CN113004570A - 用于放射性废水处理的气凝胶的制备方法及其产品和应用 - Google Patents
用于放射性废水处理的气凝胶的制备方法及其产品和应用 Download PDFInfo
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Abstract
本发明公开了用于放射性废水处理的气凝胶的制备方法及其产品和应用，将海藻酸钠与多酚化合物溶解，通过钙离子交联制得水凝胶，然后将水凝胶置于有机溶剂中进行溶剂置换，然后加入交联剂进行化学交联，干燥制得气凝胶，气凝胶表面具有大量的羧基和酚羟基活性官能团可与多种放射性核素金属阳离子进行络合，且比表面积大，机械强度高，具有大量的羧基和酚羟基活性基团，对废水中的放射性核素具有很好的吸附性能，适用于放射性废水的吸附处理。
Description
技术领域
本发明涉及材料化工领域，具体涉及用于放射性废水处理的气凝胶的制备方法，还涉及由该方法制得的产品和应用。
背景技术
在核工业的迅速发展过程中，不可避免的会发生放射性核素的泄露，导致大量放射性废水被排放到环境中。放射性废水中的核素以铀、锶等金属阳离子为主。这些放射性核素不仅具有重金属离子的化学毒性，还具有放射性，对生态环境和人体健康造成不可估量的影响。因此，如何高效去除放射性废水中共存的多种核素变得刻不容缓。
对含重金属离子的工业废水，传统的处理方法包括化学沉淀法、离子交换法、吸附法等，但这些方法都存在一定的缺陷。化学沉淀法不适于废水中低浓度重金属离子的去除，且易产生二次污染。离子交换法成本较高，缺乏特异性，易受共存离子的影响。吸附法具有操作简单、成本低廉、除去率高等优点而被广泛应用于各种重金属离子和环境污染物的去除。目前常用的吸附材料包括炭材料、生物质材料、天然及合成沸石等多孔材料。但这些吸附材料缺乏特异性，因此针对放射性核素探索高效的吸附材料具有重要的意义，解决放射性废水的处理缺乏有效的技术手段问题。
发明内容
有鉴于此，本发明的目的之一在于提供一种用于放射性废水处理的气凝胶的制备方法，利用海藻酸钠分子链中含有大量的羧基，与金属阳离子有较强的络合能力，作为吸附剂可用于重金属离子的吸附。单宁酸、没食子酸等多酚化合物结构中含有大量酚羟基，可以与多种金属离子和放射性核素络合，且不受干扰离子的影响。将海藻酸钠与钙离子发生交联反应形成水凝胶，进一步干燥可制得气凝胶，克服这些化合物的水溶性限制其应用；然后通过化学交联剂反应形成共价键，将会大大提高以海藻酸钠基气凝胶的力学性能，交联后在材料中引入酚羟基结构，提高其对金属阳离子的吸附能力。
为达到上述目的，本发明提供如下技术方案：
1、用于放射性废水处理的气凝胶的制备方法，将海藻酸钠与多酚化合物溶解，通过钙离子交联制得水凝胶，然后将水凝胶置于有机溶剂中进行溶剂置换，然后加入交联剂进行化学交联，干燥制得气凝胶。
本发明优选的，所述多酚化合物为单宁酸或没食子酸；所述有机溶剂为乙酸乙酯、丙酮、乙腈中的任意一种；所述交联剂为异氰酸酯固化剂。
本发明优选的，所述钙离子交联为加入碳酸钙，充分混匀后再加入葡萄糖酸内酯混匀；也可以使用其他钙盐化学物，使用碳酸钙时钙离子释放缓慢，形成的水凝胶均匀，葡萄糖酸内酯的作用使钙离子释放更加缓慢，形成的水凝胶更均匀。
本发明优选的，所述海藻酸钠与多酚的质量比为1:5～5:1，所述海藻酸钠和多酚总质量与交联剂的质量比为10～50:1。
优选的，所述化学交联为再温度为50℃静置至少24小时。
更优选的，具体步骤如下：将海藻酸钠与多酚化合物按质量比为2：1在水中溶解，加入相当于多酚化合物质量0.5倍的碳酸钙充分混匀后再加入与多酚化合物等量的葡萄糖酸内酯充分混合，静置得水凝胶，然后将水凝胶依次置于体积分数为60％的丙酮水溶液和丙酮中进行溶剂置换，然后加入异氰酸酯质量分数为50％的丙酮溶液，静置至少24小时后，加温至50℃静置72小时进行化学交联，再置于丙酮中静置，干燥制得气凝胶。
制得的气凝胶具有机械强度高，比表面积大，易装填使用，表面具有大量羧基和酚羟基活性基团，可与多种放射性核素进行络合吸附，适用于放射性废水的处理。
2、由所述的制备方法制得的用于放射性废水处理的气凝胶。
3、所述气凝胶用于金属阳离子的吸附剂中的应用。
4、所述气凝胶用于处理放射性废水中的应用。
优选的，所述放射性废水为含铀、锶放射性废水。
本发明的有益效果在于：利用海藻酸钠分子链中含有大量的羧基，与金属阳离子有较强的络合能力，作为吸附剂可用于重金属离子的吸附；然后与单宁酸、没食子酸等多酚化合物交联使材料引入酚羟基结构，提高其对金属阳离子的吸附能力；同时还具有如下优点：
1)获得的气凝胶材料具有高的比表面积，增大了与废水中放射性核素的接触面积；
2)交联气凝胶材料机械强度高，可直接装填入吸附柱，易于使用；解决了海藻酸钠物理交联气凝胶耐水性差、脆硬、力学强度低，限制了其在废水处理领域的应用的问题；
3)气凝胶表面和内部的多孔中具有大量来自海藻酸钠的羧基和多酚化合物的酚羟基活性官能团，可与多种放射性核素络合，吸附性能好，不受废水中干扰离子的影响；
4)气凝胶对放射性核素阳离子进行吸附后，附后的吸附柱可通过酸洗进行再生。与现有技术相比，该气凝胶材料具有比表面积高、吸附容量大、使用方便、易再生利用等优点，并能同时吸附放射性废水中共存的多种金属阳离子，适用于含铀、锶放射性废水的快速吸附处理。
附图说明
为了使本发明的目的、技术方案和有益效果更加清楚，本发明提供如下附图进行说明：
图1为本发明实施例1所得的海藻酸钠-没食子酸气凝胶材料的扫描电子显微镜照片；
图2为是本发明实施例1所得的海藻酸钠-没食子酸气凝胶材料的傅里叶变换红外光谱图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好的理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
实施例1、海藻酸钠-没食子酸气凝胶材料的制备
海藻酸钠-没食子酸气凝胶材料的制备，具体步骤如下：
1)称量2克海藻酸钠加入98克水中，搅拌2小时溶解；
2)向步骤1)中加入1克没食子酸；
3)向步骤2)中加入0.5克碳酸钙粉末，在机械搅拌500转/分搅拌下，利用IKAT25高速均质乳化机10000转/分下均质2分钟，以充分混合；
4)向步骤3)中加入1克葡萄糖酸内酯，在机械搅拌500转/分搅拌下，10000转/分均质1分钟，以充分混合；
5)静止12小时，制得水凝胶；
6)将水凝胶分别置于60％的丙酮水溶液和丙酮进行溶剂置换；
7)将水凝胶分别置于100mL 50％Desmodur N3300的丙酮溶液，静置24小时；
8)将上述溶液加温至50度，静止72小时进行交联反应；
9)将上述交联水凝胶置于丙酮中，静置24小时；
10)超临界二氧化碳干燥，制得气凝胶。
所制得的海藻酸钠-没食子酸气凝胶的扫描电子显微镜照片参见图1，结果表明所得气凝胶是一种多孔材料。经检测，所述海藻酸钠-没食子酸气凝胶的比表面积(全自动多功能气体吸附仪，Autosorb-iQ-MP，美国康塔)约为753m2/g。采用傅里叶变换红外光谱仪(NICOLET iS10，美国赛默飞世尔)对海藻酸钠-没食子酸气凝胶进行表征，结果参见图2。采用万能材料试验机(INSTRON 5944，美国英斯特朗)测试海藻酸钠-没食子酸气凝胶的力学性质，其弹性模量为80-95MPa，承压能力为39-47kg。
本实施例中碳酸钙可以用其他钙盐替换，没食子酸可以其他能够络合金属阳离子的多酚化合物替换如单宁酸。
实施例2、海藻酸钠-没食子酸气凝胶材料用于含铀、锶放射性废水处理
海藻酸钠-没食子酸气凝胶材料用于含铀、锶放射性核素废水处理，具体过程如下：
1)配制50L含钠、钾、钙、镁、铀和锶的模拟放射性核素废水溶液，用稀盐酸或氢氧化钠水溶液调节pH值到5～7之间；模拟废水的配方为：210mg/L Na(Ⅰ)、145mg/L K(Ⅰ)、90mg/L Ca(Ⅱ)、87mg/L Mg(Ⅱ)、20mg/L U(Ⅵ)、20mg/L Sr(Ⅱ)以及40mg/L洗涤剂；
2)将5g干燥后的气凝胶材料装填入吸附柱，随后通过蠕动泵将步骤1)配制的模拟放射性核素的废水通过吸附柱，流量为10mL/min；
3)每隔30min～1h，采用电感耦合等离子体质谱仪测量经过吸附柱后废水中残余的放射性核素浓度，计算气凝胶材料的饱和吸附容量，吸附柱对铀和锶的动态饱和吸附容量分别为265和302mg/g；其对铀和锶的去除率分别为97％以及93％。
说明本发明所述多孔气凝胶材料对废水中的放射性核素铀和锶具有很好的吸附性能，能有效去除废水中微量的放射性核素。
实施例3、海藻酸钠-没食子酸气凝胶材料的再生
采用质量分数为5％的稀硝酸流经吸附柱，采用电感耦合等离子体质谱仪检测流出液中放射性核素的浓度，直至检测不出，即表明气凝胶材料再生完成。
再生后的气凝胶材料吸附柱采用前述方法测量对放射性核素的吸附能力。实验结果表明再生的气凝胶吸附柱对废水中铀和锶的动态饱和吸附容量分别为237和289mg/g；其对铀和锶的去除率分别为93％以及91％。
说明气凝胶材料作为一种吸附剂用于放射性废水处理具有较好的再生性能。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例，本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换，均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。
Claims (10)
1.用于放射性废水处理的气凝胶的制备方法，其特征在于：将海藻酸钠与多酚化合物溶解，通过钙离子交联制得水凝胶，然后将水凝胶置于有机溶剂中进行溶剂置换，然后加入交联剂进行化学交联，干燥制得气凝胶。
2.根据权利要求1所述用于放射性废水处理的气凝胶的制备方法，其特征在于：所述多酚化合物为单宁酸或没食子酸；所述有机溶剂为乙酸乙酯、丙酮、乙腈中的任意一种；所述交联剂为异氰酸酯固化剂。
3.根据权利要求1所述用于放射性废水处理的气凝胶的制备方法，其特征在于：所述钙离子交联为加入碳酸钙，充分混匀后再加入葡萄糖酸内酯混匀。
4.根据权利要求1所述用于放射性废水处理的气凝胶的制备方法，其特征在于：所述海藻酸钠与多酚的质量比为1:5～5:1，所述海藻酸钠和多酚总质量与交联剂的质量比为10～50:1。
5.根据权利要求1所述用于放射性废水处理的气凝胶的制备方法，其特征在于：所述化学交联为在温度为50℃下静置至少24小时。
6.根据权利要求1～5任一项所述用于放射性废水处理的气凝胶的制备方法，其特征在于，具体步骤如下：
将海藻酸钠与多酚化合物按质量比为2：1在水中溶解，加入相当于多酚化合物质量0.5倍的碳酸钙充分混匀后再加入与多酚化合物等量的葡萄糖酸内酯充分混合，静置得水凝胶，然后将水凝胶依次置于体积分数为60％的丙酮水溶液和丙酮中进行溶剂置换，然后加入异氰酸酯质量分数为50％的丙酮溶液，静置至少24小时后，加温至50℃静置72小时进行化学交联，再置于丙酮中静置，干燥制得气凝胶。
7.由权利要求1～6任一项所述的制备方法制得的用于放射性废水处理的气凝胶。
8.权利要求7所述气凝胶用于金属阳离子的吸附剂中的应用。
9.权利要求7所述气凝胶用于处理放射性废水中的应用。
10.根据权利要求9所述的应用，其特征在于：所述放射性废水为含铀、锶放射性废水。
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