JP2012173145A - Chloridation processing method for acid chloride and oxide in molten salt, and compound ions thereof - Google Patents

Chloridation processing method for acid chloride and oxide in molten salt, and compound ions thereof Download PDF

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JP2012173145A
JP2012173145A JP2011035573A JP2011035573A JP2012173145A JP 2012173145 A JP2012173145 A JP 2012173145A JP 2011035573 A JP2011035573 A JP 2011035573A JP 2011035573 A JP2011035573 A JP 2011035573A JP 2012173145 A JP2012173145 A JP 2012173145A
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chloride
molten salt
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chlorides
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JP5594671B2 (en
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Takayuki Nagai
崇之 永井
Hajime Yamana
元 山名
Toshiyuki Fujii
俊行 藤井
Akihiro Uehara
章寛 上原
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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
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Abstract

PROBLEM TO BE SOLVED: To provide a chloridation processing method of carrying out chloridation processing without leaving new products by reaction with a reducer in molten salt like conventional chloridation processing on components in molten salt.SOLUTION: A reducer composed of tungsten metal or a reducer composed of tungsten acid chloride or tungsten chloride is supplied into the molten salt to be processed, and reaction gas composed of gaseous chlorine or gaseous hydrogen chloride or mixed gas thereof is supplied into the molten salt. Acid chloride and oxide of actinide elements, transition metal elements or rare earth elements contained in the molten salt, and compound ions thereof are subjected to chloridation processing to obtain chloride and chloride ions.

Description

本発明は、塩化物及び塩化物とフッ化物の混合物等のハロゲン化物からなる溶融塩を溶媒に用いる化学処理プロセスにおいて、電解析出又は蒸留分離等の操作による回収が困難な酸塩化物及び酸化物並びにこれら化合物イオンを、回収が容易な塩化物又は塩化物イオンの化学種に塩化処理する方法に関する。   The present invention relates to an acid chloride and an oxidation which are difficult to recover by an operation such as electrolytic deposition or distillation separation in a chemical treatment process using a molten salt composed of chloride and a halide such as a mixture of chloride and fluoride as a solvent. And a method of chlorinating these compound ions into chlorides or chemical species of chloride ions that can be easily recovered.

本発明の適用の一具体例としては、使用済核燃料の乾式再処理プロセスにおいて、溶融塩に含まれる回収対象のアクチニド元素の酸塩化物及び酸化物並びにこれら化合物イオンを、金属の形態で回収し易い塩化物又は塩化物イオンに処理する技術への適用がある。また、本発明の適用の他の具体例としては、遷移金属元素又は希土類元素の精錬プロセスにおいて、溶融塩に含まれる回収対象の遷移金属元素又は希土類元素の酸塩化物及び酸化物並びにこれら化合物イオンを、金属の化学形態で回収することが容易な塩化物又は塩化物イオンに処理する技術への適用がある。   As a specific example of the application of the present invention, in the dry reprocessing process of spent nuclear fuel, the acid chlorides and oxides of the actinide elements to be recovered contained in the molten salt and these compound ions are recovered in the form of metal. There is an application to technology that processes easily to chloride or chloride ions. Further, as other specific examples of application of the present invention, in the refining process of transition metal elements or rare earth elements, acid chlorides and oxides of transition metal elements or rare earth elements to be recovered contained in the molten salt and these compound ions Is applied to a technique for treating chlorides or chloride ions, which can be easily recovered in a metal chemical form.

ハロゲン化物溶融塩に含まれる酸塩化物及び酸化物並びにこれら化合物イオンを塩化物又は塩化物イオンに処理する従来技術として、酸素を除去する還元剤を供給する方法が知られている。このような方法の一例としては、例えば、塩化リチウム（LiCl）と塩化カリウム（KCl）の共晶塩化物溶融塩中の二酸化ウラン（UO2）等を四塩化ジルコニウム(ZrCl4）で三塩化ウランへ塩化処理する研究成果が報告されている［非特許文献１］。 As a conventional technique for treating acid chlorides and oxides contained in molten halide salts and chlorides or chloride ions of these compound ions, a method of supplying a reducing agent for removing oxygen is known. As an example of such a method, for example, uranium dioxide (UO 2 ) in eutectic chloride molten salt of lithium chloride (LiCl) and potassium chloride (KCl) is replaced with zirconium tetrachloride (ZrCl 4 ) uranium trichloride. Research results of chlorination treatment have been reported [Non-Patent Document 1].

また、還元剤による塩化処理の従来技術のうち、新たな生成物が溶融塩中に残留しない還元剤として、黒鉛（C）を投入し塩素ガスを供給する方法も知られている［特許文献１］。   In addition, among conventional techniques for chlorination with a reducing agent, a method of supplying chlorine gas by introducing graphite (C) as a reducing agent in which a new product does not remain in the molten salt is also known [Patent Document 1]. ].

さらに、酸化物を塩化物へ直接処理する従来技術として、酸素を除去する還元剤と処理対象の酸化物と混合して反応させ、対象元素の塩化物のみを揮発蒸留等により回収する方法が知られている。このような方法の一例としては、例えば、還元剤に五塩化モリブデン（MoCl5）を用いてZrO2をZrCl4へ塩化させる研究成果が報告されている［非特許文献２］。 Furthermore, as a conventional technique for directly processing oxides into chlorides, there is known a method in which a reducing agent for removing oxygen and an oxide to be treated are mixed and reacted, and only chlorides of the target element are recovered by volatile distillation or the like. It has been. As an example of such a method, for example, a research result of chlorinating ZrO 2 to ZrCl 4 using molybdenum pentachloride (MoCl 5 ) as a reducing agent has been reported [Non-patent Document 2].

特許第3143852号「使用済核燃料の塩化物への転換方法及びその装置」Patent No. 3314852 “Method and apparatus for converting spent nuclear fuel to chloride”

Y. Sakamura, T. Inoue, T. Iwai, H. Moriyama, "Chlorination of UO2, PuO2 and rare earth oxides using ZrCl4 in LiCl-KCl eutectic melt"Journal of Nuclear Materials, Vol．340(2005)39-51．Y. Sakamura, T. Inoue, T. Iwai, H. Moriyama, "Chlorination of UO2, PuO2 and rare earth oxides using ZrCl4 in LiCl-KCl eutectic melt" Journal of Nuclear Materials, Vol. 340 (2005) 39-51. T. Hijikata, M. Kurata, "Novel Chlorination of Zirconium Dioxide at Low Temperature", Electrochemistry, Vol．77, No． 8(2009)702-708・T. Hijikata, M. Kurata, "Novel Chlorination of Zirconium Dioxide at Low Temperature", Electrochemistry, Vol. 77, no. 8 (2009) 702-708

しかしながら、上述の、ハロゲン化物溶融塩に含まれる酸塩化物及び酸化物並びにこれら化合物イオンを塩化物又は塩化物イオンに処理するために、酸素を除去する還元剤を供給する方法は、供給した還元剤が酸塩化物及び酸化物並びにこれら化合物イオンと反応して新たな酸化物又は酸塩化物等の微粒子を生成し、これら生成物が溶融塩中を浮遊又は溶融塩下部に堆積するため、これら生成物を溶融塩から除去する操作が必要となる。具体的には、例えば、上述の非特許文献１に報告されている例では、ZrC14とUO2との反応によりジルコニア（ZrO2）が生成し溶融塩中に残留するため、プロセスとしてZrO2をろ過分離する操作が必要となる。 However, in order to treat the acid chlorides and oxides contained in the halide molten salt and the compound ions into chlorides or chloride ions, a method of supplying a reducing agent for removing oxygen is used in the above-described reduction. The agent reacts with acid chlorides and oxides and these compound ions to produce new oxides or acid chloride fine particles, which float in the molten salt or deposit under the molten salt. An operation for removing the product from the molten salt is required. Specifically, for example, in the example reported in Non-Patent Document 1 described above, for remaining in the reaction by zirconia (ZrO 2) is produced molten salt of ZrC1 4 and UO 2, ZrO 2 as a process It is necessary to perform an operation for separating and filtering.

また、上述の特許文献１に記載されている、黒鉛（C）を投入し塩素ガスを供給する方法は、溶融塩中に新たな生成物を発生させないものの、黒鉛を溶融塩中へ投入した場合、黒鉛の密度が小さいために溶融塩の表面を浮遊し易く、反応で消費される量よりも多い黒鉛を添加する必要があり、この黒鉛の余剰分が、塩化処理後の電解析出による対象元素の回収時に、電極間の短絡原因となるため、電解前に除去する必要がある。   In addition, the method of supplying graphite (C) and supplying chlorine gas described in Patent Document 1 described above does not generate a new product in the molten salt, but when graphite is introduced into the molten salt. Because the density of graphite is small, it is easy to float on the surface of the molten salt, and it is necessary to add more graphite than the amount consumed by the reaction. At the time of element recovery, it causes a short circuit between the electrodes and must be removed before electrolysis.

さらに、上述の非特許文献２に記載されているように、酸化物を塩化物へ直接処理する場合にも、還元剤との反応により生成する酸化物及びオキシ塩化物の粒子を分離する操作が必要となる。   Furthermore, as described in Non-Patent Document 2 described above, even when the oxide is directly processed into chloride, the operation of separating the oxide and oxychloride particles generated by the reaction with the reducing agent is performed. Necessary.

したがって、本発明の目的は、塩化物及び塩化物とフッ化物の混合物等のハロゲン化物からなる溶融塩を溶媒に用いる化学処理プロセスを対象に、還元剤との反応による新たな生成物を溶融塩中に残留させることなく、かつ余分な処理剤を溶融塩中に残すことなく、ハロゲン化物溶融塩に含まれる酸塩化物及び酸化物並びにこれら化合物イオンを、回収が容易な塩化物又は塩化物イオンに塩化処理する新しい方法を提供することにある。   Accordingly, an object of the present invention is to provide a chemical treatment process in which a molten salt composed of chloride and a halide such as a mixture of chloride and fluoride is used as a solvent. Chlorides or chloride ions which are easily recovered from acid chlorides and oxides contained in the halide molten salt and these compound ions without remaining in the molten salt and without leaving an extra treating agent in the molten salt. The aim is to provide a new method of chlorination.

本発明の一つの観点によれば、上述の新しい方法は、基本的には、処理対象物である溶融塩中に、タングステン金属からなる還元剤又はタングステン酸塩化物からなる還元剤或いはタングステン塩化物からなる還元剤を供給するとともに、塩素ガス又は塩化水素ガス或いはこれら混合ガスからなる反応ガスを前記溶融塩中に供給し、前記溶融塩に含まれるアクチニド元素又は遷移金属元素或いは希土類元素の、酸塩化物及び酸化物並びにこれら化合物イオンを、塩化物及び塩化物イオンに塩化処理するものである。   According to one aspect of the present invention, the above-described new method basically includes a reducing agent made of tungsten metal or a reducing agent made of tungstate chloride or tungsten chloride in a molten salt to be treated. And a reactive gas consisting of chlorine gas, hydrogen chloride gas or a mixed gas thereof is supplied into the molten salt, and an acid of an actinide element, transition metal element or rare earth element contained in the molten salt is supplied. Chlorides and oxides, and these compound ions are chlorinated to chloride and chloride ions.

上述の反応により生成するタングステン酸塩化物（WO2Cl2、WOCl4等）の生成物は、沸点が３００℃以下であるため、アルゴンガス等の不活性ガスを溶融塩中へ供給することで容易に溶融塩から揮発除去でき、溶融塩中に生成物は残留しない。 Since the product of tungstated chloride (WO 2 Cl 2 , WOCl 4, etc.) produced by the above reaction has a boiling point of 300 ° C. or less, an inert gas such as argon gas is supplied into the molten salt. Easily removed from the molten salt by volatilization, and no product remains in the molten salt.

本発明の他の観点に係る方法では、処理対象物である溶融塩中に、タングステン酸塩化物及びタングステン塩化物からなる還元剤を供給し、上述と同様に特定の元素の酸塩化物及び酸化物並びにこれら化合物イオンを、その塩化物及び塩化物イオンに塩化処理する。   In the method according to another aspect of the present invention, a reducing agent composed of tungstic acid chloride and tungsten chloride is supplied into a molten salt that is an object to be treated, and the acid chloride and oxidation of a specific element are performed in the same manner as described above. And the compound ions are chlorinated to their chloride and chloride ions.

この方法においても、アルゴンガスなどの不活性ガスを溶融塩中へ供給することで、還元反応による生成物を容易に溶融塩から揮発除去でき、溶融塩中に生成物が残留することはない。   Also in this method, by supplying an inert gas such as argon gas into the molten salt, the product by the reduction reaction can be easily volatilized and removed from the molten salt, and the product does not remain in the molten salt.

本発明では、塩化物及び塩化物とフッ化物の混合物等のハロゲン化物からなる溶融塩を溶媒に用いる化学処理プロセスを対象に、還元剤との反応による新たな生成物を溶融塩中に残留させることなく、かつ余分な処理剤を溶融塩中に残すことなく、ハロゲン化物溶融塩に含まれる酸塩化物及び酸化物並びにこれら化合物イオンを、回収が容易な塩化物又は塩化物イオンにすることができるので、使用済核燃料の乾式再処理プロセスや、遷移金属元素又は希土類元素の精錬プロセスを単純化できる。   In the present invention, for a chemical treatment process in which a molten salt composed of chloride and a halide such as a mixture of chloride and fluoride is used as a solvent, a new product by reaction with a reducing agent is left in the molten salt. Without making an excessive treatment agent remain in the molten salt, the acid chloride and oxide contained in the halide molten salt and these compound ions can be easily recovered as chlorides or chloride ions. Therefore, it is possible to simplify the dry reprocessing process of spent nuclear fuel and the refining process of transition metal elements or rare earth elements.

本発明の第１の形態に係る塩化処理プロセスを示す図。The figure which shows the chlorination process based on the 1st form of this invention. 本発明の第２の形態に係る塩化処理プロセスを示す図。The figure which shows the chlorination process based on the 2nd form of this invention. 本発明の第３の形態に係る塩化処理プロセスを示す図。The figure which shows the chlorination process based on the 3rd form of this invention. 本発明の第１の形態に係る塩化処理プロセスでの還元剤供給方法の説明図。Explanatory drawing of the reducing agent supply method in the chlorination process which concerns on the 1st form of this invention. 本発明の第２の形態に係る塩化処理プロセスでの還元剤供給方法の説明図。Explanatory drawing of the reducing agent supply method in the chlorination process which concerns on the 2nd form of this invention. 本発明の第３の形態に係る塩化処理プロセスでの還元剤供給方法の説明図。Explanatory drawing of the reducing agent supply method in the chlorination process which concerns on the 3rd form of this invention. 本発明の第３の形態に係る塩化処理プロセスでの還元剤供給方法の説明図。Explanatory drawing of the reducing agent supply method in the chlorination process which concerns on the 3rd form of this invention. 本発明の第３の形態に係る塩化処理プロセスでの還元剤供給方法の説明図。Explanatory drawing of the reducing agent supply method in the chlorination process which concerns on the 3rd form of this invention. 本発明の効果を実証するための吸光分光測定方法の説明図。Explanatory drawing of the absorption-spectrum measuring method for demonstrating the effect of this invention. 図７に示された吸光分光測定方法で測定された吸収スペクトルを示す図。The figure which shows the absorption spectrum measured with the absorption spectroscopy measuring method shown by FIG. 図７に示された吸光分光測定方法で測定されたタングステン塩化物（WCl6）を添加した場合の吸収スペクトルを示す図。Show an absorption spectrum of adding measured tungsten chloride at the indicated absorption spectrometry method in FIG. 7 (WCl 6).

本発明に係る、溶融塩中の酸塩化物及び酸化物並びにこれら化合物イオンの塩化処理方法を実施するための形態として、処理対象元素の酸塩化物及び酸化物並びにこれら化合物イオンを塩化処理する還元剤及び反応ガスの種類等によって、大きく分けて以下の（１）乃至（３）のいずれかのプロセスがある。なお、本願明細書中において使用する、還元剤３ａ、還元剤３ｂ、または還元剤３ｃとは、特定の物質を指すものではなく、（１）乃至（３）のプロセスによって適用する還元剤の種類が異なることを表す。特定の物質の還元剤を適用する場合は、「タングステン酸塩化物からなる還元剤３ｂ」という表現のように、修飾語によって区別する。   As a mode for carrying out the chlorination treatment method of acid chlorides and oxides and these compound ions in molten salt according to the present invention, reduction of chlorination treatment of acid chlorides and oxides of the elements to be treated and these compound ions Depending on the type of the agent and the reaction gas, there are roughly the following processes (1) to (3). In addition, the reducing agent 3a, reducing agent 3b, or reducing agent 3c used in the specification of the present application does not indicate a specific substance, but the type of reducing agent applied by the processes (1) to (3). Represents different. When a reducing agent of a specific substance is applied, it is distinguished by a modifier such as the expression “reducing agent 3b made of tungstic acid chloride”.

（１）タングステン金属と、塩素ガス又は塩化水素ガスを利用するプロセス   (1) Process using tungsten metal and chlorine gas or hydrogen chloride gas

図１は、タングステン金属（W）からなる還元剤３ａ及び反応ガス４の供給による塩化処理プロセスを示す。反応ガス４は、塩素ガス又は塩化水素ガスを用いる。処理対象元素の酸塩化物１ａ及び酸化物１ｂ並びにこれら化合物イオン１ｃを含む塩化物及び塩化物とフッ化物の混合物等のハロゲン化物からなる溶融塩２中へ、タングステン金属からなる還元剤３ａ及び反応ガス４の供給によって、溶融塩２中で処理対象元素の塩化物５ａ又は塩化物イオン５ｂに塩化するものである。   FIG. 1 shows a chlorination treatment process by supplying a reducing agent 3 a made of tungsten metal (W) and a reaction gas 4. As the reaction gas 4, chlorine gas or hydrogen chloride gas is used. Reductant 3a composed of tungsten metal and reaction into molten salt 2 composed of acid chloride 1a and oxide 1b of the element to be treated and halides such as chloride and a mixture of chloride and fluoride containing compound ion 1c. By supplying the gas 4, the molten salt 2 is salified to the chloride 5a or chloride ion 5b of the element to be treated.

供給した上記還元剤３ａ及び反応ガス４と、酸塩化物１ａ及び酸化物１ｂ並びにこれら化合物イオン１ｃとの反応により生成するタングステン酸塩化物（WO2C12、WOC14等）の生成物６は、沸点が３００℃以下であるため、アルゴンガス等の不活性ガス７を溶融塩２中へ供給することで容易に溶融塩２から揮発除去され、低温状態にあるコールドトラップ等で回収することができる。 A product 6 of tungstic acid chloride (WO 2 C1 2 , WOC1 4 etc.) produced by the reaction of the reducing agent 3a and reaction gas 4 supplied with the acid chloride 1a and oxide 1b and these compound ions 1c is Since the boiling point is 300 ° C. or less, by supplying an inert gas 7 such as argon gas into the molten salt 2, it can be easily volatilized and removed from the molten salt 2 and recovered by a cold trap or the like in a low temperature state. it can.

（２）タングステン酸塩化物又はタングステン塩化物と、塩素ガス又は塩化水素ガスを利用するプロセス   (2) Process using tungstated chloride or tungsten chloride and chlorine gas or hydrogen chloride gas

図２は、タングステン酸塩化物（WOC14等）又はタングステン塩化物（WCl5、WCl6等）からなる還元剤３ｂ及び反応ガス４の供給による塩化処理プロセスを示す。反応ガス４は、塩素ガス又は塩化水素ガスを用いる。処理対象元素の酸塩化物１ａ及び酸化物１ｂ並びにこれら化合物イオン１ｃを含む塩化物及び塩化物とフッ化物の混合物等のハロゲン化物からなる溶融塩２中へ、タングステン酸塩化物又はタングステン塩化物からなる還元剤３ｂ及び反応ガス４の供給によって、溶融塩２中で処理対象元素の塩化物５ａ又は塩化物イオン５ｂに塩化するものである。 Figure 2 shows the chloride treatment process by the supply of the reducing agent 3b and the reaction gas 4 consisting of tungsten acid chloride (WOC1 4, etc.) or tungsten chloride (WCl 5, WCl 6, etc.). As the reaction gas 4, chlorine gas or hydrogen chloride gas is used. From the tungstated chloride or tungsten chloride into the molten salt 2 composed of the acid chloride 1a and oxide 1b of the element to be treated and the compound ion 1c and a halide such as a chloride and a mixture of chloride and fluoride. By supplying the reducing agent 3b and the reaction gas 4 as described above, the salt 5a or chloride ion 5b of the element to be treated is salified in the molten salt 2.

供給した上記還元剤３ｂ及び反応ガス４と、酸塩化物１ａ及び酸化物１ｂ並びにこれら化合物イオン１ｃとの反応により生成するタングステン酸塩化物（WO2C12、WOC14等）の生成物６は、沸点が３００℃以下であるため、アルゴンガス等の不活性ガス７を溶融塩２中へ供給することで容易に溶融塩２から揮発除去され、低温状態にあるコールドトラップ等で回収される。タングステン酸塩化物又はタングステン塩化物からなる還元剤３ｂの供給方法は、溶融塩２中へ直接供給する方法、又は溶融塩２と上記還元剤３ｂを予め溶融した混合物（２＋３ｂ）を調製してこれを供給する方法がある。 A product 6 of tungstic acid chloride (WO 2 C1 2 , WOC1 4 etc.) produced by the reaction of the reducing agent 3b and reaction gas 4 supplied with the acid chloride 1a and oxide 1b and these compound ions 1c is Since the boiling point is 300 ° C. or less, the inert gas 7 such as argon gas is easily volatilized and removed from the molten salt 2 by supplying it into the molten salt 2 and recovered by a cold trap or the like in a low temperature state. The method of supplying the reducing agent 3b made of tungstated chloride or tungsten chloride can be directly supplied into the molten salt 2 or a mixture (2 + 3b) prepared by previously melting the molten salt 2 and the reducing agent 3b can be prepared. There is a way to supply.

（３）タングステン酸塩化物及びタングステン塩化物を利用するプロセス
図３は、タングステン酸塩化物（WOCl4等）及びタングステン塩化物（WCl5、WCl6等）からなる還元剤３ｃの供給による塩化処理プロセスを示す。処理対象元素の酸塩化物１ａ及び酸化物１ｂ並びにこれら化合物イオン１ｃを含む塩化物及び塩化物とフッ化物の混合物等のハロゲン化物からなる溶融塩２中へ、タングステン酸塩化物及びタングステン塩化物からなる還元剤３ｃの供給によって、溶融塩２中で処理対象元素の塩化物５ａ又は塩化物イオン５ｂに塩化するものである。 (3) Process using tungstated chloride and tungsten chloride FIG. 3 shows chlorination treatment by supplying a reducing agent 3c composed of tungstated chloride (WOCl 4 etc.) and tungsten chloride (WCl 5 , WCl 6 etc.). Indicates the process. From tungstated chloride and tungsten chloride into molten salt 2 composed of acid chloride 1a and oxide 1b of the element to be treated and halides such as a chloride and a mixture of chloride and fluoride containing these compound ions 1c By supplying the reducing agent 3c, the salt 5a or chloride ion 5b of the element to be treated is salified in the molten salt 2.

供給した上記還元剤３ｃと、酸塩化物１ａ及び酸化物１ｂ並びにこれら化合物イオン１ｃとの反応により生成するタングステン酸塩化物（WO2Cl2、WOCl4等)の生成物６は、沸点が３００℃以下であるため、アルゴンガス等の不活性ガス７を溶融塩２中へ供給することで容易に溶融塩２から揮発除去され、低温状態にあるコールドトラップ等で回収される。上記還元剤３ｃの供給方法は、溶融塩２中へ直接供給する方法、又は溶融塩２と還元剤３ｃを予め溶融した混合物（２＋３ｃ）を調製してこれを供給する方法、或いは沸点以上に還元剤３ｃを加熱によりガス化して不活性ガス７との混合ガス（３ｃ＋７）を供給する方法がある。 The product 6 of tungstic acid chloride (WO 2 Cl 2 , WOCl 4, etc.) produced by the reaction of the supplied reducing agent 3c with the acid chloride 1a and oxide 1b and these compound ions 1c has a boiling point of 300. Since the temperature is lower than or equal to ° C., the inert gas 7 such as argon gas is easily volatilized and removed from the molten salt 2 by supplying it into the molten salt 2 and recovered by a cold trap or the like in a low temperature state. The method of supplying the reducing agent 3c may be a method of supplying directly into the molten salt 2, a method of preparing a mixture (2 + 3c) in which the molten salt 2 and the reducing agent 3c are previously melted and supplying them, or a reduction to the boiling point or higher. There is a method of supplying the mixed gas (3c + 7) with the inert gas 7 by gasifying the agent 3c by heating.

次に、上述の（１）乃至（３）の各塩化処理プロセスについて、さらに具体的に説明する。   Next, each of the above chlorination processes (1) to (3) will be described more specifically.

本発明で対象とする塩化処理プロセスでは、塩化物及び塩化物とフッ化物の混合物等のハロゲン化物からなる溶融塩２に含まれる処理対象元素の酸塩化物１ａ及び酸化物１ｂ並びにこれら化合物イオン１ｃを、タングステン金属からなる還元剤３ａ及び塩素ガス又は塩化水素ガスからなる反応ガス４の供給、又はタングステン酸塩化物又はタングステン塩化物からなる還元剤３ｂ及び塩素ガス又は塩化水素ガスからなる反応ガス４の供給、或いはタングステン酸塩化物及びタングステン塩化物からなる還元剤３ｃの供給によって、溶融塩２中で処理対象元素の塩化物５ａ又は塩化物イオン５ｂに塩化するものである。   In the chlorination treatment process targeted by the present invention, the acid chloride 1a and oxide 1b of the element to be treated contained in the molten salt 2 composed of chloride and a halide such as a mixture of chloride and fluoride, and these compound ions 1c. The supply of the reducing agent 3a made of tungsten metal and the reaction gas 4 made of chlorine gas or hydrogen chloride gas, or the reducing agent 3b made of tungstic acid chloride or tungsten chloride and the reaction gas 4 made of chlorine gas or hydrogen chloride gas Or the reducing agent 3c made of tungstated chloride and tungsten chloride is chlorinated into the chloride 5a or chloride ion 5b of the element to be treated in the molten salt 2.

本発明の特徴は、塩化処理の還元剤として、タングステン金属、タングステン酸塩化物、タングステン塩化物、又はこれら化合物の混合物を用いる点にある。これらタングステン金属等からなる還元剤３ａ、３ｂ、３ｃを用いて溶融塩２に含まれる処理対象元素の酸塩化物１ａ及び酸化物１ｂ並びにこれら化合物イオン１ｃを塩化した場合の特徴として、還元剤３ａ、３ｂ及び反応ガス４との反応、或いは還元剤３ｃとの反応により生成するタングステン酸塩化物（WO2Cl2、WOCl4等）の生成物６は、沸点が３００℃以下であるため、アルゴンガス等の不活性ガス７を溶融塩２中へ供給することで容易に溶融塩２から揮発除去でき、溶融塩２中に生成物６は残留しない。 A feature of the present invention is that tungsten metal, tungstated chloride, tungsten chloride, or a mixture of these compounds is used as a reducing agent for chlorination. As a feature when the acid chloride 1a and oxide 1b of the element to be treated and the compound ion 1c contained in the molten salt 2 are chlorinated using the reducing agents 3a, 3b and 3c made of tungsten metal or the like, the reducing agent 3a Since the product 6 of tungstate (WO 2 Cl 2 , WOCl 4, etc.) produced by the reaction with 3b and the reaction gas 4 or with the reducing agent 3c has a boiling point of 300 ° C. or less, By supplying an inert gas 7 such as a gas into the molten salt 2, it can be easily volatilized and removed from the molten salt 2, and the product 6 does not remain in the molten salt 2.

本発明で対象とする塩化処理プロセスに用いる還元剤及び反応ガス４の供給方法は、還元剤の性状及び図１乃至図３に示したプロセスによって異なる。次にそれらの具体的な供給方法を、図４乃至図６を参照して説明する。   The supply method of the reducing agent and the reaction gas 4 used in the chlorination treatment process targeted in the present invention differs depending on the properties of the reducing agent and the processes shown in FIGS. Next, specific supply methods thereof will be described with reference to FIGS.

（１）のａ： 容器１１に収納した、酸塩化物１ａ及び酸化物１ｂ並びにこれら化合物イオン１ｃを含む溶融塩２中に、還元剤３ａとしてタングステン金属又はタングステンを主成分とする合金からなる棒材、板材、網、粒又は粉末を浸漬又は添加し、反応ガス４をセラミック又はガラス或いは耐食性金属で構成された供給管８により溶融塩２中へ供給する。(図４参照)   (1) a: A rod made of tungsten metal or an alloy containing tungsten as a main component as the reducing agent 3a in the molten salt 2 containing the acid chloride 1a, the oxide 1b, and these compound ions 1c contained in the container 11. A material, a plate material, a net, a grain, or a powder is immersed or added, and the reaction gas 4 is supplied into the molten salt 2 through a supply pipe 8 made of ceramic, glass, or corrosion-resistant metal. (See Figure 4)

（２）のａ： 容器１１に収納した、酸塩化物１ａ及び酸化物１ｂ並びにこれら化合物イオン１ｃを含む溶融塩２中に、還元剤３ｂとしてタングステン酸塩化物若しくはタングステン塩化物又はタングステン酸塩化物若しくはタングステン塩化物を主成分とする化合物からなるペレット、粒又は粉末を添加、或いはタングステン塩化物又はタングステン酸塩化物を表面に付着又は塗布させた棒材、板材若しくは網を浸漬又は添加し、反応ガス４をセラミック又はガラス或いは耐食性金属で構成された供給管８により溶融塩２中へ供給する。（図５ａ参照）   (2) a: Tungsten oxychloride or tungsten chloride or tungstate oxychloride as reducing agent 3b in molten salt 2 containing acid chloride 1a and oxide 1b and these compound ions 1c stored in container 11 Alternatively, pellets, grains or powders composed of compounds containing tungsten chloride as the main component are added, or rods, plates or nets with tungsten chloride or tungstated chloride attached or coated on the surface are immersed or added to react. The gas 4 is supplied into the molten salt 2 through a supply pipe 8 made of ceramic, glass or corrosion-resistant metal. (See Figure 5a)

（２）のｂ： 予め、還元剤３ｂであるタングステン酸塩化物又はタングステン塩化物或いはタングステン酸塩化物又はタングステン塩化物を主成分とする化合物を、酸塩化物１ａ及び酸化物１ｂ並びにこれら化合物イオン１ｃを含む溶融塩２と同組成又は類似組成の塩と溶融混合したペレット又は粒状或いは粉末の混合物（２＋３ｂ）に加工し、容器１１に収納した溶融塩２中にこれら混合物（２＋３ｂ）を添加して、反応ガス４をセラミック又はガラス或いは耐食性金属で構成された供給管８により溶融塩２中へ供給する。（図５ｂ参照）   (2) b: In advance, a tungstate chloride or tungsten chloride or a compound mainly composed of tungstate chloride or tungsten chloride, which is the reducing agent 3b, is converted to acid chloride 1a, oxide 1b, and these compound ions. 1c-containing molten salt 2 is processed into a mixture (2 + 3b) of pellets or granules or powder that is melt-mixed with a salt of the same composition or a similar composition, and these mixtures (2 + 3b) are added to molten salt 2 contained in container 11 Then, the reaction gas 4 is supplied into the molten salt 2 through a supply pipe 8 made of ceramic, glass or corrosion-resistant metal. (See Figure 5b)

ここで、タングステン塩化物を添加した場合の反応について、少し詳細に説明する。タングステン塩化物を添加した場合、処理対象物である溶融塩中に含まれるアクチニド元素又は遷移金属元素或いは希土類元素の酸塩化物及び酸化物並びにこれら化合物イオンとの還元反応の副反応生成物として、タングステン酸化物が発生し、溶融塩中に残留する。このため、生成したタングステン酸化物を反応ガスの供給により、タングステン酸塩化物又はタングステン塩化物を生成させ、これらタングステン酸塩化物又はタングステン塩化物を還元剤として活用する。また、タングステン酸化物から反応ガスの供給によって溶融塩中に生成させたタングステン酸塩化物又はタングステン塩化物が余剰になった場合、反応ガス又は不活性ガスを溶融塩中に供給することで溶融塩中から余剰なタングステン酸塩化物又はタングステン塩化物を容易に揮発除去できる。   Here, the reaction when tungsten chloride is added will be described in a little more detail. When tungsten chloride is added, as a side reaction product of a reduction reaction with an actinide element, transition metal element or rare earth element acid chloride and oxide contained in the molten salt that is the object to be treated, and these compound ions, Tungsten oxide is generated and remains in the molten salt. For this reason, the tungsten oxide produced or tungsten chloride is produced by supplying the reaction gas to the produced tungsten oxide, and the tungsten acid chloride or tungsten chloride is utilized as a reducing agent. In addition, when the tungsten oxychloride or tungsten chloride produced in the molten salt by supplying the reaction gas from the tungsten oxide becomes surplus, the molten salt is supplied by supplying the reaction gas or inert gas into the molten salt. Excess tungstated chloride or tungsten chloride can be easily volatilized and removed from the inside.

（３）のａ： 容器１１に収納した、酸塩化物１ａ及び酸化物１ｂ並びにこれら化合物イオン１ｃを含む溶融塩２中に、還元剤３ｃとしてタングステン酸塩化物、タングステン塩化物又はタングステン酸塩化物及びタングステン塩化物を主成分とする化合物からなるペレット、粒又は粉末を添加、或いはタングステン酸塩化物又はタングステン塩化物を表面に付着又は塗布させた棒材、板材又は網を浸漬又は添加する。（図６ａ参照）   (3) a: Tungsten oxychloride, tungsten chloride or tungstate oxychloride as reducing agent 3c in molten salt 2 containing acid chloride 1a and oxide 1b and these compound ions 1c stored in container 11 In addition, pellets, grains, or powders made of a compound containing tungsten chloride as a main component are added, or a bar, plate, or net having tungsten oxychloride or tungsten chloride attached or coated on the surface thereof is immersed or added. (See Figure 6a)

（３）のｂ： 予め、還元剤３ｃであるタングステン酸塩化物、タングステン塩化物又はタングステン酸塩化物及びタングステン塩化物を主成分とする化合物を、酸塩化物１ａ及び酸化物１ｂ並びにこれら化合物イオン１ｃを含む溶融塩３と同組成又は類似組成の塩と溶融混合したペレット又は粒状或いは粉末の混合物（２＋３ｃ）に加工し、容器１１に収納した溶融塩２中にこれら混合物（２＋３ｃ）を添加する。（図６ｂ参照）   B in (3): Tungsten oxychloride, tungsten chloride or a compound mainly composed of tungstate oxychloride and tungsten chloride, which is the reducing agent 3c, is converted into acid chloride 1a, oxide 1b, and these compound ions. 1c-containing molten salt 3 is processed into a mixture (2 + 3c) of pellets or granules or powder melted and mixed with a salt of the same composition or a similar composition, and these mixtures (2 + 3c) are added to molten salt 2 stored in container 11 . (See Figure 6b)

（３）のｃ： 還元剤３ｃであるタングステン酸塩化物、タングステン塩化物又はタングステン酸塩化物及びタングステン塩化物を主成分とする化合物を耐食性容器９内に収納して電気炉１０等により加熱してガス化し、アルゴンガス等の不活性ガス７をキャリアガスとするガス化した還元剤３ｃを含む混合ガス（３ｃ＋７）を、セラミック又はガラス或いは耐食性金属で構成された供給管８により、容器１１に収納した、酸塩化物１ａ及び酸化物１ｂ並びにこれら化合物イオン１ｃを含む溶融塩２中へ供給する。（図６ｃ参照）   (3) c: The reducing agent 3c, tungstated chloride, tungsten chloride or a compound composed mainly of tungstated chloride and tungsten chloride is housed in a corrosion-resistant vessel 9 and heated by an electric furnace 10 or the like. The mixed gas (3c + 7) containing the gasified reducing agent 3c using an inert gas 7 such as argon gas as a carrier gas is supplied to the container 11 by a supply pipe 8 made of ceramic, glass or corrosion-resistant metal. The stored acid chloride 1a and oxide 1b and the molten salt 2 containing these compound ions 1c are supplied. (See Figure 6c)

本発明による塩化処理を実施した事例（上記（１）のａによる方法）として、図７に示す吸光分光測定方法によって、塩化処理結果の評価を行った。この評価は、図７に示すように、処理対象のUO2Cl2を含む４００℃のLiCl-RbCl溶融塩（２）中に、還元剤としてのタングステン金属網３ａを浸漬し、反応ガスである塩素ガス４を供給管８から供給するやり方で行い、W浸漬前のUO2Cl2の吸収スペクトル、W浸漬後のUO2Cl及びUCl4の吸収スペクトル、及びW浸漬及びCl2供給後のUCl4の吸収スペクトルを観察した。 As an example of carrying out the chlorination treatment according to the present invention (the method according to (1) a), the chlorination treatment results were evaluated by the absorption spectroscopy measurement method shown in FIG. As shown in FIG. 7, this evaluation is performed by immersing the tungsten metal net 3a as a reducing agent in a 400 ° C. LiCl—RbCl molten salt (2) containing UO 2 Cl 2 to be treated. The chlorine gas 4 is supplied from the supply pipe 8, and the absorption spectrum of UO 2 Cl 2 before W immersion, the absorption spectrum of UO 2 Cl and UCl 4 after W immersion, and UCl after W immersion and Cl 2 supply. An absorption spectrum of 4 was observed.

より具体的には、処理対象となる酸塩化物１ａであるウラン酸塩化物（二塩化ウラニルUO2Cl2）を含む塩化リチウムと塩化ルビジウムの共晶塩（LiCl-RbCl）からなる溶融塩２を分光セル付石英セル１１中に装荷し、電気炉等で溶融塩２を400 ℃に加熱溶融し、吸光分光測定によりUO2Cl2の吸収スペクトル（図８中の細線１０１）を確認した。この状態で、溶融塩２中に還元剤３ａであるタングステン金属（W）製網を浸漬して吸光分光測定により吸収スペクトルの変化を観察したところ、一塩化ウラニル（UO2Cl）と少量の四塩化ウラン（UCl4）の生成（図８中の中太線１０２）を確認した。 More specifically, molten salt 2 comprising eutectic salt of lithium chloride and rubidium chloride (LiCl—RbCl) containing uranium chloride (uranyl dichloride UO 2 Cl 2 ), which is the acid chloride 1a to be treated. Was loaded into a quartz cell 11 with a spectroscopic cell, and the molten salt 2 was heated and melted to 400 ° C. with an electric furnace or the like, and an absorption spectrum of UO 2 Cl 2 (thin line 101 in FIG. 8) was confirmed by absorption spectroscopic measurement. In this state, a tungsten metal (W) net, which is the reducing agent 3a, was immersed in the molten salt 2 and the change in the absorption spectrum was observed by absorption spectrophotometry. As a result, uranyl monochloride (UO 2 Cl) and a small amount of 4 Formation of uranium chloride (UCl 4 ) (middle thick line 102 in FIG. 8) was confirmed.

これらUO2ClとUCl4の生成過程は、下式（反応１）に示す反応によりUO2Clと二塩化タングステン（WCl2）が生成し、生成したWCl2が下式（反応２）に示すUO2Cl2との反応によりUO2ClとUCl4を生成したことによる。 The process of generating UO 2 Cl and UCl 4 is as follows. UO 2 Cl and tungsten dichloride (WCl 2 ) are generated by the reaction shown in the following formula (reaction 1), and the generated WCl 2 is shown in the following formula (reaction 2). According to the generation of the UO 2 Cl and UCl 4 by reaction with UO 2 Cl 2.

2UO2Cl2+W→2UO2Cl+WCl2 （反応１）
7UO2Cl2+2WCl2→6UO2Cl+UCl4+2WOCl4↑ （反応２）
2UO2Cl+4W+11Cl2→2UCl4+4WOCl4↑ （反応３）
UO2Cl2+2W+5Cl2→UCl4+2WOCl4↑ （反応４） 2UO 2 Cl 2 + W → 2UO 2 Cl + WCl 2 (Reaction 1)
7UO 2 Cl 2 + 2WCl 2 → 6UO 2 Cl + UCl 4 + 2WOCl 4 ↑ (Reaction 2)
2UO 2 Cl + 4W + 11Cl 2 → 2UCl 4 + 4WOCl 4 ↑ (Reaction 3)
UO 2 Cl 2 + 2W + 5Cl 2 → UCl 4 + 2WOCl 4 ↑ (Reaction 4)

引き続きこの状態で、反応ガス４である塩素（Cl2）ガスを供給して吸光分光測定により吸収スペクトルの変化を観察したところ、UCl4のみが溶融塩２中に残留すること（図８中の太線１０３）を確認した。UCl4の生成は下式（反応３）及び（反応４）によるものであり、同時に生成したタングステン酸塩化物（WOCl4）は沸点が３００℃以下で溶融塩２中から揮発除去される。仮に、タングステン塩化物が溶融塩２中に溶存した場合、波数２０×１０３〜１０×１０３cm-1の可視光領域にブロードな大きい吸収ピークを示すため、容易に目視で判断できる。なお、上述の図８においては、Ｗ浸漬前のUO2Cl2の吸収スペクトルの吸光度が波数１８×１０３から５×１０３cm-1の範囲で吸収ピークが無いため、細線１０１の吸光度はこの範囲においてゼロになっている。 In this state, when chlorine (Cl 2 ) gas as the reaction gas 4 was supplied and the change in the absorption spectrum was observed by absorption spectroscopic measurement, only UCl 4 remained in the molten salt 2 (in FIG. 8). A thick line 103) was confirmed. UCl 4 is produced by the following formulas (reaction 3) and (reaction 4), and the tungstate chloride (WOCl 4 ) produced simultaneously is volatilized and removed from the molten salt 2 at a boiling point of 300 ° C. or lower. If tungsten chloride is dissolved in the molten salt 2, it shows a broad absorption peak in the visible light region having a wave number of 20 × 10 3 to 10 × 10 3 cm −1 , so that it can be easily judged visually. In FIG. 8 described above, since the absorbance of the absorption spectrum of UO 2 Cl 2 before W immersion does not have an absorption peak in the wave number range of 18 × 10 3 to 5 × 10 3 cm −1 , the absorbance of the thin wire 101 is It is zero in this range.

処理対象の酸塩化物１ａであるUO2Cl2は２０×１０３cm-1以上の紫外光領域に巨大な吸収ピーク（図８中の細線１０１）を示すが、処理後の吸収スペクトル（図８中の太線１０３）にこの吸収ピークは極端に低下しており、酸塩化物１ａであるUO2Cl2はほぼ全量が塩化物５ａであるUCl4に処理することを確認した。 UO 2 Cl 2, which is the acid chloride 1a to be treated, shows a huge absorption peak (thin line 101 in FIG. 8) in the ultraviolet light region of 20 × 10 3 cm −1 or more. In FIG. 8, the thick line 103) shows that the absorption peak is extremely lowered, and it was confirmed that UO 2 Cl 2 which is the acid chloride 1a is processed to UCl 4 which is almost all chloride 5a.

以上述べた通り、本発明は、塩化物及び塩化物とフッ化物の混合物等のハロゲン化物からなる溶融塩２に含まれる処理対象元素の酸塩化物１ａ及び酸化物１ｂ並びにこれら化合物イオン１ｃを、還元剤３ａ、３ｂ、３ｃ及び反応ガス４による新たな生成物６を溶融塩２中に残留させずに、塩化物５ａ又は塩化物イオン５ｂに処理することを目的にしているが、これに関して、図７の具体例に示した通り、還元剤３ａであるタングステン金属及び反応ガス４である塩素ガスを溶融塩２中に供給することで、溶融塩２中に含まれる処理対象の酸塩化物１ａであるUO2Cl2はほぼ全量塩化物UCl4へ処理でき、還元剤３ａのタングステン金属からの生成物６であるタングステン酸塩化物を溶融塩２中から揮発除去できることを確認した。 As described above, the present invention provides the acid chloride 1a and oxide 1b of the element to be treated and the compound ion 1c contained in the molten salt 2 composed of chloride and a halide such as a mixture of chloride and fluoride. The aim is to treat the reducing agent 3a, 3b, 3c and the new product 6 from the reaction gas 4 into the chloride 5a or chloride ions 5b without leaving them in the molten salt 2, As shown in the specific example of FIG. 7, by supplying tungsten metal as the reducing agent 3a and chlorine gas as the reaction gas 4 into the molten salt 2, the acid chloride 1a to be treated contained in the molten salt 2 is obtained. It was confirmed that UO 2 Cl 2 , which can be treated with almost all the amount of chloride UCl 4, was able to volatilize and remove the tungstate chloride as the product 6 from the tungsten metal of the reducing agent 3 a from the molten salt 2.

また、処理対象の酸塩化物１ａであるUO2Cl2を含む溶融塩２中へタングステン塩化物（WCl6）から成る還元剤３ｃを供給した場合の状況を、図７と同様な吸光分光測定による評価手法で確認した結果、図９に示すように溶融塩２中に含まれる処理対象の酸塩化物１ａであるUO2Cl2は塩化物UCl4へ処理でき（すなわち、UO2 2+がU4+へ還元）、上記還元剤３ｃのタングステン塩化物からの生成物６であるタングステン酸塩化物を溶融塩２中から揮発除去できることも確認した。 The situation when the reducing agent 3c made of tungsten chloride (WCl 6 ) is supplied into the molten salt 2 containing UO 2 Cl 2 which is the acid chloride 1a to be treated is the same spectroscopic measurement as in FIG. As shown in FIG. 9, UO 2 Cl 2 which is the acid chloride 1a to be treated contained in the molten salt 2 can be treated to the chloride UCl 4 (ie, UO 2 2+ is converted as shown in FIG. 9). reduced to U 4+), was also confirmed to be able to volatilization removal of tungstic acid chlorides from the molten salt 2 is a product 6 from tungsten chloride of the reducing agent 3c.

２ … 酸塩化物、酸化物、化合物イオンを含む溶融塩
３ａ、３ｂ、３ｃ … 還元剤
４ … 反応ガス
７ … 不活性ガス
８ … 供給管
９ … 還元剤気化容器
１０ … 電気炉等加熱装置
１１ … 容器
１０１ … タングステン金属を浸漬する前に観察したUO2Cl2の吸収スペクトル
１０２ … タングステン金属を浸漬した後に観察したUO2Clの吸収スペクトル
１０３ … タングステン金属を浸漬し、塩素ガスを供給した後に観察したUCl4の吸収スペクトル
２０１ … 塩化タングステン（WCl6）を添加する前に観察したUO2Cl2の吸収スペクトル
２０２ … 塩化タングステン（WCl6）を添加してUCl4が増加したことを示す吸収スペクトル 2 ... Molten salt 3a, 3b, 3c containing acid chloride, oxide, compound ion ... Reducing agent 4 ... Reactive gas 7 ... Inert gas 8 ... Supply pipe 9 ... Reducing agent vaporization vessel 10 ... Heating device 11 such as an electric furnace ... Container 101 ... UO 2 Cl 2 absorption spectrum 102 observed before immersing tungsten metal ... UO 2 Cl absorption spectrum 103 observed after immersing tungsten metal 103 ... After immersing tungsten metal and supplying chlorine gas Observed absorption spectrum 201 of UCl 4 ... Absorption spectrum of UO 2 Cl 2 observed before adding tungsten chloride (WCl 6 ) 202 Absorption showing that UCl 4 increased by adding tungsten chloride (WCl 6 ) Spectrum

Claims (9)

処理対象物である溶融塩中に、タングステン金属からなる還元剤又はタングステン酸塩化物からなる還元剤或いはタングステン塩化物からなる還元剤を供給するとともに、塩素ガス又は塩化水素ガス或いはこれら混合ガスからなる反応ガスを前記溶融塩中に供給し、前記溶融塩に含まれるアクチニド元素又は遷移金属元素或いは希土類元素の、酸塩化物及び酸化物並びにこれら化合物イオンを、塩化物及び塩化物イオンに塩化処理する方法。   A molten metal, which is an object to be treated, is supplied with a reducing agent made of tungsten metal, a reducing agent made of tungstated chloride or a reducing agent made of tungsten chloride, and made of chlorine gas, hydrogen chloride gas, or a mixed gas thereof. A reaction gas is supplied into the molten salt, and an actinide element, a transition metal element, or a rare earth element contained in the molten salt is chlorinated with chlorides and chloride ions of acid chlorides and oxides and their compound ions. Method. 処理対象物である溶融塩中に、タングステン金属からなる還元剤又はタングステン酸塩化物からなる還元剤或いはタングステン塩化物からなる還元剤を供給するとともに、塩素ガス又は塩化水素ガス或いはこれら混合ガスからなる反応ガスを前記溶融塩中に供給し、アルカリ塩化物及びアルカリ土類塩化物並びにこれらを主成分とする塩化物からなる前記溶融塩中に含まれるアクチニド元素の酸塩化物及び酸化物並びにこれら化合物イオンを、アクチニド元素の塩化物及び塩化物イオンに塩化処理する方法。   A molten metal, which is an object to be treated, is supplied with a reducing agent made of tungsten metal, a reducing agent made of tungstated chloride or a reducing agent made of tungsten chloride, and made of chlorine gas, hydrogen chloride gas, or a mixed gas thereof. Supplying a reaction gas into the molten salt, acid chlorides and oxides of actinide elements contained in the molten salt comprising alkali chlorides and alkaline earth chlorides and chlorides containing these as main components, and compounds thereof A method in which ions are chlorinated to chloride and chloride ions of actinide elements. 処理対象物である溶融塩中に、タングステン金属からなる還元剤又はタングステン酸塩化物からなる還元剤或いはタングステン塩化物からなる還元剤を供給するとともに、塩素ガス又は塩化水素ガス或いはこれら混合ガスからなる反応ガスを前記溶融塩中に供給し、アルカリ塩化物又はアルカリ土類塩化物或いはこれらを主成分とする塩化物とアルカリフッ化物又はアルカリ土類フッ化物或いはこれらを主成分とするフッ化物との混合物であるハロゲン化物からなる前記溶融塩中に含まれるアクチニド元素の酸塩化物及び酸化物並びにこれら化合物イオンを、アクチニド元素の塩化物及び塩化物イオンに塩化処理する方法。   A molten metal, which is an object to be treated, is supplied with a reducing agent made of tungsten metal, a reducing agent made of tungstated chloride or a reducing agent made of tungsten chloride, and made of chlorine gas, hydrogen chloride gas, or a mixed gas thereof. A reaction gas is supplied into the molten salt, and an alkali chloride, an alkaline earth chloride, or a chloride containing these as a main component and an alkali fluoride, an alkaline earth fluoride, or a fluoride containing these as a main component. A method of chlorinating acid chlorides and oxides of actinide elements and their compound ions contained in the molten salt comprising a halide which is a mixture into chlorides and chloride ions of actinide elements. 処理対象物である溶融塩中に、タングステン金属からなる還元剤又はタングステン酸塩化物からなる還元剤或いはタングステン塩化物からなる還元剤を供給するとともに、塩素ガス又は塩化水素ガス或いはこれら混合ガスからなる反応ガスを前記溶融塩中に供給し、アルカリ塩化物及びアルカリ土類塩化物並びにこれらを主成分とする塩化物からなる前記溶融塩中に含まれる遷移金属元素又は希土類元素の酸塩化物及び酸化物並びにこれら化合物イオンを、遷移金属元素又は希土類元素の塩化物及び塩化物イオンに塩化処理する方法。   A molten metal, which is an object to be treated, is supplied with a reducing agent made of tungsten metal, a reducing agent made of tungstated chloride or a reducing agent made of tungsten chloride, and made of chlorine gas, hydrogen chloride gas, or a mixed gas thereof. Supplying the reaction gas into the molten salt, acid chlorides and oxidations of transition metal elements or rare earth elements contained in the molten salt consisting of alkali chlorides and alkaline earth chlorides and chlorides based on these And chlorination of these compound ions into chlorides and chloride ions of transition metal elements or rare earth elements. 処理対象物である溶融塩中に、タングステン金属からなる還元剤又はタングステン酸塩化物からなる還元剤或いはタングステン塩化物からなる還元剤を供給するとともに、塩素ガス又は塩化水素ガス或いはこれら混合ガスからなる反応ガスを前記溶融塩中に供給し、アルカリ塩化物又はアルカリ土類塩化物或いはこれらを主成分とする塩化物とアルカリフッ化物又はアルカリ土類フッ化物或いはこれらを主成分とするフッ化物との混合物であるハロゲン化物からなる前記溶融塩中に含まれる遷移金属元素又は希土類元素の酸塩化物及び酸化物並びにこれら化合物イオンを、遷移金属元素又は希土類元素の塩化物及び塩化物イオンに塩化処理する方法。   A molten metal, which is an object to be treated, is supplied with a reducing agent made of tungsten metal, a reducing agent made of tungstated chloride or a reducing agent made of tungsten chloride, and made of chlorine gas, hydrogen chloride gas, or a mixed gas thereof. A reaction gas is supplied into the molten salt, and an alkali chloride, an alkaline earth chloride, or a chloride containing these as a main component and an alkali fluoride, an alkaline earth fluoride, or a fluoride containing these as a main component. Chlorination treatment of transition metal element or rare earth element acid chlorides and oxides and their compound ions contained in the molten salt comprising a halide which is a mixture into transition metal element or rare earth element chlorides and chloride ions Method. 処理対象物である溶融塩中に、タングステン酸塩化物及びタングステン塩化物からなる還元剤を供給し、アルカリ塩化物及びアルカリ土類塩化物並びにこれらを主成分とする塩化物からなる前記溶融塩中に含まれるアクチニド元素の酸塩化物及び酸化物並びにこれら化合物イオンを、アクチニド元素の塩化物及び塩化物イオンに塩化処理する方法。   In the molten salt, which is a treatment object, a reducing agent composed of tungstated chloride and tungsten chloride is supplied, and the molten salt is composed of alkali chloride, alkaline earth chloride and chloride based on these. The acid chloride and oxide of an actinide element and the compound ion contained therein are chlorinated into chloride and chloride ions of an actinide element. 処理対象物である溶融塩中に、タングステン酸塩化物及びタングステン塩化物からなる還元剤を供給し、アルカリ塩化物又はアルカリ土類塩化物或いはこれらを主成分とする塩化物とアルカリフッ化物又はアルカリ土類フッ化物或いはこれらを主成分とするフッ化物との混合物であるハロゲン化物からなる前記溶融塩中に含まれるアクチニド元素の酸塩化物及び酸化物並びにこれら化合物イオンを、アクチニド元素の塩化物及び塩化物イオンに塩化処理する手法。   Supplying a reducing agent consisting of tungstated chloride and tungsten chloride into the molten salt that is the object to be treated, and then alkali chloride or alkaline earth chloride or chloride and alkali fluoride or alkali mainly composed of these. Acid chlorides and oxides of actinide elements contained in the molten salt consisting of earth fluorides or halides that are mixtures with fluorides based on these, as well as these compound ions, chlorides of actinide elements and A technique for chlorination of chloride ions. 処理対象物である溶融塩中に、タングステン酸塩化物及びタングステン塩化物からなる還元剤を供給し、アルカリ塩化物及びアルカリ土類塩化物並びにこれらを主成分とする塩化物からなる溶融塩中に含まれる遷移金属元素又は希土類元素の酸塩化物及び酸化物並びにこれら化合物イオンを、遷移金属元素又は希土類元素の塩化物及び塩化物イオンに塩化処理する方法。   A reducing agent composed of tungstic acid chloride and tungsten chloride is supplied to the molten salt that is the object to be treated, and the molten salt composed of alkali chloride, alkaline earth chloride, and chloride containing these as a main component is supplied. A method of chlorinating an acid chloride and oxide of a transition metal element or a rare earth element and a compound ion thereof contained in the chloride and chloride ion of a transition metal element or a rare earth element. 処理対象物である溶融塩中に、タングステン酸塩化物及びタングステン塩化物からなる還元剤を供給し、アルカリ塩化物又はアルカリ土類塩化物或いはこれらを主成分とする塩化物とアルカリフッ化物又はアルカリ土類フッ化物或いはこれらを主成分とするフッ化物との混合物であるハロゲン化物からなる溶融塩中に含まれる遷移金属元素又は希土類元素の酸塩化物及び酸化物並びにこれら化合物イオンを、遷移金属元素又は希土類元素の塩化物及び塩化物イオンに塩化処理する方法。   Supplying a reducing agent consisting of tungstated chloride and tungsten chloride into the molten salt that is the object to be treated, and then alkali chloride or alkaline earth chloride or chloride and alkali fluoride or alkali mainly composed of these. Transition metal elements or rare earth element acid chlorides and oxides contained in a molten salt made of a halide which is a mixture of an earth fluoride or a fluoride containing these as a main component, and a transition metal element Alternatively, a method of chlorinating rare earth element chlorides and chloride ions.
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