本浸出工程に供してもよい。更に、浸出物を固液分離した後、水で洗浄して、浸出物に残存する共存イオンの脱塩処理を行ってもよい。この場合、浸出物を湿ケーキの形で分離し、次の本浸出工程に供する。 The amount (V) of hydrochloric acid used in the preliminary leaching is preferably 1.5 to 20 V / W with respect to the mass (W) of the pulverized product, more preferably 5 to 15, and 7 to 12 Is more preferable. Further, the preliminary leaching is preferably performed at a temperature of 80 ° C. or lower, more preferably 60 ° C. or lower. The time can be set as appropriate, and it is preferably performed for 1 to 15 hours.
Further, when the preliminary leaching is performed in the presence of a fluorine-based additive, the silica component can be dissolved, which is efficient. As the fluorine-based additive, sodium fluoride, potassium fluoride, calcium fluoride, hydrofluoric acid and the like can be used. The amount of the fluorine-based additive added can be appropriately set.
In the preliminary leaching as well as in the main leaching, a soluble reducing substance described later may be present in order to increase the elution rate and the elution amount of iron. The leached product after the preliminary leaching may be directly subjected to the next main leaching step, and the main leaching can be continuously performed by adding hydrochloric acid and a soluble reducing substance to the container after the preliminary leaching.
On the other hand, after pre-leaching, the pre-leaching exudate is solid-liquid separated by decantation, sedimentation, centrifugation, filtration, membrane separation, etc., concentrated in the form of a wet cake or slurry, and then subjected to the next main leaching step. May be served. Further, the leachate may be solid-liquid separated and then washed with water to desalt the coexisting ions remaining in the leachate. In this case, the leaching material is separated in the form of a wet cake and subjected to the next main leaching step.
更に、予備浸出はフッ素系添加剤の存在下で行うと、シリカ分を溶解できるので、効率的である。フッ素系添加剤としては、フッ化ナトリウム、フッ化カリウム、フッ化カルシウム、フッ化水素酸等が使用できる。フッ素系添加剤の添加量は適宜設定することができる。
予備浸出においても本浸出と同様に、鉄分の溶出速度、溶出量を高めるために後述の可溶性還元性物質を存在させてもよい。予備浸出後の浸出物は、そのまま次の本浸出工程に供してもよく、予備浸出後の容器に塩酸と可溶性還元性物質を添加して連続的に本浸出を行うことができる。
一方、予備浸出した後デカンテーション、沈降分離、遠心分離、濾過、膜分離等により予備浸出の浸出物を固液分離した後、湿ケーキ又はスラリーの形で濃縮した後、次の本浸出工程に供してもよい。更に、浸出物を固液分離した後、水で洗浄して、浸出物に残存する共存イオンの脱塩処理を行ってもよい。この場合、浸出物を湿ケーキの形で分離し、次の本浸出工程に供する。 The amount (V) of hydrochloric acid used in the preliminary leaching is preferably 1.5 to 20 V / W with respect to the mass (W) of the pulverized product, more preferably 5 to 15, and 7 to 12 Is more preferable. Further, the preliminary leaching is preferably performed at a temperature of 80 ° C. or lower, more preferably 60 ° C. or lower. The time can be set as appropriate, and it is preferably performed for 1 to 15 hours.
Further, when the preliminary leaching is performed in the presence of a fluorine-based additive, the silica component can be dissolved, which is efficient. As the fluorine-based additive, sodium fluoride, potassium fluoride, calcium fluoride, hydrofluoric acid and the like can be used. The amount of the fluorine-based additive added can be appropriately set.
In the preliminary leaching as well as in the main leaching, a soluble reducing substance described later may be present in order to increase the elution rate and the elution amount of iron. The leached product after the preliminary leaching may be directly subjected to the next main leaching step, and the main leaching can be continuously performed by adding hydrochloric acid and a soluble reducing substance to the container after the preliminary leaching.
On the other hand, after pre-leaching, the pre-leaching exudate is solid-liquid separated by decantation, sedimentation, centrifugation, filtration, membrane separation, etc., concentrated in the form of a wet cake or slurry, and then subjected to the next main leaching step. May be served. Further, the leachate may be solid-liquid separated and then washed with water to desalt the coexisting ions remaining in the leachate. In this case, the leaching material is separated in the form of a wet cake and subjected to the next main leaching step.
本浸出における塩酸の使用量（Ｖ）は、予備浸出後の浸出物の質量（Ｗ）に対してＶ／Ｗで１～１０とするのが好ましく、２～８とするのがより好ましい。
本浸出は９０℃以上の反応温度にて行うが、浸出液の沸点以下の温度で行うのが好ましく、時間は適宜設定することができ、２～２０時間行うのが好ましい。開放型浸出容器を使用する場合には、９０～１１０℃（沸点以下）で５～２０時間浸出を行うのが好ましく、密閉型浸出容器を使用する場合には、加圧条件によって温度、時間を適宜設定することができ、１１０～１６０℃で、２～１８時間浸出するのが好ましい。 The amount (V) of hydrochloric acid used in the main leaching is preferably 1 to 10 in V / W with respect to the mass (W) of the leachate after the preliminary leaching, and more preferably 2 to 8.
The main leaching is carried out at a reaction temperature of 90 ° C. or higher, but it is preferably carried out at a temperature equal to or lower than the boiling point of the leachate, and the time can be appropriately set, and is preferably carried out for 2 to 20 hours. When using an open leaching container, it is preferable to perform leaching at 90 to 110 ° C. (below the boiling point) for 5 to 20 hours, and when using a closed leaching container, the temperature and time are adjusted depending on the pressurizing conditions. It can be set as appropriate, and leaching is preferably performed at 110 to 160 ° C. for 2 to 18 hours.
本浸出は９０℃以上の反応温度にて行うが、浸出液の沸点以下の温度で行うのが好ましく、時間は適宜設定することができ、２～２０時間行うのが好ましい。開放型浸出容器を使用する場合には、９０～１１０℃（沸点以下）で５～２０時間浸出を行うのが好ましく、密閉型浸出容器を使用する場合には、加圧条件によって温度、時間を適宜設定することができ、１１０～１６０℃で、２～１８時間浸出するのが好ましい。 The amount (V) of hydrochloric acid used in the main leaching is preferably 1 to 10 in V / W with respect to the mass (W) of the leachate after the preliminary leaching, and more preferably 2 to 8.
The main leaching is carried out at a reaction temperature of 90 ° C. or higher, but it is preferably carried out at a temperature equal to or lower than the boiling point of the leachate, and the time can be appropriately set, and is preferably carried out for 2 to 20 hours. When using an open leaching container, it is preferable to perform leaching at 90 to 110 ° C. (below the boiling point) for 5 to 20 hours, and when using a closed leaching container, the temperature and time are adjusted depending on the pressurizing conditions. It can be set as appropriate, and leaching is preferably performed at 110 to 160 ° C. for 2 to 18 hours.
予備浸出又は本浸出にあたっては、浸出液中に可溶性の還元性物質（本願では、「可溶性還元性物質」とも称する。）を存在させることで、鉄分の溶出速度や溶出量を高めることができるとともに、チタン収率をも高めることができる。可溶性還元性物質としては、金属鉄及び／又は可溶性チタン塩が挙げられる。金属鉄は浸出液に入れると溶解して鉄イオンとなる。可溶性チタン塩としては、チタン（ＩＩＩ）塩、チタン（ＩＶ）塩等が挙げられるが、チタン（ＩＩＩ）塩が好ましい。また、チタン（ＩＩＩ）塩を系内に存在させる方法としては、チタン（ＩＩＩ）塩溶液を添加する方法の他、金属鉄粉等を浸出液に加えて系内のチタン（ＩＶ）塩をチタン（ＩＩＩ）塩に還元することもできるので、可溶性還元性物質としては、金属鉄と可溶性チタン塩を組み合わせるのが好ましい。可溶性チタン塩の添加量は、適宜設定することができ、３価の鉄分を２価に還元する量（還元当量）に対して０．８～１．５倍量が好ましく、０．９～１．２倍量がより好ましい。
In the preliminary leaching or the main leaching, the presence of a soluble reducing substance (also referred to as “soluble reducing substance” in the present application) in the leachate can increase the elution rate and elution amount of iron. The titanium yield can also be increased. Soluble reducing substances include metallic iron and / or soluble titanium salts. Metallic iron dissolves into iron ions when placed in a leachate. Examples of the soluble titanium salt include titanium (III) salt and titanium (IV) salt, and titanium (III) salt is preferable. As a method for allowing the titanium (III) salt to exist in the system, in addition to the method of adding a titanium (III) salt solution, metal iron powder or the like is added to the leachate to add titanium (IV) salt in the system to titanium (IV). III) Since it can be reduced to a salt, it is preferable to combine metallic iron and a soluble titanium salt as the soluble reducing substance. The amount of the soluble titanium salt added can be appropriately set, and is preferably 0.8 to 1.5 times the amount of reducing trivalent iron to divalent (reduction equivalent), and 0.9 to 1 . Double the amount is more preferred.
また、本浸出においては、チタン塩加水分解促進用シードを併用してもよい。これは、一般の硫酸法による二酸化チタン顔料の製造方法において、チタン塩類溶液を加水分解してチタン分を沈殿させる時に用いる種晶のことであり、これは、例えばチタニル硫酸等のチタン塩の酸性溶液を中和し、析出したコロイド状のチタン化合物を熟成したものである。チタン塩加水分解促進用シードを併用する場合、その添加量は、予備浸出後の浸出物に対するチタン塩加水分解促進用シード中のチタン分をＴｉＯ２として約０．０５～２質量％であることが好ましく、通常０．１～１質量％であることがより好ましい。
Further, in the main leaching, a seed for promoting titanium salt hydrolysis may be used in combination. This is a seed crystal used when a titanium salt solution is hydrolyzed to precipitate a titanium content in a method for producing a titanium dioxide pigment by a general sulfuric acid method, and this is an acidity of a titanium salt such as titanyl sulfuric acid. The solution is neutralized and the precipitated colloidal titanium compound is aged. When the titanium salt hydrolysis promoting seed is used in combination, the amount of titanium added in the titanium salt hydrolysis promoting seed to the leached product after the preliminary leaching should be about 0.05 to 2% by mass as TiO 2. Is preferable, and usually 0.1 to 1% by mass is more preferable.
本浸出後の浸出液に、又は、浸出液をデカンテーション、沈降分離、遠心分離、濾過、膜分離等により固液分離した浸出物をスラリーにしたものにフッ素系添加剤を添加すると、浸出物に残存するシリカ分を除去できるため好ましい。この工程を脱シリカ処理といい、フッ素系添加剤としては、前述のフッ化ナトリウム、フッ化カリウム、フッ化カルシウム、フッ化水素酸等が使用できる。フッ素系添加剤の添加量は適宜設定することができる。脱シリカ処理の温度は浸出液の沸点以下の温度で行うのが好ましく、２０～９０℃の温度がより好ましい。脱シリカ処理の時間は適宜設定することができ、０．５～１０時間行うのが好ましい。
When a fluorine-based additive is added to the leaching solution after the main leaching, or to a slurry of the leaching solution that has been solid-liquid separated by decantation, sedimentation separation, centrifugation, filtration, membrane separation, etc. It is preferable because it can remove the silica content. This step is called de-silica treatment, and as the fluorine-based additive, the above-mentioned sodium fluoride, potassium fluoride, calcium fluoride, hydrofluoric acid and the like can be used. The amount of the fluorine-based additive added can be appropriately set. The temperature of the desilicaization treatment is preferably a temperature equal to or lower than the boiling point of the leachate, more preferably a temperature of 20 to 90 ° C. The time for the desilicaization treatment can be appropriately set, and is preferably 0.5 to 10 hours.
予備浸出と本浸出、更には脱シリカ処理により、鉄分とシリカ分等の不純物を除去した浸出物（すなわち、チタン濃縮物）は、デカンテーション、沈降分離、遠心分離、濾過、膜分離等により固液分離する。その後、洗浄して、浸出物に残存する共存イオンの脱塩処理を行うのが好ましい。脱塩処理は電気伝導度が０．１Ｓ／ｍ以下となるまで洗浄するのが好ましい。その後、浸出物は、通常、粉体とするために乾燥することができる。乾燥温度は適宜設定することができる。また、乾燥後、必要に応じて粉砕、造粒してもよい。以上のようにして製造されたチタン濃縮物はＴｉＯ２品位が極めて高く、好ましくは９５質量％以上のものとなる。
The leachate (that is, titanium concentrate) from which impurities such as iron and silica have been removed by pre-leaching, main leaching, and desilicaization is solidified by decantation, sedimentation, centrifugation, filtration, membrane separation, etc. Liquid separation. After that, it is preferable to wash and desalinate the coexisting ions remaining in the leachate. The desalting treatment is preferably washed until the electric conductivity becomes 0.1 S / m or less. The leachate can then be usually dried to form a powder. The drying temperature can be set as appropriate. Further, after drying, it may be crushed and granulated as needed. The titanium concentrate produced as described above has an extremely high TiO 2 grade, preferably 95% by mass or more.
前記の乾燥の際に造粒を同時に行うと、流動塩素化に適した粒度と硬度を持たせることができるため好ましい。このような造粒乾燥は、通常の造粒乾燥機を用いることができ、流動層造粒乾燥機、スプレードライがより好ましい。スプレードライヤーにより造粒乾燥するには、前記の湿ケーキをスラリーにし、必要に応じて湿式粉砕した後、噴霧乾燥するのが好ましい。造粒乾燥によりチタン濃縮物を３０～３００μｍの粒度に整粒することができ、また、適切な硬度を有することができる。
It is preferable to carry out granulation at the same time as the above-mentioned drying because the particle size and hardness suitable for fluid chlorination can be obtained. For such granulation drying, a normal granulation dryer can be used, and a fluidized bed granulation dryer and spray drying are more preferable. In order to granulate and dry the cake with a spray dryer, it is preferable to make the wet cake into a slurry, wet-pulverize it if necessary, and then spray-dry it. The titanium concentrate can be sized to a particle size of 30 to 300 μm by granulation drying, and can have an appropriate hardness.
本発明のチタン濃縮物の製造方法では、予備浸出と本浸出、更には本浸出後に固液分離して得られた浸出物（好ましくは、脱シリカ処理を行った後の浸出物）の洗浄後に乾燥、特に造粒乾燥すると、ルチル構造を有する酸化チタンを含むチタン濃縮物を製造することができる。本発明の方法では高温で焼成しなくても、乾燥を行うとルチル型構造を有する酸化チタンのみを含有するチタン濃縮物が製造できる。ルチル型構造を有する酸化チタンは、塩素ガスとの反応性がよいため塩素化が効率よく行われる。得られたルチル構造を有する酸化チタンを含むチタン濃縮物は、必要に応じて硬度と純度を高めるために、６００～１０００℃の温度で焼成することができる。
In the method for producing a titanium concentrate of the present invention, after pre-leaching and main leaching, and further cleaning of the leachate obtained by solid-liquid separation after the main leaching (preferably, the leachate after desilicing treatment). Drying, especially granulation drying, can produce a titanium concentrate containing titanium oxide with a rutile structure. In the method of the present invention, a titanium concentrate containing only titanium oxide having a rutile-type structure can be produced by drying without firing at a high temperature. Titanium oxide having a rutile-type structure has good reactivity with chlorine gas, so that chlorination is efficiently performed. The resulting titanium concentrate containing titanium oxide having a rutile structure can be calcined at a temperature of 600 to 1000 ° C. to increase hardness and purity, if necessary.
次に、本発明を実施例及び比較例に基づいて具体的に説明するが、本発明は、以下の実施例及び比較例によって何ら限定されるものではない。
Next, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to the following Examples and Comparative Examples.
用いた原料イルメナイト鉱石の主な成分組成を表１に示し、粒度分布を図１に示す。なお、各表中の総ＴｉＯ２は組成物中のＴｉ含有率をＴｉＯ２換算で表した値である。組成は、容量分析（Ｔｉ分及びＦｅ分）とＩＣＰ発光分光分析で分析した。粒度分布はレーザ回折／散乱式粒子径分布測定装置 ＬＡ－９５０（株式会社堀場製作所製）で測定した。
The main composition of the raw material ilmenite ore used is shown in Table 1, and the particle size distribution is shown in FIG. The total TiO 2 in each table is a value obtained by expressing the Ti content in the composition in terms of TiO 2 . The composition was analyzed by volumetric analysis (Ti and Fe) and ICP emission spectroscopy. The particle size distribution was measured with a laser diffraction / scattering type particle size distribution measuring device LA-950 (manufactured by HORIBA, Ltd.).
実施例１
前記のイルメナイト鉱石をボールミルにて粉砕し３３０メッシュ（４４μｍ）の篩を通過することを確認した。この粉砕物の粒度分布を図２に示す。得られた粉砕物と１０質量％塩酸をＶ／Ｗ＝１０となるように、撹拌機付きの反応容器に入れて混合し、３０℃で２時間撹拌しながら、予備浸出させた。その後、濾過と水洗によって固液分離し、得られた湿ケーキをコンデンサー付き反応槽に移し、Ｖ／Ｗ＝３．７７となるように、１９質量％塩酸と混合し、１還元当量倍（すなわち、３価の鉄分を２価に還元する量（還元当量）に対して１倍量）のＴｉＣｌ３とともに、１０８℃（沸点）で１０時間本浸出させた。反応終了後、濾過と水洗によって固液分離して、次いで、スラリーにした後、スプレードライヤーにて噴霧乾燥してチタン濃縮物を得た。チタン濃縮物としてはスプレードライヤーのノズル交換により、平均粒度４０μｍの粒状乾燥物と平均粒度２００μｍの粒状乾燥物の二種を得た。得られたチタン濃縮物の主な成分組成を表２に示した。総ＴｉＯ２の全量は、ルチル構造を有する酸化チタンであり、アナタース型構造酸化チタンやアモルファスの酸化チタンは含まれていなかった。表中の総Ｆｅは、分析したＦｅＯとＦｅ２Ｏ３の合計量をＦｅ換算で表したものである。 Example 1
It was confirmed that the ilmenite ore was crushed by a ball mill and passed through a 330 mesh (44 μm) sieve. The particle size distribution of this pulverized product is shown in FIG. The obtained pulverized product and 10% by mass hydrochloric acid were placed in a reaction vessel equipped with a stirrer so as to have V / W = 10, mixed, and pre-leached while stirring at 30 ° C. for 2 hours. Then, solid-liquid separation was performed by filtration and washing with water, and the obtained wet cake was transferred to a reaction vessel with a condenser, mixed with 19% by mass hydrochloric acid so that V / W = 3.77, and multiplied by 1 reduction equivalent (that is, 1 reduction equivalent). It was leached at 108 ° C. (boiling point) for 10 hours together with TiCl 3 (1 times the amount of reducing trivalent iron to divalent (reduction equivalent)). After completion of the reaction, solid-liquid separation was performed by filtration and washing with water, and then a slurry was prepared and then spray-dried with a spray dryer to obtain a titanium concentrate. Two types of titanium concentrates were obtained by exchanging the nozzles of the spray dryer, a granular dried product having an average particle size of 40 μm and a granular dried product having an average particle size of 200 μm. The main component compositions of the obtained titanium concentrate are shown in Table 2. The total amount of total TiO 2 was titanium oxide having a rutile structure, and did not contain anatas-type structure titanium oxide or amorphous titanium oxide. The total Fe in the table represents the total amount of the analyzed FeO and Fe 2 O 3 in terms of Fe.
前記のイルメナイト鉱石をボールミルにて粉砕し３３０メッシュ（４４μｍ）の篩を通過することを確認した。この粉砕物の粒度分布を図２に示す。得られた粉砕物と１０質量％塩酸をＶ／Ｗ＝１０となるように、撹拌機付きの反応容器に入れて混合し、３０℃で２時間撹拌しながら、予備浸出させた。その後、濾過と水洗によって固液分離し、得られた湿ケーキをコンデンサー付き反応槽に移し、Ｖ／Ｗ＝３．７７となるように、１９質量％塩酸と混合し、１還元当量倍（すなわち、３価の鉄分を２価に還元する量（還元当量）に対して１倍量）のＴｉＣｌ３とともに、１０８℃（沸点）で１０時間本浸出させた。反応終了後、濾過と水洗によって固液分離して、次いで、スラリーにした後、スプレードライヤーにて噴霧乾燥してチタン濃縮物を得た。チタン濃縮物としてはスプレードライヤーのノズル交換により、平均粒度４０μｍの粒状乾燥物と平均粒度２００μｍの粒状乾燥物の二種を得た。得られたチタン濃縮物の主な成分組成を表２に示した。総ＴｉＯ２の全量は、ルチル構造を有する酸化チタンであり、アナタース型構造酸化チタンやアモルファスの酸化チタンは含まれていなかった。表中の総Ｆｅは、分析したＦｅＯとＦｅ２Ｏ３の合計量をＦｅ換算で表したものである。 Example 1
It was confirmed that the ilmenite ore was crushed by a ball mill and passed through a 330 mesh (44 μm) sieve. The particle size distribution of this pulverized product is shown in FIG. The obtained pulverized product and 10% by mass hydrochloric acid were placed in a reaction vessel equipped with a stirrer so as to have V / W = 10, mixed, and pre-leached while stirring at 30 ° C. for 2 hours. Then, solid-liquid separation was performed by filtration and washing with water, and the obtained wet cake was transferred to a reaction vessel with a condenser, mixed with 19% by mass hydrochloric acid so that V / W = 3.77, and multiplied by 1 reduction equivalent (that is, 1 reduction equivalent). It was leached at 108 ° C. (boiling point) for 10 hours together with TiCl 3 (1 times the amount of reducing trivalent iron to divalent (reduction equivalent)). After completion of the reaction, solid-liquid separation was performed by filtration and washing with water, and then a slurry was prepared and then spray-dried with a spray dryer to obtain a titanium concentrate. Two types of titanium concentrates were obtained by exchanging the nozzles of the spray dryer, a granular dried product having an average particle size of 40 μm and a granular dried product having an average particle size of 200 μm. The main component compositions of the obtained titanium concentrate are shown in Table 2. The total amount of total TiO 2 was titanium oxide having a rutile structure, and did not contain anatas-type structure titanium oxide or amorphous titanium oxide. The total Fe in the table represents the total amount of the analyzed FeO and Fe 2 O 3 in terms of Fe.
実施例２
実施例１と同様にして得られた粉砕物と１９質量％塩酸をＶ／Ｗ＝３．２５となるように、撹拌機付きの反応容器に入れて混合し、６０℃で２時間循環撹拌しながら、１還元当量倍のＴｉＣｌ３に相当するＦｅ（０）（すなわち、金属鉄）存在下のもとで予備浸出させた。その後、コンデンサー付き反応槽に移し、Ｖ／Ｗ＝３．５０となるように、１９質量％塩酸を追加混合し、１０８℃（沸点）で１０時間、前記のＦｅ（０）により還元したチタン（ＩＩＩ）塩存在下のもとで本浸出させた。反応終了後、濾過と水洗によって固液分離して、次いで、スラリーにした後、３％フッ酸溶液（フッ化水素酸水溶液）と混合して７０℃で２時間撹拌して脱シリカ処理を行った。脱シリカ処理終了後、濾過と水洗によって固液分離して、次いで、スラリーにした後、スプレードライヤーにて噴霧乾燥してチタン濃縮物を得た。チタン濃縮物としてはスプレードライヤーのノズル交換により、平均粒度４０μｍの粒状乾燥物と平均粒度２００μｍの粒状乾燥物の二種を得た。チタン濃縮物の主な成分組成を表３に示した。総ＴｉＯ２の全量は、ルチル構造を有する酸化チタンであり、アナタース型構造の酸化チタンやアモルファスの酸化チタンは含まれていなかった。表中の総Ｆｅは、分析したＦｅＯとＦｅ２Ｏ３の合計量をＦｅ換算で表したものである。 Example 2
The pulverized product obtained in the same manner as in Example 1 and 19% by mass hydrochloric acid were placed in a reaction vessel equipped with a stirrer so as to have V / W = 3.25, mixed, and circulated and stirred at 60 ° C. for 2 hours. However, it was pre-leached in the presence of Fe (0) (that is, metallic iron) corresponding to TiCl 3 which was 1 reduction equivalent. Then, the mixture was transferred to a reaction vessel with a condenser, 19% by mass hydrochloric acid was additionally mixed so that V / W = 3.50, and titanium (reduced by Fe (0)) was reduced at 108 ° C. (boiling point) for 10 hours. III) This leaching was carried out in the presence of salt. After completion of the reaction, solid-liquid separation was performed by filtration and washing with water, and then a slurry was prepared, mixed with a 3% hydrofluoric acid solution (hydrofluoric acid aqueous solution), and stirred at 70 ° C. for 2 hours for desilicaization. It was. After completion of the desilica treatment, solid-liquid separation was performed by filtration and washing with water, and then a slurry was prepared and then spray-dried with a spray dryer to obtain a titanium concentrate. Two types of titanium concentrates were obtained by exchanging the nozzles of the spray dryer, a granular dried product having an average particle size of 40 μm and a granular dried product having an average particle size of 200 μm. The main constituent compositions of the titanium concentrate are shown in Table 3. The total amount of TiO 2 was titanium oxide having a rutile structure, and did not contain titanium oxide having an anatas-type structure or amorphous titanium oxide. The total Fe in the table represents the total amount of the analyzed FeO and Fe 2 O 3 in terms of Fe.
実施例１と同様にして得られた粉砕物と１９質量％塩酸をＶ／Ｗ＝３．２５となるように、撹拌機付きの反応容器に入れて混合し、６０℃で２時間循環撹拌しながら、１還元当量倍のＴｉＣｌ３に相当するＦｅ（０）（すなわち、金属鉄）存在下のもとで予備浸出させた。その後、コンデンサー付き反応槽に移し、Ｖ／Ｗ＝３．５０となるように、１９質量％塩酸を追加混合し、１０８℃（沸点）で１０時間、前記のＦｅ（０）により還元したチタン（ＩＩＩ）塩存在下のもとで本浸出させた。反応終了後、濾過と水洗によって固液分離して、次いで、スラリーにした後、３％フッ酸溶液（フッ化水素酸水溶液）と混合して７０℃で２時間撹拌して脱シリカ処理を行った。脱シリカ処理終了後、濾過と水洗によって固液分離して、次いで、スラリーにした後、スプレードライヤーにて噴霧乾燥してチタン濃縮物を得た。チタン濃縮物としてはスプレードライヤーのノズル交換により、平均粒度４０μｍの粒状乾燥物と平均粒度２００μｍの粒状乾燥物の二種を得た。チタン濃縮物の主な成分組成を表３に示した。総ＴｉＯ２の全量は、ルチル構造を有する酸化チタンであり、アナタース型構造の酸化チタンやアモルファスの酸化チタンは含まれていなかった。表中の総Ｆｅは、分析したＦｅＯとＦｅ２Ｏ３の合計量をＦｅ換算で表したものである。 Example 2
The pulverized product obtained in the same manner as in Example 1 and 19% by mass hydrochloric acid were placed in a reaction vessel equipped with a stirrer so as to have V / W = 3.25, mixed, and circulated and stirred at 60 ° C. for 2 hours. However, it was pre-leached in the presence of Fe (0) (that is, metallic iron) corresponding to TiCl 3 which was 1 reduction equivalent. Then, the mixture was transferred to a reaction vessel with a condenser, 19% by mass hydrochloric acid was additionally mixed so that V / W = 3.50, and titanium (reduced by Fe (0)) was reduced at 108 ° C. (boiling point) for 10 hours. III) This leaching was carried out in the presence of salt. After completion of the reaction, solid-liquid separation was performed by filtration and washing with water, and then a slurry was prepared, mixed with a 3% hydrofluoric acid solution (hydrofluoric acid aqueous solution), and stirred at 70 ° C. for 2 hours for desilicaization. It was. After completion of the desilica treatment, solid-liquid separation was performed by filtration and washing with water, and then a slurry was prepared and then spray-dried with a spray dryer to obtain a titanium concentrate. Two types of titanium concentrates were obtained by exchanging the nozzles of the spray dryer, a granular dried product having an average particle size of 40 μm and a granular dried product having an average particle size of 200 μm. The main constituent compositions of the titanium concentrate are shown in Table 3. The total amount of TiO 2 was titanium oxide having a rutile structure, and did not contain titanium oxide having an anatas-type structure or amorphous titanium oxide. The total Fe in the table represents the total amount of the analyzed FeO and Fe 2 O 3 in terms of Fe.
比較例１
実施例１で用いた粉砕前のイルメナイト鉱石と１９質量％塩酸をＶ／Ｗ＝３．７７となるように、コンデンサー付き反応槽に入れて、１還元当量倍のＴｉＣｌ３とともに、１０８℃（沸点）で１０時間浸出させた。反応終了後、濾過と水洗によって固液分離して、チタン濃縮物を得た。この時のチタン濃縮物乾燥品の主な成分組成を表４に示した。 Comparative Example 1
The ilmenite ore before pulverization and 19% by mass hydrochloric acid used in Example 1 were placed in a reaction vessel with a capacitor so that V / W = 3.77, and together with TiCl 3 having a reduction equivalent of 1, 108 ° C. (boiling point). ) Was leached for 10 hours. After completion of the reaction, solid-liquid separation was performed by filtration and washing with water to obtain a titanium concentrate. Table 4 shows the main component compositions of the dried titanium concentrate product at this time.
実施例１で用いた粉砕前のイルメナイト鉱石と１９質量％塩酸をＶ／Ｗ＝３．７７となるように、コンデンサー付き反応槽に入れて、１還元当量倍のＴｉＣｌ３とともに、１０８℃（沸点）で１０時間浸出させた。反応終了後、濾過と水洗によって固液分離して、チタン濃縮物を得た。この時のチタン濃縮物乾燥品の主な成分組成を表４に示した。 Comparative Example 1
The ilmenite ore before pulverization and 19% by mass hydrochloric acid used in Example 1 were placed in a reaction vessel with a capacitor so that V / W = 3.77, and together with TiCl 3 having a reduction equivalent of 1, 108 ° C. (boiling point). ) Was leached for 10 hours. After completion of the reaction, solid-liquid separation was performed by filtration and washing with water to obtain a titanium concentrate. Table 4 shows the main component compositions of the dried titanium concentrate product at this time.
実施例１及び実施例２と比較例１のチタン濃縮物を比較すると、実施例１及び実施例２のもののＴｉＯ２品位が比較例１のものより高く、シリカ分、鉄分の含有量も少なくなっていることがわかった。また、実施例１及び実施例２のチタン濃縮物を用いて、流動塩素化を行ったところ、炉外に飛散されないため、生産設備に悪影響を与えることがないこと、また、効率的に流動塩素化を行うことができ、高い収率で四塩化チタンを製造できることがわかった。
Comparing the titanium concentrates of Example 1 and Example 2 with those of Comparative Example 1, the TiO 2 grades of those of Example 1 and Example 2 are higher than those of Comparative Example 1, and the silica and iron contents are also lower. It turned out that. Further, when the titanium concentrates of Examples 1 and 2 were used for fluid chlorination, they were not scattered outside the furnace, so that the production equipment was not adversely affected, and the fluid chlorine was efficiently fluidized. It was found that titanium tetrachloride can be produced in high yield.
本発明のチタン濃縮物の製造方法は、鉄分とシリカ分等の不純物を大量に含有している変成度の低い含チタン鉄鉱石等を出発原料にした場合でも、簡便な方法で、効率的に高品位なチタン濃縮物を製造することができ、高い収率で四塩化チタンを得ることができるなど産業上有用な技術である。
The method for producing a titanium concentrate of the present invention is a simple method and efficiently even when a titanium-containing iron ore having a low degree of alteration containing a large amount of impurities such as iron and silica is used as a starting material. It is an industrially useful technique such as being able to produce a high-quality titanium concentrate and obtaining titanium tetrachloride in a high yield.
Claims (13)
- 含チタン鉄鉱石又はその類似物を３３０メッシュの篩を通過する粒度に粉砕して得た粉砕物を、１～２０質量％の塩酸初期濃度で８０℃以下の反応温度にて予備浸出を行った後、可溶性還元性物質の存在下、１５～２０質量％の塩酸初期濃度で９０℃以上の反応温度にて本浸出を行うことを含むチタン濃縮物の製造方法。 A pulverized product obtained by pulverizing a titanium-containing iron ore or a similar product to a particle size passing through a 330-mesh sieve was preliminarily leached at a reaction temperature of 80 ° C. or lower at an initial concentration of 1 to 20% by mass of hydrochloric acid. After that, a method for producing a titanium concentrate, which comprises performing the main leaching at a reaction temperature of 90 ° C. or higher at an initial concentration of hydrochloric acid of 15 to 20% by mass in the presence of a soluble reducing substance.
- １～１５質量％の塩酸初期濃度で予備浸出を行う請求項１に記載のチタン濃縮物の製造方法。 The method for producing a titanium concentrate according to claim 1, wherein pre-leaching is performed at an initial concentration of hydrochloric acid of 1 to 15% by mass.
- 前記の本浸出を行った後、固液分離して得られた浸出物を洗浄し、乾燥することを含む請求項１又は２に記載のチタン濃縮物の製造方法。 The method for producing a titanium concentrate according to claim 1 or 2, which comprises washing and drying the leachate obtained by solid-liquid separation after the main leaching.
- 乾燥が造粒乾燥である請求項３に記載のチタン濃縮物の製造方法。 The method for producing a titanium concentrate according to claim 3, wherein the drying is granulation drying.
- 乾燥して得られた乾燥物を６００～１０００℃の温度で焼成することを含む請求項３又は４に記載のチタン濃縮物の製造方法。 The method for producing a titanium concentrate according to claim 3 or 4, which comprises calcining the dried product obtained by drying at a temperature of 600 to 1000 ° C.
- 本浸出を浸出液の沸点以下の温度で行う請求項１～５の何れか一項に記載のチタン濃縮物の製造方法。 The method for producing a titanium concentrate according to any one of claims 1 to 5, wherein the main leaching is performed at a temperature equal to or lower than the boiling point of the leachate.
- 予備浸出をフッ素系添加剤の存在下で行う請求項１～６の何れか一項に記載のチタン濃縮物の製造方法。 The method for producing a titanium concentrate according to any one of claims 1 to 6, wherein the preliminary leaching is performed in the presence of a fluorine-based additive.
- 予備浸出を可溶性還元物質の存在下で行うことを含む請求項１～７の何れか一項に記載のチタン濃縮物の製造方法。 The method for producing a titanium concentrate according to any one of claims 1 to 7, which comprises performing preliminary leaching in the presence of a soluble reducing substance.
- 前記の本浸出を行った後、フッ素系添加剤を添加する工程を行う請求項１～８の何れか一項に記載のチタン濃縮物の製造方法。 The method for producing a titanium concentrate according to any one of claims 1 to 8, wherein the step of adding a fluorine-based additive is performed after the main leaching is performed.
- チタン濃縮物がルチル構造を有する酸化チタンを含む請求項１～９の何れか一項に記載のチタン濃縮物の製造方法。 The method for producing a titanium concentrate according to any one of claims 1 to 9, wherein the titanium concentrate contains titanium oxide having a rutile structure.
- 前記の乾燥を行って、ルチル構造を有する酸化チタンを含むチタン濃縮物を製造する請求項３又は４に記載のチタン濃縮物の製造方法。 The method for producing a titanium concentrate according to claim 3 or 4, wherein the drying is performed to produce a titanium concentrate containing titanium oxide having a rutile structure.
- 可溶性還元性物質が、金属鉄及び／又は可溶性チタン塩である請求項１～１１の何れか一項に記載のチタン濃縮物の製造方法。 The method for producing a titanium concentrate according to any one of claims 1 to 11, wherein the soluble reducing substance is metallic iron and / or a soluble titanium salt.
- 可溶性還元性物質が、チタン(III)塩である請求項１２に記載のチタン濃縮物の製造方法。 The method for producing a titanium concentrate according to claim 12, wherein the soluble reducing substance is a titanium (III) salt.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112723311A (en) * | 2020-12-28 | 2021-04-30 | 宜宾天原海丰和泰有限公司 | Method for comprehensively utilizing artificial rutile mother liquor by utilizing iron ore |
| CN113604671A (en) * | 2021-07-30 | 2021-11-05 | 四川顺应动力电池材料有限公司 | Method for preparing high-purity titanium slag from high-calcium-magnesium titanium concentrate |
| WO2022059534A1 (en) * | 2020-09-18 | 2022-03-24 | 石原産業株式会社 | Recovery method of alkali metal fluorides and use method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06501741A (en) * | 1990-03-02 | 1994-02-24 | ウィメラ インダストリアル ミネラルズ プロプライアタリー リミティド | Production of synthetic rutile |
| JPH07500145A (en) * | 1991-05-20 | 1995-01-05 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | TiO↓2 ore refining method |
| JPH07509279A (en) * | 1992-07-31 | 1995-10-12 | アールジーシー ミネラル サンドズ リミテッド | Treatment of titanium-containing substances |
| CN102978378A (en) * | 2012-11-30 | 2013-03-20 | 重庆地质矿产研究院 | Method for leaching metallic titanium of coal-series stratum co-associated titanium deposit |
| WO2014125275A1 (en) * | 2013-02-15 | 2014-08-21 | Tioxide Europe Limited | Method for producing titanium oxide and iron oxide |
| US20150252448A1 (en) * | 2014-03-05 | 2015-09-10 | Fouad F. KAMALEDDINE | Production of high-grade synthetic rutile from low-grade titanium-bearing ores |
-
2020
- 2020-06-29 WO PCT/JP2020/025551 patent/WO2021002332A1/en active Application Filing
- 2020-06-29 TW TW109121761A patent/TW202111132A/en unknown
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06501741A (en) * | 1990-03-02 | 1994-02-24 | ウィメラ インダストリアル ミネラルズ プロプライアタリー リミティド | Production of synthetic rutile |
| JPH07500145A (en) * | 1991-05-20 | 1995-01-05 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | TiO↓2 ore refining method |
| JPH07509279A (en) * | 1992-07-31 | 1995-10-12 | アールジーシー ミネラル サンドズ リミテッド | Treatment of titanium-containing substances |
| CN102978378A (en) * | 2012-11-30 | 2013-03-20 | 重庆地质矿产研究院 | Method for leaching metallic titanium of coal-series stratum co-associated titanium deposit |
| WO2014125275A1 (en) * | 2013-02-15 | 2014-08-21 | Tioxide Europe Limited | Method for producing titanium oxide and iron oxide |
| US20150252448A1 (en) * | 2014-03-05 | 2015-09-10 | Fouad F. KAMALEDDINE | Production of high-grade synthetic rutile from low-grade titanium-bearing ores |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022059534A1 (en) * | 2020-09-18 | 2022-03-24 | 石原産業株式会社 | Recovery method of alkali metal fluorides and use method thereof |
| CN112723311A (en) * | 2020-12-28 | 2021-04-30 | 宜宾天原海丰和泰有限公司 | Method for comprehensively utilizing artificial rutile mother liquor by utilizing iron ore |
| CN113604671A (en) * | 2021-07-30 | 2021-11-05 | 四川顺应动力电池材料有限公司 | Method for preparing high-purity titanium slag from high-calcium-magnesium titanium concentrate |
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| JPWO2021002332A1 (en) | 2021-01-07 |
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