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US20080250901A1 - Method of High-Melting-Point Metal Separation and Recovery - Google Patents

Method of High-Melting-Point Metal Separation and Recovery Download PDF

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Publication number
US20080250901A1
US20080250901A1 US11/886,323 US88632306A US2008250901A1 US 20080250901 A1 US20080250901 A1 US 20080250901A1 US 88632306 A US88632306 A US 88632306A US 2008250901 A1 US2008250901 A1 US 2008250901A1
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Prior art keywords
melting
point metal
molten salt
cacl
separation
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US11/886,323
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Tadashi Ogasawara
Makoto Yamaguchi
Katsunori Dakeshita
Masahiko Hori
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Osaka Titanium Technologies Co Ltd
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Osaka Titanium Technologies Co Ltd
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Assigned to OSAKA TITANIUM TECHNOLOGIES CO., LTD. reassignment OSAKA TITANIUM TECHNOLOGIES CO., LTD. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: SUMITOMO TITANIUM CORPORATION
Assigned to SUMITOMO TITANIUM CORPORATION reassignment SUMITOMO TITANIUM CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DAKESHITA, KATSUNORI, HORI, MASAHIKO, OGASAWARA, TADASHI, YAMAGUCHI, MAKOTO
Publication of US20080250901A1 publication Critical patent/US20080250901A1/en
Abandoned legal-status Critical Current

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    • 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
    • C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
    • C22B34/1272—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams reduction of titanium halides, e.g. Kroll process
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1295—Refining, melting, remelting, working up of titanium
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
    • 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 separating and recovering a high-melting-point metal such as Ti by heating and melting a molten salt such as calcium chloride (CaCl 2 ) in which the high-melting-point metal.
  • a high-melting-point metal such as Ti
  • a molten salt such as calcium chloride (CaCl 2 ) in which the high-melting-point metal.
  • a Kroll method for reducing titanium tetrachloride (TiCl 4 ) by Mg is generally used as an industrial production method of the high-melting-point metal such as metallic Ti.
  • the Kroll method molten Mg is loaded in a reactor vessel, a TiCl 4 liquid is supplied from above a liquid surface thereof, and the metallic Ti is produced by reducing TiCl 4 with Mg near the liquid surface of the molten Mg.
  • the high-purity sponge Ti is obtained through the Kroll method.
  • a feed rate of TiCl 4 is restricted because reaction undergoes near the liquid surface of the molten Mg in the reactor vessel.
  • Ti granules produced are aggregated because of an adhesion property between Ti and the molten Mg, and the Ti granules are sintered to generate size-wise grown granules by the heat from the molten liquid. Therefore, it is difficult to taking out the produced Ti to the outside of the reactor vessel, and it is also difficult to continuously produce Ti.
  • Japanese Patent Application Publication No. 2004-52037 proposes a metallic titanium refining method in which reduction is performed using Ca and a univalent calcium ion (Ca + ) which are generated by electrolysis in a mixed molten salt including titanium oxide (TiO 2 ), calcium chloride (CaCl 2 ), calcium oxide (CaO), and/or calcium (Ca).
  • International Patent Application No. 2002-517613 discloses a method for removing oxygen (O 2 ) from a metallic compound and the like (for example, TiO 2 ) by the electrolysis in the molten salt such as CaCl 2 .
  • the inventors have also proposed a method in which a metallic chloride containing TiCl 4 is used as a raw material and Ti granules or Ti alloy granules are produced in the molten salt by causing the metallic chloride to react with Ca melted in the molten salt containing the molten CaCl 2 .
  • the inventors disclose Japanese Patent Application Publication No. 2005-133195 in which, in order to economically replenish Ca in the molten salt, the Ca being consumed by the reducing reaction between TiCl 4 and Ca, Ca produced by the electrolysis of the molten CaCl 2 is utilized and Ca is circularly used.
  • the titanium oxide or the titanium chloride is reduced to produce Ti in these methods, and the obtained Ti exists in the state in which Ti of a solid matter (powdery matter or granular matter) is mixed with the molten salt because the molten salt provides a reaction field where the reducing reaction undergoes at that time. Therefore, a manipulation (process) is required to separate Ti from the molten salt in which Ti exists in the mixed state.
  • the Kroll method generally used as an industrial metallic Ti production method, because the yet-to-be-reacted Mg and a magnesium chloride (MgCl 2 ) which is of a by-product are mixed in the sponge metallic Ti obtained through the reducing process, the yet-to-be-reacted Mg and MgCl 2 are vaporized and removed by heating through a vacuum separation process, and the high-purity sponge metallic Ti is separated and recovered. According to the Kroll method, the high-quality metallic Ti is obtained. However, a large amount of thermal energy is required to evaporate Mg and MgCl 2 which permeated into the sponge's fine structure.
  • MgCl 2 magnesium chloride
  • the molten CaCl 2 liquid in which the powdery and granular metallic Ti is mixed is taken out to the outside of the reactor vessel and Ti is separated by a squeezing manipulation of mechanical compression.
  • the adhering molten salt is removed by the water washing or the like after the separation.
  • An object of the invention is to provide a method for separating and recovering the high-quality high-melting-point metal from the molten salt in which the high-quality high-melting-point metal is mixed, particularly a method for with less energy efficiently separating and recovering the high-quality Ti or Ti alloy from the CaCl 2 -containing molten salt in which the Ti or Ti alloy produced by reducing TiCl 4 by Ca is mixed.
  • the inventors studied a method in which the mechanical squeezing manipulation and the water washing were not used, and the inventors performed experiments to study a possibility of the Ti separation (liquid phase separation) in the state where the mixed substance is heated to a temperature at which the Ti is melted (dissolved) and the mixed substance exists in the liquid phase, when the metallic Ti is separated and recovered from the mixed substance in which the metallic Ti produced by the Ca reduction, the molten CaCl 2 , and the remaining yet-to-be-reacted Ca are mixed.
  • CaCl 2 has a boiling point (2008° C.) higher than a melting point (1680° C.) of Ti, and CaCl 2 has a specific gravity of about 2 in the liquid-phase state while Ti has a specific gravity of about 4.5, so that the liquid phase separation between CaCl 2 and Ti can be achieved when the mixed substance is kept at temperatures not less than the melting point of Ti.
  • the metallic Ti and CaCl 2 whose quantities are substantially equal to each other are loaded in a water-cooled copper crucible, the metallic Ti and CaCl 2 are heated to temperatures not less than the melting point of Ti, and the whole of the metallic Ti and CaCl 2 is melted. As a result, the experiment shows that the metallic Ti and CaCl 2 are clearly separated according to a difference in specific gravity.
  • a composition that is, mixed ratio of “Ti, CaCl 2 , and residual Ca” or “Ti, MgCl 2 , and yet-to-be-reacted Mg” of the mixed substance is properly premised according to an actual condition to estimate thermal energies (equivalent to electric power) necessary for the recovery.
  • thermal energies equivalent to electric power
  • the inventors also found that Ca melted in CaCl 2 plays an important role in separating Ti and CaCl 2 . That is, in performing the liquid phase separation of Ti by heating and melting CaCl 2 in which Ti is mixed, Ti starts to dissolve in CaCl 2 and gets mixed in the granular form when Ca does not exist. However, when Ca is melted in CaCl 2 even slightly, the melting of Ti into CaCl 2 is suppressed and the Ti concentration in CaCl 2 is remarkably decreased after Ti is separated.
  • the decrease in Ti recovery percentage can be suppressed by melting Ca in CaCl 2 .
  • Ca is circulated while CaCl 2 is used as a medium in the method for producing Ti or Ti alloys by reducing TiCl 4 with Ca, proposed by the inventor. Therefore, when Ti is mixed in CaCl 2 , there likely arises problems in the electrolysis process. However, the risk of raising the problem is erased by the invention.
  • the invention is made based on such ideas and the results of the studies, and a gist of the invention pertains to a following high-melting-point metal separation and recovery method.
  • the invention is a high-melting-point metal separation and recovery method in which a molten salt mixed with a high-melting-point metal is melted in an inert gas atmosphere to perform liquid phase separation of the high-melting-point metal, the molten salt being used as a reaction field.
  • Ti and Zr can be cited as an example of the “high-melting-point metal”.
  • being mixed shall mean that the mixed state is not a homogeneous phase. That is, “(be) mixed” shall mean that the high-melting-point metal in the solid phase exists in the molten salt, whereas the substance containing the “mixed” component is also referred to as “mixed substance”.
  • reaction field shall mean a region where the reaction undergoes.
  • reaction field shall mean the molten salt which acts as the reaction field, i.e., the molten salt where the reaction of some kind is in progress.
  • the “melting” shall mean a manipulation for heating the molten salt, in which the high-melting-point metal is mixed, to transform the whole of the molten salt into the liquid state.
  • liquid phase separation shall mean, as described above, the separation in a state of having the mixed substance in the liquid phase.
  • the “liquid phase separation” shall mean that the high-melting-point metal and the molten salt are vertically separated by the difference in specific gravity while existing in the liquid phase.
  • the molten salt in which the high-melting-point metal is mixed is not one in which the high-melting-point metal is simply mixed in the usual molten salt, but the one that acts as the reaction field, i.e., the one that is taken out from an arbitrary process.
  • the molten salt may be solidified and apparently formed in the solid-phase state, when the separation and recovery method of the invention is applied. This is because the molten salt becomes the molten state in the melting process.
  • the molten salt in which the high-melting-point metal is mixed is melted to implement the separation and recovery method of the invention. That is, the molten salt in which the high-melting-point metal is mixed is heated until the whole of the molten salt becomes the liquid state, which separates the high-melting-point metal and the molten salt as the reaction field in the liquid phase. That is, the separation undergoes by a difference in specific gravity, whereby usually the molten salt is located in an upper layer while the high-melting-point metal is located in a lower layer.
  • the high-melting-point metal having the melting point M can be used as the target.
  • the kinds of the molten salt that can be used in practice are relatively limited due to restrictions by handling difficulties, characteristics (particularly, a harmful effect on an environment), prices, and the like.
  • the molten salt may be represented by CaCl 2 (boiling point of 2008° C.), LaCl 3 (boiling point of 1710° C.), SnCl 3 (boiling point of 2040° C.), CaF 2 (boiling point of 2510° C.), or BaF 2 (boiling point of 2137° C.).
  • FIG. 1 is a view schematically illustrating the way that the high-melting-point metal separation and recovery method according to the invention is implemented to separate the high-melting-point metal from the molten salt.
  • the molten salt in which the high-melting-point metal is mixed is loaded in a reactor vessel 1 , and the molten salt and the high-melting-point metal are heated to a molten state.
  • the liquid phase separation undergoes between the high-melting-point metal and the molten salt in the molten state due to the difference in specific gravity.
  • the liquid phase separation undergoes in such a manner that a molten salt 2 is located in the upper layer while a high-melting-point metal 3 is located in the lower layer, and the high-melting-point metal 3 can be taken out and recovered from a high-melting-point metal discharge port 4 disposed at a bottom of the heating vessel 1 .
  • the molten salt 2 can be taken from a molten salt discharge port 5 disposed in the vicinity of an intermediate-height portion of the reactor vessel 1 .
  • the positions where the high-melting-point metal discharge port 4 and molten salt discharge port 5 are disposed may appropriately be determined in consideration of a mixed ratio of the high-melting-point metal and the molten salt.
  • any of discharge ports may selectively be used according to each liquid level of the upper layer and lower layer. Loading the molten salt in which the high-melting-point metal is mixed and taking out the high-melting-point metal 3 and the molten salt 2 are performed systematically, which allows the recovery to be semi-continuously or continuously performed.
  • a heating vessel having high resistance to high temperatures is used so as not to allow a melt leakage of the loaded materials.
  • a water-cooled copper vessel can be used in the case where CaCl 2 is used as the molten salt while Ti is the high-melting-point metal.
  • a plasma melting method and a high-frequency induction melting method can be employed as a heating and melting means.
  • the reason why the melting is performed in the inert gas atmosphere is that the reaction of the high-melting-point metal with oxygen or other gases and absorption of the oxygen or other gases by the high-melting-point metal are prevented because reactivity is enhanced in any substance in the system under the high-temperature condition.
  • a pressure of the inert gas during melting is not particularly limited, usually the melting is performed at a normal pressure (atmospheric pressure).
  • the molten salt may be used as the reaction field in producing the high-melting-point metal and the molten salt mixed with the high-melting-point metal obtained by a reaction in the reaction field is used (this embodiment mode is referred to as Embodiment 1).
  • the method of Embodiment 1 is the method in which a condition that a molten salt is used as the reaction field in producing the high-melting-point metal to be mixed in said molten salt is added as the subject-matter.
  • a condition that a boiling point of the molten salt is higher than a melting point of the high-melting-point metal is clearly expressed as one of subject-matters, and the condition may be added (Embodiment 2).
  • the molten salt containing CaCl 2 may be used (Embodiment 3).
  • the “molten salt containing CaCl 2 ” shall mean a molten salt containing only the molten CaCl 2 or a molten salt in which CaF 2 and the like are added to the molten CaCl 2 to lower the melting point or to adjust its viscosity or the like.
  • the suitable reaction field can be formed by applying the method of Embodiment 3 in the case of the embodiment mode in which the high-melting-point metal obtained by reducing a after-mentioned high-melting-point metal compound (for example, TiCl 4 ) with Ca is separated and recovered.
  • a after-mentioned high-melting-point metal compound for example, TiCl 4
  • the molten salt contains Ca and the high-melting-point metal may be obtained by causing the high-melting-point metal compound to react with Ca in the molten salt” (Embodiment 4).
  • a high-melting-point metal chloride such as TiCl 4 can be cited as an example of the high-melting-point metal compound. That is, in the method of Embodiment 4, a molten salt is specified as the molten salt in which the high-melting-point metal obtained by causing the high-melting-point metal chloride such as TiCl 4 to react with Ca is mixed.
  • the high-melting-point metal is Ti or a Ti alloy and the high-melting-point metal compound contains TiCl 4 (Embodiment 5)”.
  • the mode wherein the liquid phase separation of the metallic Ti is performed by melting the molten salt, in which the metallic Ti obtained by causing TiCl 4 to react with Ca is mixed corresponds to the method of Embodiment 5.
  • the other metallic chloride is simultaneously reduced with Ca to thereby end up having the Ti alloy mixed in the molten salt, so that the Ti alloy can be separated and recovered.
  • a high-melting-point metal is Ti or a Ti alloy
  • the molten salt contains CaCl 2 and Ca
  • the melting is performed in an inert gas atmosphere or in vacuum (Embodiment 6).
  • Ca melted in the CaCl 2 -containing molten salt suppresses the melting of Ti or the Ti alloy in the molten salt and significantly decreases the Ti concentration in the molten salt after the Ti or the Ti alloy is separated, when the molten salt in which the high-melting-point metal is mixed is heated to perform the liquid phase separation between the molten salt and such a metal.
  • Ti is melted in the molten salt in the range of 0.5 to 1% by mass when the melted Ca does not exists in CaCl 2 , and the Ti concentration in the molten salt is decreased to 50 ppm when CaCl 2 contains Ca of 1% by mass.
  • the application of the method of Embodiment 6 can suppress the melting of Ti or the Ti alloy in the molten salt by a factor of 1/100 or less.
  • the lower limit of the Ca concentration in the molten salt is not limited because this effect can be recognized even if Ca is slightly melted in the molten salt.
  • the upper limit of the Ca concentration in the molten salt is not particularly limited because the effect exhibits even if the Ca concentration is close to a saturation concentration in the CaCl 2 -containing molten salt. To stretch a point, the upper limit of the Ca concentration is the saturation concentration (in the case of CaCl 2 , about 1.5% by mass) in the CaCl 2 -containing molten salt.
  • the Ca may be contained in a molten salt before the molten salt mixed with Ti or the Ti alloy is melted (i.e., at any time before the melting is started).
  • a molten salt before the molten salt mixed with Ti or the Ti alloy is melted (i.e., at any time before the melting is started).
  • the melting is performed in the inert gas atmosphere. This is because the reaction of the high-melting-point metal with oxygen or other gases and the absorption of the oxygen or other gases in the high-melting-point metal are prevented.
  • the inert gas such as Ar is used.
  • the melting may be performed in vacuum in melting the CaCl 2 -containing molten salt in which Ti or the Ti alloy is mixed.
  • the “vacuum” shall mean a low-pressure state. A level of vacuum may appropriately be set to an extent in which the oxidation of Ti or the Ti alloy or reaction of the high-melting-point metal with oxygen or other gases in the high-melting-point metal are prevented.
  • a Ca concentration of the molten salt is adjusted in the range of 0.1 to 1.5% by mass before a mixed substance of the molten salt and Ti or the Ti alloy is melted (Embodiment 7).
  • the effect of suppressing the melting of Ti or the Ti alloy in the molten salt is rather low when the Ca concentration in the molten salt is lower than 0.1% by mass, and a risk of Ca precipitation is generated by a fluctuation in operation condition when the Ca concentration exceeds 1.5% by mass. More desirably the Ca concentration ranges from 0.3 to 1.0% by mass.
  • the effect of suppressing the melting of Ti or the Ti alloy in the molten salt is discerned even if Ca is slightly melted in the molten salt. Furthermore, the melting of Ti in CaCl 2 can effectively be suppressed when the method of Embodiment 7 in which the Ca concentration in the molten salt is adjusted within the above range is applied before the melting.
  • a Ca concentration in the molten salt is lower than 0.1% by mass before the mixed substance of the molten salt and Ti or the Ti alloy is melted (Embodiment 8).
  • the method of Embodiment 8 is the one specifying an operational mode in which the Ca concentration in the molten salt is controlled and properly adjusted before the melting.
  • the melting of Ti can effectively be suppressed to assuredly perform the separation between CaCl 2 and Ti or the Ti alloy.
  • the Ca concentration may indirectly be controlled based on material balances of an actual operation performance.
  • the methods of Embodiments 4 to 8 are the ones which can be suitably performed when the molten salt contains CaCl 2 while Ti or the Ti alloy is the high-melting-point metal. That is, the presence of the melted Ca in CaCl 2 suppresses the melting of Ti or the Ti alloy in CaCl 2 to significantly decrease the Ti concentration in CaCl 2 after the liquid phase separation, which allows the Ti recovery percentage to be enhanced.
  • the application of the method of Embodiment 9 can save the thermal energies necessary to melt the solidified-state mixed substance consisted of the high-melting-point metal and the molten salt. Desirably the whole of the mixed substance is maintained in a molten state. However, the thermal energies can be saved even if part of the mixed substance is melted.
  • Ca may be vaporized and separated when the molten salt with remnants of Ca is melted in an inert gas atmosphere after the reaction with the high-melting-point metal compound (Embodiment 10).
  • Ca can be removed from the molten salt after Ti or the Ti alloy is separated, and the method of Embodiment 10 is a desirable method when the molten salt separated from the high-melting-point metal compound is reused.
  • Embodiment 10 will specifically be described later in an application example of the separation and recovery method of the invention.
  • TiCl 4 is reduced with Ca to produce the metallic Ti
  • the method of Embodiment 10 when the method of Embodiment 10 is applied to the process of separating the metallic Ti, desirably Ca which obstructs the electrolysis can be removed in performing the electrolysis of the molten salt including CaCl 2 .
  • FIG. 1 is a view schematically illustrating a state in which a high-melting-point metal separation and recovery method according to the invention is implemented to separate a high-melting-point metal from a molten salt;
  • FIG. 2 is a view illustrating a configuration example of an apparatus for producing a metallic Ti by reducing TiCl 4 with Ca.
  • a process enabling to implement a separation and recovery method of Embodiment 6 is incorporated into the configuration of FIG. 2 .
  • a reducing agent feed pipe 7 for feeding Ca which is of a reducing agent is provided in a ceiling portion of a reactor vessel 6 .
  • a bottom of the reactor vessel 6 is tapered downward while a diameter of the reactor vessel 6 is gradually reduced in order to promote discharge of produced Ti granules.
  • a Ti discharge pipe 8 is provided in a central portion at lower end of the reactor vessel 6 to discharge the produced Ti granules.
  • a cylindrical separation wall 9 is disposed inside the reactor vessel 6 while a predetermined gap is provided between the separation wall 9 and an inner surface of a straight body portion of the reactor vessel 6 .
  • a molten salt discharge pipe 10 is provided in an upper portion of the reactor vessel 6 to discharge CaCl 2 in the reactor vessel 6 to the side.
  • a raw material feed pipe 11 for feeding TiCl 4 which is of a raw material to Ti is provided in a lower portion of the reactor vessel 6 while piercing through the separation wall 9 to reach a central portion of the reactor vessel 6 .
  • the molten CaCl 2 liquid in which Ca is melted is held as the molten salt in the reactor vessel 6 .
  • a level of the molten CaCl 2 liquid is set higher than the molten salt discharge pipe 10 and lower than an upper end of the separation wall 9 .
  • the molten Ca liquid is held on the molten CaCl 2 liquid inside the separation wall 9 .
  • a TiCl 4 gas is supplied to the molten CaCl 2 liquid located inside the separation wall 9 through the raw material feed pipe 11 .
  • This enables TiCl 4 to be reduced by Ca in the molten CaCl 2 liquid inside the separation wall 9 to produce the granular metallic Ti in the molten CaCl 2 liquid.
  • the Use of the raw material in which the TiCl 4 gas and other metallic chloride gas are mixed can produce the Ti alloy.
  • the TiCl 4 gas and other metallic chloride gas are simultaneously reduced by Ca, so that the Ti alloy granules can be produced.
  • the Ti granules produced in the molten CaCl 2 liquid located inside the separation wall 9 in the reactor vessel 6 move downward through the molten CaCl 2 liquid and deposited on the bottom of the reactor vessel 6 .
  • the deposited Ti granules are appropriately taken out downward from the Ti discharge pipe 8 along with the molten CaCl 2 liquid, and the deposited Ti granules are delivered to a separation process 12 . In this case, some amount of yet-to-be-reacted Ca remains in the CaCl 2 liquid taken out.
  • the molten CaCl 2 liquid whose Ca is consumed by the reducing reaction inside the separation wall 9 moves upward at the outside of the separation wall 9 via the bottom of the separation wall 9 , and the molten CaCl 2 liquid is discharged from the molten salt discharge pipe 10 .
  • the discharged molten CaCl 2 liquid is delivered to an electrolysis process 13 .
  • Ca is replenished to the molten CaCl 2 liquid from the molten Ca liquid held on the molten CaCl 2 liquid. At the same time, Ca is replenished onto the molten CaCl 2 liquid through the reducing agent feed pipe 7 .
  • the Ti granules taken out along with the molten CaCl 2 liquid are loaded in a heating vessel 15 , the Ti granules are also heated to be in a molten state, and the separation is generated by the difference in specific gravity, whereby a molten CaCl 2 liquid 16 is located in an upper layer while a metallic Ti 17 is located in a lower layer.
  • the molten CaCl 2 liquid 16 in the upper layer is taken out from a molten salt discharge port 19 , and the molten CaCl 2 liquid 16 is delivered to the electrolysis process 13 along with the molten CaCl 2 liquid taken out from the reactor vessel 6 .
  • the metallic Ti 17 in the lower layer is taken out from a high-melting-point metal discharge port 18 , and the metallic Ti 17 is solidified to yield an ingot.
  • a temperature during melting ranges from 1680 to 1750° C. Because the melting temperature of Ti is 1680° C., the Ti granules are not melted when the temperature is lower than this.
  • the temperature exceeding 1750° C. easily reduces durability of facilities such as the heating vessel.
  • the temperature exceeding 1750° C. is disadvantageous from the viewpoint of energies necessary for heating.
  • the molten CaCl 2 liquid introduced from the reactor vessel 6 and the separation process 12 is separated into Ca and the Cl 2 gas through the electrolysis.
  • Ca and CaCl 2 are returned to the reactor vessel 6 . Because CaCl 2 in which Ca is melted is used in the reactor vessel 6 , it is not necessary to separate Ca and CaCl 2 .
  • the Cl 2 gas generated in the electrolysis process 13 is delivered to a chlorination process 14 .
  • TiO 2 is chlorinated to produce TiCl 4 .
  • the oxygen of the by-product is discharged in the form of CO 2 by simultaneously using carbon powders (C).
  • the produced TiCl 4 is introduced into the reactor vessel 6 through the raw material feed pipe 11 .
  • Ca which is of the reducing agent and Cl 2 gas are circulated by the circulation of CaCl 2 .
  • the metallic Ti production process is an example to which the separation and recovery method of Embodiment 6 is applied.
  • the separation and recovery method of Embodiment 6 the molten salt in which the metallic Ti is mixed is melted to perform the liquid separation of the metallic Ti.
  • the metallic Ti production process the metallic Ti is continuously produced just by essentially replenishing TiO 2 and C.
  • Embodiment 9 When Embodiment 9 is applied to the example of the metallic Ti production process shown in FIG. 2 , the mixed substance of the Ti granules taken out from the Ti discharge pipe 8 and the molten CaCl 2 liquid is maintained in a molten state until being delivered to the separation process 12 and loaded in the heating vessel 15 . That is, the mixed substance of the Ti granules is loaded in the heating vessel 15 while the Ti granules are mixed in the molten CaCl 2 liquid. Even if part of the molten CaCl 2 liquid is solidified, although the energy is required to melt the part of the molten CaCl 2 liquid again, there is no trouble on the separation and recovery manipulation. Application of the method of Embodiment 9 can save the thermal energies necessary to heat and melt the mixed substance to put the whole of the mixed substance in a molten state.
  • the method of Embodiment 10 is a method for vaporizing and separating Ca when the molten salt having the remnants of Ca after the reaction with the high-melting-point metal compound is melted in an inert gas atmosphere, in the separation and recovery method (one of methods of Embodiment 4 to 9) of the invention.
  • the molten CaCl 2 liquid is separated into Ca and the Cl 2 gas by the electrolysis in the electrolysis process 13 .
  • a reverse reaction in which Ca reacts with Cl 2 produced by the electrolysis to return to CaCl 2 is generated near the anode electrode, which decreases current efficiency.
  • the separation and recovery method of Embodiment 10 is applied, Ca in the molten CaCl 2 liquid is removed, so that the decrease in current efficiency caused by the reverse reaction can be suppressed.
  • the molten salt contains only CaCl 2 like the above example, because Ca is melted at 845° C. and vaporized at 1420° C., the large amount of Ca is vaporized and removed in the procedure of melting the mixed substance of the Ti granules and the molten CaCl 2 liquid which are taken out from the Ti discharge pipe 8 .
  • the metallic Ti or the Ti alloy can be recovered with the extremely small amount of energies.
  • the continuous work and saving in labor can also be achieved in the high-melting-point metal separation and recovery method of the invention, and the high-melting-point metal separation and recovery method of the invention can contribute largely to the reduction of production costs.
  • the obtained Ti has good quality because there is no risk of mixing water having the adverse effect on the Ti quality.
  • the high-melting-point metal separation and recovery method of the invention can effectively be utilized as the separation and recovery method in producing the high-melting-point metal, particularly producing Ti or the Ti alloy through the Ca reduction of TiCl 4 .

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US11/886,323 2005-03-15 2006-03-08 Method of High-Melting-Point Metal Separation and Recovery Abandoned US20080250901A1 (en)

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JP2005072854 2005-03-15
JP2005-072854 2005-03-15
PCT/JP2006/304456 WO2006098199A1 (fr) 2005-03-15 2006-03-08 Methode de separation du metal a haut point de fusion et recuperation

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AU (1) AU2006224012B2 (fr)
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WO2008067614A1 (fr) * 2006-12-08 2008-06-12 Commonwealth Scientific And Industrial Research Organisation Procédé de séparation pour la récupération d'un métal
JP2009299098A (ja) * 2008-06-10 2009-12-24 Osaka Titanium Technologies Co Ltd 金属の製造方法
US8475540B2 (en) * 2009-08-12 2013-07-02 Sri International Multi-stage system for reaction and melt coalescence and separation
RU2504591C2 (ru) * 2011-08-12 2014-01-20 Федеральное государственное автономное образовательное учреждение высшего профессионального образования Уральский федеральный университет им. первого Президента России Б.Н. Ельцина ЭЛЕКТРОЛИЗЕР ДЛЯ НАСЫЩЕНИЯ РАСПЛАВА CaCl2 КАЛЬЦИЕМ
AU2013270660B2 (en) * 2012-06-06 2017-09-21 Csir Process for the production of crystalline titanium powder
CN104313645B (zh) * 2014-10-28 2017-08-08 苏州萨伯工业设计有限公司 含钪铝合金材料的制备装置及制备工艺
JP7272752B2 (ja) * 2018-03-26 2023-05-12 株式会社大阪チタニウムテクノロジーズ 金属チタン製造方法

Citations (3)

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Publication number Priority date Publication date Assignee Title
US2205854A (en) * 1937-07-10 1940-06-25 Kroll Wilhelm Method for manufacturing titanium and alloys thereof
US4725312A (en) * 1986-02-28 1988-02-16 Rhone-Poulenc Chimie Production of metals by metallothermia
US7648560B2 (en) * 2003-10-10 2010-01-19 Osaka Titanium Technologies Co., Ltd. Method for producing Ti or Ti alloy through reduction by Ca

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JPH028332A (ja) * 1988-06-24 1990-01-11 Kobe Steel Ltd 希土類金属又は希土類合金の製造方法
JP3195156B2 (ja) * 1994-03-15 2001-08-06 株式会社住友シチックス尼崎 チタンの製造方法
JP3615466B2 (ja) * 2000-06-14 2005-02-02 東邦チタニウム株式会社 スポンジチタンの製造方法及び製造装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2205854A (en) * 1937-07-10 1940-06-25 Kroll Wilhelm Method for manufacturing titanium and alloys thereof
US4725312A (en) * 1986-02-28 1988-02-16 Rhone-Poulenc Chimie Production of metals by metallothermia
US7648560B2 (en) * 2003-10-10 2010-01-19 Osaka Titanium Technologies Co., Ltd. Method for producing Ti or Ti alloy through reduction by Ca

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WO2006098055A1 (fr) 2006-09-21
CN101142330A (zh) 2008-03-12
CN100516255C (zh) 2009-07-22
WO2006098199A1 (fr) 2006-09-21
AU2006224012A1 (en) 2006-09-21
NO20074597L (no) 2007-10-12
CA2601113A1 (fr) 2006-09-21
EP1873265A1 (fr) 2008-01-02
AU2006224012B2 (en) 2009-03-12
EA011056B1 (ru) 2008-12-30
EA200701982A1 (ru) 2008-02-28

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