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化学进展  2011 

综述KBS-3处置库近场还原性环境对处置安全的裨益

, PP. 1411-1428

Keywords: 乏燃料,处置容器,氢气,催化剂,处置库化学

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Abstract:

核能为减小温室气体排放引起的气候变化的风险起到了重要的不可替代的作用,但是自福岛核电站事故以来公众对核能安全越来越关注。为了消除人们的忧虑,确保核能的持续发展,国际社会将加强旨在提高整个核燃料循环各个领域安全的研究。核废物,特别是高水平放射性废物的处置安全,同核电反应堆运行安全一样是核能安全的一个重要环节。乏燃料占世界高放废物中的大部分,其中所含放射性核素需要与世隔绝十万年才能衰变到无害水平。因为很难预知此时段环境的变化,评价乏燃料中放射性核素从深地层处置库通过地质圈和生物圈向人类环境的迁移将具有很大的不确定性。相对来说,我们能比较容易地验证在最不利的处置库近场环境下处置容器和乏燃料的化学行为。如果我们能证明一个核废物处置库的工程屏障(近场)和地质屏障(远场)能够独立地保证处置库安全,象喷气客机的两个发动机能独立保证飞机飞行一样,证明近场工程屏障能确保放射性核素在十万年内从处置库向外迁移的速率足够慢,即使远场对放射性核素迁移的阻滞比较小,也能保证处置库的安全,(反之亦然),我们就能确定此处置方案是安全可行的。本文就近十几年来对乏燃料在深地层处置库近场化学行为的研究进行了总结。文章首先简单介绍了世界首个确定库址的高水平放射性废物处置库瑞典KBS-3乏燃料处置库的设计和库址特性,之后列举了文献报道的和作者本人主导的一系列实验成果,就容器铸铁部分腐蚀所产生的氢气对乏燃料腐蚀的抑制作用和可能的乏燃料中裂变产物合金颗粒的催化剂作用进行了综述;随后着重总结了作者本人主导的在模拟处置初期的γ辐射条件下(0.9Gy/h)地下水溶液(2mMNaHCO3)中放射性同位素从乏燃料中浸出和在铸铁容器表面沉积的实验结果,证明了(1)在用氩气除氧2mMNaHCO3溶液中乏燃料所含裂变产物(Sr-Cs-Tc-Mo)和锕系核素(238U和237Np)的浸出速率(与总含量之比)分别为10-6/天和10-7/天;高毒性的239Pu浸出速率为5×10-9/天;(2)在含10%氢气的氩气平衡的相同溶液中,核素从乏燃料中的浸出会被完全阻断,甚至以前已浸出的多价态核素238U,237Np,99Tc和79Se等也会在乏燃料所含裂变产物合金颗粒的催化作用下被氢气还原并沉淀;(3)在与亚铁矿物(FeCO3)平衡的水溶液中,亚铁离子会被乏燃料表面水辐解产生的氧化性产物(H2O2,O2,OH·)氧化并沉淀在乏燃料表面和裂隙之中,并对乏燃料的近一步氧化腐蚀有明显的抑制作用;(4)在铜容器壳破损以后的很长时间内,从乏燃料浸出的多价态核素U,Tc,Se和Np能够被铸铁材料表面还原并沉淀;(5)在处置初期铜容器表面的腐蚀速率受γ辐射的影响不大,约为1—2μm/年,并将会随着乏燃料中137Cs的衰变而减缓。本文证明了KBS-3处置库具有的还原性环境对乏燃料处置安全的裨益,为核废物处置库选址在还原性地层和设计具有铜包壳和大量铁材料的废物容器提供了依据,谨望对国内高放废物处置库的设计和安全评价具有一定的借鉴作用。

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