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Direct Ingot Making of Titanium by Electro-winning from Molten Salt, Using Metal Pool of Titanium

Research Project

Project/Area Number 15206084
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field Metal making engineering
Research InstitutionToyohashi University of Technology

Principal Investigator

KAWAKAMI Masahiro  Toyohashi University of Technology, Professor, 工学部, 教授 (30016597)

Co-Investigator(Kenkyū-buntansha) TAKENAKA Toshihide  Toyohashi University of Technology, Associate Professor, 工学部, 助教授 (60197324)
深澤 英一  東邦チタニウム(株), 技術開発センター, 主任技師(研究職)
Project Period (FY) 2003 – 2005
Project Status Completed (Fiscal Year 2005)
Budget Amount *help
¥48,100,000 (Direct Cost: ¥37,000,000、Indirect Cost: ¥11,100,000)
Fiscal Year 2005: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Fiscal Year 2004: ¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000)
Fiscal Year 2003: ¥37,570,000 (Direct Cost: ¥28,900,000、Indirect Cost: ¥8,670,000)
Keywordsmolten salt electorysis with metal pool / direct ingot making of titanium / ESR unit / twin cell / current efficiency of electrolysis / composition of molten salt / reaction model / thermo-analysis of process / 単セル電解 / ツインセル電解 / チタン電解 / チタンESR / 反応機構 / 金属霧 / 電極間距離の影響 / 電流効率 / チタン電析 / ESR / 溶融塩電解 / メタルプール形状 / 電導度 / TiO_2添加効果 / 冷却水系統 / DC-ESR / チタンインゴット / 溶融チタン浴 / 再溶解 / プラズマ加熱
Research Abstract

The purpose of the present research project is to develop the direct ingot making process of titanium by electro-winning of titanium, where the metal pool of titanium is used as the cathode. By using ESR unit, the thermo-analysis of process, electrode reaction mechanism and contamination mechanism were examined.
At first, the electrical conductivity of CaO-CaF_2-TiO_2 slag was measured. The effect of TiO_2 addition was so small that the electronic conduction could be neglected. Thus, the addition of TiO_2 to the slag was possible at relatively large amount.
By operating ESR unit with steel rod, the relation between shape of metal pool and current-voltage condition was clarified. In the case of ESR, the metal pool could not be obtained at far higher temperature than the melting point of pure titanium. It was seen that the melting point of titanium rose by the absorption of oxygen. Thus, the atmosphere of the whole apparatus, especially, cathode part, must be innert.
In the single cell oper … More ation with CaO-CaF_2-TiO_2 slag, the maximum cathodic current efficiency was 12%, and the anodic current efficiency was far less than 100%. The reasons must be 1) formation of metal fog of Ca and its re-oxidation at the anode, 2) formation of Ti^<2+> by the reaction of Ti with Ti^<4+> and its re-oxidation at the anode, and 3) formation of Ti^<2+> by the insufficient amount of Ca and its re-oxidation at the anode. Thus, it is important to control the electrodes distance properly and to control the TiO_2 content properly.
On the contrary, by the addition of Al_2O_3 to the slag, c.a. 70 g of electro-deposit and c.a. 60% of cathodic current efficiency were obtained. The reasons must be that the temperature of molten slag should be kept higher temperature by the addition, and that the Al deposit should act as the reductant of Ti^<4+> in the slag. This process is good for producing Ti-Al alloy, but not good for producing pure Ti, because the electro-deposit contained much Al.
On the base on the above results, the new apparatus was designed. It consists of twin cell, one of which is anode cell and the other, cathode cell, connected with molten salt bridge. By this apparatus, the distance between cathode and anode can be kept long, resulting in the larger current efficiency and better quality of electro-deposit. The apparatus was successfully operated. Thus, the proposed process is very promising. The above results are published in 6 papers. Less

Report

(4 results)
  • 2005 Annual Research Report   Final Research Report Summary
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • Research Products

    (20 results)

All 2006 2005 2004 2003 Other

All Journal Article (16 results) Patent(Industrial Property Rights) (2 results) Publications (2 results)

  • [Journal Article] An Attempt at Direct Ingot Making of Titanium by the Electro-winning from Molten Salt with DC-ESR Unit2006

    • Author(s)
      M.Kawakami, M.Orisaka, T.Hashimoto, T.Takenaka
    • Journal Title

      Proc. the Sohn International Symposium, San Diego (掲載決定)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] An Attempt at Direct Ingot Making of Titanium by the Electro-winning from Molten Salt with DC-ESR Unit2006

    • Author(s)
      M.Kawakami, M.Orisaka, T.Hashimoto, T.Takenaka
    • Journal Title

      Proc.The Sohn Internantional Symposium, San Diego (in printing)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] An Attempt at Direct Ingot Making of Titanium by the Electro-winning from Molten Salt with DC=ESR Unit2006

    • Author(s)
      M.Kawakani, T.Takenaka, M.Orisaka, T.Kawabata, A.Matsuyama, S.Yokoyama
    • Journal Title

      Proc.The Sohn International Symposium

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Electrochemical Reduction of Ti Ion in Various Molten Salt Systems2005

    • Author(s)
      Toshihide Takennaka, Masahiro Kawakami
    • Journal Title

      Journal of Rare Earths 23・Spec.Issue

      Pages: 21-25

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Difference in electrochemical reduction of Ti ion in various molten salt systems2005

    • Author(s)
      T.Takenaka, M.Kawakami
    • Journal Title

      Proc. 1^<st> Asia and 9^<th> China-Japan Bilateral Conference on Molten Salt Chemistry and Technology, Wuhu

      Pages: 78-81

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Dependence of DC-ESR operation upon TiO_2 concentration in molten fluoride-oxide mixture2005

    • Author(s)
      T.Hashimoto, T.Noichi, M.Orisaka, T.Kawabata, H.Tanigawa, T.Takenaka, M.Kawakami
    • Journal Title

      Proc. 1^<st> Asia and 9^<th> China-Japan Bilateral Conference on Molten Salt Chemistry and Technology, Wuhu

      Pages: 113-115

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Electro-winning of Titanium from Molten Salt with ERS Unit2005

    • Author(s)
      M.Kawakami, M.Orisaka, T.Hashimoto, T.Takenaka
    • Journal Title

      Proc. MS7 International Symposium on Molten Salts Chemistry and Technology, Toulouse

      Pages: 135-138

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Electrochemical Reduction of Ti Ion in Various Molten Salt System2005

    • Author(s)
      Toshihide Takenaka, Masahiro Kawakami
    • Journal Title

      Journal of Rare Earths 23・Spec.Issue

      Pages: 21-25

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Difference in electrochemical reduction of Ti ion in various molten salt systems2005

    • Author(s)
      T.Takenaka, M.Kawakami
    • Journal Title

      Proc.1^<st> Asia and 9^<th> China-Japan Bilateral Conference on Molten Salt Chemistry and Technology, Wuhu

      Pages: 78-81

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Dependence of DC-ESR operation upon TiO_2 concentration in molten fluoride-oxide mixture2005

    • Author(s)
      T.Hashimoto, T.Noichi, M.Orisaka, T.Kawabata, H.Tanigawa, M.Kawakami
    • Journal Title

      Proc.1^<st> Asia and 9^<th> China-Japan Bilateral Conference on Molten Salt Chemistry and Technology, Wuhu

      Pages: 113-115

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Electro-winning of Titanium from Molten Salt with ERS Unit2005

    • Author(s)
      M.Kawakami, M.Orisaka, T.Hashimoto, T.Takenaka
    • Journal Title

      Proc.MS7 International Symposium on Molten Salts chemistry and Technology, Toulouse

      Pages: 135-138

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Dependence of DC-ESR operation upon TiO_2 concentration in molten fluoride-oxide mixture2005

    • Author(s)
      T.Hashimoto, T.Noichi, M.Orisaka, T.Kawabata, H.Tanigawa, T.Takenaka, M.Kawakami
    • Journal Title

      Proc.1^<st> Asia and 9^<th> China-Japan Bilateral Conference on Molten Salt Chemistry and Technology, Wuhu

      Pages: 113-115

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Electro-winning of Titanium from Molten Salt with ERS Unit2005

    • Author(s)
      M.Kawakami, M.Orisaka, T.Hashimoto, T.Takenaka
    • Journal Title

      Proc.MS7 International Symposium on Molten Salts Chemistry and Technology, Toulouse

      Pages: 135-138

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Direct Electrowinning of Titanium : Combination of Electrolysis and Melting of Titanium Metal by DC-ESR Apparatus2004

    • Author(s)
      Toshihide Takenaka, Masahiro Kawakami
    • Journal Title

      Ti-2003 Science and Technology vol.I

      Pages: 221-228

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Direct Electro-winning of Titanium : Combination of Electrolysis and Melting of Titanjum metal by DC-ESR Apparatus2003

    • Author(s)
      T.Takenaka, M.Kawakami
    • Journal Title

      Proc. Ti-2003 Science and Technology, Hamburg vol.1

      Pages: 221-228

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Direct "Electro-winning of Titanium : Combination of Electrolysis and Melting of Titanium metal by DC-ESR Apparatus"2003

    • Author(s)
      T.Takenaka, M.Kawakami
    • Journal Title

      Proc.Ti-2003 Science and Technology, Hamburg vol.1

      Pages: 221-228

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Patent(Industrial Property Rights)] 金属の溶融塩電解装置およびこの装置を用いた金属の製造法2006

    • Inventor(s)
      川上 正博, 竹中 俊英, 深澤 英一
    • Industrial Property Rights Holder
      豊橋技術科学大学
    • Industrial Property Number
      2006-023243
    • Filing Date
      2006-01-31
    • Related Report
      2005 Annual Research Report
  • [Patent(Industrial Property Rights)] 金属の溶融塩電解装置およびこの装置を用いた金属の製造法

    • Inventor(s)
      川上正博, 竹中俊英, 深澤英一
    • Industrial Property Rights Holder
      特願2006-023243
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Publications] Toshihide Takenaka, Masahiro Kawakami: "Direct Electrowinning of Titanium : Combination of Electrolysis and Melting of Titanium Metal by"Proceedings of Ti 2003. (in press).

    • Related Report
      2003 Annual Research Report
  • [Publications] 竹中俊英, 野村恭平, 川上正博: "溶融フッ化物-酸化物中でのチタンの電極反応"電気化学会第71回大会講演要旨集. 1B04 (2004)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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