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JP4124133B2 - Method of extracting and separating Np (IV), Pu (III), Pu (IV), Am (III), and Cm (III) in a 1-6M nitric acid solution at once with an oxapentanediamine compound - Google Patents

Method of extracting and separating Np (IV), Pu (III), Pu (IV), Am (III), and Cm (III) in a 1-6M nitric acid solution at once with an oxapentanediamine compound Download PDF

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JP4124133B2
JP4124133B2 JP2004031834A JP2004031834A JP4124133B2 JP 4124133 B2 JP4124133 B2 JP 4124133B2 JP 2004031834 A JP2004031834 A JP 2004031834A JP 2004031834 A JP2004031834 A JP 2004031834A JP 4124133 B2 JP4124133 B2 JP 4124133B2
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祐二 佐々木
伸一 鈴木
由美 須郷
貴海 木村
英哉 鈴木
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独立行政法人 日本原子力研究開発機構
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    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/30—Nuclear fission reactors
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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原子力分野では、高レベル放射性廃液（ＨＬＬＷ）、または使用済み核燃料(ＳＦ)から、効率的に３，４価のアクチノイドイオンを抽出分離することが重要であり、本発明はこれら金属を一括抽出する方法に関わる。   In the nuclear field, it is important to efficiently extract and separate trivalent and tetravalent actinide ions from high-level radioactive liquid waste (HLLW) or spent nuclear fuel (SF), and the present invention collectively extracts these metals. Involved in the method.

ＰＵＲＥＸ法に利用されるリン酸トリブチル（ＴＢＰ）に代表されるように、多くの抽出剤は４価又は６価のアクチノイドイオンと強く錯形成するが、３価のアクチノイドとの結合は弱く抽出しにくい。３価のアクチノイドに対して比較的高い分配比を示す、オクチル（フェニル）−Ｎ，Ｎ−ジイソブチルカルバモイルメチルホスフィンオキシド（ＣＭＰＯ）は、プロセスに利用されるｎ−ドデカンのような無極性溶媒中でやや溶解しにくく、安定化剤のＴＢＰを加えている（例えば、非特許文献１）。このことは有機相内での複雑な反応を生じさせることや経済性の面にも影響する。
W. Liansheng, M. Casarci, G.M. Gasparini, Solv. Extr. Ion Exch., 8, 49(1990) As represented by tributyl phosphate (TBP) used in the PUREX method, many extractants strongly complex with tetravalent or hexavalent actinoid ions, but the bond with trivalent actinoids is weakly extracted. Hateful. Octyl (phenyl) -N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO), which exhibits a relatively high distribution ratio to trivalent actinoids, is used in nonpolar solvents such as n-dodecane utilized in the process. It is slightly difficult to dissolve, and a stabilizer TBP is added (for example, Non-Patent Document 1). This affects the complex reaction in the organic phase and the economic aspect.
W. Liansheng, M. Casarci, GM Gasparini, Solv. Extr. Ion Exch., 8, 49 (1990)

プロセス開発において、効率的にＮｐ（ＩＶ），Ｐｕ（ＩＩＩ），Ｐｕ（ＩＶ），Ａｍ（ＩＩＩ），Ｃｍ（ＩＩＩ）及びランタノイド（Ｌｎ（ＩＩＩ））のような３，４価のアクチノイド（ランタノイド）イオンを一括抽出することは、使用済み核燃料再処理、あるいは高レベル廃液の群分離などにおいて重要な課題である。従来法の主要な課題は次のとおりである。   In process development, trivalent and tetravalent actinoids (lanthanoids) such as Np (IV), Pu (III), Pu (IV), Am (III), Cm (III) and lanthanoids (Ln (III)) ) Extraction of ions at once is an important issue in reprocessing spent nuclear fuel or group separation of high-level waste liquid. The main problems of the conventional method are as follows.

（１）３，４価のアクチノイドイオンともに高い分配比を示す抽出剤は数少ない。
（２）これまでに提案されたプロセスに利用される抽出剤はｎ−ドデカンのような無極性溶媒中の溶解性がやや低く、不安定なものが多い。 (1) There are few extractants that show a high distribution ratio for both trivalent and tetravalent actinoid ions.
(2) The extractant used in the processes proposed so far has a slightly low solubility in a nonpolar solvent such as n-dodecane, and is often unstable.

（３）第三相が生成した場合、プロセス設計が困難になり、かつ有機相に抽出できる金属量は限定される。   (3) When the third phase is generated, process design becomes difficult, and the amount of metal that can be extracted into the organic phase is limited.

本発明は、上記課題を解決するために、次の特徴を有する抽出剤を開発した。
（１）Ｎｐ（ＩＶ），Ｐｕ（ＩＩＩ），Ｐｕ（ＩＶ），Ａｍ（ＩＩＩ），Ｃｍ（ＩＩＩ）及びＬｎ（ＩＩＩ）のような３，４価のアクチノイド（ランタノイド）イオンに高い分配比を示す抽出剤を開発した。 In order to solve the above problems, the present invention has developed an extractant having the following characteristics.
(1) High partition ratio for trivalent and tetravalent actinoid (lanthanoid) ions such as Np (IV), Pu (III), Pu (IV), Am (III), Cm (III) and Ln (III) The extractant shown was developed.

（２）該当する抽出剤はプロセス利用されるｎ−ドデカンのような無極性溶媒に安定であり、いかなる比率でも混ざり合う抽出剤である。
（３）第三相の生成をできるだけ抑制できる抽出剤、及び条件を見出した。即ち、本発 明の新規三座配位子のＤＧＡ化合物である、ＴＯＤＧＡ（Ｎ
，Ｎ，Ｎ’，Ｎ’−テトラオクチル−１，３−オキサペンタンジアミド），ＴＤＤＧＡ（Ｎ，Ｎ，Ｎ’，Ｎ’−テトラデシル−１，３−オキサペンタンジアミド）及びＴＤｄＤＧＡ（Ｎ，Ｎ，Ｎ’，Ｎ’−テトラドデシル−１，３−オキサペンタンジアミド）を開発した。 (2) The relevant extractant is stable to a nonpolar solvent such as n-dodecane used in the process, and is an extractant that mixes in any ratio.
(3) The extraction agent and conditions which can suppress the production | generation of a 3rd phase as much as possible were discovered. That is, TODGA (N), a novel tridentate DGA compound of the present invention.
, N, N ′, N′-tetraoctyl-1,3-oxapentanediamide), TDDGA (N, N, N ′, N′-tetradecyl-1,3-oxapentanediamide) and TDdDGA (N, N, N ′, N′-tetradodecyl-1,3-oxapentanediamide) was developed.

本発明においては、使用済み核燃料（ＳＦ）溶解液あるいは高レベル放射性廃液（ＨＬＬＷ）のような硝酸水溶液から金属イオンを溶媒抽出する際に、効率的に３，４価のアクチノイド、ランタノイドを抽出できるＤＧＡ化合物の合成方法を開発し、プロセスに応用することが可能となった。   In the present invention, when metal ions are extracted from an aqueous nitric acid solution such as spent nuclear fuel (SF) solution or high-level radioactive liquid waste (HLLW), trivalent and tetravalent actinides and lanthanoids can be efficiently extracted. A method for synthesizing DGA compounds has been developed and can be applied to processes.

前述の従来の抽出剤使用に起因する欠点に対して、本発明の抽出剤の利点をまとめると、次のとおりである。
１）本発明の上記抽出剤化合物は長い炭化水素鎖を有し、無極性溶媒のｎ−ドデカンと非常に良く混ざり合い、１Ｍのような高い濃度のＤＧＡ／ｎ−ドデカン抽出溶媒の調製が可能である。 The advantages of the extractant of the present invention are summarized as follows with respect to the drawbacks caused by the use of the above-mentioned conventional extractant.
1) The above extractant compound of the present invention has a long hydrocarbon chain, and mixes very well with the nonpolar solvent n-dodecane, allowing the preparation of a DGA / n-dodecane extraction solvent with a high concentration such as 1M. It is.

２）上記抽出剤をｎ−ドデカンに溶解した抽出溶媒は、使用済み核燃料（ＳＦ）溶解液あるいは高レベル放射性廃液（ＨＬＬＷ）のような硝酸水溶液中の３，４価のランタノイド、アクチノイドに対し高い分配比を示し、効率的にこれら金属を抽出できる。   2) The extraction solvent in which the above extractant is dissolved in n-dodecane is higher than the trivalent and tetravalent lanthanoids and actinides in nitric acid aqueous solution such as spent nuclear fuel (SF) solution or high-level radioactive liquid waste (HLLW). It shows the distribution ratio and can extract these metals efficiently.

３）この金属錯体はｎ−ドデカン中で非常に安定であり、特に、ＴＤｄＤＧＡは過剰Ｎｄ（ＩＩＩ）濃度に由来する第三相を殆ど生成しない。ＴＯＤＧＡは高濃度のＮｄ（ＩＩＩ）を含む水溶液と反応させた場合、第三相を生成するが、十分な濃度の安定化剤のモノアミドを添加した系では第三相を生成しない。   3) This metal complex is very stable in n-dodecane, in particular TDdDGA produces little third phase derived from excess Nd (III) concentration. When TODGA is reacted with an aqueous solution containing a high concentration of Nd (III), a third phase is generated, but a third phase is not generated in a system to which a sufficient concentration of the stabilizer monoamide is added.

４）安定化剤のモノアミドを加えた系でも全ての抽出剤はＣ，Ｈ，Ｏ，Ｎ元素から成り、使用後は焼却処分可能であり、２次的に発生する廃棄物を低減できる。   4) Even in a system to which a monoamide as a stabilizer is added, all the extractants are composed of C, H, O, and N elements, which can be incinerated after use, and can reduce waste generated secondarily.

（実施例１）
ＴＯＤＧＡを用いて、Ｎｐ（ＩＶ），Ｐｕ（ＩＩＩ），Ｐｕ（ＩＶ），Ａｍ（ＩＩＩ），及びＣｍ（ＩＩＩ）の抽出分配比を測定した。水相に各アクチノイドイオンを含む硝酸溶液を、有機相に０．１Ｍ ＴＯＤＧＡ／ｎ−ドデカン溶媒を用いて、得られた分配比を硝酸濃度に対してプロットした。硝酸濃度が増加すると各イオンの分配比は増加し、１Ｍ（＝ｍｏｌ／ｄｍ3）以上の硝酸溶液から最低３０の分配比が得られ、この数字は少なくとも６Ｍまで硝酸濃度増加とともに増加した。これは１Ｍ硝酸の条件でバッチ抽出において、９７％の回収が可能であることを示唆する。 (Example 1)
The extraction partition ratio of Np (IV), Pu (III), Pu (IV), Am (III), and Cm (III) was measured using TODGA. Using the nitric acid solution containing each actinoid ion in the aqueous phase and 0.1 M TODGA / n-dodecane solvent in the organic phase, the obtained distribution ratio was plotted against the nitric acid concentration. As the nitric acid concentration increased, the distribution ratio of each ion increased, and a minimum 30 distribution ratio was obtained from a nitric acid solution of 1M (= mol / dm 3 ) or more, and this figure increased with increasing nitric acid concentration to at least 6M. This suggests that 97% recovery is possible in batch extraction with 1M nitric acid.

（実施例２）
ＴＯＤＧＡを用いて、Ｌａ（ＩＩＩ），Ｃｅ（ＩＩＩ），Ｐｒ（ＩＩＩ），Ｎｄ（ＩＩＩ），Ｓｍ（ＩＩＩ），Ｅｕ（ＩＩＩ），及びＧｄ（ＩＩＩ）の抽出分配比を測定した。水相に各ランタノイドイオンを含む硝酸溶液を、有機相に０．１Ｍ ＴＯＤＧＡ／ｎ−ドデカン溶媒を用いて、得られた分配比を硝酸濃度に対してプロットした。それら抽出挙動はアクチノイドイオンとほぼ同様な傾向が見られた。最も低い分配比はＬａ（ＩＩＩ）の１Ｍ硝酸濃度条件で４であり、ミキサセトラで多段抽出すれば十分抽出可能であることを示す。 (Example 2)
Using TODGA, the extraction partition ratios of La (III), Ce (III), Pr (III), Nd (III), Sm (III), Eu (III), and Gd (III) were measured. Using a nitric acid solution containing each lanthanoid ion in the aqueous phase and 0.1M TODGA / n-dodecane solvent in the organic phase, the obtained distribution ratio was plotted against the nitric acid concentration. These extraction behaviors showed almost the same tendency as actinoid ions. The lowest distribution ratio is 4 under the condition of 1M nitric acid concentration of La (III), which indicates that extraction can be sufficiently performed by multistage extraction with a mixer setra.

本発明により、ＳＦ溶解液あるいはＨＬＬＷから効率的に３，４価アクチノイドイオンを溶媒抽出分離でき、プロセス設計・評価が容易になり、工程の簡素化・プロセス規模の縮小化が期待される。   According to the present invention, the trivalent and tetravalent actinide ions can be efficiently extracted and separated from the SF solution or HLLW, the process design / evaluation is facilitated, and the simplification of the process and the reduction of the process scale are expected.

Ｎｐ（ＩＶ），Ｐｕ（ＩＩＩ），Ｐｕ（ＩＶ），Ａｍ（ＩＩＩ），及びＣｍ（ＩＩＩ）分配比の硝酸濃度依存性（有機相；０．１Ｍ ＴＯＤＧＡ／ｎ−ドデカン）を示す図である。It is a figure which shows the nitric acid concentration dependence (organic phase; 0.1M TODGA / n-dodecane) of Np (IV), Pu (III), Pu (IV), Am (III), and Cm (III) distribution ratio. . Ｌａ（ＩＩＩ），Ｃｅ（ＩＩＩ），Ｐｒ（ＩＩＩ），Ｎｄ（ＩＩＩ），Ｓｍ（ＩＩＩ），Ｅｕ（ＩＩＩ），及びＧｄ（ＩＩＩ）分配比の硝酸濃度依存性（有機相；０．１Ｍ ＴＯＤＧＡ／ｎ−ドデカン）を示す図である。La (III), Ce (III), Pr (III), Nd (III), Sm (III), Eu (III), and Gd (III) distribution ratio dependence on nitric acid concentration (organic phase; 0.1M TODGA It is a figure which shows / n-dodecane.

Claims (1)

使用済み核燃料溶解液又は高レベル放射性廃液から選ばれる１Ｍ〜６Ｍの硝酸水溶液から、ＴＯＤＧＡ（Ｎ，Ｎ，Ｎ’，Ｎ’−テトラオクチル−１，３−オキサペンタンジアミド），ＴＤＤＧＡ（Ｎ，Ｎ，Ｎ’，Ｎ’−テトラデシル−１，３−オキサペンタンジアミド）、又はＴＤｄＤＧＡ（Ｎ，Ｎ，Ｎ’，Ｎ’−テトラドデシル−１，３−オキサペンタンジアミド）により、無極性有機溶媒相へＮｐ（ＩＶ），Ｐｕ（ＩＩＩ），Ｐｕ（ＩＶ）、Ａｍ（ＩＩＩ），及びＣｍ（ＩＩＩ）を一括抽出する方法。 From 1 M to 6 M nitric acid aqueous solution selected from spent nuclear fuel solution or high-level radioactive liquid waste, TODGA (N, N, N ′, N′-tetraoctyl-1,3-oxapentanediamide), TDDGA (N, N , N ′, N′-tetradecyl-1,3-oxapentanediamide), or TDdDGA (N, N, N ′, N′-tetradodecyl-1,3-oxapentanediamide) to the nonpolar organic solvent phase A method of extracting Np (IV), Pu (III), Pu (IV), Am (III), and Cm (III) at once.
JP2004031834A 2004-02-09 2004-02-09 Method of extracting and separating Np (IV), Pu (III), Pu (IV), Am (III), and Cm (III) in a 1-6M nitric acid solution at once with an oxapentanediamine compound Expired - Fee Related JP4124133B2 (en)

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