CN109012621B - 一种重金属离子吸附和检测型复合水凝胶纤维 - Google Patents

一种重金属离子吸附和检测型复合水凝胶纤维 Download PDF

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CN109012621B
CN109012621B CN201811120275.3A CN201811120275A CN109012621B CN 109012621 B CN109012621 B CN 109012621B CN 201811120275 A CN201811120275 A CN 201811120275A CN 109012621 B CN109012621 B CN 109012621B
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赵义平
文梦娟
姜文哲
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Tianjin Jinlin Water Treatment Science & Technology Co ltd
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Abstract

本发明公开了一种重金属离子吸附和检测型复合水凝胶纤维，属于高分子材料领域。本发明产品其特征在于既可以有效地对水中的重金属离子进行定性检测，又可吸附水中的重金属离子。本发明产品对废水中低浓度镍、铬、铅、汞等重金属离子的吸附去除率均达到90％以上。本发明产品制备不需要特殊设备、工业化实施容易，产品成本不高。本发明所述复合凝胶纤维产品应用方便，可集束使用，也可编织成织物或组装成分离组件。本发明产品吸附重金属离子后，可通过清洗液清洗高效回收吸附的重金属离子，可一次性洗脱掉95％以上所吸附的重金属离子，纤维可以重复使用。

Description

一种重金属离子吸附和检测型复合水凝胶纤维
本申请是以下申请的分案申请：申请日为2016年12月07日，申请号为201611116739.4，发明名称为一种重金属离子吸附和检测型复合水凝胶纤维及其制备方法。
技术领域
本发明涉及高分子材料领域，具体涉及一种对镍、铬、铅、汞等重金属离子具有良好检测功能和吸附功能的复合高分子水凝胶纤维及其制备方法。该复合水凝胶既可以有效地对水中的常规重金属离子进行定性检测，又可以吸附水中的重金属离子，可应用于电镀工业、化学工业等污水的处理领域。
背景技术
随着化学工业和冶金工业等的快速发展，重金属离子污染对人体产生严重危害。目前，无害化处理含重金属离子废水的主要方法有膜分离法、电化学沉淀法、离子交换法、吸附及生物处理法等。其中，吸附法对重金属离子的去除率高，吸附量大，吸附速率快，操作简便。但是，可吸附重金属离子的吸附剂一般价格都较为昂贵。因此，用价格低廉的材料复合改性现有吸附剂开发低成本和高吸附效率的新型吸附剂，是可吸附重金属离子的吸附剂研究的一个重要方向。
凹凸棒土(ATP)作为一种天然非金属矿物质材料，是一种具有链层状结构的含水富镁硅酸盐粘土矿物，其特殊的结构使其具有很大的比表面积，物理吸附能力很强；另一方面，凹凸棒土带有层面负电荷，在层间吸附了具有可交换性的阳离子以使电荷平衡，这样凹凸棒土就具有了强的离子吸附交换能力，可以应用到含重金属离子的废水处理中。但是，凹凸棒土在水中有很好的悬浮性，尽管其具有很好的吸附能力，对于水处理领域来说，粉末状的凹凸棒土无法直接投入水中使用，需要采取一定的方法进行处理。目前，较好的处理方法是采用一定的载体固载凹凸棒土，再投入水中使用。本发明人在前期发明中公开了一种吸附型高分子复合水凝胶的制备方法及其产品(专利号ZL201020595998.1)，利用高分子水凝胶作载体，固载凹凸棒土，从而很好地发挥凹凸棒土的吸附作用。另外，公开了一种对重金属离子吸附量大、吸附效率高的壳聚糖复合絮凝剂的制备方法及其产品(CN103274509A)。
海藻酸钠(SA)是无臭、无味、淡黄色不定形粉末，性能优良，在食品、纺织、医药及日用化工等众多领域有着广泛应用，易于在钙离子溶液中形成海藻酸钙(CA)凝胶，对重金属离子有良好吸附性能。Guerra D L等将天然ATP改性加入到海藻酸钙薄膜中制备了杂化复合薄膜，研究了杂化膜对Th的吸附性能【Guerra D L,Viana R R,da Costa L P,etal.RETRACTED:Sodium alginate films modified by raw and functionalizedattapulgite for use of thorium(IV)adsorption:A thermodynamic approach[J].Journal of Physics and Chemistry of Solids,2009,70(11):1413-1421.】。Li Y等将碳纳米管固定于海藻酸钙中，制备出纤维状复合凝胶，研究结果表明，纤维状凝胶可增加其比表面积，提高对铜离子的吸附性能【Li Y,Liu F,Xia B,et al.Removal of copper fromaqueous solution by carbon nanotube/calcium alginate composites[J].Journal ofHazardous Materials,2010,177(1):876-880.】。因此，用海藻酸钙凝胶为载体包覆、固定凹凸棒土，可充分利用其良好的吸附性能和优良成形性的特点，协同凹凸棒土的重金属离子吸附作用，制备重金属离子吸附型凝胶材料。
但是，目前重金属离子吸附材料一般只具有单一的重金属离子吸附功能，不能同时对重金属离子进行检测。国内外很多科研工作者致力于重金属离子污染研究，设计一种既具良好的吸附性能又可现场快速检测重金属存在的吸附材料仍是一项挑战。
碳量子点(CD)无毒或低毒、分子量低、粒径小、造价低廉，具有非常奇特的化学和物理性质且拥有强烈的荧光性、水溶性和生物相容性等，可应用于生物成像、医学诊断、催化剂、光伏器件中，同时易于被金属离子淬灭的特性近年来引起研究者们的极大关注，用以对重金属离子的检测应用中。Gogoi N等将壳聚糖碳点溶液与明胶液混合，微波成型，制备出明胶/碳点杂化平板膜，研究了对重金属的分离和检测性能【Gogoi N,Barooah M,Majumdar G,et al.Carbon dots rooted agarose hydrogel hybrid platform foroptical detection and separation of heavy metal ions[J].ACS appliedmaterials&interfaces,2015,7(5):3058-3067.】。但总体来说，水处理领域中探索同时具备吸附和检测重金属离子的材料还不多，即吸附和荧光检测型复合材料具有很大应用前景。
发明内容
针对现有技术的不足，本发明拟解决的技术问题是提供一种可同时吸附和监测重金属离子的高分子水凝胶的制备方法。该复合水凝胶为一种海藻酸钙/凹凸棒土/碳点复合水凝胶纤维，既可以有效地对水中的常规重金属离子进行定性检测，又可以吸附水中的重金属离子。
本发明所述产品采用海藻酸钠和凹凸棒土为原料，采用湿法纺丝工艺制备纺制出纤维，在钙离子溶液中可交联形成海藻酸钙水凝胶纤维CA/ATP。本发明所述产品采用市售碳点，用偶联剂3-缩水甘油基氧基丙基三甲氧基硅烷(KH560)对其进行改性处理，制备出KH560改性碳点。
本发明所述重金属离子吸附和检测型复合水凝胶纤维由以下方法制得：
(1)CA/ATP复合凝胶的制备。将一定量SA溶解于100g去离子水中，配成浓度为1％～5％的SA溶液。向SA溶液中加入SA含量10％～50％的ATP，搅拌使得ATP在溶液中充分分散，得到纺丝液。将纺丝液倒入湿法纺丝机料釜内，密封纺丝机料釜，加热纺丝机料釜，使纺丝料液温度在25℃～50℃，静置12小时，然后抽真空脱泡处理20～60分钟。纺丝料液脱泡处理完毕后，打开料釜出口开关，向釜内通入氮气加压，打开计量泵开关，调整转速8～20转/分钟，开始纺丝。纺出的丝快速注入浓度为1％～5％的CaCl2溶液中，交联凝固10h～15h成型，得到纤维状CA/ATP水凝胶。产物用蒸馏水不断洗涤，以除去产物表面的Ca2+。洗涤所得水凝胶产物后进行冷冻干燥，备用。
(2)KH560改性碳点的制备。称取一定质量的CD固体，将其溶解于去离子水中，配成溶液浓度为1～5mg/mL的CD溶液。添加一定量的KH560于碳点水溶液中，KH560的添加量为CD溶液体积的5％～20％。20℃～50℃下均匀搅拌15～30h，得到CD-KH560溶液。
(3)CA/ATP/CD复合凝胶制备。称取10mg步骤(1)中所制备CA/ATP纤维状凝胶，按CA/ATP复合凝胶1％～5％的质量比计算称取一定体积的步骤(2)所制备的CD-KH560溶液，将纤维状凝胶浸入CD-KH560溶液中，20℃～40℃摇床中避光震荡6h～24h，所得产物蒸馏水洗三次后冷冻干燥，即得本发明一种重金属离子吸附和检测型CA/ATP/CD复合水凝胶纤维。
有益效果：
本发明所制备的是监测和去除重金属离子的复合凝胶，采用的是共混和表面接枝法，该复合凝胶纤维产品可同时吸附和监测重金属离子，且重金属离子吸附性优良，荧光淬灭性突出，是一种新型海藻酸钙复合水凝胶产品。本发明所述复合凝胶纤维产品在重金属离子溶液中荧光呈现减弱或淬灭作用，此种响应性可对水质达到实时监测目的。本发明所述复合凝胶纤维产品对低浓度镍、铬、铅、汞等重金属离子的吸附去除率均达到90％以上。因此，本发明产品不仅对重金属离子有优良的去除作用，还能对水质中的重金属离子有实时监测作用
与现有技术相比，本发明复合凝胶制备方法具有工艺简单、不需要特殊设备、工业化实施容易。本发明产品技术CA对ATP有较大的包覆量，从而产品成本低，而且材料间相容性良好。
本发明所述凹凸棒土作为一种天然非金属无机矿物质材料，价格低廉，储藏丰富。本发明所述碳点为普通市售碳点。采用本发明技术，ATP可很容易表面接枝CD。
本发明所述复合凝胶纤维产品机械性能良好，应用方便，可集束使用，也可以编织成织物，或组装成分离组件。本发明所述纤维吸附重金属离子后，可通过清洗液清洗高效回收吸附的重金属离子，可一次性洗脱掉95％以上所吸附的重金属离子，纤维可以重复使用。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应该理解，这些实施例仅用于说明本发明而不是用于限制本发明的范围。除非特别说明，实施方式中未描述的技术手段均可以用本领域技术人员所公知的方式实现。对于本领域技术人员而言，在不背离本发明实质和范围的前提下，对这些实施方案中的常规变量的各种修改、替换、改进，这些等价形式也同样落于本申请所附权利要求书所限定的范围。特别说明，本发明所限定的具体参数应有可允许的误差范围。
实施例1
(1)CA/ATP复合凝胶的制备。将一定量SA溶解于100g去离子水中，配成浓度为1％的SA溶液。向SA溶液中加入SA含量10％的ATP，搅拌使得ATP在溶液中充分分散，得到纺丝液。将纺丝液倒入湿法纺丝机料釜内，密封纺丝机料釜，加热纺丝机料釜，使纺丝料液温度在25℃，静置12小时，然后抽真空脱泡处理20分钟。纺丝料液脱泡处理完毕后，打开料釜出口开关，向釜内通入氮气加压，打开计量泵开关，调整转速8转/分钟，开始纺丝。纺出的丝快速注入浓度为1％的CaCl2溶液中，交联凝固10h成型，得到纤维状CA/ATP水凝胶。产物用蒸馏水不断洗涤，以除去产物表面的Ca2+。洗涤所得水凝胶产物后进行冷冻干燥，备用。
(2)KH560改性碳点的制备。称取一定质量的CD固体，将其溶解于去离子水中，配成溶液浓度为1mg/mL的CD溶液。添加一定量的KH560于碳点水溶液中，KH560的添加量为CD溶液体积的5％。20℃下均匀搅拌15h，得到CD-KH560溶液。
(3)CA/ATP/CD复合凝胶制备。称取10mg步骤(1)中所制备CA/ATP纤维状凝胶，按CA/ATP复合凝胶1％的质量比计算称取一定体积的步骤(2)所制备的CD-KH560溶液，将纤维状凝胶浸入CD-KH560溶液中，20℃摇床中避光震荡6h，所得产物蒸馏水洗三次后冷冻干燥，即得本发明一种重金属离子吸附和检测型CA/ATP/CD复合水凝胶纤维。
实施例2
(1)CA/ATP复合凝胶的制备。将一定量SA溶解于100g去离子水中，配成浓度为2％的SA溶液。向SA溶液中加入SA含量20％的ATP，搅拌使得ATP在溶液中充分分散，得到纺丝液。将纺丝液倒入湿法纺丝机料釜内，密封纺丝机料釜，加热纺丝机料釜，使纺丝料液温度在30℃，静置12小时，然后抽真空脱泡处理30分钟。纺丝料液脱泡处理完毕后，打开料釜出口开关，向釜内通入氮气加压，打开计量泵开关，调整转速10转/分钟，开始纺丝。纺出的丝快速注入浓度为2％的CaCl2溶液中，交联凝固10h成型，得到纤维状CA/ATP水凝胶。产物用蒸馏水不断洗涤，以除去产物表面的Ca2+。洗涤所得水凝胶产物后进行冷冻干燥，备用。
(2)KH560改性碳点的制备。称取一定质量的CD固体，将其溶解于去离子水中，配成溶液浓度为2mg/mL的CD溶液。添加一定量的KH560于碳点水溶液中，KH560的添加量为CD溶液体积的8％。20℃下均匀搅拌15h，得到CD-KH560溶液。
(3)CA/ATP/CD复合凝胶制备。称取10mg步骤(1)中所制备CA/ATP纤维状凝胶，按CA/ATP复合凝胶2％的质量比计算称取一定体积的步骤(2)所制备的CD-KH560溶液，将纤维状凝胶浸入CD-KH560溶液中，20℃摇床中避光震荡10h，所得产物蒸馏水洗三次后冷冻干燥，即得本发明一种重金属离子吸附和检测型CA/ATP/CD复合水凝胶纤维。
实施例3
(1)CA/ATP复合凝胶的制备。将一定量SA溶解于100g去离子水中，配成浓度为3％的SA溶液。向SA溶液中加入SA含量30％的ATP，搅拌使得ATP在溶液中充分分散，得到纺丝液。将纺丝液倒入湿法纺丝机料釜内，密封纺丝机料釜，加热纺丝机料釜，使纺丝料液温度在40℃，静置12小时，然后抽真空脱泡处理40分钟。纺丝料液脱泡处理完毕后，打开料釜出口开关，向釜内通入氮气加压，打开计量泵开关，调整转速12转/分钟，开始纺丝。纺出的丝快速注入浓度为1％的CaCl2溶液中，交联凝固15h成型，得到纤维状CA/ATP水凝胶。产物用蒸馏水不断洗涤，以除去产物表面的Ca2+。洗涤所得水凝胶产物后进行冷冻干燥，备用。
(2)KH560改性碳点的制备。称取一定质量的CD固体，将其溶解于去离子水中，配成溶液浓度为5mg/mL的CD溶液。添加一定量的KH560于碳点水溶液中，KH560的添加量为CD溶液体积的20％。50℃下均匀搅拌30h，得到CD-KH560溶液。
(3)CA/ATP/CD复合凝胶制备。称取10mg步骤(1)中所制备CA/ATP纤维状凝胶，按CA/ATP复合凝胶3％的质量比计算称取一定体积的步骤(2)所制备的CD-KH560溶液，将纤维状凝胶浸入CD-KH560溶液中，40℃摇床中避光震荡24h，所得产物蒸馏水洗三次后冷冻干燥，即得本发明一种重金属离子吸附和检测型CA/ATP/CD复合水凝胶纤维。
实施例4
(1)CA/ATP复合凝胶的制备。将一定量SA溶解于100g去离子水中，配成浓度为3％的SA溶液。向SA溶液中加入SA含量40％的ATP，搅拌使得ATP在溶液中充分分散，得到纺丝液。将纺丝液倒入湿法纺丝机料釜内，密封纺丝机料釜，加热纺丝机料釜，使纺丝料液温度在50℃，静置12小时，然后抽真空脱泡处理20分钟。纺丝料液脱泡处理完毕后，打开料釜出口开关，向釜内通入氮气加压，打开计量泵开关，调整转速20转/分钟，开始纺丝。纺出的丝快速注入浓度为4％的CaCl2溶液中，交联凝固12h成型，得到纤维状CA/ATP水凝胶。产物用蒸馏水不断洗涤，以除去产物表面的Ca2+。洗涤所得水凝胶产物后进行冷冻干燥，备用。
(2)KH560改性碳点的制备。称取一定质量的CD固体，将其溶解于去离子水中，配成溶液浓度为4mg/mL的CD溶液。添加一定量的KH560于碳点水溶液中，KH560的添加量为CD溶液体积的15％。40℃下均匀搅拌20h，得到CD-KH560溶液。
(3)CA/ATP/CD复合凝胶制备。称取10mg步骤(1)中所制备CA/ATP纤维状凝胶，按CA/ATP复合凝胶3％的质量比计算称取一定体积的步骤(2)所制备的CD-KH560溶液，将纤维状凝胶浸入CD-KH560溶液中，30℃摇床中避光震荡12h，所得产物蒸馏水洗三次后冷冻干燥，即得本发明一种重金属离子吸附和检测型CA/ATP/CD复合水凝胶纤维。
实施例5
(1)CA/ATP复合凝胶的制备。将一定量SA溶解于100g去离子水中，配成浓度为5％的SA溶液。向SA溶液中加入SA含量50％的ATP，搅拌使得ATP在溶液中充分分散，得到纺丝液。将纺丝液倒入湿法纺丝机料釜内，密封纺丝机料釜，加热纺丝机料釜，使纺丝料液温度在35℃，静置12小时，然后抽真空脱泡处理60分钟。纺丝料液脱泡处理完毕后，打开料釜出口开关，向釜内通入氮气加压，打开计量泵开关，调整转速20转/分钟，开始纺丝。纺出的丝快速注入浓度为5％的CaCl2溶液中，交联凝固15h成型，得到纤维状CA/ATP水凝胶。产物用蒸馏水不断洗涤，以除去产物表面的Ca2+。洗涤所得水凝胶产物后进行冷冻干燥，备用。
(2)KH560改性碳点的制备。称取一定质量的CD固体，将其溶解于去离子水中，配成溶液浓度为5mg/mL的CD溶液。添加一定量的KH560于碳点水溶液中，KH560的添加量为CD溶液体积的20％。40℃下均匀搅拌24h，得到CD-KH560溶液。
(3)CA/ATP/CD复合凝胶制备。称取10mg步骤(1)中所制备CA/ATP纤维状凝胶，按CA/ATP复合凝胶5％的质量比计算称取一定体积的步骤(2)所制备的CD-KH560溶液，将纤维状凝胶浸入CD-KH560溶液中，30℃摇床中避光震荡18h，所得产物蒸馏水洗三次后冷冻干燥，即得本发明一种重金属离子吸附和检测型CA/ATP/CD复合水凝胶纤维。

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1.一种重金属离子吸附和检测型复合水凝胶纤维，其特征在于所述重金属离子吸附和检测型复合水凝胶纤维的制备方法如下：
(1)海藻酸钙/凹凸棒土复合凝胶的制备：将一定量海藻酸钠溶解于100g去离子水中，配成浓度为3％的海藻酸钠溶液；向海藻酸钠溶液中加入海藻酸钠含量30％的凹凸棒土，搅拌使得凹凸棒土在溶液中充分分散，得到纺丝液；将纺丝液倒入湿法纺丝机料釜内，密封纺丝机料釜，加热纺丝机料釜，使纺丝料液温度在40℃，静置12小时，然后抽真空脱泡处理40分钟；纺丝料液脱泡处理完毕后，打开料釜出口开关，向釜内通入氮气加压，打开计量泵开关，调整转速12转/分钟，开始纺丝；纺出的丝快速注入浓度为1％的CaCl2溶液中，交联凝固15h成型，得到纤维状海藻酸钙/凹凸棒土水凝胶；产物用蒸馏水不断洗涤，以除去产物表面的Ca2+；洗涤所得水凝胶产物后进行冷冻干燥，备用；
(2)3-缩水甘油基氧基丙基三甲氧基硅烷KH560改性碳点的制备：称取一定质量的碳量子点固体，将其溶解于去离子水中，配成溶液浓度为5mg/mL的碳量子点溶液；添加一定量的3-缩水甘油基氧基丙基三甲氧基硅烷KH560于碳量子点水溶液中，3-缩水甘油基氧基丙基三甲氧基硅烷KH560的添加量为碳量子点溶液体积的20％；50℃下均匀搅拌30h，得到碳量子点-3-缩水甘油基氧基丙基三甲氧基硅烷KH560溶液；
(3)海藻酸钙/凹凸棒土/碳量子点复合凝胶制备：称取10mg步骤(1)中所制备海藻酸钙/凹凸棒土纤维状凝胶，按海藻酸钙/凹凸棒土复合凝胶3％的质量比计算称取一定体积的步骤(2)所制备的碳量子点-3-缩水甘油基氧基丙基三甲氧基硅烷KH560溶液，将纤维状凝胶浸入碳量子点-3-缩水甘油基氧基丙基三甲氧基硅烷KH560溶液中，40℃摇床中避光震荡24h，所得产物蒸馏水洗三次后冷冻干燥，即得一种重金属离子吸附和检测型海藻酸钙/凹凸棒土/碳量子点复合水凝胶纤维。
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CN105214635B (zh) * 2015-10-26 2019-03-05 上海理工大学 一种复合光催化剂及其制备方法和应用
CN105921125A (zh) * 2016-06-16 2016-09-07 江苏麦阁吸附剂有限公司 一种凹土/海藻酸钠复合型重金属吸附剂及其制备方法
CN106007006B (zh) * 2016-07-14 2019-04-30 济宁学院 一种用于重金属有机废水的微生物水处理剂
CN106076214B (zh) * 2016-07-15 2019-12-17 沈阳化工大学 一种具有核壳结构的海藻酸钙微球制备方法

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