CN113457615A - 一种放射性碘吸附剂及其制备方法 - Google Patents
一种放射性碘吸附剂及其制备方法 Download PDFInfo
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 53
- 239000011630 iodine Substances 0.000 title claims abstract description 53
- 230000002285 radioactive effect Effects 0.000 title claims abstract description 51
- 239000003463 adsorbent Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 31
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000741 silica gel Substances 0.000 claims description 19
- 229910002027 silica gel Inorganic materials 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002594 sorbent Substances 0.000 claims 3
- 238000007598 dipping method Methods 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 239000000941 radioactive substance Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000003758 nuclear fuel Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002901 radioactive waste Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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Abstract
本发明属于放射性物质处理技术领域，涉及一种放射性碘吸附剂及其制备方法。制备所述的吸附剂的原料按重量配比包含：二价铜盐0.8‑1.2份，还原剂1.4‑2.0份，多孔材料80‑120份。利用本发明的放射性碘吸附剂及其制备方法，能够更好的制备放射性碘吸附剂，制得放射性碘吸附剂能够高效、安全、低成本的吸附净化放射性单质碘和有机碘。
Description
技术领域
本发明属于放射性物质处理技术领域，涉及一种放射性碘吸附剂及其制备方法。
背景技术
在核燃料循环的后处理厂溶解器放射性废气的处理系统中，需要使用附银硅胶以吸附净化放射性单质碘和有机碘。附银硅胶是将硝酸银或其它银盐溶液浸渍到硅胶表面并干燥处理后形成的。此种附银硅胶的使用存在如下问题：1)成本比较高；2)银是国家管控的贵金属；3)硅胶浸渍硝酸银后必须充分保护并立即使用，否则容易失效。因此，附银硅胶吸附净化放射性单质碘和有机碘的应用受到很多限制。
此外，核电厂通风净化系统及废气处理系统一般用浸渍活性炭吸附净化气体中的放射性单质碘和有机碘，但活性炭是一种可燃物质，有潜在的着火风险和安全隐患。另一方面，活性炭所用的浸渍剂一般为碘化钾和三甲基二胺，其中的碘化钾只是起到了同位素交换作用，并不能长久吸附固定放射性碘，三甲基二胺则易于被气流吹走而损失致活性炭失效。
发明内容
本发明的首要目的是提供一种放射性碘吸附剂，以能够高效、安全、低成本的吸附净化放射性单质碘和有机碘。
为实现此目的，在基础的实施方案中，本发明提供一种放射性碘吸附剂，制备所述的吸附剂的原料按重量配比包含：二价铜盐0.8-1.2份，还原剂1.4-2.0份，多孔材料80-120份。
本发明中放射性碘的吸附净化机理在于利用了放射性单质碘或有机碘首先与硫代硫酸钠反应，然后与二价铜反应生成碘化亚铜，从而固定于硅胶孔道内的物理及化学特性。目前并未发现有人利用这一机理制作核工业放射性气体中放射性碘的固体吸附净化剂。
在一种优选的实施方案中，本发明提供一种放射性碘吸附剂，其中所述的二价铜盐选自硫酸铜、硝酸铜、碳酸铜、磷酸铜中的一种或几种。
在一种优选的实施方案中，本发明提供一种放射性碘吸附剂，其中所述的还原剂选自硫代硫酸钠和/或硫代硫酸钾。
在一种优选的实施方案中，本发明提供一种放射性碘吸附剂，其中所述的多孔材料选自硅胶、分子筛、活性炭中的一种或几种。
本发明的第二个目的是提供一种如上所述放射性碘吸附剂的制备方法，以能够更好的制备上述放射性碘吸附剂，制得放射性碘吸附剂能够高效、安全、低成本的吸附净化放射性单质碘和有机碘。
为实现此目的，在基础的实施方案中，本发明提供一种如上所述放射性碘吸附剂的制备方法，所述的制备方法是用所述的二价铜盐与所述的还原剂浸渍所述的多孔材料。
将上述制得浸渍多孔材料装填入放射性气体净化系统中碘吸附器的方式可以多样，不受限制，其即可以应用于现有核电厂的通风净化系统及放射性气体处理系统，也可以应用于核燃料后处理厂的废气净化系统，特别是溶解器废气处理系统中。
本发明的二价铜盐浸渍多孔材料与还原剂浸渍多孔材料的使用温度适用于目前核工业通风净化系统或放射性气体处理系统的设计使用温度。
在一种优选的实施方案中，本发明提供一种如上所述放射性碘吸附剂的制备方法，其中所述的制备方法用所述的二价铜盐浸渍部分所述的多孔材料，用所述的还原剂浸渍剩余的所述的多孔材料，然后合并两部分浸渍后的所述的多孔材料。
在一种更加优选的实施方案中，本发明提供一种如上所述放射性碘吸附剂的制备方法，其中所述的二价铜盐浸渍部分所述的多孔材料的时间为1-20分钟，二价铜盐的质量百分比浓度为1-45％。
在一种更加优选的实施方案中，本发明提供一种如上所述放射性碘吸附剂的制备方法，其中所述的还原剂浸渍剩余的所述的多孔材料的时间为1-20分钟，还原剂的质量百分比浓度为2-82％。
在一种更加优选的实施方案中，本发明提供一种如上所述放射性碘吸附剂的制备方法，其中二价铜盐浸渍的多孔材料与还原剂浸渍的多孔材料的质量比为1:10-10:1。
在一种更加优选的实施方案中，本发明提供一种如上所述放射性碘吸附剂的制备方法，其中二价铜盐浸渍的多孔材料与还原剂浸渍的多孔材料的质量比为1:2。
本发明的有益效果在于，利用本发明的放射性碘吸附剂及其制备方法，能够更好的制备放射性碘吸附剂，制得放射性碘吸附剂能够高效、安全、低成本的吸附净化放射性单质碘和有机碘。
本发明利用铜盐配合硫代硫酸钠混分浸渍硅胶、活性炭及其它多孔材料，制备放射性碘吸附剂，经过多次试验证实，所得放射性碘吸附剂对于放射性单质碘的吸附净化效率在99％以上，对于放射性甲基碘的吸附净化效率在80％以上(按照美国ASTM D3803标准方法测试)。
本发明的放射性碘吸附剂相比于目前核电厂用的浸渍活性炭，因不燃性而具有更高的安全性，且相比于核燃料后处理厂所用的附银硅胶成本更低。
具体实施方式
以下结合实施例对本发明的具体实施方式作出进一步的说明。
实施例1：
(1)将1g的硝酸铜溶于5g的蒸馏水中，均匀喷淋于100g硅胶中，并用干空气干燥。
(2)将1.69g的硫代硫酸钠溶于5g的蒸馏水中，均匀喷淋于100g硅胶中，并用干空气干燥。
(3)将上述两种浸渍硅胶均匀混合。
(4)将混合后的硅胶装填入试验盒中，并装入按照美国ASTM D3803标准建立的试验装置中。
(5)按照美国ASTM D3803的试验程序进行固体吸附剂去除放射性单质碘和甲基碘的效率试验。
(6)根据试验结果，计算固体吸附剂去除放射性单质碘的效率和放射性甲基碘的效率。结果按照上述方法制备的混合后的硅胶去除放射性单质碘的效率大于99％(硅胶层厚度5cm)，去除放射性甲基碘的效率大于80％(硅胶层厚度5cm)。
上述实施例只是对本发明的举例说明，本发明也可以以其它的特定方式或其它的特定形式实施，而不偏离本发明的要旨或本质特征。因此，描述的实施方式从任何方面来看均应视为说明性而非限定性的。本发明的范围应由附加的权利要求说明，任何与权利要求的意图和范围等效的变化也应包含在本发明的范围内。
Claims (10)
1.一种放射性碘吸附剂，其特征在于，制备所述的吸附剂的原料按重量配比包含：二价铜盐0.8-1.2份，还原剂1.4-2.0份，多孔材料80-120份。
2.根据权利要求1所述的吸附剂，其特征在于：所述的二价铜盐选自硫酸铜、硝酸铜、碳酸铜、磷酸铜中的一种或几种。
3.根据权利要求1所述的吸附剂，其特征在于：所述的还原剂选自硫代硫酸钠和/或硫代硫酸钾。
4.根据权利要求1所述的吸附剂，其特征在于：所述的多孔材料选自硅胶、分子筛、活性炭中的一种或几种。
5.一种根据权利要求1-4之一所述的吸附剂的制备方法，其特征在于：所述的制备方法是用所述的二价铜盐与所述的还原剂浸渍所述的多孔材料。
6.根据权利要求5所述的制备方法，其特征在于：所述的制备方法用所述的二价铜盐浸渍部分所述的多孔材料，用所述的还原剂浸渍剩余的所述的多孔材料，然后合并两部分浸渍后的所述的多孔材料。
7.根据权利要求6所述的制备方法，其特征在于：所述的二价铜盐浸渍部分所述的多孔材料的时间为1-20分钟，二价铜盐的质量百分比浓度为1-45％。
8.根据权利要求6所述的制备方法，其特征在于：所述的还原剂浸渍剩余的所述的多孔材料的时间为1-20分钟，还原剂的质量百分比浓度为2-82％。
9.根据权利要求6所述的制备方法，其特征在于：二价铜盐浸渍的多孔材料与还原剂浸渍的多孔材料的质量比为1:10-10:1。
10.根据权利要求6所述的制备方法，其特征在于：二价铜盐浸渍的多孔材料与还原剂浸渍的多孔材料的质量比为1:2。
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