CN110255568B - 一种内外双层胺基改性SiO2气凝胶的合成方法及其应用 - Google Patents
一种内外双层胺基改性SiO2气凝胶的合成方法及其应用 Download PDFInfo
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Abstract
一种内外双层胺基改性SiO2气凝胶的合成方法及其应用，具体步骤为：取20ml水玻璃，用阳离子交换树脂柱去除水玻璃中的钠离子；用0.1～2.0mol/L氨溶液和0.1～2.0mol/L盐酸溶液，将得到的硅酸溶液调节pH值为4.0～8.0；迅速将盛有硅酸溶液的烧杯进行超声，并依次向硅酸溶液中加入体积比为1：1：1：16的环氧氯丙烷、APTES、乙二胺和正己烷的混合改性剂，在超声条件下缓慢摇晃烧杯直至溶液成胶，之后将凝胶在30～65℃条件下放置5～24h，再将28ml正己烷加入凝胶中，在30～65℃条件下，连续振荡5～24h。最后，湿气凝胶用真空冷冻干燥法进行干燥10～48h，即获得内外双层胺基改性SiO2气凝胶。该气凝胶的吸附初始浓度为1211mg/L的腐殖酸溶液，可在90分钟内达到吸附平衡，吸附量高达1194.4mg/g。
Description
技术领域
本发明涉及吸附剂制备技术领域，具体是一种内外双层胺基改性SiO2气凝胶的合成方法及其应用。
背景技术
全球经济的快速发展衍生出了严重的环境污染问题，环境污染也成为社会可持续发展过程中的一个严峻挑战。近年来，难降解有机物为主的水污染日益加剧，开发低成本、绿色的处理方法将是十分关键。在难降解有机污染物中，腐殖酸类的高浓度有机物作为垃圾处理过程产生的二次污染物，一直是水处理行业的难点。当腐殖酸类的高浓度有机污染物污染了水体后，会导致水体色度和浊度变高的现象，其腐殖酸络合体，能增加其生物毒性[1]，同时，腐殖酸还能在消毒过程中和含氯消毒剂反应生成具有“三致效应”(致突变、致癌和致畸效应) 的消毒副产物[2]。
目前，处理腐殖酸类高浓度有机污染物的方法有生化处理法、高级氧化法，例如，光催化、臭氧氧化、臭氧+光催化氧化、臭氧催化氧化和新型材料吸附法以及膜处理技术等[3-7]。对于“老化”的渗滤液中腐殖酸污染物，由于这些污染物的可生化性差，所以生物处理基本无效。吴伟等人研究了TiO2光催化降解腐殖酸，其研究结果表明腐殖酸的降解是由大分子酸到小分子酸的过程，光催化不仅能使腐殖酸褪色，而且还大大降低了消毒副产物的产生[8]。但是像这类传统的光催化材料通常存在两个方面的问题：1、大多数光催化剂只能利用紫外光进行反应，无法利用太阳光的可见光部分；2、催化剂由于其细小的粒径尺寸容易发生团聚，导致催化剂与污染物的反应活性位点数减少。吸附法的优势在于它的去除效率高，操作简便，而且通常不会产生副反应对水体产生二次污染。因此，开发出能够具有优异的分散性和高比表面积的光催化剂吸附剂对于处理腐殖酸类高浓度有机污染物是十分迫切和重要的。
吸附过程与吸附材料本身的表面性质和材料结构等性质息息相关，通常吸附又分为物理吸附、化学吸附和离子交换吸附，往往这三种吸附过程或者其中两种可能都存在。目前，活性炭、沸石分子筛和树脂类吸附剂是应用比较广泛的吸附剂。然而，活性炭主要存在难再生和难以去除亲水性小分子物质两个方面的问题，这导致它难以实现大规模的工业化应用。目前，高比表面积二氧化硅气凝胶成为目前研究的热点。二氧化硅气凝胶是一种由纳米量级颗粒相互聚合形成的连续三维网络结构，孔隙中充满空气介质的高分散轻质多孔非晶态材料。 1931年，斯坦福大学的Kistler教授首次通过溶胶－凝胶法制备出二氧化硅气凝胶[1]。气凝胶是一种具有微纳米网络结构的固态物质，其特有的大比表面积、低密度、低热导率等特性使得它在众多领域都有巨大的应用价值。随着科研工作者对制备二氧化硅气凝胶的硅源、改性、表征等几个方面进行深入研究，二氧化硅气凝胶逐渐在环境治理、催化、节能、药物负载、航天领域等有广阔的应用前景。但是，如何根据腐殖酸类有机污染污染物的特点对二氧化硅气凝胶进行高效胺基改性是本发明的关键科学问题。
发明内容
本发明的目的在于提供一种内外双层胺基改性SiO2气凝胶的合成方法及其应用，确保内外双层胺基改性SiO2气凝胶能够拥有针对腐殖酸类污染物的吸附具有高选择性，同时又保持二氧化硅气凝胶高比表面积优异的结构特性，解决腐殖酸去除率低的问题。
本发明所采用的技术方案是：一种内外双层胺基改性SiO2气凝胶的合成方法，由如下步骤组成：
(1)用分析天平准确称取5～60g稻壳灰和5～28g氢氧化钠置于圆底烧瓶中，加热至 50～150℃，回流搅拌反应1～10小时；
(2)将反应后的产物冷却到室温后进行真空抽滤，即可获得模数为1.5～4.2的水玻璃；
(3)取10～40ml水玻璃，通过强酸性阳离子交换树脂001*7(732型)进行离子交换，去除水玻璃中的钠离子，获得硅酸溶液；
(4)用0.1～2.0mol/L氨溶液和0.1～2.0mol/L盐酸溶液，将得到的硅酸溶液调节至pH 值为4.0～8.0，然后迅速将盛有硅酸溶液的烧杯进行超声，并依次向硅酸溶液中加入0.1～2.5ml 环氧氯丙烷、0.1～2.5ml APTES、0.1～2.5ml乙二胺和5.0～30.0ml正己烷，在超声条件下缓慢摇晃烧杯直至溶液成胶，之后将凝胶在30～65℃条件下放置5～24h；所述环氧氯丙烷：APTES：乙二胺的体积比为1：1：1。
(5)将10～40ml正己烷加入凝胶中，在30～65℃条件下，连续振荡5～24h；
(6)最后，湿气凝胶采用真空冷冻干燥的方法进行干燥10～48h，即可得到所述内外双层胺基改性SiO2气凝胶。
胺基改性剂分别为市售环氧氯丙烷、3-胺基丙基三乙氧基硅烷、乙二胺。
所述内外双层胺基改性SiO2气凝胶在净化废水中的应用，在需要净化的腐殖酸废水中，加入所述内外双层胺基改性SiO2气凝胶，在25℃、pH为2.0～9.0的条件下吸附腐殖酸，吸附 0.1～1.5h后收集腐殖酸与内外双层胺基改性SiO2气凝胶的沉淀物，即可达吸附处理效果。
所述的内外双层胺基改性SiO2气凝胶在净化废水中的应用，欲净化的水体中的腐殖酸的浓度为5～1200mg/L。
本发明相关化学反应方程式：
本发明以农业废弃物稻壳灰为硅源，采用溶胶-凝胶技术合成内外双层胺基改性SiO2气凝胶。
本发明制备得的水玻璃模数是4.26，远比市售工业水玻璃的模数高。
本发明所用设备均为常规实验室设备。
本发明突出的有益效果在于：
1、通过设计内外双层胺基改性，提高了胺基负载量并同时克服了改性基团的空间位阻效应，使本材料吸附处理腐殖酸类高浓度有机污染物时，具有快速和高吸附量的性能。
2、所采用的原料是农业固体废弃物，廉价易得，属于资源再生利用，合成过程简便实用。
附图说明
图1为本发明所述的内外双层胺基改性SiO2气凝胶的合成方法的工艺流程图。
图2为本发明所述的内外双层胺基改性SiO2气凝胶样品的场发射扫描电镜图。
图3本发明所述的内外双层胺基改性SiO2气凝胶样品Zeta电位。
具体实施方式
下面结合实施例对本发明的技术方案做进一步的详细说明。
实施例1
本实施例为本发明所述的内外双层胺基改性SiO2气凝胶的合成方法的一个实例，采用溶胶凝胶法来合成，由以下步骤组成：
(1)用分析天平准确称取30g稻壳灰和8g氢氧化钠置于圆底烧瓶中，加热至100℃，回流搅拌反应3.5小时；
(2)将反应后的产物冷却到室温后进行真空抽滤，即可获得模数为4.26的水玻璃；
(3)取20ml由稻壳灰制备的模数为4.26水玻璃，通过强酸性阳离子交换树脂001*7(732 型)进行离子交换，去除水玻璃中的钠离子，获得硅酸溶液；
(4)用1mol/L氨溶液和1mol/L盐酸溶液将得到的硅酸溶液调节pH值为4.5。然后迅速将盛有硅酸溶液的烧杯进行超声，并依此向硅酸溶液中加入0.93ml环氧氯丙烷、0.93mlAPTES、0.93ml乙二胺和16ml正己烷。在超声条件下缓慢摇晃烧杯直至溶液成胶，将凝胶在45℃条件下放置12h。
(5)再将28ml正己烷加入凝胶中，在45℃条件下，连续振荡6h。
(6)最后将湿气凝胶采用真空冷冻干燥的方法进行干燥24h，即可得到内外双层胺基改性SiO2气凝胶。
实施例2
本实施例为本发明制备得的内外双层胺基改性SiO2气凝胶在净化废水中的应用实例，以双层胺基改性SiO2气凝胶作为吸附剂净化高浓度腐殖酸溶液，试验条件为：腐殖酸溶液的初始浓度为1211mg/L，吸附时间为90分钟，其他条件同实施例1，采用0.45μm的滤膜过滤，检测和计算出双层胺基改性SiO2气凝胶对腐殖酸的吸附量为1205.4mg/g、去除率为99.02％。
可见，本发明制备得的内外双层胺基改性SiO2气凝胶对于高浓度腐殖酸溶液具有快速高吸附量的处理效果。
实施例3
本实施例为本发明制备得的内外双层胺基改性SiO2气凝胶在净化废水中的应用另一个实例，以双层胺基改性SiO2气凝胶作为吸附剂，溶液的pH为3，其他条件同实施例1，采用 0.45μm的滤膜过滤，检测和计算出双层胺基改性SiO2气凝胶对腐殖酸的吸附量为48.75mg/g、去除率为85.28％。
实施例4
本实施例为本发明制备得的内外双层胺基改性SiO2气凝胶在净化废水中的应用第三个实例，以双层胺基改性SiO2气凝胶作为吸附剂，溶液的pH为5，其他条件同实施例1，采用 0.45μm的滤膜过滤，检测和计算出双层胺基改性SiO2气凝胶对腐殖酸的吸附量为47.84mg/g、去除率为94.85％。
实施例5
本实施例为本发明制备得的内外双层胺基改性SiO2气凝胶在净化废水中的第四个应用实例，以双层胺基改性SiO2气凝胶作为吸附剂，溶液的pH为9，其他条件同实施例1，采用 0.45μm的滤膜过滤，检测和计算出双层胺基改性SiO2气凝胶对腐殖酸的吸附量为47.17mg/g、去除率为93.84％。
可见双层胺基改性SiO2气凝胶能够对pH在3～9范围内的腐殖酸具有快速、高效的吸附处理效果。
Claims (4)
1.一种内外双层胺基改性SiO2气凝胶的合成方法，其特征在于，由如下步骤组成：
(1)用分析天平准确称取10～40g稻壳灰和5～20g氢氧化钠置于圆底烧瓶中，加热至50～150℃，回流搅拌反应3～10小时；
(2)将反应后的产物冷却到室温后进行真空抽滤，即可获得模数为4.26的水玻璃；
(3)取20ml水玻璃，通过强酸性阳离子交换树脂001*7(732型)进行离子交换，去除水玻璃中的钠离子，获得硅酸溶液；
(4)用0.1～2.0mol/L氨溶液和0.1～2.0mol/L盐酸溶液，将获得的硅酸溶液调节pH值为4.0～8.0，然后迅速将盛有硅酸溶液的烧杯进行超声，并依次向硅酸溶液中加入0.2～5.0ml环氧氯丙烷、0.2～5.0ml APTES、0.2～5.0ml乙二胺三种试剂充当胺基改性剂和10～36ml正己烷，在超声条件下缓慢摇晃烧杯直至溶液成胶，之后将凝胶在30～65℃条件下放置5～24h；
(5)将10～48ml正己烷加入凝胶中，在30～65℃条件下，连续振荡5～24h；
(6)最后，湿气凝胶采用真空冷冻干燥的方法进行干燥10～48h，即得到所述内外双层胺基改性SiO2气凝胶。
2.根据权利要求1所述的内外双层胺基改性SiO2气凝胶的合成方法，其特征在于，胺基改性剂为市售的环氧氯丙烷、3-胺基丙基三乙氧基硅烷、乙二胺。
3.权利要求1制备得的内外双层胺基改性SiO2气凝胶在净化废水中的应用，其特征在于，在需要净化的废水中，加入所述内外双层胺基改性SiO2气凝胶，在25℃、pH为2.0～9.0的条件下吸附腐殖酸，吸附0.1～24h后收集腐殖酸与内外双层胺基改性SiO2气凝胶的沉淀物，即达到吸附处理效果。
4.根据权利要求3所述的内外双层胺基改性SiO2气凝胶在净化废水中的应用，其特征在于，欲净化的水体中的腐殖酸浓度为5～1211mg/L。
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