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

核燃料后处理提取过程中形成的“第三阶段”的基础研究

• 批准号: 63580179
• 负责人: MIYAKE Chie
• 金额: $ 1.15万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-63580179/
• 关键词: fuel 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

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

采用元素分析的方法，系统地考察了Zr体系和TBP贫辐射产物HDBP、H_2MBP、H_3PO_1体系中沉淀物或“第三相”的形成条件、成分和结构。 X射线衍射、红外光谱和^1H-NMR。已证实，第三相最重要的来源之一是Zr离子与TBP耗尽产物之间的络合。还阐明了以下几点：(1)当贫化产物彼此共存时，在低酸溶液中出现对沉淀形成的协同效应。 (2)沉淀物的形成取决于HDBP/Zr的摩尔比。摩尔比约为2时，沉淀物的量达到最大，并随着HDBP浓度的增加而减少，最终在约10时消失。 (3)摩尔比约为2时形成的沉淀物的化学式为Zr(NO_3)_2(HDBP)_2(OH)_2。 (4) Zr-H_2MBP体系中的析出物… More m在H_2MBP浓度比Zr HDBP体系中HDBP小一个数量级时开始出现。通过EXAES(扩展X射线吸收精细结构)测量来研究Zr(IV)-单丁基磷酸盐和Zr(IV)-沉淀物中Zr周围的局部结构。 磷酸二丁酯，是所谓“第三阶段”的主要品种之一。凝胶状样品和干燥样品均显示出相同的 Zr(IV)-单丁基磷酸盐和 Zr(IV)-二丁基磷酸盐的傅里叶变换光谱。 Zr(IV)-单丁基磷酸盐中的沉淀物在Zr离子之间具有桥联磷酸盐，Zr-磷酸盐-Zr。以及Zr离子之间的桥接羟基，Zr-OH-Zr，而Zr(IV)-二丁基磷酸盐中没有桥接磷酸盐。这一事实表明本报告第(I)部分中描述的Zr(IV)-单丁基磷酸盐具有16A^^ﾟ距离的层结构。至于在部分（I）中观察到随着磷酸三丁酯的增加，磷酸二丁酯沉淀物重新溶解。 Zr(IV)-二丁基磷酸盐中桥联磷酸盐的缺失起着重要作用。通过元素分析确定化学结构。红外光谱。 (I)部分中的 1 H-NMR和X射线衍射由EXAFS的当前结果详细证实。已证实ZrO 2- ，即氧锆离子，不存在于水溶液中。较少的

项目成果

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 Tech

C. Miyake、M. Hirose、T. Yoshimura、M. Ikeda、S. Imoto 和 M. Sano：“燃料后处理中萃取过程的“Thied 相”（I）Zr 中沉淀物的成分和结构。 -TBP系统的降解产物”J.核科学与技术

C.Miyake: Journal of Nuclear Science and Technology. (1989)

C.Miyake：核科学与技术杂志。

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

Chie MIYAKE、Mistuhiro HIROSE、Yuhito YONEDA 和 Mitsuru SANO：“燃料再处理中萃取过程的“第三阶段”，(II) 单丁基磷酸锆和二丁基磷酸锆的 EXAFS 研究”J.Nuclear Science and Technology. 27. 256-261 ( 1990年

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.

Chie MIYAKE、M. Hirose 和 M. Iida：“燃料再加工中萃取过程的“第三阶段”，(III)Zr-二丁基磷酸盐再溶解成二丁基磷酸”J.Nuclear Science and Technology。

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)

C. Miyake、M. Sano、M. Hirose 和 Y. Yoneda：“燃料后处理中提取过程的“Thied 阶段”，(II) Zr-Monobulithos 和 Zr-Dibutylithos EXAFS 研究”J. Nuclear Science and Technology。 27.No3 (1990)