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Fundamental Study of "The Third Phase" formed in Extraction Processes of Nucler Fuel Reprocessing

Research Project

Project/Area Number 63580179
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field Nuclear engineering
Research InstitutionOsaka University

Principal Investigator

MIYAKE Chie  Osaka Univ., Faculty of Eng., Associate Prof., 工学部, 助教授 (70028976)

Project Period (FY) 1988 – 1989
Project Status Completed (Fiscal Year 1989)
Budget Amount *help
¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 1989: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1988: ¥1,100,000 (Direct Cost: ¥1,100,000)
Keywordsfuel reprocessing / Purex process / third phase / zirconium phosphates / layers / RuNO / ^<31>P-NMR / EXAFS / Zrー燐酸塩 / ^<31>PーNMR / 発熱反応 / Zr燐酸塩 / EXAFSジブチル燐酸 / モノブチル燐酸 / 不溶解残渣
Research Abstract

Formation conditions, compositions and structures of precipitates or "the third phase" were systematically examined in the systems of Zr and radiation depleted products of TBP, such as HDBP, H_2MBP, H_3PO_1, by means of elemental analysis. X-ray diffraction, infrared spectra and ^1H-NMR. It was confirmed that one of the most important origins for the third phase is a complexation between Zr ion and the depleted products of TBP. Followings were also elucidated:
(1) When the depleted products co-exist with each other, the cooperative effects on the pre- cipitate formation appear in low acid solutions. (2) Precipitate formation depends on the mole ratio of HDBP/Zr. The amount of precipitate reaches the maximum at the mole ratio of approximately 2 and decreases with increasing concentration of HDBP and finally disappeals at approximately 10. (3) Precipitate formed at the mole ratio of approximately 2 has the chemical formula, Zr(NO_3)_2(HDBP)_2(OH)_2. (4) Precipitates of the Zr-H_2MBP syste … More m begin to appear at the concentration of H_2MBP in one order of magnitude smaller than of HDBP in Zr HDBP system.
EXAES (Extended X-ray Absorption Fine Structure) measurement was carried out for the study of the local structure around Zr in precipitates of Zr(IV)-monobutylphosphate and Zr(IV)- dibutylphosphate, which are one of the main species of so-called "The Third Phase". Both gelatinous and dried samples show the same Fourier transform spectra for Zr(IV)-monobutyl- phosphate and Zr(IV)-dibutylphosphate. The precipitates in Zr(IV)-monobutylphosphate have the bridging phosphate between Zr ions, Zr-phosphate-Zr. as well as the bridging hydroxyl between Zr ions, Zr-OH-Zr, while no bridging phosphate in Zr(IV)-dibutylphosphate. This fact indicates the layer structure with 16A^^゚ distance for Zr(IV)-monobutylphosphate described in Part (I) of the present reports. As for the re-dissolution of Zr(IV)-dibutylphosphate precipitates with increasing tributylphosphate observed in Part (I). the absence of the bridging phosphate in Zr(IV)-dibutylphosphate plays an important role. The chemical structures pospuiated by elemental analysis. infrared spectra. ^1H-NMR and X-ray diffraction in Part (I) were confirmed in detail from the present results of EXAFS. It was confirmed ZrO^<2->, zirconyl ion, does not exist in aqueous solutions. Less

Report

(3 results)
  • 1989 Annual Research Report   Final Research Report Summary
  • 1988 Annual Research Report
  • Research Products

    (11 results)

All Other

All Publications (11 results)

  • [Publications] Chie MIYAKE,Mitsuhiro HIROSE,Toshikazu YOSHIMURA,Masayoshi IKEDA,Shosuke IMOTO and Mitsuru SANO: "“The Third Phase"of Extraction Processes in Fuel Reprocessing,(I)Formation Conditions Compositions and Structures of Precipitates in Zr-Degradation Products of TBP Systems" J.Nuclear Science and Technology.27. 157-166 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Chie MIYAKE,Mistuhiro HIROSE,Yuhito YONEDA and Mitsuru SANO: "“The Third Phase"of Extraction Processes in Fuel Reprocessing,(II)EXAFS Study of Zirconium Monobutylphosphate and Zirconium Dibutylphosphate" J.Nuclear Science and Technology. 27. 256-261 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Chie MIYAKE,M.Hirose and M.Iida: "“The Third Phase"of Extraction Processes in Fuel Reprocessing,(III)Redissolution of Zr-Dibutylphosphate into Dibutylphoshoric Acid" J.Nuclear Science and Technology.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Chie MIYAKE: ""The Third Phase"of Extraction Processes in Fuel Reprocessing, (I) Formation Conditions, Compositions and Structure of Precipitates in Zr-Degradation Products of TBP Systems" J.Nuclear Science and Technology. 27. 157-166 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Chie MIYAKE: ""The Third Phase"of Extraction Processes in Fuel Reprocessing, (II) EXAFS Study of Zirconium Monobutylphosphate and Zirconium Dibutylphosphate" J.Nuclear Science and Technology, 27 (1990) 256-261.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Chie MIYAKE: ""The Third Phase"of Extraction Processes in Fuel Reprocessing, (III) Redissolution of Zr-Dibutylphosphate into Dibutylphosphoric Acid" J.Nuclear Science and Technology.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] C.Miyake,M.Hirose,T.Yoshimura,M.Ikeda,S.Imoto and M.Sano: "“The Thied Phase"of Extraction Processes in Fuel Reprocessing(I).Formation Conditon,Compositions and Structure of Procipitates in ZrーDegradation Products of TBP Systems" J.Nuclear Science and Technology. 27. 157-166 (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] C.Miyake,M.Sano,M.Hirose and Y.Yoneda: "“The Thied Phase"of Extraction Processes in Fuel Reprocessing,(II)EXAFS Study of ZrーMonobutylphosphate and ZrーDibutylphosphate" J.Nuclear Science and Technology. 27. No3 (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] M.Hirose,C.Miyake and M.Iida: "“The Thied Phase" of Extraction Processes in Fuel Reprocessing,(III)Redissolution of ZrーDibutylphosphate into Dibutyphosphoric Acid" J.Nuclear Science and Technology.

    • Related Report
      1989 Annual Research Report
  • [Publications] C.Miyake: Journal of Nuclear Science and Technology. (1989)

    • Related Report
      1988 Annual Research Report
  • [Publications] C.Miyake: Journal of Nuclear Science and Technology. (1989)

    • Related Report
      1988 Annual Research Report

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Published: 1988-04-01   Modified: 2016-04-21  

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