WO2024257526A1 - Procédé de production d'une matière première électrolytique à base de titane et procédé de production de titane métallique ou d'un alliage de titane - Google Patents

Procédé de production d'une matière première électrolytique à base de titane et procédé de production de titane métallique ou d'un alliage de titane Download PDF

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Publication number
WO2024257526A1
WO2024257526A1 PCT/JP2024/017693 JP2024017693W WO2024257526A1 WO 2024257526 A1 WO2024257526 A1 WO 2024257526A1 JP 2024017693 W JP2024017693 W JP 2024017693W WO 2024257526 A1 WO2024257526 A1 WO 2024257526A1
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titanium
raw material
producing
based electrolytic
electrolytic raw
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Japanese (ja)
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秀樹 藤井
健一 森
和宏 熊本
明治 渡辺
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Toho Titanium Co Ltd
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Toho Titanium Co 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
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium

Definitions

  • This invention relates to a method for producing titanium-based electrolytic raw materials used in molten salt electrolytic refining to obtain titanium or titanium alloys, and a method for producing titanium or titanium alloys.
  • Titanium metal (pure titanium) and titanium alloys are generally produced from titanium metal sponge, an intermediate product obtained from titanium ore using a method based on the Kroll process, which is suitable for mass production.
  • electrolytic refining using a molten salt bath may make it easier to produce titanium metal and titanium alloys with fewer impurities than the method based on the Kroll process. Examples of this type of technology are described in Patent Documents 1 and 2.
  • Patent Document 1 describes a method for extracting a titanium product from titanium ore, comprising the steps of: mixing a chemical blend containing titanium ore and a reducing agent, the ratio of the titanium ore to the reducing agent being 0.9 to 2.4, the mass ratio of the titanium oxide component in the titanium ore to the reducing agent being equivalent to the mass ratio of the reducing metal in the reducing agent to the titanium oxide component in the titanium ore; heating the chemical blend to start an extraction reaction, the chemical blend being heated at an increasing rate of 1° C. to 50° C./min; maintaining the chemical blend at a reaction temperature of 1500 to 1800° C.
  • Patent Document 2 also describes a similar method.
  • the chemical blend includes one or more viscosity agents to achieve a desired slag viscosity.
  • a viscosity agent is selected that only affects the viscosity of the chemical blend and the resulting slag and only affects heating of the chemical blend to a limited extent.
  • Calcium fluoride (CaF 2 ) is one example of such a viscosity agent. CaF 2 does not participate in the chemical reaction between the titanite and the reducing agent, but only assists in adjusting the viscosity of the molten material. In general, components that do not participate in the reaction and assist in adjusting the viscosity of the slag are good candidates.
  • various alkali halides, alkaline earth halides, and certain oxides may be used as viscosity agents" (paragraph 0042).
  • Patent Document 1 states that "The final temperature is between 1500°C and 1800°C, and if the final temperature is higher than 1800°C, the extraction reaction will produce a titanium product containing a higher amount of contaminants because the molten titanium product reacts with the reaction vessel and slag" (paragraph 0052).
  • Patent Document 2 also has a similar statement (see paragraphs 0031 and 0033).
  • Patent Document 3 does not relate to molten salt electrolytic refining, it discloses a method for producing a Ti-Al alloy in which "low-grade titanium raw material containing a large amount of titanium oxide ( TiO2 ), such as low-grade sponge titanium, scrap titanium, or rutile ore, is added to an aluminum raw material and dissolved to deoxidize the mixture, thereby producing a high-grade, i.e., low-oxygen Ti-Al alloy.” More specifically, the method describes a process for producing a Ti-Al alloy, which comprises: adding a flux containing 35% by weight or more of calcium fluoride in calcium oxide to a molten raw material made of titanium and aluminum materials and containing 50% by weight or more of Al; charging the molten raw material to which the flux has been added into a water-cooled copper crucible having a tapping port formed at the bottom thereof; inducing melting by creating an atmosphere of 1.33 Pa or more inside the water-cooled copper crucible; pouring the molten raw material induction-melted
  • Patent Document 3 also states that "The content of CaF2 in the flux ⁇ is set to 35 mass% or more so that the melting point of the flux ⁇ is 1800K or less. Also, the content of CaF2 in the flux ⁇ is set to less than 95 mass% so that the Ti-Al alloy Z obtained as a product is not contaminated by fluorine in the CaF2 .”
  • a crude titanium-based material containing Ti, Al, and O and having electrical conductivity is used as the anode in the molten salt bath in an electrolytic cell, and a voltage is applied between the anode and cathode.
  • Patent Documents 1 and 2 To obtain titanium-based electrolytic raw materials for use in electrolytic refining, for example, as described in Patent Documents 1 and 2, the reducing agent Al is reacted with titanium oxide contained in titanium ore at high temperatures in a melt to reduce the titanium oxide.
  • the methods described in Patent Documents 1 and 2 were unable to sufficiently reduce the aluminum content and oxygen content of the titanium-based electrolytic raw materials.
  • the object of this invention is to provide a method for producing titanium-based electrolytic raw materials that can produce titanium-based electrolytic raw materials with relatively low aluminum and oxygen contents, and a method for producing metallic titanium or titanium alloys.
  • titanium alloy product titanium-based electrolytic raw material
  • the method for producing titanium-based electrolytic raw materials of the present invention is a method for producing titanium-based electrolytic raw materials to be used in molten salt electrolytic refining to obtain metallic titanium or titanium alloys, and includes a reaction step in which titanium oxide, aluminum elemental substance and/or alloy, and calcium halide are reacted in a melt at a temperature of 1870°C or higher, and a titanium alloy product containing Al and O is obtained in a molten state by a reaction that includes deoxidation of a portion of the O in the titanium oxide.
  • the reaction step it is preferable to include a separation step in which the temperature of the melt is reduced to 1800°C or less and the solid titanium alloy product is separated from the liquid slag.
  • the reaction process it is preferable to melt the titanium oxide and the calcium halide, and then add the aluminum element and/or alloy to form the melt.
  • the calcium halide may be at least one selected from the group consisting of calcium fluoride, calcium chloride, calcium bromide, and calcium iodide.
  • the separation step it is preferable to include a remelting step in which the solid titanium alloy product obtained in the separation step is remelted under a reduced pressure atmosphere.
  • the method for producing titanium-based electrolytic raw material of the present invention preferably includes a casting step in which the molten titanium alloy product is poured into a mold and cast after the remelting step.
  • the method for producing a titanium-based electrolytic raw material of the present invention can produce a titanium-based electrolytic raw material having an aluminum content of 8 mass% or less and an oxygen content of 8 mass% or less.
  • the titanium-based electrolytic raw material preferably has an aluminum content of 5 mass% or less and/or an oxygen content of 5 mass% or less.
  • the method for producing a titanium-based electrolytic raw material of the present invention can produce a titanium-based electrolytic raw material having a resistivity of 10 ⁇ m to 150 ⁇ m.
  • the melt preferably contains Al in a ratio of 0.2 to 1.0 and calcium halide in a ratio of 0.1 to 0.8, based on the mass ratio of the titanium oxide content.
  • the reaction temperature in the reaction step is preferably 1900° C. or higher and 3000° C. or lower.
  • the method for producing metallic titanium or a titanium alloy of the present invention includes electrolytic refining in which a crude titanium-based material in an anode is dissolved in a molten salt bath and a refined titanium-based material is deposited on a cathode, and the titanium-based electrolytic raw material produced by any of the above-mentioned methods for producing titanium-based electrolytic raw materials is used as the crude titanium-based material in the anode.
  • the molten salt bath is preferably a chloride bath.
  • the chloride bath preferably contains magnesium chloride and titanium dichloride.
  • the manufacturing method of titanium-based electrolytic raw materials of this invention makes it possible to produce titanium-based electrolytic raw materials with relatively low aluminum and oxygen contents.
  • a method for producing a titanium-based electrolytic raw material is a method for producing a titanium-based electrolytic raw material used in molten salt electrolytic refining to obtain metallic titanium or a titanium alloy.
  • the method for producing the titanium-based electrolytic raw material includes a reaction step.
  • titanium oxide, aluminum and/or alloys, and calcium halide are reacted in the melt at a temperature of 1870°C or higher.
  • some of the O (oxygen) in the titanium oxide is deoxidized to produce various reaction products, and the reaction products obtained in the melt are titanium alloy products containing Al and O (also simply called "titanium alloy products") and slag as residues or residues in a molten state.
  • a separation process may be performed, in which the temperature of the melt is lowered to 1800°C or lower to separate the solid titanium alloy products from the liquid slag.
  • the titanium alloy product thus obtained can be used as a raw material for molten salt electrolytic refining, i.e., a titanium-based electrolytic raw material, and can be provided for the production of metallic titanium or titanium alloys by molten salt electrolytic refining.
  • a titanium-based electrolytic raw material is used as the anode as the crude titanium-based material, which is the raw material for molten salt electrolytic refining, and a refined titanium-based material is precipitated on the cathode by applying a voltage between the anode and cathode.
  • the crude titanium-based material used as the titanium-based electrolytic raw material has a low aluminum and oxygen content, so that it has low electrical resistance and can keep power consumption during electrolytic refining low.
  • this method of producing metallic titanium or titanium alloys by electrolytic refining can reduce the amount of carbon used and the associated carbon dioxide emissions compared to methods based on the Kroll process, which involves chlorinating titanium ore, and can therefore contribute greatly to the realization of a carbon-neutral, and ultimately decarbonized, society.
  • titanium oxide or a mixture containing titanium oxide is heated to form a melt, the remaining substances are added as necessary, and the titanium oxide, aluminum elemental and/or alloy, and calcium halide are reacted in the melt at a temperature of 1870°C or higher.
  • the mixture may contain at least one of titanium oxide, aluminum elemental and/or alloy, and calcium halide in advance, or at least one of them may be added after melting. It is sufficient that titanium oxide, aluminum elemental and/or alloy, and calcium halide are contained in the melt at the time of reaction.
  • titanium ore containing titanium oxide may be used.
  • the embodiment described here can be applied to the smelting of titanium ore.
  • titanium ore include natural rutile, upgraded ilmenite (UGI) or upgraded slag (UGS) that has been subjected to leaching or other upgrading treatments as necessary.
  • the content of TiO 2 in the titanium ore may be, for example, 50 mass% or more, typically 80 mass% or more, and particularly 90 mass% or more.
  • metallic titanium or titanium alloy scrap, etc. may be included.
  • Titanium oxide includes TiO 2 , TiO, and TiO 2-x (0 ⁇ x ⁇ 2).
  • the calcium halide is preferably at least one selected from the group consisting of calcium fluoride, calcium chloride, calcium bromide and calcium iodide, and preferably contains at least calcium fluoride, and more preferably is calcium fluoride alone.
  • the melt preferably contains 0.2 to 1.0 mass percent Al and 0.1 to 0.8 mass percent calcium halide relative to the titanium oxide content.
  • the composition of the melt can be determined appropriately depending on the target composition of the titanium-based electrolytic raw material, etc.
  • the melt may also contain inevitable impurities such as Ca, Na, Mg, Cu, Si, Fe, etc., which are derived from impurities contained in the raw materials used in the reaction process, such as titanium oxide, metallic aluminum, aluminum alloy, and calcium halide.
  • the right side of the following formula (3) shows CaO, a typical calcium oxide, but it is presumed that it also contains compounds of complex composition other than CaO (Ca-O-Ti-Al-halogen (halogen is F, Cl, Br, I, etc. derived from calcium halide)). Therefore, here, the calcium oxide on the right side of the following formula (3) is represented as Ca(O).
  • Ti on the right side of the following formulas (1) and (3) contains a certain amount of Al and O, and may contain small amounts of Fe, Si, V, Cr, Ni, Mn, etc.
  • reaction can be expressed by the following formula (4).
  • 3TiO 2 +4Al ⁇ 3Ti+2Al 2 O 3 (1) 2Al+CaF 2 ⁇ Ca+2AlF (2) or 4Al+2CaF 2 ⁇ 2Ca+4AlF (2') 2Ca+TiO 2 ⁇ 2CaO+Ti (3) (1)+(2')+(3) 4TiO 2 +8Al+2CaF 2 ⁇ 4Ti+2Al 2 O 3 +2CaO+4AlF (4)
  • titanium oxide occurs not only by Al but also by Ca, which promotes the deoxidation of titanium oxide, and ultimately results in a titanium-based electrolytic raw material (Ti in formulas (1), (3), and (4)) with a sufficiently low oxygen content.
  • the aluminum in the aluminum element and/or alloy is used to deoxidize titanium oxide as shown in the above formula (1), and also removes halogen from calcium halide to become aluminum halide as shown in the reaction shown in the above formula (2).
  • Aluminum halide evaporates vigorously at high temperatures of 1870°C or higher and can be separated from the melt. This reduces the amount of Al in the melt, and therefore the amount of Al mixed into the final titanium-based electrolytic raw material (Ti in formulas (1), (3), and (4)) is also reduced. This is thought to contribute to obtaining titanium-based electrolytic raw material with a low aluminum content.
  • the order of melting the titanium oxide, aluminum and/or alloy, and calcium halide is not particularly important, but it is preferable to melt the titanium oxide and calcium halide in advance and then add aluminum and/or alloy to obtain the above melt.
  • the titanium oxide may be melted in advance and then the aluminum and/or alloy and calcium halide may be added thereto. Since aluminum is relatively easy to evaporate by itself, if it is added and melted from the beginning, only the stable aluminum that did not evaporate during the temperature rise will be consumed in the reactions of the above formulas (1) and (2), and there is a concern that the reaction will be insufficient. On the other hand, when aluminum is added later, the reactions of the above formulas (1) and (2) occur almost instantly after it is added.
  • titanium oxide, aluminum elemental matter and/or alloys, and calcium halide may be mixed to form a mixture, and the mixture may be melted to form a melt. After obtaining a melt from such a mixture, aluminum elemental matter and/or alloys may be added later.
  • the temperature during the reaction process is 1870°C or higher, preferably 1900°C or higher, more preferably 1950°C or higher, and particularly preferably 2000°C or higher, in order to cause the above-mentioned reaction.
  • the temperature during the reaction may be, for example, 3000°C or lower, typically 2500°C or lower, but there is no particular upper limit as long as the reaction process can be carried out appropriately taking into account the equipment, etc.
  • a water-cooled copper crucible, a water-cooled copper alloy crucible, a calcia (CaO) crucible, or the like can be used as a container for holding the melt.
  • a water-cooled copper crucible or a water-cooled copper alloy crucible is used, and the reaction is caused in a state in which a skull formed by a part of the melt solidifying is present on the inner surface of the crucible.
  • an inert gas atmosphere such as argon gas or helium gas, rather than a vacuum atmosphere, in the reaction process.
  • arc melting, plasma arc melting, or induction skull melting under an inert gas atmosphere can be used.
  • the plasma arc melting method is particularly preferable because it is easy to maintain the temperature in the high temperature range that needs to be controlled in the reaction process.
  • the substances reacted in the reaction process may contain many substances that are non-conductive at low temperatures such as room temperature, when using the induction skull melting method, it may be better to heat at least aluminum alone and/or an alloy, and further heat a mixture containing metallic titanium, titanium alloy, etc., from the viewpoint of ensuring conductivity during heating to obtain the melt.
  • a separation step can be performed to separate the titanium alloy product, which is one of the reaction products in the melt, from the slag.
  • the difference in melting points between the titanium alloy product and the slag is utilized to fully separate the titanium alloy product.
  • the temperature of the melt is lowered to a temperature of 1800 ° C or lower.
  • the titanium alloy product mainly containing Ti, Al, and O becomes solid, while the slag containing Al2O3 and Ca(O) maintains its liquid state.
  • the solid titanium alloy product has a larger specific gravity than the liquid slag, and therefore sinks and accumulates on the lower side.
  • the solid titanium alloy product is preferentially generated at the bottom. Then, the molten slag is transferred to another container by pouring or the like and removed, or the solid titanium alloy product in the melt is taken out from the slag, and a solid titanium alloy product from which the liquid slag has been separated is obtained.
  • the titanium alloy product and slag separated in the vessel may be taken out together from the vessel, and then the titanium alloy product and slag may be separated by sieving, taking advantage of the difference in specific gravity or size.
  • the temperature of the melt to be lowered in the separation process may be equal to or higher than the temperature at which the molten state of the slag is maintained, and may be equal to or lower than 1800°C.
  • the temperature after the lowering of the melt may be equal to or higher than 1400°C, or even equal to or higher than 1500°C, or may be equal to or higher than 1600°C, or even equal to or higher than 1700°C.
  • the time to hold such a temperature may be, for example, 3 minutes or more, or even 5 minutes or more, and is preferably equal to or lower than 60 minutes in consideration of productivity.
  • the solid titanium alloy product is separated from the liquid slag by settling the solid titanium alloy product during the temperature drop by slowing down the temperature drop rate, it may not be necessary to hold the solid titanium alloy product at a temperature higher than the temperature at which the molten state of the slag is maintained.
  • the temperature may be lowered to a lower temperature (for example, room temperature).
  • induction skull melting which makes it easy to maintain the above temperature.
  • the melting method can be changed from plasma arc melting to induction skull melting.
  • the temperature is not maintained in the separation process and is lowered at a slow rate, it may be preferable to use plasma arc melting.
  • the separation process is also preferably performed under an inert gas atmosphere.
  • the plasma arc melting method can easily perform high-temperature heating, it can be difficult to control temperatures below 1800°C.
  • the induction skull melting method has difficulties in heating and melting the substances to be reacted in the reaction process, but it is easy to stably control temperatures below 1800°C. From these perspectives, it is also preferable to perform the reaction process using the plasma arc melting method and the separation process using the induction skull melting method.
  • the solid titanium alloy product separated from the slag in the separation step may be heated in a reduced pressure atmosphere and melted again in a remelting step, if necessary.
  • a part of the Al and O that may be contained in the titanium alloy product is evaporated and removed in the form of atomic aluminum or Al2O (aluminum suboxide), so that the aluminum content and oxygen content of the titanium-based electrolytic raw material can be further reduced.
  • the degree of vacuum is preferably 1 ⁇ 10 ⁇ 3 Pa to 1 Pa in order to effectively evaporate aluminum and Al 2 O.
  • the temperature in the remelting step is not particularly limited as long as it is a temperature at which the titanium alloy product melts, but may be 1900° C. to 2500° C.
  • the time for which the molten metal is held may be, for example, 5 minutes to 1 hour.
  • a high vacuum electron beam melting method or an induction skull melting method is preferably used in order to effectively remove many of the above-mentioned impurities.
  • a casting process may be performed after the remelting process.
  • molten salt electrolytic refining it is advantageous for the titanium-based electrolytic raw material to have a large surface area to be dissolved, and from this perspective, granular titanium-based electrolytic raw material may be used.
  • titanium-based electrolytic raw material with low aluminum and oxygen contents has high toughness, and may be difficult to mold or pulverize for use in molten salt electrolytic refining.
  • a casting process may be performed to mold the material into a desired shape, which can then be used as an anode in molten salt electrolytic refining.
  • the titanium alloy product melted in the remelting process described above is not cooled, and can be poured into a mold or die shaped like an anode by pouring or the like while maintaining the molten state.
  • the titanium-based electrolytic raw material produced as described above contains Ti, Al, and O as well as unavoidable impurities and has electrical conductivity.
  • the titanium-based electrolytic raw material preferably has an aluminum content of 8 mass% or less, more preferably 5 mass% or less, and even more preferably 3 mass% or less, and an oxygen content of 8 mass% or less, more preferably 5 mass% or less, and even more preferably 3 mass% or less.
  • the aluminum content of the titanium-based electrolytic raw material may be 0.1 mass% or more, more preferably 0.3 mass% or more, and especially 1 mass% or more, and the oxygen content may be 0.3 mass% or more, more preferably 0.5 mass% or more, and especially 1.5 mass% or more.
  • the resistivity of the titanium-based electrolytic raw material measured at room temperature is, for example, 10 ⁇ m to 150 ⁇ m, or, for example, 10 ⁇ m to 100 ⁇ m.
  • the titanium-based electrolytic raw material can be used to carry out molten salt electrolytic refining.
  • molten salt electrolytic refining a voltage is applied between electrodes including an anode and a cathode, which are immersed in a molten salt bath in an electrolytic cell.
  • an anode containing the titanium-based electrolytic raw material as a crude titanium-based material is used.
  • Ti is dissolved from the crude titanium-based material of the anode, and is electrodeposited on the cathode to precipitate a refined titanium-based material.
  • the anode is not particularly limited as long as it contains the titanium-based electrolytic raw material, which is the crude titanium-based material in electrolytic refining.
  • the plate-shaped titanium-based electrolytic raw material obtained after the casting process described above can be used as the anode as it is.
  • granular or powdered titanium-based electrolytic raw material can be placed in a cage-shaped container that can be electrically connected and has many through holes, and this can be used as the anode.
  • the cage-shaped container may have a plate-shaped or cylindrical outer shape and may be made of nickel, nickel-based alloy, Hastelloy, or steel coated with nickel or nickel-based alloy, etc., and may have many through holes.
  • the cathode can be one whose surface is at least made of titanium, and can be, for example, a titanium plate or titanium rod made entirely of titanium. It is possible to arrange a bipolar electrode between the anode and the cathode, but a bipolar electrode is not necessary.
  • the molten salt bath may be a chloride bath mainly containing metal chlorides, for example, alkali metal chlorides and/or alkaline earth metal chlorides, for example, 70 mol% or more, further 90 mol% or more, and further 95 mol% or more.
  • Such chloride baths are preferred because they are less corrosive, have a lower environmental impact, and are less expensive than fluoride baths, bromide baths, and iodide baths.
  • a chloride bath containing magnesium chloride (MgCl 2 ) is used, a purified titanium-based material can be obtained in which not only the oxygen content but also the aluminum content is sufficiently reduced.
  • the magnesium chloride content in the chloride bath is preferably 30 mol% or more, further 50 mol% or more, further 80 mol% or more, further 85 mol% or more, and particularly 95 mol% or more.
  • the chloride bath may contain one or more metal chlorides selected from lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), rubidium chloride (RbCl), cesium chloride (CsCl), beryllium chloride ( BeCl2 ), calcium chloride ( CaCl2 ), strontium chloride ( SrCl2 ), and barium chloride ( BaCl2 ), for example, at 70 mol% or less, further 50 mol% or less, further 20 mol% or less, further 10 mol% or less, and further 5 mol% or less.
  • the molten salt bath may contain, as necessary, a lower titanium chloride having a lower Ti valence than titanium tetrachloride, specifically titanium dichloride ( TiCl2 ) or titanium trichloride ( TiCl3 ), etc.
  • the content of Ti ions in the molten salt bath is preferably 3 mol% or more, more preferably 5 mol% or more, even more preferably 6 mol% or more, and may even be 10 mol% or more, and is preferably 20 mol% or less.
  • the chloride bath preferably contains magnesium chloride and titanium dichloride.
  • the titanium dichloride may partially become titanium trichloride due to a disproportionation reaction.
  • the content of metal chlorides and metal ions in the molten salt bath can be measured by ICP emission spectrometry or atomic absorption spectrometry.
  • the content of Ti ions is calculated as a percentage of the total content of metal ions in the molten salt bath.
  • the conditions for electrolytic refining may include, for example, a temperature of the molten salt bath of 450°C to 900°C and a current density at the cathode of 0.01 A/ cm2 to 3 A/ cm2 .
  • the electrodes may pass a current continuously or may pass a pulse current in which a current-passing period and a current-passing period are alternately repeated, with a current-passing stop period during which the current value is set to zero.
  • the maximum voltage between the electrodes may be, for example, 0.2 V to 3.5 V.
  • the inside of the electrolytic cell is preferably maintained in an inert gas atmosphere such as argon.
  • Electrolytic refining can be repeated multiple times to further refine the refined titanium-based material obtained.
  • the refined titanium-based material deposited on the cathode in the previous electrolytic refining is used as the crude titanium-based material for the anode containing the crude titanium-based material.
  • refined titanium-based material from which impurities have been further removed is deposited on the cathode.
  • the titanium-based electrolytic raw material produced by the method described above has a reduced aluminum and oxygen content, so good metallic titanium or titanium alloy can be produced even with a few electrolytic refining cycles. It is preferable to perform electrolytic refining only once rather than two or more times. However, even when electrolytic refining is performed two or more times, it is possible to suppress power consumption and improve yields due to the low aluminum and oxygen contents of the titanium-based electrolytic raw material.
  • the aluminum content of the finally obtained titanium metal is, for example, 0.1 mass% or less, preferably 0.01 mass% or less, and the oxygen content is, for example, 0.2 mass% or less, preferably 0.10 mass% or less, and more preferably 0.05 mass% or less.
  • the finally obtained titanium alloy may have an aluminum content of, for example, 3 mass% or less, preferably 2 mass% or less, and an oxygen content of 0.3 mass% or less, preferably 0.15 mass% or less.
  • granular titanium ore (mixture of UGS and UGI) containing 90% or more by mass of titanium oxide TiO2 , granular calcium halides (ceramic grade) shown in Table 1, and metallic aluminum shot (granules) as a simple aluminum substance were used.
  • the mass ratio of titanium oxide ( TiO2 ):aluminum:calcium halide was 1:0.5:0.5.
  • half of the calcium halide by mass was CaCl2 , and the remaining half was CaF2 .
  • CaO was further added in an amount equivalent to 10% of the mass of CaF2 .
  • the titanium ore, calcium halide, and aluminum shot were melted in a water-cooled copper crucible under an argon gas atmosphere using the plasma arc melting method, and the melt was heated to the maximum temperature shown in Table 1 to cause a reaction.
  • Example 1 a mixture of titanium ore, calcium halide (except Comparative Example 5), and metallic aluminum shot was placed in a water-cooled copper crucible before melting and melted together.
  • Example 8 the mixture of titanium ore and calcium halide was melted first, and then the entire amount of metallic aluminum shot was added thereto.
  • Example 9 a mixture of titanium ore, calcium halide, and half the amount of metallic aluminum shot was melted first, and then the remaining half of the amount of metallic aluminum shot was added.
  • Example 5 the melt was poured into a slit-type water-cooled copper crucible for the induction skull melting method, and cooled to the temperature shown in Table 1 in an argon gas atmosphere and maintained at that temperature, or slowly cooled to room temperature at a rate of about 0.5°C/s. After that, the slag was removed from the water-cooled copper crucible by pouring, and the titanium alloy product was separated from the slag. Note that in Example 5, slow cooling to room temperature was performed, and the slag and titanium alloy product solidified separately in the upper and lower parts of the crucible, so a titanium alloy product was obtained in the lower layer. In Example 5, too, it was thought that the titanium alloy product was generated in a solid phase and sank to the bottom while the slag was in a molten state during slow cooling.
  • Comparative Example 2 the temperature in the separation process was relatively high, while in Comparative Example 3 the separation process was omitted, and in Comparative Example 4 the temperature was lowered to a level at which the slag solidified at a relatively fast rate, resulting in insufficient separation of the slag and the titanium alloy product and insufficient production of titanium-based electrolytic raw material.
  • Comparative Example 5 calcium halide was not used, resulting in insufficient deoxidation reaction and insufficient production of titanium-based electrolytic raw material.
  • Examples 1 to 14 and Comparative Example 1 sufficient amounts of titanium-based electrolytic raw materials could be obtained as titanium alloy products, so their aluminum and oxygen contents were measured.
  • the aluminum content was measured by ICP atomic emission spectrometry using a PS3520UVDDII manufactured by Hitachi High-Tech Science Corporation, and the oxygen content was measured by inert gas fusion-infrared absorption method using an ON736 manufactured by LECO Corporation.
  • the titanium-based electrolytic raw materials consisted of titanium and unavoidable impurities as the remainder, other than aluminum and oxygen.
  • the resistivity values of the titanium-based electrolytic raw materials were also measured by the two-terminal measurement method using a low-resistance meter 3566-RY manufactured by Tsuruga Electric Co., Ltd.
  • the resistivity values were measured at room temperature, and the magnitude relationship between the values can be used to infer the magnitude relationship between the resistivity values at high temperatures during molten salt electrolytic refining. The results are shown in Table 1.
  • Example 2 In Examples 15 to 18, the titanium alloy products obtained by carrying out the same reaction and separation steps as in Example 1 or 8 were subjected to a remelting step or a casting step to obtain titanium-based electrolytic raw materials. More details are as follows.
  • the remelting step was carried out in a vacuum atmosphere (within the range of 1 ⁇ 10 -3 Pa or more and 5 ⁇ 10 -1 Pa or less).
  • Example 15 the titanium alloy product obtained in the same manner as in Example 1 was remelted in a vacuum atmosphere by an electron beam using the so-called drip melt method, while being poured into a water-cooled copper crucible, to produce a titanium-based electrolytic raw material.
  • Example 16 the titanium alloy product obtained in the same manner as in Example 1 was remelted in a hearth under a vacuum atmosphere using an electron beam, and then poured into a mold to produce a titanium-based electrolytic raw material.
  • Example 17 the titanium alloy product after removing the slag in the separation process in the same manner as in Example 1 was remelted in a vacuum atmosphere without being removed from the water-cooled copper crucible used in the induction skull melting method, and the molten material was poured into a mold to produce a titanium-based electrolytic raw material.
  • Example 18 the titanium alloy product obtained in the same manner as in Example 8 was remelted in a vacuum atmosphere using the drip melt method with an electron beam while being poured into a water-cooled copper crucible to produce a titanium-based electrolytic raw material.
  • Table 2 shows that the titanium-based electrolytic raw materials of Examples 15 to 18 have lower aluminum and oxygen contents and smaller resistivity values than the titanium-based electrolytic raw materials of Examples 1 and 8 shown in Table 1.
  • Test Example 3 Using each of the titanium-based electrolytic raw materials of Comparative Example 1, Example 1 or Example 8 of Test Example 1, or Example 18 of Test Example 2, molten salt electrolytic refining was carried out to produce metallic titanium or a titanium alloy.
  • the molten salt electrolytic refining a voltage was applied between the anode and the cathode in a molten salt bath having the composition shown in Table 3, and the crude titanium-based material in the anode was dissolved and the refined titanium-based material was precipitated on the cathode.
  • the molten salt bath contained 4% to 6% by mass of TiCl 2 , and in the example containing a plurality of other bath components in addition to TiCl 2 , the other bath components were contained in equal proportions on a mass basis.
  • the titanium-based electrolytic raw materials of Comparative Example 1, Example 1, and Example 8 were crushed to obtain crude titanium-based materials, which were then housed in a nickel cage-shaped container having a large number of through holes.
  • the titanium-based electrolytic raw material of Example 18 was poured into a plate-shaped crucible to produce a plate-shaped crude titanium-based material, which was used as the anode.
  • the cathode was a titanium plate.
  • the cathode was removed and the titanium metal or titanium alloy deposited on the cathode was collected and washed with dilute hydrochloric acid, then washed with water, and then air-dried at a temperature of about 50°C to 60°C.
  • the aluminum content, oxygen content, and resistivity of the titanium metal or titanium alloy were measured in the same manner as for the titanium-based electrolytic raw material in Test Example 1. The results are also shown in Table 3.
  • Comparative Examples 6 to 8 the titanium-based electrolytic raw material obtained in Comparative Example 1 was used, and so the yield was low. On the other hand, Examples 19 to 27 all had high yields.
  • Examples 22 and 25 titanium alloys with the desired aluminum and oxygen contents were obtained in a single electrolytic refining step, eliminating the need for multiple electrolytic refining steps.
  • the titanium metal in Examples 26 and 27 had sufficiently low aluminum and oxygen contents even with a single electrolytic refining step, and was of such a quality that further electrolytic refining was not necessary. It is believed that in the other Examples as well, two electrolytic refining steps would result in high-quality titanium metal or titanium alloys.

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Abstract

Le procédé de production d'une matière première électrolytique à base de titane selon l'invention produit une matière première électrolytique à base de titane utilisée dans le raffinage électrolytique en sels fondus pour obtenir du titane métallique ou un alliage de titane. Le procédé comprend une étape de réaction pour faire réagir un oxyde de titane, de l'aluminium élémentaire et/ou un alliage, et un halogénure de calcium dans une masse fondue à une température de 1870°C ou plus, et obtenir un produit d'alliage de titane comprenant Al et O généré par une réaction comprenant la désoxydation d'une partie de O dans l'oxyde de titane dans un état fondu.
PCT/JP2024/017693 2023-06-14 2024-05-13 Procédé de production d'une matière première électrolytique à base de titane et procédé de production de titane métallique ou d'un alliage de titane Pending WO2024257526A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60238430A (ja) * 1984-05-04 1985-11-27 コンパニア　バレ　ド　リオ　ドセ アルミニウムテルミツト法およびマグネシウムテルミツト法によりアナターゼ精鉱から金属チタンを得る方法
JP2009518544A (ja) * 2005-12-06 2009-05-07 マテリアルズ アンド エレクトロケミカル リサーチ コーポレイション 金属生成のための熱および電気化学的処理
JP2013079446A (ja) * 2011-09-30 2013-05-02 Pangang Group Panzhihua Iron & Steel Research Inst Co Ltd 金属チタンの製造方法およびこの方法を用いて得られた金属チタン
JP2015507696A (ja) * 2011-12-22 2015-03-12 ユニヴァーサル テクニカル リソース サービシーズ インコーポレイテッド チタンの抽出および精錬のための装置および方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60238430A (ja) * 1984-05-04 1985-11-27 コンパニア　バレ　ド　リオ　ドセ アルミニウムテルミツト法およびマグネシウムテルミツト法によりアナターゼ精鉱から金属チタンを得る方法
JP2009518544A (ja) * 2005-12-06 2009-05-07 マテリアルズ アンド エレクトロケミカル リサーチ コーポレイション 金属生成のための熱および電気化学的処理
JP2013079446A (ja) * 2011-09-30 2013-05-02 Pangang Group Panzhihua Iron & Steel Research Inst Co Ltd 金属チタンの製造方法およびこの方法を用いて得られた金属チタン
JP2015507696A (ja) * 2011-12-22 2015-03-12 ユニヴァーサル テクニカル リソース サービシーズ インコーポレイテッド チタンの抽出および精錬のための装置および方法

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