CN101994133B - 用于氧化物乏燃料干法后处理的熔盐体系 - Google Patents
用于氧化物乏燃料干法后处理的熔盐体系 Download PDFInfo
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- 150000003839 salts Chemical class 0.000 title claims abstract description 68
- 239000002915 spent fuel radioactive waste Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 8
- JNVYCANIFQDNST-UHFFFAOYSA-I uranium pentafluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[U+5] JNVYCANIFQDNST-UHFFFAOYSA-I 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 17
- 239000000463 material Substances 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 150000001450 anions Chemical class 0.000 abstract description 4
- MZFRHHGRNOIMLW-UHFFFAOYSA-J uranium(4+);tetrafluoride Chemical compound F[U](F)(F)F MZFRHHGRNOIMLW-UHFFFAOYSA-J 0.000 abstract 2
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 229910052770 Uranium Inorganic materials 0.000 description 6
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 230000004927 fusion Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229910052778 Plutonium Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- WJWSFWHDKPKKES-UHFFFAOYSA-N plutonium uranium Chemical compound [U].[Pu] WJWSFWHDKPKKES-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000906946 Sphingomonas carri Species 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- -1 anion salt Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SHZGCJCMOBCMKK-KGJVWPDLSA-N beta-L-fucose Chemical compound C[C@@H]1O[C@H](O)[C@@H](O)[C@H](O)[C@@H]1O SHZGCJCMOBCMKK-KGJVWPDLSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012913 prioritisation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
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- Electrolytic Production Of Metals (AREA)
Abstract
本发明公开了一种用于氧化物乏燃料干法后处理的熔盐体系。该熔盐体系以四氟化铀为熔盐主体,添加占熔盐总质量0.1~10%的五氟化铀或四氟化铀的过氟化混合物。它是既能将氧化物乏燃料熔解在熔盐中,又可避免熔盐中的强络阴离子对设备材料严重腐蚀的熔盐体系。
Description
技术领域
本发明属于辐照后的燃料组件经非水溶液再处理流程的技术领域,具体涉及一种用于氧化物乏燃料干法后处理的熔盐体系。
背景技术
干法后处理技术是由美国的ANL和俄罗斯的RIAR、RICT发展起来的。俄罗斯以几千克的氧化物乏燃料进行干法电解后处理,证明该技术在原理上是可行的。美国进行金属乏燃料的干法电解后处理实验室放大实验也已取得成功。目前,熔盐过程是研究最为活跃的四种干法后处理技术之一。其原理是用含对铀、钚有强络合性能的络阴离子盐,如Cl-、F-、SO4 2-等,熔融后,使乏燃料熔解在该熔盐种,处理的元件以氧化物元件为主要对象。
为使乏燃料在熔盐中达到一定的熔解度,目前,国际上采用两种方法转型氧化物乏燃料:氯化或还原。氯化是通过反应(1)将氧化物乏燃料转化为金属氯化物。
MOx+HCl→MCly (1)
还原则是通过反应(2)将氧化物还原为金属。
MOx+Li(Ca)→M+Li2O(CaO) (2)
目标都是要将氧化物燃料转化为可熔解在熔盐中化合物,又要避免使用对设备材料有强腐蚀作用的熔盐体系。
金属氧化物乏燃料,尤其是MOX乏燃料的干法后处理过程中,氧化物乏燃料在熔盐中熔解和熔盐对设备材料的腐蚀间存在难以调和的矛盾。增加熔盐中强配合作用的络阴离子,如F-,熔盐中可以获得氧化物乏燃料的较大熔解度,使以熔盐为基础的后处理过程得以实现,但熔盐中强配合作用的络阴离子浓度的增加,又使设备材料腐蚀加剧,使设备材料不能满足熔盐体系后处理过程的要求。在2001年出版的中国核科技报告《干法后处理技术典型流程综述》(CNIC-01638/38)一文中,欧阳应根综述了多种熔盐过程所采用的熔盐体系,其中比较典型的是美国阿贡实验室提出的金属锂还原氧化物电解精炼流程,在LiCl熔盐中先将乏燃料氧化物还原成相应的金属,然后再进行电解精炼回收铀钚。但是氯化物熔盐的溶解能力较低,溶解UO2比较困难。俄罗斯人将MOX粉末中的铀、钚氧化物在熔盐中直接氯化氧化到六价熔解,然后使铀钚在有Cl2+O2气氛的阴极还原电沉积为铀钚混合氧化物。MOX的氯化氧化熔解过程取决于熔盐组成与熔盐工作温度。该流程最早使用的是LiCl+KCl熔盐体系,工作温度500℃左右。为提高熔盐工作温度,现改为含NaCl、CsCl的熔盐体系。使用NaCl(熔点800℃)主要是为了提高熔盐的工作温度,使用CsCl是为了提高六价钚的生成百分比。实验发现,CsCl的添加可以大大提高钚的熔解度和熔解速度。尽管如此,钚的收率仍然难以达到满意指标。
发明内容
(一)发明目的
针对目前干法后处理技术熔盐体系所存在的问题,本发明旨在提供一种既能将氧化物乏燃料熔解在熔盐中,又可避免熔盐中的强络阴离子对设备材料严重腐蚀的熔盐体系。
(二)技术方案
一种用于氧化物乏燃料干法后处理的熔盐体系,该体系以四氟化铀为熔盐主体,添加占熔盐总质量0.1~10%的五氟化铀或四氟化铀的过氟化混合物。
作为一种优化方案,在熔盐体系运行的过程中,加入占熔盐总质量0.1~3%的LiF。
(三)发明效果
本发明使用四氟化铀熔盐体系,熔融时熔盐中铀在阴极沉积后释放出氟离子,与金属氧化物(如UO2)发生反应(3)而使氧化物熔入熔盐中:
反应(3)产生的MOF2中的金属在阴极沉积后,又释放出F-,使熔盐体系中的F-在熔解-沉积过程中循环,从而使金属氧化物在熔盐电解过程中转化为金属。反应(3)产生在电解过程的阳极以氧气方式释出。此过程中,熔盐体系中因反应(3)产生的F-被氧化物优先结合,使体系的F-浓度保持足够低,不至于对设备材料造成严重腐蚀。使熔盐干法后处理氧化物到金属过程可以直接实现,而不需要氧化物转型,或预还原等步骤。添加五氟化铀或四氟化铀的过氟化混合物可以改善熔盐体系温度和熔解特性。
具体实施方式
下面通过实施例,对本发明所提供的技术方案作进一步阐述。
实施例1
采用UF4,添加LiF和UF5,以改善熔盐体系的温度和熔解特性,以UO2为原料,直接电解沉积出金属铀。
具体操作过程是:
1)配制合适的熔盐。取UF4和UF5各128g和0.13g。
2)控制温度600~650℃,使熔盐在坩埚中熔化。
3)添加3.84g LiF。
4)加入6.60g UO2。
5)当盐熔化时,用不锈钢条搅拌熔体,然后取上层清液,以分析UO2的溶解度。取样完成后,进行CV扫描,根据CV扫描所得的信息进行恒电位沉积。结果表明,恒电位沉积在不锈钢阴极上得到枝状沉积物。
实施例2
采用UF4,添加UF4的过氟化混合物和LiF,以UO2为原料,直接电解沉积出金属铀。
具体操作过程是:
1)配制合适的熔盐。取UF4和UF4的过氟化混合物各100g和5g。
2)控制温度650~700℃,使熔盐在坩埚中熔化。
3)添加1.58g LiF。
4)加入5.33g UO2。
5)当盐熔化时,用不锈钢条搅拌熔体,然后取上层清液,以分析UO2的溶解度。取样完成后,进行CV扫描,根据CV扫描所得的信息进行恒电位沉积。结果表明,恒电位沉积在不锈钢阴极上得到枝状沉积物。
实施例3
采用UF4,添加LiF和UF5,以UO2为原料,直接电解沉积出金属铀。
具体操作过程是:
1)配制合适的熔盐。取UF4和UF5各80g和8g。
2)控制温度600~650℃,使熔盐在坩埚中熔化。
3)添加0.09g LiF。
4)加入4.84g UO2。
5)当盐熔化时,用不锈钢条搅拌熔体,然后取上层清液,以分析UO2的溶解度。取样完成后,进行CV扫描,根据CV扫描所得的信息进行恒电位沉积。结果表明,恒电位沉积在不锈钢阴极上得到枝状沉积物。
显然本领域的技术人员可以对本发明进行各种修改和变型而不脱离本发明的精神和范围。这样,假若本发明的这些修改和变型属于本发明权利要求其等同技术的范围内,则本发明也意图包含这些修改和变型。
Claims (3)
1.一种用于氧化物乏燃料干法后处理的熔盐体系,该体系以四氟化铀为熔盐主体,添加占熔盐总质量0.1~10%的五氟化铀,或添加占熔盐总质量0.1~10%的四氟化铀的过氟化混合物。
2.根据权利要求1所述的用于氧化物乏燃料干法后处理的熔盐体系,其特征在于:在熔盐体系运行的过程中,加入占熔盐总质量0.1~3%的LiF。
3.根据权利要求1所述的用于氧化物乏燃料干法后处理的熔盐体系,其特征在于:熔盐熔化的温度控制600~700℃。
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US4297174A (en) * | 1979-03-09 | 1981-10-27 | Agip Nucleare, S.P.A. | Pyroelectrochemical process for reprocessing irradiated nuclear fuels |
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Title |
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刘学刚."乏燃料干法后处理技术研究进展".《核化学与放射化学》.2009,第31卷35-44. |
欧阳应根."干法后处理技术典型流程综述".《中国核科技报告》.2001,367-381. |
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