CN114960182B - 一种抗生物粘附复合多孔水凝胶材料及其制备方法和在处理含重金属离子废水中的应用 - Google Patents
一种抗生物粘附复合多孔水凝胶材料及其制备方法和在处理含重金属离子废水中的应用 Download PDFInfo
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Abstract
本发明公开了一种抗生物粘附复合多孔水凝胶材料的制备方法，包括将70mg聚偕胺肟溶解于氢氧化钠溶液中，随后依次加入40mg磺基甜菜碱甲基丙烯酸酯、30mg聚(乙二醇)二丙烯酸酯和1mg 2‑羟基‑2‑甲基‑1‑[4‑(2‑羟基乙氧基)苯基]‑1‑丙酮充分搅拌溶解获得混合液，后将碱化的聚酯纤维过滤棉完全浸入混合液中，最后置于密封模具中并在紫外灯下光照聚合获得FC/ZW‑PAO复合水凝胶。采用本发明方法制备的过滤棉/两性离子‑聚偕胺肟复合多孔水凝胶，不仅在保持良好的抗生物粘附性能的同时具有更高的力学强度，拉伸强度可从0.23MPa提升到6.93MPa，可重复利用；且在模拟重金属废水中对钒和铀酰离子有较好的选择吸附性，吸附平衡效率显著提高。
Description
技术领域
本发明涉及废水处理用新材料领域，尤其涉及一种抗生物粘附复合多孔水凝胶材料及其制备方法和其在处理含重金属离子废水中的应用。
背景技术
由于科技以及工业的发展，水污染问题已经受到极大的关注，而水污染问题中较为典型的是重金属(HM)污染。含有重金属的废水在排放过程中，不仅污染环境，也是资源浪费，尤其是通过食物链进入人体还会对人体造成伤害。本着生态保护和经济效益角度，对废水中的重金属进行处理回收势在必行。
目前重金属处理技术应用最广泛的是吸附法，一般是将溶解状态的重金属离子转变为不溶性化合物沉淀，从而分离回收，但工业上普遍使用的吸附剂价格昂贵或效果不佳，限制了其应用。近几年，有学者陆续研究出含有羟基、氨基、磺酸基或羧基等功能高分子材料，以提升重金属离子的吸附量和吸附选择性。如偕胺肟化合物以其对金属离子优秀的螯合性能使其在多种重金属离子的提取回收和含重金属污水的净化处理等领域得到了良好的应用，如海南大学前期研究了一种水溶性偕胺肟基聚合物及其制备方法和应用(专利号：CN201910017858.1)，可选择性吸附多种重金属离子，但由于其力学性能差，难以工业化应用。
由于废水中重金属离子(包含V、U、Cu、Zn等)组成复杂而浓度较低，提取困难，尤其是真实废水中大量的微生物在吸附剂表面粘附和生长，产生严重的生物污损阻碍重金属离子的重复高效提取。因此有必要研究一种可高效吸附废水中重金属离子的抗生物粘附复合多孔水凝胶材料。
发明内容
有鉴于此，本发明提供了一种抗生物粘附复合多孔水凝胶材料，解决现有吸附剂由于真实废水中大量的微生物在吸附剂表面粘附和生长，产生严重的生物污损阻碍重金属离子不能高效处理或提取、或其力学性能差导致不能重复使用问题。
本发明一方面采用一种抗生物粘附复合多孔水凝胶材料的制备方法，包括将70mg聚偕胺肟溶解于氢氧化钠溶液中，随后依次加入40mg磺基甜菜碱甲基丙烯酸酯、30mg聚(乙二醇)二丙烯酸酯和1mg 2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮充分搅拌溶解获得混合液，后将碱化的聚酯纤维过滤棉完全浸入混合液中，最后置于密封模具中并在紫外灯下光照聚合获得FC/ZW-PAO复合水凝胶。
优选地，碱化的聚酯纤维由以下方法制备而得：将聚酯纤维过滤棉浸没于无水乙醇中超声处理30min，后放入烘箱中烘干，再将过滤棉片置于质量浓度为10％的氢氧化钠溶液中并在70℃下处理40min，最后取出后洗涤至中性并烘干后备用。
优选地，聚偕胺肟由以下方法制备而得：称量5.6g NH2OH·HCl溶解于60mL DMF中，后加入4.12g Na2CO3和1.6g的NaOH,在45℃的水浴锅中搅拌1h后，缓慢加入4g的PAN，溶解5min，后将水浴锅的温度升高到65℃反应24h；再加入30mL DMF和2.8g NH2OH·HCl充分溶解后，依次加入2.06g Na2CO3和0.8g NaOH，隔10min后拧紧盖子反应24h，对混合液进行离心分离，在无水乙醇中缓慢滴入离心后的上清液获得白色絮状沉淀，经过过滤洗涤后，置于真空干燥箱内60℃下干燥过夜，得到产物PAO。
另一方面提供抗生物粘附复合多孔水凝胶材料及该材料在处理含重金属离子废水中的应用。
本发明一方面提供的FC/ZW-PAO复合水凝胶的制备方法，先利用高温浸碱法对聚酯纤维过滤棉进行处理，使其表面出现大量羟基，使凝胶与纤维结合的更牢固；后使用氢氧化钠溶液溶解两性离子单体和聚偕胺肟，再将碱处理过的聚酯纤维浸入前驱液中，在引发剂和交联剂的作用下进行紫外光聚合，使两性离子-聚偕胺肟水凝胶包裹在具有多孔结构的聚酯纤维骨架上，方法简易，易于工业化推广。
另一方面利用本方法制备了一种抗生物粘附型两性离子-聚偕胺肟(ZW-PAO)复合水凝胶吸附剂，既通过两性离子固有的“反聚电解质效应”，增强了水凝胶在废水中的溶胀能力，又通过离子-偶极相互作用在凝胶表面形成致密的水合层，使其拥有了优异的抵抗微生物、贝类等海洋生物粘附的性能，从而在废水中可保持较长时期的重金属吸附性能。尤其是与ZW-PAO水凝胶相比，本发明凝胶材料不仅在保持良好的抗生物粘附性能的同时具有更高的力学强度，拉伸强度可从0.23MPa提升到6.93MPa；基于该FC/ZW-PAO复合水凝胶的多孔结构，可基于过滤废水实现快速高效的重金属废水处理性能：其中在模拟废水中仅5h便可接近达到吸附平衡，比原先无孔ZW-PAO水凝胶的吸附速率提升了2.5倍左右，说明该FC/ZW-PAO多孔复合水凝胶可望在未来实现高效、低成本且大规模的含重金属离子废水处理工业应用。
附图说明
图1为本发明的FC/ZW-PAO复合水凝胶的制备流程示意图；
图2为实施例一制备的FC/ZW-PAO复合水凝胶以及PAO和PAN的红外光谱图；
图3为聚酯纤维过滤棉(a和c)和FC/ZW-PAO复合水凝胶(b和d)的扫描电镜图和EDS-Mapping图；
图4为聚酯纤维、FC/ZW-PAO复合水凝胶和ZW-PAO水凝胶的力学强度对比；
图5为聚酯纤维和FC/ZW-PAO复合水凝胶的接触角变化测试结果；
图6为FC/ZW-PAO复合水凝胶在模拟废水中的离子选择性测试；
图7为过滤棉(a)和FC/ZW-PAO复合水凝胶(b)的抗生物(大肠杆菌和金黄色葡萄球菌)粘附测试结果菌落数的统计结果；
图8为FC/ZW-PAO复合水凝胶在是否添加细菌的模拟废水中吸附效果对比；
图9为FC/ZW-PAO复合水凝胶在32ppm模拟废水中的吸附动力学曲线；
图10为FC/ZW-PAO复合水凝胶在模拟废水中的吸附过程示意图。
具体实施方式
以下对本发明的原理和特征进行描述，所举实施例只用于解释本发明，并非用于限定本发明的范围。
本专利涉及的聚酯纤维过滤棉(DF1-3500)购自于东莞市莞郦无纺科技有限公司，磺基甜菜碱甲基丙烯酸酯购自于美国默克公司，聚(乙二醇)二丙烯酸酯购自于上海麦克林生化科技有限公司，2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮购自于北京百灵威科技有限公司。
实施例一：如图1，FC/ZW-PAO复合水凝胶的制备方法，包括以下步骤：
(1)聚酯纤维碱化处理：将聚酯纤维过滤棉裁成3cm×3cm×0.5mm的薄片，浸没于无水乙醇中超声处理30min，后放入烘箱中烘干，再将过滤棉片置于质量浓度为10％的氢氧化钠溶液中，在70℃下处理40min，最后取出后用超纯水多次洗涤至中性，烘干后备用。
(2)聚偕胺肟(PAO)的制备：
称量5.6g NH2OH·HCl溶解于60mL DMF中，完全溶解后，加入4.12g Na2CO3和1.6g的NaOH,在45℃的水浴锅中搅拌1h后，缓慢加入4g的PAN，溶解5min，后将水浴锅的温度升高到65℃反应24h；再加入30mL DMF和2.8g NH2OH·HCl，充分溶解后，依次加入2.06g Na2CO3和0.8g的NaOH，隔10min后拧紧盖子，反应24h后，对混合液进行离心分离，转速为10000r/min，在无水乙醇中缓慢滴入离心后的上清液，可以看到有白色絮状沉淀。沉淀物经过过滤洗涤后，置于真空干燥箱内60℃下干燥过夜，取出后磨成细粉，得到产物PAO。
(3)将70mg步骤(2)制备的聚偕胺肟溶解于1mL氢氧化钠溶液(浓度为0.5mol/L)中，随后依次加入40mg磺基甜菜碱甲基丙烯酸酯(SBMA/两性离子单体)、30mg聚(乙二醇)二丙烯酸酯(PEGDA/交联剂)和1mg2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮(I-2959，光引发剂)充分搅拌溶解获得混合液，后将碱化的聚酯纤维完全浸入混合液中，取出后轻轻挤压出多余的溶液防止交联后堵塞孔道，最后将置于石英玻璃和硅橡胶组成的密封模具中，在紫外灯下光照聚合30min，得到FC/ZW-PAO复合水凝胶。
对比例一：对比例一和实施例一的区别在于未加入碱化的聚酯纤维进行复合，ZW-PAO水凝胶具体由以下方法制备而得：将70mg实施例一步骤(2)制备的聚偕胺肟溶解于1mL氢氧化钠溶液(浓度为0.5mol/L)中，随后依次加入40mg磺基甜菜碱甲基丙烯酸酯(SBMA/两性离子单体)、30mg聚(乙二醇)二丙烯酸酯(PEGDA/交联剂)和1mg 2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮(I-2959，光引发剂)充分搅拌溶解获得混合液，将混合液置于石英玻璃和硅橡胶组成的密封模具中，在紫外灯下光聚30min，得到FC/ZW-PAO复合水凝胶。
对实施例一制备的FC/ZW-PAO复合水凝胶进行表征及性能测试，结果如下：
(1)使用傅里叶红外光谱仪(FTIR)对FC/ZW-PAO复合水凝胶、PAO和PAN进行表征，结果如图2，从红外光谱中可以看出，PAN在2246cm-1处的氰基(-C≡N)特征吸附峰在肟化反应后完全消失，被1659cm-1(-C＝N)和941cm-1(-N-O)处的两个特征吸附峰取代，这证明PAN已完全转化成PAO。此外在FC/ZW-PAO复合水凝胶上也能明显的看到-C＝N和-N-O的两个特征峰，这证明我们已经成功的将PAO制备到了水凝胶上。
(2)使用场发射扫描电镜对原始的过滤棉和FC/ZW-PAO复合水凝胶进行表征，结果如图3所示，可清晰的看到与原始的过滤棉相比，FC/ZW-PAO表面(图3b)复合有一层凝胶，且EDS-Mapping图(图3d)证明了其表面出现了S元素，证明多孔FC/ZW-PAO复合水凝胶成功制备，孔径均匀。
(3)使用拉力测试仪测试了原始过滤棉、FC/ZW-PAO复合水凝胶和ZW-PAO水凝胶的力学强度，如图4所示，ZW-PAO水凝胶的力学性能较差，拉伸强度仅有0.23±0.02MPa(厚度500±10μm)，利用具有较高的拉伸强度(12.67±1.49MPa)的原始过滤棉(厚度200±5μm)可以显著增强其力学性能，FC/ZW-PAO复合水凝胶(500±20μm)的拉伸强度可以达到6.93±0.74MPa，能够抵抗废水中恶劣的环境，从而保证其能在废水中长时间、可持续的吸附重金属离子。
(4)使用接触角测量仪测试原始过滤棉和FC/ZW-PAO复合水凝胶的亲水性，结果如图5所示，原始的过滤棉在0.4s和8.0s后的接触角分别为85.17°和83.16°，FC/ZW-PAO在0.4s和8.0s后的接触角分别为36.68°和15.03°，有利于废水中金属离子的捕获。说明实施例一的FC/ZW-PAO复合水凝胶具有良好的亲水性，对于金属离子在凝胶中的运动具有积极的正向作用。
(5)测定FC/ZW-PAO复合水凝胶在模拟废水中的离子选择性吸附性能，选取了十种常见重金属离子元素(钒(V)、铀(U)、铅(Pb)、镉(Cd)、铬(Cr)、铁(Fe)、镍(Ni)、钴(Co)、铜(Cu)、锌(Zn)等)，其中各离子的浓度均为100ppb，使用图10装置进行吸附测试，实验所用模拟废水的体积为10L，FC/ZW-PAO凝胶质量为2.5g(其中可以吸附重金属的ZW-PAO凝胶质量为500±50mg)，如图6结果可知，可以看到FC/ZW-PAO复合水凝胶对钒、铀、铜、锌离子均具有吸附性，尤其是对铀离子和钒离子具有较强的选择性螯合能力。
(6)FC/ZW-PAO复合水凝胶的抗生物粘附性能测试
废水中存在大量的细菌和藻类微生物，它们容易粘附在吸附剂表面并快速生长，从而阻挡了吸附剂对铀离子的吸附，这严重限制了吸附剂的长期使用，两性离子水凝胶可以与水分子通过离子-偶极作相互用形成致密的水合层，具有优异的抗生物粘附效果。为了验证FC/ZW-PAO复合水凝胶的抗生物粘附的能力，本文以E.coli和S.aureus为模型细菌，将粘附在过滤棉和凝胶表面的细菌超声到PBS溶液中，稀释后进行培养并统计菌落数量。从图7(a)中可以看出，FC/ZW-PAO复合水凝胶表面粘附的细菌远少于疏水的过滤棉表面。对菌落数进行统计计算得到图7(b)，结果表明FC/ZW-PAO复合水凝胶的抗生物粘附(以细菌为例)能力远高于原始的过滤棉，这说明FC/ZW-PAO复合多孔水凝胶在复杂的废水环境中可以抵抗生物粘附，从而可望在废水中可以较长时间高效吸附钒、铀、铜、锌等离子。
为了进一步模拟FC/ZW-PAO复合水凝胶在真实废水中对V、U、Cu、Zn的吸附，如图8，在模拟废水中添加最终浓度为102CFU/mL的E.coli，在经过24h的循环吸附后，与未添加细菌的模拟废水相比吸附量误差在10％内，说明FC/ZW-PAO复合水凝胶具有良好的抗生物粘附性。
(7)测定FC/ZW-PAO复合水凝胶在高浓度重金属离子模拟废水中的吸附测试
取100mg的FC/ZW-PAO复合水凝胶(其中能吸附重金属的ZW-PAO水凝胶质量约为20mg，在含有32ppm V、U、Cu、Zn的模拟废水中(1L)吸附8h，定时取样得到如图9所示的吸附动力学曲线。在约5h时，FC/ZW-PAO复合多孔水凝胶在模拟废水中不同重金属均可达饱和吸附，吸附量分别为601±18mg/g(V)、544±15mg/g(U)、129±8mg/g(Cu)和67±8mg/g(Zn)，其吸附效率是原来无孔ZW-PAO复合水凝胶(厚0.5mm)的2.5倍左右。
(8)基于FC/ZW-PAO复合水凝胶的循环过滤提取重金属离子装置的设计和应用
为了验证本发明材料对含有重金属离子废水的处理能力，我们设计了一款循环过滤废水处理装置如图10，可望用于未来较大规模的废水处理。过滤器主要由盖子、分水挡板、滤芯和壳体组成，分水挡板为实心圆盘状，只有边缘开有四个小孔，可控制水流只流向圆柱型滤芯的外围，随后在水压的作用下，水流从圆柱滤芯的外围渗透进内层，以达到过滤水的目的。该过滤器的关键点在于分水挡板可以控制水流仅充斥在滤芯的外围，随后渗透进内层，这增加了水流与滤芯的接触面积，有利于用来高效快速的过滤废水。
综上所述，采用本发明所提供的过滤棉/两性离子-聚偕胺肟(FC/ZW-PAO)复合多孔水凝胶。与ZW-PAO水凝胶相比，该凝胶在保持良好的抗生物粘附性能的同时具有更高的力学强度，拉伸强度可从0.23MPa提升到6.93MPa。更重要的是该凝胶在模拟重金属废水中对钒和铀离子有较好的选择吸附性。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明保护的范围之内。
Claims (3)
1.一种抗生物粘附复合多孔水凝胶材料的制备方法，其特征在于包括以下步骤：将70mg聚偕胺肟溶解于氢氧化钠溶液中，随后依次加入40mg磺基甜菜碱甲基丙烯酸酯、30mg聚(乙二醇)二丙烯酸酯和1mg 2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮充分搅拌溶解获得混合液，后将碱化的聚酯纤维过滤棉完全浸入混合液中，最后置于密封模具中并在紫外灯下光照聚合获得FC/ZW-PAO复合水凝胶；
所述碱化的聚酯纤维由以下方法制备而得：将聚酯纤维过滤棉浸没于无水乙醇中超声处理30min，后放入烘箱中烘干，再将过滤棉片置于质量浓度为10％的氢氧化钠溶液中并在70℃下处理40min，最后取出后洗涤至中性并烘干后备用；
所述聚偕胺肟由以下方法制备而得：称量5.6g NH2OH·HCl溶解于60mL DMF中，后加入4.12g Na2CO3和1.6g的NaOH,在45℃的水浴锅中搅拌1h后，缓慢加入4g的PAN，溶解5min，后将水浴锅的温度升高到65℃反应24h；再加入30mL DMF和2.8g NH2OH·HCl充分溶解后，依次加入2.06g Na2CO3和0.8g NaOH，隔10min后拧紧盖子反应24h，对混合液进行离心分离，在无水乙醇中缓慢滴入离心后的上清液获得白色絮状沉淀，经过过滤洗涤后，置于真空干燥箱内60℃下干燥过夜，得到产物PAO。
2.一种根据权利要求1所述的方法制备而得的抗生物粘附复合多孔水凝胶材料。
3.权利要求2所述的抗生物粘附复合多孔水凝胶材料在处理含重金属离子废水中的应用。
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