CN110447077A - 处理放射性溶液的方法 - Google Patents

处理放射性溶液的方法 Download PDF

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CN110447077A
CN110447077A CN201880007102.2A CN201880007102A CN110447077A CN 110447077 A CN110447077 A CN 110447077A CN 201880007102 A CN201880007102 A CN 201880007102A CN 110447077 A CN110447077 A CN 110447077A
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A.A.里辛
S.V.托米林
S.S.波利亚德
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Abstract

本发明涉及环境保护领域，更具体地，涉及处理放射性废物的领域，并且可用于安全有效地处理由于对箱和室的防护设备进行去污而形成的大量的各种放射性活度水平的液体放射性废物，且可以通过固化废物并将其掺入陶瓷基质中来减少储存废物的体积。为此目的，将防护设备表面去污后的放射性溶液作为含有氢氧化钠、高锰酸钾、草酸和硝酸的碱性和酸性溶液蒸发直至形成固体残留物，煅烧，将煅烧产物与含有钛、钙、铁(III)、锆和锰(IV)和铝的氧化物的熔融混合物的组分以特定比率混合，并熔融。

Description

处理放射性溶液的方法
本发明涉及环境保护领域，更具体地，涉及处理放射性废物的领域，并且可用于安全有效地处理由于对箱和室的防护设备进行去污而形成的大量的各种放射性活度水平的液体放射性废物，且可以通过固化废物并将其掺入陶瓷基质中来减少储存废物的体积。
已知一种将放射性废物掺入陶瓷材料中的方法(RF专利号2153717，G21F9/16)，其由以下组成：对含有放射性核素U、Th、Am、Cm、Pu和Np以及放射性稀土元素Zr、Mo、Ru、Cs、Pd、Sr、Ba和Rb的放射性废物施以热浓缩，将浓缩物与氧化物以下列组分比例（重量％）混合：放射性废物浓缩物（以氧化物计）— 15-30；TiO2 — 50-60；CaO — 5-10；ZrO2 — 5-20；Al2O3 — 3-5；BaO — 3-10，然后将所得熔融混合物与以总熔融混合物重量的 3-10重量％的量取用的含碳材料混合，并且将所得的含碳熔融混合物的水分含量调节至5-20重量％。然后将水分含量为5-20重量％的含碳熔融混合物供应到工作温度为1,400-1,500℃的熔融陶瓷材料的表面上，将含碳熔融混合物和熔融陶瓷材料的混合物保持直至形成均化的熔体，其中通过在供应含碳熔融混合物的同时不断加热熔融陶瓷材料并使其保持来保持熔融陶瓷材料的工作温度，之后将均化的熔体冷却以形成其中包含放射性废物的整体陶瓷材料(Synroc)（最终产品），其适合于长期储存，并且放射性废物掺入陶瓷材料的整个过程在低于大气压的压力下进行。通过放射性废物（其总是含有水）的不完全脱水（蒸发或干燥）进行热浓缩，其中使用不完全脱水的放射性废物代替煅烧产物防止了在熔融混合物制备阶段形成粉尘，这增加了所实施的方法的安全性。热浓缩的放射性废物不仅掺入所得的Synroc陶瓷材料中，而且也是合成钙钛矿、钙钛锆石（zirconolite）和碱硬锰矿（hollandite）的起始组分之一，所述钙钛矿、钙钛锆石和碱硬锰矿是Synroc陶瓷材料的组成部分。
所提出的方法的缺点如下：
-高能耗；
-熔融混合物应与含碳材料连续混合，以保持材料的恒定熔化温度在1,400-1,500℃的范围内，这需要使用额外的计量器；
-该过程在低于大气压的压力下进行，这需要使用额外的设备来产生真空；
-在感应熔化器中进行该过程需要感应熔化设备（高频辐射发生器、高进给电流和在某些情况下的水冷却系统）。
将高放废物固定在陶瓷基质中的方法(2006年5月22日的RF专利号2315381，“Method for immobilizing high-level waste in a ceramic matrix”，G21F 9/16)是最接近的等同物，具有最大数量的与要求保护的发明共同的实质特征。
所述方法包括煅烧（脱硝）高放废物并将其与氧化物混合（以下列比例：高放废物的煅烧产物 — 10-20重量％； TiO2 — 50-60重量％；CaO — 7.5-12.5重量％；MnO —7.5-12.5重量％；Fe2O3 — 2.5-7.5重量％；Аl2O3 — 2.5-7.5重量％），将所得混合物在不低于大气压力的压力下加热至最高工作温度2,000℃，在工作温度保持并冷却直至形成整体材料。
所述方法旨在掺入具有高含量的锕系元素和稀土元素的高放废物，并且旨在固定化和长期地质储存在乏核燃料处理过程中形成的放射性废物的锕系元素和稀土部分。所提出的方法没有描述掺入含有大量碱金属阳离子的高盐废物（包括含有用于对防护设备进行去污的酸性和碱性溶液的组分的那些）的可能性。
该过程非常耗能。
本技术方案的目的是创建一种可靠且简单的方法来固定非工艺废物，以产生适合长期地质储存的整体材料。
为了实现这一目的，提出了一种用于处理防护设备表面去污后的放射性溶液的方法，该方法包括合并蒸发碱性和酸性溶液以及随后煅烧，煅烧产物与含有钛、钙、铁(III)和铝的氧化物的熔融混合物的组分以一定比例混合，以及热处理和合并熔化所有组分以产生陶瓷基质，其特征在于以下列组分比例（重量％）将锆氧化物和锰氧化物进一步引入煅烧产物和钛、钙、铁(III)和铝的氧化物的混合物中：
高放废物的煅烧产物 10. 0-20.0
TiO2 53.0-57.0
CaO 9.0-11.0
Fe2O3 4.5-5.5
Al2O3 4.5-5.5
ZrO2 4.5-5.5，
且MnO2在混合物中的总含量不超过10重量％。
由去污溶液的蒸发产生的固体残留物在750-800℃煅烧，以完全分解硝酸盐和碳酸盐。
将煅烧产物与熔融混合物在1,350℃或更高温度熔融1小时，以生产整体熔融陶瓷材料。
熔融混合物中二氧化锆和二氧化锰的存在降低了陶瓷熔化温度，这使得该过程耗能较少。
熔融混合物中的氧化锰含量根据去污后过程溶液中以锰计的高锰酸钾的实际含量而变化。
熔融混合物中二氧化锰含量高于10％是不合适的，因为它提高了混合物的熔化温度。
如果二氧化锆含量低于下限，则陶瓷材料的相组成可能改变。
将熔融混合物中二氧化锆的含量增加到高于5.5％是不合适的。
当实施所述过程操作时，去污后的溶液可以蒸发成盐，并且在其热处理形成氧化物之后，它们可以与用于生产陶瓷材料的熔融混合物的组分混合，陶瓷材料继而可以通过熔融所有组分来形成适合放射性废物长期地质储存的整体材料来获得。
两种组成（酸性（含有5％HNO3、0.5％H2C2O4和0.5％EDTA）和碱性（含有0.5％KMnO4和5％NaOH））的去污溶液以相等的体积比例混合在一起。将所得溶液在95℃蒸发，水蒸发后，将温度升至350℃。将所得残留物与含有钛、锰(IV)、铝、铁(III)、钙和锆的氧化物的陶瓷熔融混合物的组分以一定方式混合，使得所得陶瓷材料的组成符合表1中所列的组分比例。由于去污溶液（熔点：323℃）的蒸发产生的残留物中存在吸湿性氢氧化钠，因此在350℃蒸发和热处理后产物不会变得完全干燥，并且不需要额外引入富含水分的产品来防止粉尘形成。当产物与熔融混合物混合时，这减少了气溶胶的排放，并简化了熔化目标陶瓷材料的工艺条件。
氧化锰含量可以根据去污后过程溶液中以锰计的高锰酸钾的实际含量来调节。如果酸性和碱性溶液没有均匀地混合，并且如果在过程放射性溶液中高锰酸钾分数增加或减少，可通过减少或增加初始熔融混合物中MnO2的含量来调节表 1中所示的组成。
在将固化的溶液与熔融混合物组分混合后，将整个组合物在800℃热处理以分解硝酸盐和碳酸盐，然后将所得组合物在1350℃熔化1小时。根据X射线相分析数据，在冷却至室温后获得的熔融材料由具有钛锌钠矿（murataite）结构（立方晶格参数a=14.63±0.01A）的主相和具有钙钛矿结构的附加相形成。当材料在90℃在热双蒸水中浸出时，基质的主要组分（阳离子）的浸出率为每24小时 10-6-10-7g/cm2（在第3天、第7天和第14天取样）。
表1. 用于生产陶瓷材料的组分
。

Claims (3)

1.用于处理防护设备表面去污后的放射性溶液的方法，该方法包括将含有氢氧化钠、高锰酸钾、草酸和硝酸的碱性和酸性溶液合并蒸发成固体残留物，随后煅烧并将煅烧产物与含有钛、钙、铁(III)和铝的氧化物的熔融混合物的组分以一定比例混合，并将所有组分合并熔化以产生陶瓷基质，其特征在于以下列组分比例（重量％）将锆氧化物和锰(IV)氧化物进一步引入煅烧产物和钛、钙、铁(III)和铝的氧化物的混合物中：
高放废物的煅烧产物10.0-20.0
TiO253.0-57.0
CaO9.0-11.0
Fe2O34.5-5.5
Al2O34.5-5.5
ZrO24.5-5.5，
且MnO2在混合物中的总含量不超过10重量％。
2.权利要求1所述的方法，其特征在于，由去污溶液的蒸发产生的固体残留物在750-800℃煅烧以完全分解硝酸盐和碳酸盐。
3.权利要求1所述的方法，其特征在于，将煅烧产物在1350℃或更高温度熔融1小时，以生产整体熔融陶瓷材料。
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WO2018132041A1 (ru) 2018-07-19
JP2020505590A (ja) 2020-02-20
EP3570293B1 (en) 2022-04-13
CN110447077B (zh) 2023-05-05
EP3570293A4 (en) 2020-10-28
KR20190111925A (ko) 2019-10-02
JP6636680B1 (ja) 2020-01-29

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