US20070187255A1 - Method for producing ti or ti alloy through reduction by ca - Google Patents

Method for producing ti or ti alloy through reduction by ca Download PDF

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Publication number
US20070187255A1
US20070187255A1 US10/589,879 US58987905A US2007187255A1 US 20070187255 A1 US20070187255 A1 US 20070187255A1 US 58987905 A US58987905 A US 58987905A US 2007187255 A1 US2007187255 A1 US 2007187255A1
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Prior art keywords
ticl
molten salt
molten
cacl
generated
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Abandoned
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US10/589,879
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English (en)
Inventor
Tadashi Ogasawara
Makoto Yamaguchi
Masahiko Hori
Toru Uenishi
Katsunori Dakeshita
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Allergan Medical GmbH
Osaka Titanium Technologies Co Ltd
Toho Titanium Co Ltd
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EndoArt SA
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Assigned to TOHO TITANIUM CO., LTD., SUMITOMO TITANIUM CORPORATION reassignment TOHO TITANIUM CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DAKESHITA, KATSUNORI, HORI, MASAHIKO, OGASAWARA, TADASHI, UENISHI, TORU, YAMAGUCHI, MAKOTO
Publication of US20070187255A1 publication Critical patent/US20070187255A1/en
Assigned to OSAKA TITANIUM TECHNOLOGIES CO., LTD. reassignment OSAKA TITANIUM TECHNOLOGIES CO., LTD. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: SUMITOMO TITANIUM CORPORATION
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—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
    • C22B34/129—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 by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts

Definitions

  • the present invention relates to a method for producing Ti or Ti alloys through reduction by Ca, in which a metallic chloride containing titanium tetrachloride (TiCl 4 ) is reduced by Ca to produce Ti metals or Ti alloys.
  • a metallic chloride containing titanium tetrachloride TiCl 4
  • a Kroll method for reducing TiCl 4 by Mg is generally used as a method for industrially producing the Ti metals.
  • TiCl 4 is obtained by chlorinating titanium oxide (TiO 2 ).
  • the Ti metals are produced through a reduction step and a vacuum distillation step.
  • the reduction step TiCl 4 is reduced by Mg in a reactor vessel.
  • the vacuum distillation step unreacted Mg and MgCl 2 formed as a by-product are removed from the sponge metallic Ti produced in the reactor vessel.
  • the reactor vessel is filled with the molten Mg, and the TiCl 4 liquid is supplied from above on a liquid surface of the molten Mg.
  • the generated Ti metals move sequentially downward.
  • the molten MgCl 2 which is of the by-product is generated near the liquid surface.
  • a specific gravity of molten MgCl 2 is larger than that of the molten Mg.
  • the molten MgCl 2 which is of the by-product moves downward due to the specific-gravity difference, and the molten Mg emerges in the liquid surface instead.
  • the molten Mg is continuously supplied to the liquid surface by the specific-gravity difference substitution, and the reducing reaction of TiCl 4 proceeds continuously.
  • the supplied TiCl 4 becomes lower grade chloride gases (referred to as “unreacted gas”) such as an unreacted TiCl 4 gas and a TiCl 3 gas, and the unreacted gas is discharged outside the reactor vessel, which reduces utilization efficiency of TiCl 4 . It is necessary to avoid the generation of the unreacted gas, because a rapid increase in inner pressure of the reactor vessel is associated with the generation of the unreacted gas. Thus, there is a limit of the feed rate of TiCl 4 because of the above reasons.
  • Japanese Patent Application Publication No. 8-295955 proposes a method in which the reaction efficiency is enhanced by supplying liquid TiCl 4 in a dispersive manner to the liquid surface in which the molten Mg exists, and thereby the Ti precipitation is suppressed in the inner surface of the upper portion of the reactor vessel.
  • the method proposed in Japanese Patent Application Publication No. 8-295955 is not enough to suppress the Ti precipitation.
  • Ti is generated in the particulate form near the liquid surface of the molten Mg, and aggregated because of wetting properties (adhesion properties) of the molten Mg, and the Ti particles is made move downward while aggregated, and then the Ti particles are sintered to grow the Ti particles by the heat generated from the molten liquid during the downward travel. Therefore, it makes difficult to recover the generated Ti by taking out Ti as fine particles to the outside of the reactor vessel, whereby the continuous production is difficult to perform and the improvement of the productivity is fettered. By reason of this, the Ti is produced in the batch process in the form of the sponge titanium.
  • U.S. Pat. No. 2,205,854 describes that, in addition to Mg, for example, Ca can be used as the reducing agent of TiCl 4 .
  • U.S. Pat. No. 4,820,339 describes a method for producing Ti through the reducing reaction by Ca, in which the molten salt of CaCl 2 is held in the reactor vessel, the metallic Ca powder is supplied into the molten salt from above, Ca is dissolved in the molten salt, and TiCl 4 gas is supplied from below to react the dissolved Ca with TiCl 4 in the molten salt of CaCl 2 .
  • the Ti metals are generated from TiCl 4 by the reaction of the following chemical formula (1), and CaCl 2 as the by-product is also generated at the same time: TiCl 4 +2Ca ⁇ Ti+2CaCl 2 (1)
  • Ca has an affinity for Cl stronger than that of Mg, and Ca is suitable to the reducing agent of TiCl 4 in principle.
  • Ca is used while dissolved in the molten CaCl 2 .
  • an area (reaction field) where the reaction is created is enlarged compared with the Kroll method in which TiCl 4 is supplied to the liquid surface of the reducing agent in the reactor vessel. Therefore, because the exothermic area is also enlarged to facilitate the cooling, the feed rate of TiCl 4 can be largely enhanced, and the remarkable improvement of the productivity can be also expected.
  • U.S. Pat. No. 2,845,386 describes another Ti production method (Olsen method) in which TiO 2 is directly reduced by Ca not through TiCl 4 .
  • the method described in U.S. Pat. No. 2,845,386 is a kind of oxide direct-reduction method and is highly efficient.
  • the oxide direct-reduction method is not suitable to the production of the high-purity Ti because it is necessary to use high-purity TiO 2 .
  • the present inventors consider it indispensable that TiCl 4 be reduced by Ca, and the present inventors look into the method for utilizing Ca dissolved in the molten salt of CaCl 2 described in U.S. Pat. No. 4,820,339.
  • the method for replenishing Ca, consumed in the reduction of TiCl 4 , with Ca generated by the electrolysis can also be achieved by respectively performing the reduction and the electrolysis in a reduction cell and an electrolytic cell to circulate the molten CaCl 2 between the cells.
  • the reactor cell can commonly be used as the reduction cell and the electrolytic cell. Therefore, because it is not necessary to separately provide the reduction cell and the electrolytic cell, there is also a great advantage from a viewpoint of installation cost compared with the case in which the molten CaCl 2 is circulated between the reduction cell and the electrolytic cell.
  • the present invention is made based on the above conception, and the gist of the present invention pertains to a method for producing Ti or Ti alloys.
  • a method for producing Ti or Ti alloys through reducing reaction by Ca includes: a reduction electrolysis step comprising holding a molten salt in a reactor cell to perform electrolysis in the molten salt in the reactor cell, the molten salt containing CaCl 2 and having Ca dissolved in the molten salt and generating Ti or Ti alloys in the molten salt by supplying a metallic chloride containing TiCl 4 to the molten salt so as to react with Ca generated on a cathode electrode side by the electrolysis; and a Ti separation step of separating Ti or the Ti alloy from the molten salt in the reactor cell or outside the reactor cell.
  • the method of the present invention for producing Ti or Ti alloys through reduction by Ca is a method of reducing TiCl 4 in which a high-purity material is easily obtained, so that the method of the present invention can produce high-purity Ti metals or high-purity Ti alloys.
  • Ca is used as the reducing agent to cause the metallic chloride containing TiCl 4 to react with Ca in the molten salt containing CaCl 2 , so that the feed rate of TiCl 4 can be increased. Because the Ti particles or Ti alloy particles are generated in CaCl 2 , the aggregation of the particles and the particle growth caused by the sintering are significantly lessened, whereby it becomes possible to discharge these particles outside reactor cell, thus enabling the continuous operation to be performed. The reducing reaction and the electrolytic reaction are simultaneously caused to proceed, and Ca is replenished by the electrolytic reaction while consumed in the reducing reaction, which allows Ca to be utilized in the state in which Ca is always dissolved in the molten salt.
  • the production method of the present invention can efficiently and economically produce high-purity Ti metals or high-purity Ti alloys.
  • FIG. 1 is a block diagram showing a Ti metal production apparatus which exhibits an embodiment mode according to the present invention.
  • TiCl 4 is reduced by Ca dissolved in the molten salt to generate Ti metals in the form of the particulate or powder (hereinafter referred to as “Ti particles”).
  • Ti particles Ti metals in the form of the particulate or powder
  • Mg is produced by electrolyzing MgCl 2 , and the generated Mg can efficiently be recovered because Mg is hardly dissolved in MgCl 2 .
  • Na can efficiently be produced by electrolyzing NaCl.
  • Ca is produced by electrolyzing CaCl 2 , and it is difficult to efficiently separate only Ca because the generated Ca is dissolved in CaCl 2 by about 1.5%.
  • the reducing reaction field is expanded and the heat generation/exothermic area is also enlarged.
  • Mg has vapor pressure of 6.7 kPa (50 mmHg) at 850° C. while Ca has extremely small vapor pressure of 0.3 kPa (2 mmHg). Therefore, in the case where Ca is used for the reduction, the Ti precipitation amount becomes dramatically lessened in the inner surface of the upper portion of the reactor cell compared with Mg. Accordingly, in the method of the present invention for producing Ti or Ti alloys through reduction by Ca, the feed rate of TiCl 4 can largely be increased.
  • Ca is inferior in wetting properties (adhesion properties) to Mg, and Ca adhering to the precipitated Ti particles is dissolved in CaCl 2 , so that the aggregation in the generated titanium particles and the particle growth caused by the sintering are significantly lessened. Therefore, the generated Ti can be taken out from the reactor cell in the form of particles, and the Ti production can continuously be operated.
  • TiCl 4 For a supply mode of TiCl 4 to the molten CaCl 2 liquid, it is particularly desirable that TiCl 4 be directly supplied in the gaseous state inside the molten CaCl 2 liquid, because the contact efficiency of TiCl 4 to Ca in the molten CaCl 2 liquid is enhanced. Alternatively, it is also possible that TiCl 4 is supplied in the gaseous or liquid state to the liquid surface of the molten CaCl 2 liquid, or it is also possible that the liquid or gaseous TiCl 4 is supplied to the liquid surface or inside the molten Ca liquid held on the molten CaCl 2 liquid.
  • the reducing reaction is performed by supplying the TiCl 4 liquid to the liquid surface of the molten Ca held on the surface of the molten CaCl 2 liquid
  • the reaction is rendered to take place at the molten Ca layer as well as at the molten CaCl 2 layer, and the Ti can continuously be generated even if the specific-gravity difference substitution cannot keep up with the reaction rate due to the increase in feed rate of TiCl 4 .
  • the TiCl 4 liquid is supplied to the liquid surface of the molten Mg liquid. It is tried that the TiCl 4 gas is supplied into the molten Mg liquid in order to enlarge the reaction field.
  • the Mg has the high vapor pressure, the Mg vapor intrudes in a supply nozzle of the TiCl 4 gas to react with TiCl 4 , which causes a supply nozzle to be choked.
  • the nozzle choking is hardly generated and the TiCl 4 gas can be supplied inside the molten CaCl 2 liquid.
  • One of the reasons why the nozzle choking is hardly generated is the small vapor pressure of the molten Ca.
  • TiCl 4 be directly supplied in the gaseous state inside the molten CaCl 2 liquid, and this supply mode can be applied without any problem in the actual operation. It is also possible that the liquid or gaseous TiCl 4 is supplied to the liquid surface of the molten CaCl 2 liquid, or it is also possible that the liquid or gaseous TiCl 4 is supplied to the liquid surface or inside the molten Ca liquid held on the molten CaCl 2 liquid.
  • the Ti particles and the molten CaCl 2 liquid may be separated from each other outside the reactor cell by utilizing the Ti generated in the particulate form to discharge the Ti particles outside the reactor cell along with the molten CaCl 2 liquid.
  • the Ti particles can simply be separated from the molten CaCl 2 liquid by a squeezing operation and the like by means of mechanical compression.
  • Ti is produced by the method of the present invention
  • TiCl 4 is used as a raw material.
  • the Ti alloy can also be produced by using a mixture of TiCl 4 and other metallic chloride. Because TiCl 4 and other metallic chloride are simultaneously reduced by Ca, the Ti alloy can be produced by this method. Said other metallic chloride may be used either in the gaseous or liquid state.
  • the back reaction and the wearing of the reactor material become of issues.
  • Ca Ca generated on the cathode electrode side or unreacted Ca
  • Cl 2 generated on the anode electrode side to return to CaCl 2 .
  • the wearing of the reactor material is caused by high reactivity of Ca.
  • the molten salt is formed not by single CaCl 2 but by the mixed salt, and a melting point of the molten salt is decreased to effectively decrease the temperature of the molten salt (namely, bath temperature).
  • CaCl 2 having the melting point of 780° C.
  • a binary system molten salt such as CaCl 2 —NaCl and CaCl 2 —KCl
  • a ternary system molten salt such as CaCl 2 —NaCl—KCl
  • at least one kind of other salts for example, NaCl, KCl, LiCl, and CaF 2
  • the melting point of the salt is decreased, the temperature of the molten salt (bath temperature) can be decreased.
  • the melting point can be decreased to about 500° C. at the lowest.
  • FIG. 1 is a block diagram showing a Ti metals production apparatus according to an embodiment mode of the present invention.
  • a reactor cell 1 in which the reducing reaction and the electrolytic reaction are concurrently generated is used in the embodiment.
  • the reactor cell 1 holds the Ca-rich molten CaCl 2 in which a relatively large amount of Ca is dissolved.
  • CaCl 2 has the melting point of about 780° C., and the molten salt of CaCl 2 is heated to the temperature of the melting point or more.
  • the molten CaCl 2 which is of the molten salt is electrolyzed by passing the electric current between a anode electrode 2 and a cathode electrode 3 , the Cl 2 gas is generated on the side of anode electrode 2 , and Ca is generated on the side of cathode electrode 3 .
  • the inside of the reactor cell 1 is divided into the anode electrode side and the cathode electrode side by a partition wall 4 . However, in the partition wall 4 , the lower portion is opened in order that the transfer of the molten salt is not prevented.
  • the gaseous TiCl 4 is injected in the dispersive manner inside the molten salt on the cathode electrode side in parallel with the electrolysis of the molten salt. Therefore, the injected TiCl 4 is reduced to generate the particulate metallic Ti by the Ca dissolved in the molten salt. The generated Ti particles moves downward by the specific gravity difference and accumulated at the bottom on the cathode electrode side in the reactor cell 1 .
  • the Ti particles accumulated at the bottom of the reactor cell 1 are discharged from the reactor cell 1 along with the molten salt existing at the bottom of the reactor cell 1 , and the Ti particles and the molten salt are sent to the Ti separation step (not shown).
  • the Ti separation step the Ti particles discharged along with the molten salt from the reactor cell 1 are separated from the molten salt. Specifically, the Ti particles are compressed to squeeze the molten salt.
  • the Ti particles obtained in the Ti separation step is melted to yield Ti ingots.
  • the molten salt separated from the Ti particles in the Ti separation step is the molten salt after use, in which Ca is consumed to decrease the Ca concentration. It is desirable to reuse the molten salt after use by returning it to the reactor cell.
  • both the above separated molten salt and the molten salt after use separately discharged from the reactor cell 1 are introduced to the anode electrode side in the reactor cell 1 .
  • Ca in the molten salt is consumed on the cathode electrode side in the reactor cell 1 as the Ti particles are generated by the reducing reaction.
  • Ca is generated near the surface of the cathode electrode 3 in the cell by the electrolysis which proceeds simultaneously in the cell, and a consumed amount of Ca is replenished by the Ca generated by the electrolysis. That is, TiCl 4 supplied into the molten salt is sequentially reduced in a direct manner by Ca generated near the surface of the cathode electrode 3 .
  • the molten salt after use is sent from the Ti separation step onto the anode electrode side in the reactor cell 1 . Therefore, a unidirectional flow of the molten salt is formed from the anode electrode side toward the cathode electrode side in the reactor cell 1 to avoid the flow of Ca generated on the cathode electrode side into the anode electrode side.
  • the partition wall 4 shown in FIG. 1 is provided, the flow of Ca into the anode electrode side is effectively prevented by the combination of the partition wall 4 and the formation of the unidirectional flow.
  • the molten salt introduced onto the anode electrode side in the reactor cell 1 is moved onto the cathode electrode side to be replenished with Ca and to become as the Ca-rich molten salt, thereby enabling to be reused for the reducing reaction.
  • the Cl 2 gas generated on the anode electrode side in the reactor cell 1 be reused in a chlorination step (not shown).
  • a chlorination step TiCl 4 which is of the raw material of Ti is generated by the chlorination of TiO 2 .
  • the generated TiCl 4 is introduced to the reactor cell 1 , and TiCl 4 is circularly used to generate the Ti particles by the Ca reduction.
  • the generation of the Ti particles by the Ca reduction i.e., the Ca consumption and the Ca replenishment by the electrolysis are concurrently performed in the reactor cell 1 . Therefore, it is not necessary to replenish or take out Ca in the solid state, and the high-quality Ti particles are continuously and economically produced by the Ca reduction.
  • the reactor cell 1 is commonly used as the reduction cell and the electrolytic cell, which contributes largely to an economical merit from the viewpoint of installation. The flow of Ca generated on the cathode electrode side into the anode electrode side is avoided in the reactor cell 1 , so that the back reaction in which Ca reacts with the Cl 2 gas generated on the anode electrode side can be prevented.
  • the molten salt is managed at a temperature higher than the melting point (about 780° C.) of CaCl 2 in the reactor cell 1 .
  • the feed rate of TiCl 4 which is of the raw material can be enhanced, and the continuous production can be realized. Further, the reducing reaction and the electrolytic reaction are simultaneously caused to proceed in the reactor cell, and Ca consumed in the reducing reaction can be replenished by the electrolytic reaction, so that it is not necessary to independently handle Ca by itself.
  • the production method of the present invention can effectively be used as means for efficiently and economically producing high-purity Ti metals or high-purity Ti alloys, so that the production method of the present invention can widely be applied as the industrial method for producing Ti or Ti alloys.

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US10/589,879 2004-02-20 2005-02-16 Method for producing ti or ti alloy through reduction by ca Abandoned US20070187255A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2004044827 2004-02-20
JP2004-044827 2004-02-20
JP2004281341A JP4342413B2 (ja) 2004-02-20 2004-09-28 Ｃａ還元によるＴｉ又はＴｉ合金の製造方法
JP2004-281341 2004-09-28
PCT/JP2005/002291 WO2005080643A1 (fr) 2004-02-20 2005-02-16 PROCÉDÉ DE FABRICATION DE Ti OU D’UN ALLIAGE DE Ti PAR RÉDUCTION DE Ca

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EP (1) EP1724376A4 (fr)
JP (1) JP4342413B2 (fr)
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060219053A1 (en) * 2003-08-28 2006-10-05 Tadashi Ogasawara Method and apparatus for producing metal
US20110178416A1 (en) * 2005-07-25 2011-07-21 Vascular Dynamics Inc. Devices and methods for control of blood pressure
CN103451681A (zh) * 2013-09-03 2013-12-18 广州有色金属研究院 一种金属钛的提取方法
CN103898555A (zh) * 2012-12-25 2014-07-02 攀钢集团攀枝花钢铁研究院有限公司 一种生产金属钛的方法
US8923972B2 (en) 2005-07-25 2014-12-30 Vascular Dynamics, Inc. Elliptical element for blood pressure reduction
US9125567B2 (en) 2005-07-25 2015-09-08 Vascular Dynamics, Inc. Devices and methods for control of blood pressure
US9592136B2 (en) 2005-07-25 2017-03-14 Vascular Dynamics, Inc. Devices and methods for control of blood pressure
US9642726B2 (en) 2005-07-25 2017-05-09 Vascular Dynamics, Inc. Devices and methods for control of blood pressure

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007119826A1 (fr) * 2006-04-14 2007-10-25 Osaka Titanium Technologies Co., Ltd. processus de fabrication de poudre Ti
CN103290433B (zh) * 2013-06-26 2016-01-20 石嘴山市天和铁合金有限公司 一种双电解槽熔盐电解制备纯钛的装置及其工艺
CN108546964B (zh) * 2018-05-29 2019-12-24 钢研晟华科技股份有限公司 一种金属钛的制备装置以及制备方法

Citations (4)

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US2205854A (en) * 1937-07-10 1940-06-25 Kroll Wilhelm Method for manufacturing titanium and alloys thereof
US2845386A (en) * 1954-03-16 1958-07-29 Du Pont Production of metals
US4820339A (en) * 1985-05-17 1989-04-11 Cerex Production of metal powders by reduction of metal salts in fused bath
US6074545A (en) * 1997-02-04 2000-06-13 Cathingots Limited Process for the electrolytic production of metals

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3718691B2 (ja) * 2002-04-18 2005-11-24 財団法人生産技術研究奨励会 チタンの製造方法、純金属の製造方法、及び純金属の製造装置

Patent Citations (4)

* 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
US2845386A (en) * 1954-03-16 1958-07-29 Du Pont Production of metals
US4820339A (en) * 1985-05-17 1989-04-11 Cerex Production of metal powders by reduction of metal salts in fused bath
US6074545A (en) * 1997-02-04 2000-06-13 Cathingots Limited Process for the electrolytic production of metals

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060219053A1 (en) * 2003-08-28 2006-10-05 Tadashi Ogasawara Method and apparatus for producing metal
US20110178416A1 (en) * 2005-07-25 2011-07-21 Vascular Dynamics Inc. Devices and methods for control of blood pressure
US8923972B2 (en) 2005-07-25 2014-12-30 Vascular Dynamics, Inc. Elliptical element for blood pressure reduction
US9125732B2 (en) 2005-07-25 2015-09-08 Vascular Dynamics, Inc. Devices and methods for control of blood pressure
US9125567B2 (en) 2005-07-25 2015-09-08 Vascular Dynamics, Inc. Devices and methods for control of blood pressure
US9457174B2 (en) 2005-07-25 2016-10-04 Vascular Dynamics, Inc. Elliptical element for blood pressure reduction
US9550048B2 (en) 2005-07-25 2017-01-24 Vascular Dynamics, Inc. Elliptical element for blood pressure reduction
US9592136B2 (en) 2005-07-25 2017-03-14 Vascular Dynamics, Inc. Devices and methods for control of blood pressure
US9642726B2 (en) 2005-07-25 2017-05-09 Vascular Dynamics, Inc. Devices and methods for control of blood pressure
US10384043B2 (en) 2005-07-25 2019-08-20 Vascular Dynamics, Inc. Devices and methods for control of blood pressure
CN103898555A (zh) * 2012-12-25 2014-07-02 攀钢集团攀枝花钢铁研究院有限公司 一种生产金属钛的方法
CN103451681A (zh) * 2013-09-03 2013-12-18 广州有色金属研究院 一种金属钛的提取方法

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EP1724376A1 (fr) 2006-11-22
JP4342413B2 (ja) 2009-10-14
WO2005080643A1 (fr) 2005-09-01
JP2005264319A (ja) 2005-09-29
EP1724376A4 (fr) 2007-07-25

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