WO2023007918A1 - 電析物の製造方法 - Google Patents

電析物の製造方法 Download PDF

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Publication number
WO2023007918A1
WO2023007918A1 PCT/JP2022/020864 JP2022020864W WO2023007918A1 WO 2023007918 A1 WO2023007918 A1 WO 2023007918A1 JP 2022020864 W JP2022020864 W JP 2022020864W WO 2023007918 A1 WO2023007918 A1 WO 2023007918A1
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Prior art keywords
anodes
titanium
based material
anode
cathode
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English (en)
French (fr)
Japanese (ja)
Inventor
和宏 熊本
雄太 中條
大輔 鈴木
松秀 堀川
秀樹 藤井
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Toho Titanium Co Ltd
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Toho Titanium Co Ltd
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Priority to JP2023538292A priority Critical patent/JP7661496B2/ja
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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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing

Definitions

  • This invention relates to a method for producing a Ti-containing electrodeposit by electrolytic refining using molten salt electrolysis.
  • Titanium metal and titanium alloys are generally manufactured using the Kroll method, which is suitable for mass production.
  • this method requires chlorination and reduction of the titanium ore, crushing of sponge titanium lumps, and production of metallic magnesium by electrolysis. can be produced efficiently and at low cost.
  • Patent Document 1 describes "a method for extracting a titanium product from a titaniferous ore, characterized by comprising the following steps: a chemical blend containing a titaniferous ore and a reducing agent, wherein the titanium mixing said chemical blend corresponding to the mass ratio of titanium oxide component in said titaniferous ore to reducing metal in said reducing agent with a ratio of ore to said reducing agent of 0.9 to 2.4; heating the blend to initiate the extraction reaction, wherein the chemical blend is heated at a rate of increase of 1° C. to 50° C./min; maintaining a reaction temperature of 1500-1800° C.; cooling the chemical blend to a temperature below 1670° C.; and separating the titanium product from the residual slag.
  • Patent Document 2 describes “A method of electrorefining titanium-aluminide for producing a titanium master alloy, comprising: a. titanium-aluminide containing more than 10 mass percent aluminum and at least 10 mass percent oxygen; placing an aluminide in a reaction vessel, said reaction vessel being designed with an anode, a cathode, and an electrolyte, said electrolyte comprising a halogen salt of an alkali metal or alkaline earth metal or combination thereof; b heating the electrolyte to a temperature of 500° C.-900° C. sufficient to produce a molten electrolyte mixture c directing an electric current from the anode through the molten electrolyte mixture to the cathode; d. dissolving said titanium-aluminide from said anode to deposit a titanium aluminum master alloy on said cathode.
  • electrolytic refining using molten salt electrolysis uses a conductive crude titanium-based material containing Ti, Al, and O as an anode in a molten salt bath in an electrolytic cell, and an anode and a cathode Apply a voltage between As a result, a purified titanium-based material having a higher purity than the crude titanium-based material is deposited on the cathode, and an electrodeposit as the purified titanium-based material can be obtained.
  • An object of the present invention is to provide a method for producing an electrodeposit that allows electrolytic deposition over a relatively long period of time.
  • the inventor found that the molten salt bath can still be used for electrolytic deposition even after the anode containing Ti, Al and O has become unusable. Based on this finding, the inventors used a plurality of anodes and staggered the end of use of some of them with the end of use of the rest, thereby electrolytically depositing a purified titanium-based material on the cathode. can be prolonged.
  • the method for producing an electrodeposit according to the present invention is a method for producing an electrodeposit containing Ti by electrolytic refining using molten salt electrolysis, wherein Ti, Al and an electrode having a cathode containing a crude titanium-based material containing O and O, and depositing a refined titanium-based material on the cathode to obtain an electrodeposit.
  • the electrode in the electrodeposition step, has a plurality of anodes, and among the plurality of anodes, the end of use of some of the anodes is shifted from the end of use of the remaining anodes, and the purification is performed on the cathode It is intended to precipitate a titanium-based material.
  • the electrode may have a plurality of cathodes.
  • the number of the anodes of the electrodes is preferably larger than the number of the cathodes.
  • an electrode in which a plurality of anodes are arranged around the cathode can be used.
  • an anode replacement step is included in which a part of the anodes and/or the remaining anodes that have reached the end of use are replaced with new anodes.
  • the electrodeposition step it is preferable to perform the anode exchange step while continuing to deposit the purified titanium-based material on the cathode.
  • a mixture containing a titanium raw material containing titanium oxide, a reducing agent containing aluminum, and a separating agent is heated to extract the crude titanium-based material from the molten mixture. May include an extraction step.
  • the method for producing an electrodeposit of the present invention includes a plurality of electrodeposition steps as the electrodeposition step, and in the subsequent electrodeposition step, the purified titanium-based material deposited on the cathode in the previous electrodeposition step is deposited. It is preferable to use anodes containing a crude titanium-based material, and to shift the end of use of some of the anodes from the end of use of the remaining anodes in at least one electrodeposition step.
  • electrolytic deposition can be carried out over a relatively long period of time.
  • FIG. 1 is a cross-sectional view in the depth direction of a molten salt bath, showing an example of an electrolytic bath that can be used in the method for producing an electrodeposit according to one embodiment of the present invention
  • FIG. FIG. 2 is a cross-sectional view in a direction perpendicular to the depth direction of the molten salt bath along line II-II in FIG. 1
  • FIG. 4 is a cross-sectional view in a direction orthogonal to the depth direction, showing another example of the arrangement of electrodes in the electrolytic cell
  • FIG. 4 is a cross-sectional view in a direction orthogonal to the depth direction, showing another example of the arrangement of electrodes in the electrolytic cell
  • FIG. 1 is a cross-sectional view in the depth direction of a molten salt bath, showing an example of an electrolytic bath that can be used in the method for producing an electrodeposit according to one embodiment of the present invention
  • FIG. FIG. 2 is a cross-sectional view in a direction perpendicular to
  • FIG. 4 is a cross-sectional view in a direction orthogonal to the depth direction, showing another example of the arrangement of electrodes in the electrolytic cell
  • FIG. 10 is a cross-sectional view in a direction perpendicular to the depth direction, showing the arrangement of electrodes in the electrolytic cell of Comparative Example 2;
  • a voltage is applied between electrodes including an anode and a cathode that are immersed in a molten salt bath to perform electrolytic deposition on the cathode.
  • Electrodeposition process is included.
  • the molten salt bath is a chloride bath.
  • the anode includes a crude titanium-based material containing Ti, Al and O (oxygen). This crude titanium-based material has electrical conductivity and can be subjected to electrolytic refining using molten salt electrolysis.
  • a purified titanium-based material having relatively higher purity than the crude titanium-based material is deposited on the cathode.
  • the refined titanium-based material has a lower content of at least one component other than Ti, such as Al and O, as compared with the crude titanium-based material.
  • an extraction step for obtaining the above crude titanium-based material may be further included as an optional step that can be omitted.
  • a step of removing the molten salt bath such as water washing and drying of the purified titanium-based material, vacuum heat treatment of the purified titanium-based material, and the like may be further included.
  • an electrode having a plurality of anodes is used in the electrodeposition process.
  • the purified titanium-based material is deposited on the cathode so that the end of use of some of the plurality of anodes does not coincide with the end of use of the remaining anodes.
  • the other anode, the part or the remainder can still be used.
  • electrolytic deposition can be carried out over a long period of time as compared with the case where there is only one anode or the case where some of the anodes and the rest of the anodes end their use at the same time.
  • an anode exchange process is performed in which some of the anodes that have reached the end of use are exchanged with new anodes.
  • the crude titanium-based material contains at least Ti, Al and O. Further, the purified titanium-based material contains at least Ti and may further contain Al and/or O.
  • the purified titanium-based material may be metallic titanium consisting of Ti and impurities, or may be a titanium alloy containing alloying elements and the balance being Ti and impurities.
  • extraction process In the extraction step, a mixture containing a titanium raw material containing titanium oxide such as titanium oxide (TiO 2 ), a reducing agent containing aluminum (Al), and a separating agent is heated. It is speculated that titanium oxide is reduced with aluminum in the reducing agent, for example, based on the thermite reaction of 3TiO 2 +4Al ⁇ 3Ti+2Al 2 O 3 .
  • the heating temperature may be 1500°C to 1800°C.
  • the separating agent separates the crude titanium-based material from the slag due to the difference in density, so that the crude titanium-based material can be extracted.
  • the titanium raw material may contain titanium oxide, and examples thereof include titanium ore that has been subjected to upgrade treatment such as leaching and other treatments as required.
  • the content of TiO 2 in titanium ore used as a titanium raw material may be, for example, 50% by mass or more, typically 80% by mass or more, and particularly 90% by mass or more.
  • a separating agent is used to facilitate separation of the crude titanium-based material from the slag after heating.
  • the separating agent is preferably one or more selected from calcium fluoride, aluminum fluoride, potassium fluoride, magnesium fluoride, calcium oxide and sodium fluoride. ) is particularly suitable because it provides excellent separation of the crude titanium-based material from the mixture and has little effect on anything other than the separation.
  • the reducing agent can substantially contain aluminum (Al) alone, and may further contain Ca, Na, or the like.
  • Al aluminum
  • Ca Ca
  • mixtures may be made with TiO 2 :Al:CaF 2 adjusted to a molar ratio of 3:4-7:2-6.
  • the crude titanium-based material obtained in the extraction step contains Ti, Al and O (oxygen). The content may be 8% by mass to 30% by mass. Further, the crude titanium-based material has a Ti content of 50% by mass or more and 85% by mass or less, an Al content of 3% by mass or more and 40% by mass or less, and an O content of 0.2% by mass or more and 40% by mass. % or less. Typically, the crude titanium-based material may have a Ti content of 60% by mass or more, an Al content of 20% by mass or less, and an O content of 20% by mass or less.
  • Such a crude titanium-based material has electrical conductivity, and can be used for molten salt electrolysis by being included in the anode in the electrodeposition step described later.
  • the specific resistance of the crude titanium-based material is, for example, 1 ⁇ 10 ⁇ 8 ⁇ m to 1 ⁇ 10 ⁇ 4 ⁇ m, typically 1 ⁇ 10 ⁇ 7 ⁇ m to 5 ⁇ 10 ⁇ 5 ⁇ m. be.
  • the illustrated electrolytic bath 1 includes a bath main body 2 in the form of a container or the like in which molten salt is stored to form a molten salt bath Bm, and an anode 3a at least partially immersed in the molten salt bath Bm. and a cathode 3b, and a power source (not shown) to which the electrode 3 is connected.
  • the tank main body 2 may have an openable and closable cover member, and a gas passage used for supplying inert gas such as argon gas and discharging gas may be connected to the inside.
  • the interior of the electrolytic cell 1 can be heated by a heater (not shown) arranged around the cell body 2 .
  • the molten salt bath Bm is a chloride bath containing mainly metal chlorides, for example, alkali metal chlorides and/or alkaline earth metal chlorides, for example, 70 mol % or more, further 80 mol % or more, furthermore 90 mol %. It may contain more than Such chloride baths are preferable to fluoride baths, bromide baths, and iodide baths because of their low corrosiveness, low environmental load, and low cost. Among others, when a chloride bath containing magnesium chloride (MgCl 2 ) is used, a purified titanium-based material with sufficiently reduced not only O content but also Al content can be obtained.
  • MgCl 2 magnesium chloride
  • the content of MgCl 2 in the chloride bath is preferably at least 30 mol %, more preferably at least 50 mol %, more preferably at least 80 mol %, more preferably at least 85 mol %, especially at least 90 mol %.
  • Chloride baths include lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), rubidium chloride (RbCl), cesium chloride (CsCl), beryllium chloride ( BeCl2 ), calcium chloride ( CaCl2),
  • a lower titanium chloride having a Ti valence lower than that of titanium tetrachloride specifically TiCl 2 (titanium dichloride), TiCl 3 (titanium trichloride), etc.
  • the content of titanium ions in the molten salt bath Bm is preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 6 mol% or more, particularly preferably 10 mol% or more, and may be 20 mol% or less.
  • the content of metal chlorides and metal ions in the molten salt bath Bm can be measured by ICP emission spectrometry or atomic absorption spectrometry. The content of titanium ions is obtained as a percentage of the total content of metal ions in the molten salt bath Bm.
  • the anode 3a for example, one containing a crude titanium-based material obtained in the extraction process described above is used.
  • the anode 3a has a cage-like container made of a metal such as Ni, a Ni-based alloy, or Hastelloy, which has a lower ionization tendency than Ti. material can be placed.
  • the shape of the anode 3a is not limited to this.
  • the shape of the anode 3a may be rod-shaped, column-shaped, plate-shaped, or any other shape produced by melting and casting a crude titanium-based material.
  • a cathode 3b made of Ti can be used, and its shape is not particularly limited, and can be appropriately determined according to, for example, the shape of the anode 3a.
  • the electrode 3 may further have a double electrode arranged between the anode 3a and the cathode 3b.
  • the anode 3a and the cathode 3b of the electrodes 3 are energized from a power source, and a voltage is applied between the electrodes 3.
  • titanium ions are eluted from the crude titanium-based material contained in the anode 3a into the molten salt bath Bm, and the titanium ions are deposited on the cathode 3b as a refined titanium-based material.
  • the purified titanium-based material deposited on the cathode 3b corresponds to the electrodeposit.
  • the electrical resistance of the anode 3a increases due to the gradual decrease in the Ti content in the crude titanium-based material in the anode 3a.
  • the amount of purified titanium-based material deposited on the cathode 3b per unit time decreases, and the purified titanium-based material does not deposit in a desired form on the cathode 3b. become difficult to use.
  • the end of use of the anode 3a can be determined based on the current value flowing through the anode 3a, the relationship between the theoretical Ti elution amount, and the like.
  • the above theoretical Ti elution amount is obtained by calculating the Ti elution amount at the anode 3a from the amount of electricity applied to the electrode 3, and from the Ti elution amount and the Ti content of the crude titanium-based material in the anode 3a before the start of energization.
  • the formula: theoretical Ti elution amount (Ti elution amount calculated from electric quantity/Ti content of crude titanium-based material) ⁇ 100.
  • the valence of Ti ions in the molten salt bath which is a chloride bath, is set to two.
  • the theoretical Ti elution amount reaches 50% or more, it is preferable to consider that the anode 3a has reached the end of use from the viewpoint of maintaining the production rate and the quality of the purified titanium-based material for the cathode.
  • the end of use of the anode 3a is not limited to the above method, and may be appropriately determined based on the configuration of the electrode 3 and the like.
  • the operation of the electrolytic cell 1 is stopped, the electrolytic cell 1 is cleaned, and then the electrolytic cell 1 is rebuilt and the molten salt bath Bm is formed and operated. was restarting.
  • the molten salt bath Bm contains MgCl 2
  • MgCl 2 has hygroscopic properties. It is necessary to heat for a certain long period of time until the moisture is completely removed. Stopping and restarting the operation of the electrolytic cell 1 each time the anode 3a becomes unusable in this way increases the work load and causes a decrease in production efficiency.
  • a plurality of anodes 3a are provided, and some of the plurality of anodes 3a (for example, one anode 3a) are used.
  • Deposition of the purified titanium-based material on the cathode 3b is performed so that the timing of termination is shifted from the timing of termination of use of the remaining anodes 3a (for example, the other one anode 3a).
  • the electrodeposition process can be performed over a long period of time.
  • the use start time (energization start time) of some of the anodes 3a and the remaining anodes 3a is staggered, and the anodes It is possible to vary the content and composition of the crude titanium-based material contained in 3a. In particular, by staggering the use start times of some of the anodes 3a and the remaining anodes 3a, it becomes easier to control the shift of the use end times. For example, energization and use of the remaining anodes 3a can be started when 30% to 70% of the period of use from the start of use to the end of use of some of the anodes 3a has elapsed.
  • a plurality of cylindrical anodes 3a are preferably arranged around a cylindrical cathode 3b, for example, as shown in FIG.
  • titanium ions eluted from any of the anodes 3a are likely to deposit as a purified titanium-based material on the cathode 3b inside those anodes 3a in a cross section orthogonal to the depth direction of the molten salt bath.
  • one cathode 3b is arranged substantially at the center of a line connecting two anodes 3a in the cross-sectional view.
  • four anodes 3a are arranged at equal intervals on a circumference around the cathode 3b in the cross-sectional view. It is preferable to arrange the anodes 3a and the cathodes 3b such that the distances between the anodes 3a and the cathodes 3b are substantially equal.
  • anodes 3a When three or more anodes 3a are used, one or more but less than the total number of those anodes 3a are used as part of the anodes 3a, and the remaining one or more and less than the total number of anodes 3a are used as the remaining anodes. As for 3a, it is possible to shift the end of use timing between the part of the anodes 3a and the remaining anodes 3a. In the example shown in FIG. 3, since four anodes 3a are used, one to three of them are used as partial anodes 3a, and the rest are used as remaining anodes 3a. When there are a plurality of remaining anodes, it is not necessary to treat all of them in the same manner, and the remaining anodes may be further grouped to manage the end of use.
  • the electrodes 3 may include multiple anodes 3a and multiple cathodes 3b. As shown in FIG. 4, a plurality of anodes 3a are arranged around each of a plurality of cathodes 3b. More specifically, in FIG. 4, four anodes 3a are positioned at equal intervals around each of three cathodes 3b, and two anodes 3a are shared by adjacent cathodes 3b. and In the example of FIG. 4, in the cross section, between two rows of anodes 3a in one direction (vertical direction in FIG. 3) and four columns in the orthogonal direction (horizontal direction in FIG. 4), cathodes 3b in one row and three columns are positioned at the center of the anode 3a in the one direction and in the orthogonal direction, respectively.
  • the number of anodes 3a is preferably greater than the number of cathodes 3b.
  • the frequency of the anode exchange process can be reduced for the same amount of purified titanium-based material produced.
  • the number of the anodes 3a and the number of the cathodes 3b may be the same.
  • the shapes of the anode 3a and the cathode 3b are not limited to columnar shapes such as the columnar shape as described above.
  • a plurality of plate-shaped anodes 3a and a plurality of cathodes 3b are alternately arranged.
  • Anodes 3a are located on both sides of the periphery of each cathode 3b. Even in this case, if the end of use of some of the plurality of anodes 3a differs from that of the remaining anodes 3a, when the end of use of some or the remaining anodes 3a comes, Electrolysis between the available anode 3a and cathode 3b allows continued deposition of purified titanium-based material on said cathode 3b. It is also possible to have the same number of anodes 3a and cathodes 3b in the arrangement shown in FIG.
  • the temperature of the molten salt bath Bm may be 450° C. to 900° C.
  • the current density at the cathode 3b may be 0.01 A/cm 2 to 5 A/cm 2 .
  • the electrode 3 may be supplied with a current continuously, or may be provided with a discontinued period for reducing the current value to zero, and may be supplied with a pulse current in which the energized period and the discontinued period are alternately repeated.
  • the maximum voltage across the electrodes 3 can be, for example, 0.2-3.5V.
  • the interior of the electrolytic cell 1 is preferably maintained in an inert atmosphere such as argon.
  • the refined titanium-based material deposited on the cathode 3b by electrolytic deposition can be recovered by physically peeling it off from the cathode 3b using a cutting tool or the like.
  • the purified titanium-based material, together with the cathode 3b on which it is electrodeposited, or after being stripped from the cathode 3b, can be acid washed and/or water washed to remove molten salts. After that, vacuum drying may be performed as necessary. Further, instead of the washing and drying described above, vacuum separation may be performed to remove the molten salt under high temperature and reduced pressure conditions. Since the purity of titanium in the purified titanium-based material increases as the number of electrodeposition steps increases, the number of electrodeposition steps may be appropriately determined in view of the desired purity of titanium. This makes it possible to produce an electrodeposit of titanium metal, titanium alloy, or the like.
  • Anode exchange process It is preferable to replace some of the anodes 3a whose use has ended in the middle of the electrodeposition process with new anodes 3a in the anode replacement process. By performing the anode exchange process, when the remaining anodes 3a reach the end of use, it becomes possible to further continue the electrolytic deposition with the new anodes 3a.
  • the anode exchange step can be performed while continuing to deposit the purified titanium-based material on the cathode 3b using the remaining anode 3a.
  • the electrolytic deposition can be prolonged even further.
  • the end times of use of some of the anodes 3a and the remainder of the anodes 3a are shifted, the anode replacement process of the some of the anodes 3a and the remainder of the anodes 3a is also performed at different times.
  • two of the four anodes 3a are located on both sides in one direction (vertical direction in FIG. 3) across the cathode 3b in a cross section orthogonal to the depth direction of the molten salt bath.
  • the end times can be set at the same time.
  • one of the two anodes 3a located on both sides in one direction or the two anodes 3a located on both sides in the orthogonal direction reaches the end of use, one of the two anodes 3a is replaced.
  • the other two anodes 3a can be replaced when the other one reaches the end of use.
  • the used anode 3a (residue) is electrically disconnected from the power supply, and the used anode 3a is taken out of the electrolytic cell 1.
  • a new anode 3a is then placed immersed in the molten salt bath Bm in the electrolytic cell 1 and connected to a power supply. Thereafter, when energization to the new anode 3a is started, electrolytic deposition can be performed using the new anode 3a.
  • each anode 3a When performing the anode replacement process, it is also possible to periodically check the current value flowing through each anode 3a, for example, and determine the end of use and necessity of replacement of each anode 3a based on the current value. . When the value of the current flowing through the anode 3a falls below the reference value, it may be determined that the anode 3a should be replaced.
  • anode replacement step is not performed, some of the anodes 3a that have reached the end of use may be left electrically disconnected from the power source or removed from the electrolytic cell 1.
  • multi-stage electrodeposition process For further purification, it is also possible to carry out the above-described electrodeposition step in multiple steps.
  • the refined titanium-based material deposited on the cathode 3b in the preceding electrodeposition process is used as the crude titanium-based material in the subsequent electrodeposition process. That is, in the subsequent electrodeposition step, the purified titanium-based material deposited on the cathode 3b in the preceding electrodeposition step is used as the crude titanium-based material, and the anode 3a containing the crude titanium-based material is used.
  • a purified titanium-based material obtained by further removing impurities from the crude titanium-based material is deposited on the cathode 3b.
  • the multi-stage electrodeposition process can also be performed continuously using the same electrolytic bath 1 and molten salt bath Bm.
  • the polarities of the anode 3a and the cathode 3b in the preceding electrodeposition step are reversed, and the cathode 3b on which the purified titanium-based material is deposited can be used as the anode 3a in the subsequent electrodeposition step.
  • a new cathode 3b is placed in the place where the anode 3a was placed in the preceding electrodeposition step.
  • the end of use of some of the anodes 3a be shifted from the end of use of the remaining anodes 3a, as described above.
  • the above-mentioned anode exchange process may be performed during the electrodeposition process. As a result, it is possible to lengthen the electrodeposition process.
  • the total content of impurities other than Ti is preferably 5000 ppm by mass or less, more preferably 3000 ppm by mass or less, in the electrodeposit as a purified titanium-based material obtained by a single-stage or multiple-stage electrodeposition process.
  • the one-step electrodeposited product has, for example, an Al content of 800 mass ppm to 0.4 mass% and an O content of 1000 mass ppm to 2.0 mass. %.
  • the product obtained by the multi-stage electrodeposition process has an Al content of 5 mass ppm to 1000 mass ppm, an O content of 100 mass ppm to 500 mass ppm, and the balance may be Ti and unavoidable impurities. . Since the Al content and O content may increase due to exchange of anodes in the electrodeposition process, long-term electrodeposition using the same anode, etc., the target values for these contents are It may be determined appropriately in view of the operating conditions.
  • the electrodeposit may be derived from ores or chloride baths.
  • the electrodeposit has an N (nitrogen) content of 0.03% by mass or less, a C (carbon) content of 0.01% by mass or less, and an Fe content of 0.010% by mass or less, a Mg content of 0.05% by mass or less, a Ni content of 0.01% by mass or less, a Cr content of 0.03% by mass or less, and a Si content amount is 0.005% by mass or less, the Mn content is 0.05% by mass or less, and the Sn content is 0.01% by mass or less.
  • the appearance of the electrodeposit obtained as a purified titanium-based material is almost granular when visually observed, and when observed with a microscope, it may have a three-dimensional shape in which polyhedral fine particles are linked.
  • the sieved ratio may be, for example, 25% or more, further 50% or more, particularly 70% or more, based on mass.
  • the sieving is performed after pulverizing the electrodeposits to such an extent that they are not crushed or pulverized in an argon atmosphere glove box with an oxygen concentration of 5% by volume or less.
  • a mixture containing a titanium raw material containing TiO 2 , Al as a reducing agent, and CaF 2 as a separating agent is heated to 1500° C. to 1800° C. in an argon atmosphere to extract Ti, Al and O from the molten mixture.
  • the metal component is the ICP emission spectrometry (PS3520UVDDII, manufactured by HITACHI), the oxygen is the inert gas fusion-infrared absorption method (TC-436AR, manufactured by LECO), and the nitrogen is an inert gas fusion-thermal conductivity method (TC-436AR, manufactured by LECO), carbon is analyzed by a combustion-infrared absorption method (EMIA-920V2, manufactured by Horiba, Ltd.), and the impurity content of the crude titanium-based material is determined. It was measured. The balance other than the impurities is titanium.
  • EMIA-920V2 combustion-infrared absorption method
  • Electrolytic refining using molten salt electrolysis was performed on the above crude titanium-based material.
  • the electrolytic cell one having an internal dimension of 400 mm long and 800 mm wide was used.
  • a molten salt bath inside the electrolytic cell was prepared by dissolving only MgCl 2 and had a depth of 400 mm.
  • the chloride bath temperature was maintained at about 750° C.
  • the current density at the cathode was 0.4 A/cm 2
  • the maximum voltage between adjacent anodes and cathodes was 1.8 V. .
  • Example 1 the anode and cathode arranged as shown in FIGS. 1 and 2 were used.
  • Example 3 plate-shaped anodes and cathodes were arranged as shown in FIG.
  • Comparative Example 2 as shown in FIG. 6, a cylindrical anode was arranged to surround a cylindrical cathode.
  • the anode has a Ni cage-shaped container having a large number of through holes and into which molten salt can enter, and crude titanium is placed in the cage-shaped container. A system material was placed.
  • the anode and cathode were each cylindrical with a diameter of 100 mm and a height of 200 mm.
  • the weight of the crude titanium-based material in the basket-like container in the anodes of Examples 1, 2 and 4 and Comparative Example 1 was about 3.5 kg per cage-like container.
  • Example 3 the anode was a flat plate with a length of 200 mm, a width of 200 mm, and a thickness of 40 mm, and the cathode was a flat plate with a length of 200 mm, a width of 200 mm, and a thickness of 20 mm.
  • the weight of the crude titanium-based material in the basket-shaped container in the anode of Example 3 was about 3.6 kg per basket-shaped container.
  • the cathode was the same as in Examples 1, 2 and 4 and Comparative Example 1, and the anode was cylindrical with an outer diameter of 240 mm, an inner diameter of 200 mm, and a height of 200 m.
  • the weight of the crude titanium-based material in the basket-like container in the anode of Comparative Example 2 was about 6.2 kg.
  • Example 1 the start and end times of use of the plurality of anodes were staggered as shown in Table 3, and the electrolytic deposition was terminated when all the anodes were finished.
  • Example 3 the first and third anodes from the left in FIG. 5 and the second and fourth anodes from the left in FIG.
  • Example 2 the electrolytic deposition was continued by replacing the anode once at the end of use, and the electrolytic deposition was terminated when the new anode after replacement reached the end of use.
  • Example 4 the electrolytic deposition was continued by replacing the anode twice at the end of use, and the electrolytic deposition was terminated when the new anode after replacement reached the end of use.
  • Example 2 used a total of three anodes and Example 4 used a total of four anodes.
  • Comparative Example 1 when the use of a plurality of anodes was started at the same time, the anodes became unusable at the same time, and electrolytic deposition was terminated. In Comparative Example 2, the electrolytic deposition was terminated when the use of the anode was terminated.
  • Table 3 shows the total electrodeposition time and the amount of electrodeposits per cathode for Examples 1 to 4 and Comparative Examples 1 and 2.
  • Table 4 shows the Ti, Al and O contents of the deposits obtained in Examples 1 to 4 and Comparative Examples 1 and 2.
  • Example 3 electrolytic refining was performed in the same manner as in Example 3, except that the time lag between the start and end of use of the anode was set to zero hours (the start and end of use of the anode were set at the same time). rice field. As a result, the total electrodeposition time was shorter than that of Example 3 by 10 minutes. Therefore, even when the shape of the electrode was changed as in Example 3, the same effect was obtained.

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4944919A (https=) * 1972-07-18 1974-04-27
JPH06173065A (ja) * 1992-12-09 1994-06-21 Japan Energy Corp Ｔｉの精製方法
JP2005105374A (ja) * 2003-09-30 2005-04-21 Nippon Light Metal Co Ltd 金属酸化物の還元方法及び金属酸化物の還元装置
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
JP2018012861A (ja) * 2016-07-21 2018-01-25 日立金属株式会社 溶融塩電解を行うための装置および溶融塩電解方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4944919A (https=) * 1972-07-18 1974-04-27
JPH06173065A (ja) * 1992-12-09 1994-06-21 Japan Energy Corp Ｔｉの精製方法
JP2005105374A (ja) * 2003-09-30 2005-04-21 Nippon Light Metal Co Ltd 金属酸化物の還元方法及び金属酸化物の還元装置
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
JP2018012861A (ja) * 2016-07-21 2018-01-25 日立金属株式会社 溶融塩電解を行うための装置および溶融塩電解方法

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