CN113828279A - 一种壳聚糖/生物炭复合气凝胶球、其制备的方法及应用 - Google Patents
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Abstract
本发明涉及一种壳聚糖/生物炭复合气凝胶球、其制备的方法,壳聚糖/生物炭复合气凝胶球以壳聚糖和生物炭为基材,利用环氧氯丙烷交联,在碱性混凝剂中成型,最后经真空冷冻干燥得到复合气凝胶球。生物质玉米芯经过氢氧化钾活化以及高温热解得到多孔生物炭,可作为壳聚糖基质的骨架支撑材料,提高复合气凝胶球的机械强度,利用环氧氯丙烷交联,提高复合气凝胶球的化学稳定性,复合气凝胶球规整的形貌有利于使用及分离回收。本发明所制备的壳聚糖/生物炭复合气凝胶球具有丰富的官能团和高度发达的三维多孔结构,其对抗炎药酮洛芬的吸附容量达102mg/g。吸附后的复合气凝胶球可利用乙醇浸泡脱附。本发明所制备的壳聚糖/生物炭复合气凝胶球可用于对含酮洛芬废水的高效分离。
Description
技术领域
本发明属于功能材料的技术领域,具体涉及一种壳聚糖/生物炭复合气凝胶球、其制备的方法及应用。
背景技术
随着医疗和个人护理领域的快速发展,抗炎药、抗生素、激素等有机药物在水体中产生了高痕量浓度(从ng/L到μg/L),这引起了各界人士的极大关注。这些有机微污染物由医院,工厂通过废水不断排放到天然水域中。然而,药物污染物其不可生物降解性和严重的毒性将会对水生生物造成潜在的影响,并威胁到人类的生命健康。这些严重的后果导致药物污染物已被列入欧盟水框架指令的动态“观察名单”和联合国教科文组织“水中新兴污染物”名单。酮洛芬(2-(3-苯甲酰基苯基)丙酸),CAS NO:22071-15-4)是一种典型的抗炎药物,主要用于缓解轻至中度疼痛。由于酮洛芬药物的广泛使用,处置不当和不可降解,导致在地下水、河水以及海洋等各类水域中被检测到。
壳聚糖(CAS NO:9012-76-4)是甲壳素的部分脱乙酰产物,含有丰富的官能团,如羟基(-OH)和氨基(-NH2)。重要的是,壳聚糖具有良好的生物降解性、生物相容性、低成本等特性,其被广泛用作去除各种污染物。壳聚糖气凝胶具有高度发达的三维多孔结构且可以通过氢键或静电相互作用与有机药物分子有效结合。然而,壳聚糖气凝胶由于机械强度低,化学稳定性差以及不规则的形貌等问题限制了其工业化的应用。另一方面,生物质热解制备的生物炭具有环保,经济等优点,是近年来广泛用于修复污染废水的市售材料。
如何有效的提高壳聚糖气凝胶机械强度及化学稳定性,改善壳聚糖气凝胶的形貌以及充分的利用生物质原料是壳聚糖/生物炭复合气凝胶球从水体中去除抗炎药酮洛芬急需解决的问题。
发明内容
为了解决壳聚糖气凝胶在机械强度,化学稳定性以及形貌方面的问题,本发明提供一种壳聚糖/生物炭复合气凝胶球的制备方法。该复合气凝胶球以壳聚糖和生物炭为基材,利用环氧氯丙烷交联,在碱性混凝剂中成型,最后经真空冷冻干燥得到复合气凝胶球。本发明提供的壳聚糖/生物炭复合气凝胶球具有高度发达的三维多孔结构,良好的机械强度和化学稳定性以及规整的球体形貌特点。同时,该复合气凝胶球对水体中抗炎药酮洛芬表现出优越的吸附性能。另外,壳聚糖/生物炭复合气凝胶球是一种可生物降解、经济环保型材料,符合可持续发展理念。
本发明要解决上述问题,所采用的技术方案是:
一种壳聚糖/生物炭复合气凝胶球的制备方法,包括如下制备步骤:
(1)利用氢氧化钾活化及高温热解生物质玉米芯得到生物炭;
(2)将壳聚糖溶于醋酸溶液中得到壳聚糖溶液,将生物炭和交联剂环氧氯丙烷加入壳聚糖溶液中,混合后得到反应混合溶液,反应混合溶液中生物炭与壳聚糖的质量比为5~15%;
(3)将反应混合溶液通过注射器泵均速地滴入碱性混凝剂中,得到成型的壳聚糖/生物炭复合水凝胶;
(4)将壳聚糖/生物炭复合水凝胶经真空冷冻干燥得到所述壳聚糖/生物炭复合气凝胶球。
优选,生物炭制备包括以下步骤:
(1)将收集的生物质玉米芯冲洗干净,烘干待用;
(2)将重量比为1:2的生物质玉米芯与氢氧化钾混合并放入瓷舟,于氮气介质中在600℃管式炉内保持热解1h,然后自然降温,得到热解产物;
(3)将热解产物经洗涤、研磨和烘干后,得到多孔的生物炭。
优选,所述瓷舟的尺寸为50*20*20mm,管式炉的加热速率为4℃/min。
优选,洗涤时采用的洗涤剂为去离子水和95%的乙醇溶液。
优选,壳聚糖溶液的浓度为5%,醋酸溶液的重量百分含量为2wt.%。
优选,反应混合溶液在65℃下超声混匀,时间为3h,真空冷冻干燥时间为12h,温度为-80℃,压力为0.1mbar。
优选,所述注射器的体积为5mL,注射器泵的速率为1滴/s,碱性混凝剂为(H2O:C2H5OH:NaOH=5:4:1,w/w)。
一种壳聚糖/生物炭复合气凝胶球,以壳聚糖和生物炭为基材,采用上述方法制得,壳聚糖/生物炭复合气凝胶球的直径为1.5--2.5mm,可应用于含酮洛芬废水的吸附处理。
本发明的有益效果:
1)本发明利用壳聚糖与生物炭复合,经环氧氯丙烷交联,在碱性混凝剂中成型后制成复合气凝胶球,由此提高了复合气凝胶球的使用性能,分离性能以及改善了复合气凝胶的形貌。生物炭均匀地分散在壳聚糖基质中,可作为壳聚糖的骨架支撑材料,有效提高复合气凝胶球的机械强度;
2)本发明利用环氧氯丙烷交联,避免了壳聚糖在酸性条件下溶解,有效提高了复合气凝胶球的化学稳定性;
3)本发明以生物炭为基材,原料简单易得,经济环保,符合可持续发展的理念;
4)本发明制备的复合气凝胶球不需要模板,通过注射器均速地滴入碱性混凝剂就能成型,具有规整的表面形貌,易于使用和从水体中分离;
5)本发明制备的壳聚糖/生物炭复合气凝胶球,具有发达的三维多孔结构及优越的吸附性能,其对酮洛芬的吸附容量优于其它的吸附材料,可用于含抗生素酮洛芬废水中高效分离。
利用壳聚糖/生物炭复合气凝胶球吸附含抗生素酮洛芬废水的实验结果表明,在温度为25℃、pH=4、酮洛芬初始浓度50mg/L,吸附剂用量0.2g/L(固液比)时,其对酮洛芬的吸附容量达106mg/g,优于普通吸附材料,图3显示了生物炭/壳聚糖质量比为5~15%作为吸附剂,随着接触时间的增加,其吸附酮洛芬的变化情况,吸附后的复合气凝胶球可利用乙醇浸泡脱附,且可重复使用性良好。
说明书附图
图1为壳聚糖/生物炭复合水凝胶球在碱性混凝剂中的形态;
图2为生物炭及复合气凝胶球的形貌,其中:(a)是生物炭的电镜图;(b-d)分别是生物炭/壳聚糖质量比为5、10%、15%气凝胶球的形貌图:(e)是复合气凝胶球内部的三维多孔结构:(f)为生物炭嵌入壳聚糖表面图;
图3是生物炭/壳聚糖质量比为5~15%作为吸附剂,随着接触时间的增加,其吸附酮洛芬的变化图。
具体实施方式
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体图示,进一步阐述本发明:
实施例1:一种壳聚糖/生物炭复合气凝胶球的制备方法,其制备过程包括:首先利用氢氧化钾活化及高温热解生物质玉米芯制备生物炭,然后将壳聚糖溶于醋酸溶液中,再加入预先制备的生物炭和交联剂环氧氯丙烷,充分地分散在壳聚糖基质中,再将其通过注射器泵均速地滴入碱性混凝剂中,得到成型的壳聚糖/生物炭复合水凝胶,最后经真空冷冻干燥制成壳聚糖/生物炭复合气凝胶球;
具体步骤为:
(1)制备生物炭;将收集的生物质玉米芯表面冲洗干净,烘干待用,1.0g生物质玉米芯与2.0g的氢氧化钾固体混合并放入瓷舟(50*20*20mm),于氮气介质中在600℃管式炉内(加热速率为4℃/min)保持热解1h,然后自然降温。所得热解产物经洗涤(去离子水和95%的乙醇溶液)、研磨和烘干后,得到多孔生物炭;
(2)制备壳聚糖/生物炭复合气凝胶球;
1)0.2g壳聚糖加入3.8mL醋酸溶液(2wt.%)中,搅拌至完全溶解,得5%壳聚糖溶液;
2)按一定配比(生物炭/壳聚糖质量比为5%)于上述壳聚糖溶液加入0.01g生物炭,并加入0.1g的环氧氯丙烷,于65℃下超声3h混匀;
3)于上述混合液冷却至室温后,加入(5mL)注射器内并通过注射器泵,均速地(1滴/s)滴入碱性混凝剂(H2O:C2H5OH:NaOH=5:4:1,w/w)中,得到成型的壳聚糖/生物炭复合水凝胶球;
4)将上述复合水凝胶球冲洗后放入冰箱中预冷冻3h,再经真空冷冻干燥12h(温度为-80℃,压力为0.1mbar),得到壳聚糖/生物炭复合气凝胶球(1.5--2.5mm)。
利用壳聚糖/生物炭复合气凝胶球吸附含酮洛芬废水的实验结果表明,在温度为25℃、pH=4、酮洛芬初始浓度50mg/L,吸附剂用量0.2g/L(固液比)时,其对酮洛芬的吸附容量达106mg/g,吸附后的复合气凝胶球可利用乙醇浸泡脱附,且可重复使用良好。
实施例2:一种壳聚糖/生物炭复合气凝胶球的制备方法,包括如下制备步骤:
(1)制备生物炭;将收集的生物质玉米芯表面冲洗干净,烘干待用。1.0g生物质玉米芯与2.0g的氢氧化钾固体混合并放入瓷舟(50*20*20mm),于氮气介质中在600℃管式炉内(加热速率为4℃/min)保持热解1h,然后自然降温。所得热解产物经洗涤(去离子水和95%的乙醇溶液)、研磨和烘干后,得到多孔生物炭;
(2)制备壳聚糖/生物炭复合气凝胶球;
1)0.2g壳聚糖加入3.8mL醋酸溶液(2wt.%)中,搅拌至完全溶解,得5%壳聚糖溶液;
2)按一定配比(生物炭/壳聚糖质量比为10%)于上述壳聚糖溶液加入0.02g生物炭,并加入0.1g的环氧氯丙烷,于65℃下超声3h混匀;
3)于上述混合液冷却至室温后,加入(5mL)注射器内并通过注射器泵,均速地(1滴/s)滴入碱性混凝剂(H2O:C2H5OH:NaOH=5:4:1,w/w)中,得到成型的壳聚糖/生物炭复合水凝胶球;
4)将上述复合水凝胶球冲洗后放入冰箱中预冷冻3h,再经真空冷冻干燥12h(温度为-80℃,压力为0.1mbar),得到壳聚糖/生物炭复合气凝胶球(1.5--2.5mm)。
利用壳聚糖/生物炭复合气凝胶球吸附含酮洛芬废水的实验结果表明,在温度为25℃、pH=4、酮洛芬初始浓度50mg/L时,吸附剂用量0.2g/L(固液比)时,其对酮洛芬的吸附容量达102mg/g。吸附后的复合气凝胶球可利用乙醇浸泡脱附,且可重复使用良好。
实施例3:
(1)制备生物炭;
将收集的生物质玉米芯表面冲洗干净,烘干待用。1.0g生物质玉米芯与2.0g的氢氧化钾固体混合并放入瓷舟(50*20*20mm),于氮气介质中在600℃管式炉内(加热速率为4℃/min)保持热解1h,然后自然降温。所得热解产物经洗涤(去离子水和95%的乙醇溶液)、研磨和烘干后,得到多孔生物炭;
(2)制备壳聚糖/生物炭复合气凝胶球;
1)0.2g壳聚糖加入3.8mL醋酸溶液(2wt.%)中,搅拌至完全溶解,得5%壳聚糖溶液;
2)按一定配比(生物炭/壳聚糖质量比为15%)于上述壳聚糖溶液加入0.03g生物炭,并加入0.1g的环氧氯丙烷,于65℃下超声3h混匀;
3)于上述混合液冷却至室温后,加入(5mL)注射器内并通过注射器泵,均速地(1滴/s)滴入碱性混凝剂(H2O:C2H5OH:NaOH=5:4:1,w/w)中,得到成型的壳聚糖/生物炭复合水凝胶球;
4)将上述复合水凝胶球冲洗后放入冰箱中预冷冻3h,再经真空冷冻干燥12h(温度为-80℃,压力为0.1mbar),得到壳聚糖/生物炭复合气凝胶球(1.5--2.5mm)。
利用壳聚糖/生物炭复合气凝胶球吸附含酮洛芬废水的实验结果表明,在温度为25℃、pH=4、酮洛芬初始浓度50mg/L时,吸附剂用量0.2g/L(固液比)时,其对酮洛芬的吸附容量达90mg/g。吸附后的复合气凝胶球可利用乙醇浸泡脱附,且可重复使用良好。
上述实施例结果表明,实施例生物炭/壳聚糖质量比为5%时制备的壳聚糖/生物炭复合气凝胶球对抗炎药酮洛芬的吸附量最高。然而,基于形貌方面考虑,生物炭/壳聚糖质量比为5%时制备的壳聚糖/生物炭复合气凝胶球形貌不佳(图2b)。另外,生物炭含量的增加,吸附容量反而下降,这是由于生物炭在壳聚糖基质的聚集,导致吸附位点减少所致。因此,生物炭/壳聚糖质量比为10%时制备的壳聚糖/生物炭复合气凝胶球是最佳的复合气凝胶球,其对酮洛芬吸附容量达102mg/g,这是由于复合气凝胶球具有丰富的官能团和高度发达的三维多孔结构,有利于吸附废水中的酮洛芬。
本领域技术人员可通过借鉴本文内容,适当改变原料、工艺参数等环节实现。本发明的方法与产品已通过较佳实施例子进行了描述,相关技术人员明显能在不脱离本发明内容、精神和范围内对本文所述的方法和产品进行改动或适当变更与组合,来实现本发明技术。特别需要指出的是,所有相类似的替换和改动对本领域技术人员来说是显而易见的,他们都被视为包括在本发明精神、范围和内容中。
Claims (10)
1.一种壳聚糖/生物炭复合气凝胶球的制备方法,其特征在于包括如下制备步骤:
(1)利用氢氧化钾活化及高温热解生物质玉米芯得到生物炭;
(2)将壳聚糖溶于醋酸溶液中得到壳聚糖溶液,将生物炭和交联剂环氧氯丙烷加入壳聚糖溶液,混合后得到反应混合溶液;
(3)将反应混合溶液通过注射器泵均匀地滴入碱性混凝剂中,得到成型的壳聚糖/生物炭复合水凝胶;
(4)将壳聚糖/生物炭复合水凝胶经真空冷冻干燥得到所述壳聚糖/生物炭复合气凝胶球。
2.根据权利要求1所述的一种壳聚糖/生物炭复合气凝胶球的制备方法,其特征在于,生物炭制备包括以下步骤:
(1)将收集的生物质玉米芯冲洗干净,烘干待用;
(2)将重量比为1:2的生物质玉米芯与氢氧化钾混合并放入瓷舟,于氮气介质中在600℃管式炉内保持热解1h,然后自然降温,得到热解产物;
(3)将热解产物经洗涤、研磨和烘干后,得到多孔的生物炭。
3.根据权利要求2所述的一种壳聚糖/生物炭复合气凝胶球的制备方法,其特征在于,所述瓷舟的尺寸为50*20*20mm,管式炉的加热速率为4℃/min。
4.根据权利要求2所述的一种壳聚糖/生物炭复合气凝胶球的制备方法,其特征在于,洗涤时采用的洗涤剂为去离子水和95%的乙醇溶液。
5.根据权利要求1所述的一种壳聚糖/生物炭复合气凝胶球的制备方法,其特征在于,反应混合溶液中生物炭与壳聚糖的质量比为5~15%,壳聚糖溶液的浓度为5%,醋酸溶液的重量百分含量为2wt.%。
6.根据权利要求1所述的一种壳聚糖/生物炭复合气凝胶球的制备方法,其特征在于,反应混合溶液在65℃下超声混匀,时间为3h,真空冷冻干燥时间为12h,温度为-80℃,压力为0.1mbar。
7.根据权利要求1所述的一种壳聚糖/生物炭复合气凝胶球的制备方法,其特征在于,所述注射器的体积为5mL,注射器泵的速率为1滴/s,碱性混凝剂为(H2O:C2H5OH:NaOH=5:4:1,w/w)。
8.一种壳聚糖/生物炭复合气凝胶球,其特征在于,采用如权利要求1-7任一所述制备方法制得。
9.根据权利要求8所述的壳聚糖/生物炭复合气凝胶球,其特征在于,壳聚糖/生物炭复合气凝胶球的直径为1.5-2.5mm。
10.一种如权利要求8所述的壳聚糖/生物炭复合气凝胶球在吸附含酮洛芬废水中的应用。
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