CN113185749A - 一种高吸附性壳聚糖气凝胶的制备方法 - Google Patents
一种高吸附性壳聚糖气凝胶的制备方法 Download PDFInfo
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Abstract
本发明涉及一种高吸附性壳聚糖气凝胶的制备方法。第一步将壳聚糖溶于酸性水溶液,第二步将稀释过的α,β‑不饱和醛交联于壳聚糖溶液成胶,第三步用去离子水洗净,冷冻干燥后得到壳聚糖凝胶材料。本发明合成方法简单,得到的凝胶材料为功能化改性的壳聚糖气凝胶材料,对于废水中的阴离子染料尤其是甲基蓝染料具有吸附容量大、吸附效果好、稳定性好、重复利用性高且易于分离。
Description
技术领域
本发明属于壳聚糖材料技术领域,更具体地,涉及一种高吸附性壳聚糖气凝胶的制备方法。
背景技术
随着化学工业的迅速发展,有机废水的处理问题愈发严重。其中最具代表性的是纺织印染行业产生的污染废水。未经处理的染料废水直接排放会对水生物种和人类造成威胁,从而破坏生态系统和生态环境。如何高效、简单、安全地治理染料废水污染已成为研究热点。
吸附法作为染料废水的处理方法之一,具有运行成本低、处理效果好等优点,在去除有机污染物方面有很大的应用潜力。然而,由于传统吸附剂如活性炭、大孔树脂、膨润土等大多存在再生困难、回收率低、应用成本高等缺点,限制了其应用。因此研究人员试图使用具有可生物降解性、可重复利用性、生物相容性好且廉价的天然生物质吸附材料来替代传统的吸附材料。
壳聚糖作为自然界中发现的唯一天然碱性多糖,在化妆品、食品添加剂、医疗以及水处理等领域广泛应用。然而,由于壳聚糖存在机械性能低、在酸性溶液中稳定性差、比表面积小等固有缺陷,仍需对壳聚糖进行结构改性和化学改性,以满足复杂的应用环境和多种应用目的。因此,开发一种吸附能力强、稳定性好且重复利用性高的壳聚糖吸附材料具有重要的研究意义和应用价值。
之前也有制备壳聚糖气溶胶的报道,如CN106800662B,将壳聚糖溶液通过物理交联或化学交联形成水凝胶,再用无水乙醇置换,超临界干燥后得到壳聚糖气凝胶。现有技术中化学交联采用的一般是环氧化合物或醛类化合物,尤其是戊二醛。但是制备的壳聚糖气溶胶吸附性依然不够。
发明内容
针对现有技术中的存在的上述技术问题,本发明提供一种高吸附性壳聚糖气凝胶的制备方法。
本发明解决其技术问题所采用的技术方案是:
一种高吸附型壳聚糖气凝胶的制备方法,包括如下过程:
(1)将壳聚糖溶于酸性水溶液中,搅拌至壳聚糖完全溶解;
(2)将稀释后的α,β-不饱和醛加入(1)中的壳聚糖溶液中,机械搅拌均匀,静置成水凝胶;
(3)用去离子水多次浸泡、洗涤(2)中的水凝胶,然后进行冷冻干燥,得到壳聚糖气凝胶材料。
作为一个优选方案,所述酸性水溶液包括冰醋酸水溶液、甲酸水溶液、盐酸水溶液、硝酸水溶液和硫酸水溶液。
作为一个优选方案,步骤(1)中,所述酸性水溶液的体积浓度为0.01%~10%。
作为一个优选方案,步骤(1)中,所述每100mL酸性水溶液中掺杂壳聚糖的质量为0.1g~10g。
作为一个优选方案,步骤(2)中,所述每100mL壳聚糖溶液中掺杂α,β-不饱和醛为0.1mL~5mL。
作为一个优选方案,步骤(2)中,所述α,β-不饱和醛包括丙烯醛,反式丁烯醛,苯丙烯醛等。
作为一个优选方案,步骤(2)中,所述温度范围为0~80℃。
作为一个优选方案,步骤(3)中,用纯水浸泡洗涤0.1h~48h较佳。
本发明的有益效果:本发明方法制备的壳聚糖气凝胶材料为功能化改性的壳聚糖气凝胶材料,对于废水中的阴离子染料尤其是甲基蓝染料具有吸附容量大、吸附效果好、稳定性好、重复利用性高且易于分离等优点,在染料废水处理领域有良好的应用前景。
附图说明
图1为新型壳聚糖凝胶吸附材料的红外光谱图。
图2为时间对新型壳聚糖凝胶吸附材料吸附量的影响。
图3为pH对新型壳聚糖凝胶吸附材料去除率的影响。
图4为新型壳聚糖凝胶吸附材料的循环再生性能。
图5为时间对壳聚糖/戊二醛凝胶吸附材料吸附量的影响。
具体实施方式
下面结合具体的实施例,对本发明作进一步说明,所述的实施例只是为了解释本发明,而不能理解为对本发明的限制。
实施例1
将2.0853g壳聚糖加入至100mL1%v/v盐酸水溶液中进行搅拌2h,静置1h至壳聚糖溶液清亮透明;将1.5mL丙烯醛加入壳聚糖溶液中,在25℃下搅拌1h再静置3h得到水凝胶;用纯水多次浸泡、洗涤18h后,将凝胶进行冷冻干燥,得到即为壳聚糖气凝胶吸附材料,凝胶质量为0.4167g。该吸附材料对甲基蓝的吸附容量为500mg/g(甲基蓝溶液初始浓度为500mg/L,反应溶液pH值为6,反应温度为308K)。
实施例2
将0.5052g壳聚糖加入至100mL0.5%v/v冰醋酸水溶液中进行搅拌1h,再超声0.5h至壳聚糖溶液清亮透明;将360μL丙烯醛加入壳聚糖溶液中,在35℃下超声0.5h再静置2h得到水凝胶;用纯水多次浸泡、洗涤21h后,将凝胶进行冷冻干燥,得到即为壳聚糖气凝胶吸附材料,凝胶质量为0.2438g。该吸附材料对甲基蓝的吸附容量为772mg/g(甲基蓝溶液初始浓度为450mg/L,反应溶液pH值为6,反应温度为308K)。
实施例3
将8.574g壳聚糖加入至100mL2%v/v硝酸水溶液中进行机械搅拌2h,再静置3h至壳聚糖溶液清亮透明;将6.0mL丙烯醛稀释于30mL纯水中后,缓慢加入至壳聚糖溶液中,在80℃下机械搅拌0.1h再静置0.1h得到水凝胶;用纯水多次浸泡、洗涤48h后,将凝胶进行冷冻干燥,得到即为壳聚糖气凝胶吸附材料,凝胶质量为6.757g。该吸附材料对甲基蓝的吸附容量为687mg/g(甲基蓝溶液初始浓度为450mg/L,反应溶液pH值为6,反应温度为308K)。
实施例4
将1.2518g壳聚糖加入至100mL0.2%v/v冰醋酸水溶液中进行搅拌1h,再超声0.5h至壳聚糖溶液清亮透明;将625μL戊二醛缓慢加入至壳聚糖溶液中,在35℃下超声1h再静置2h得到壳聚糖/戊二醛水凝胶;用纯水多次浸泡、洗涤48h后,将凝胶进行冷冻干燥,得到即为壳聚糖/戊二醛凝胶吸附材料,凝胶质量为0.6880g。该吸附材料对甲基蓝的吸附容量为442mg/g(甲基蓝溶液初始浓度为400mg/L,反应溶液pH值为6,反应温度为308K)。
实施例5
将0.18g壳聚糖加入至100mL5%v/v甲酸水溶液中进行搅拌2h,再超声1h至壳聚糖溶液清亮透明;将0.2mL丙烯醛加入壳聚糖溶液中,在50℃下超声0.5h再静置2h得到水凝胶;用纯水多次浸泡、洗涤48h后,冷冻干燥得到壳聚糖气凝胶吸附材料,凝胶质量为0.0825g。该吸附材料对甲基蓝的吸附容量为479mg/g(甲基蓝溶液初始浓度为450mg/L,反应溶液pH值为5,反应温度为318K)。
实施例6
将1.2503g壳聚糖加入至100mL0.5%v/v冰醋酸水溶液中进行搅拌0.5h,再超声0.5h至壳聚糖溶液清亮透明;将800μL反式丁烯醛加入壳聚糖溶液中,在0℃下反应10h再静置24h得到水凝胶;用纯水多次浸泡、洗涤24h后,将凝胶进行冷冻干燥,得到即为壳聚糖气凝胶吸附材料,凝胶质量为0.1643g。该吸附材料对甲基蓝的吸附容量为335mg/g(甲基蓝溶液初始浓度为500mg/L,反应溶液pH值为6,反应温度为308K)。
实施例7
将1.2516g壳聚糖加入至100mL0.5%v/v冰醋酸水溶液中进行搅拌0.5h,再超声0.5h至壳聚糖溶液清亮透明;将1.2mL苯丙烯醛加入壳聚糖溶液中,在50℃下超声0.5h再静置3h得到水凝胶;用纯水多次浸泡、洗涤24h后,将凝胶进行冷冻干燥,得到即为壳聚糖气凝胶吸附材料,凝胶质量为0.3284g。该吸附材料对甲基蓝的吸附容量为451mg/g(甲基蓝溶液初始浓度为500mg/L,反应溶液pH值为6,反应温度为308K)。
实施例8、壳聚糖凝胶材料的形貌表征
下面通过红外光谱对本发明新型壳聚糖气凝胶吸附材料的结构进行表征。
图1为壳聚糖(CS)和实施例1制备的新型壳聚糖凝胶(A/CS)的红外光谱图,显示出壳聚糖的主要光谱特征,包括3369cm-1(-OH伸缩)以及在2927cm-1和2875cm-1(C-H拉伸)、1665cm-1(酰胺II拉伸)、1594cm-1(NH2弯曲)、1380cm-1(酰胺III拉伸,C-N拉伸)、1420cm-1(C-H弯曲)、1157cm-1(C-O-C拉伸)和1079cm-1(C-O拉伸)的吸收谱带。与壳聚糖的红外光谱相比,新型壳聚糖凝胶在1665cm-1和1594cm-1处的峰值强度降低且发生明显移位,说明壳聚糖与丙烯醛发生了交联反应。
实施例9、新型壳聚糖凝胶材料的吸附性能
(1)时间对吸附量的影响
为了探究时间对新型壳聚糖凝胶材料吸附性能的影响,测试了实施例3制备的新型壳聚糖凝胶材料在0~420min内对甲基蓝染料的吸附容量(甲基蓝溶液初始浓度为400mg/L和450mg/L,反应溶液pH值为6,反应温度为308K)。测试结果如图2所示,吸附量在前30min内急剧增加。随着反应的进行,染料分子在吸附剂表面的有效吸附位点逐渐减少,在反应时间从30min持续到300min时吸附速率也变慢。300min后吸附量基本保持不变,说明基本达到吸附平衡。
(2)pH对吸附量的影响
为了探究pH对新型壳聚糖凝胶材料吸附性能的影响,测试了pH在2~8范围内实施例3制备的新型壳聚糖凝胶材料对甲基蓝染料的吸附容量(甲基蓝溶液初始浓度为450mg/L,反应温度为308K)。测试结果如图3所示,当pH值从2增加到3时,甲基蓝去除率从98.5%降低到95.7%。在pH=6之前,吸附容量和去除率基本保持不变。到pH=8时,去除率显著降低至55.8%。测试结果表明,随着染料溶液pH值的增加,吸附量逐渐降低。在pH=2~6范围内,新型壳聚糖凝胶材料对甲基蓝染料的去除率较高,说明对壳聚糖的交联改性提高了其耐酸性能和吸附性能,大大扩展了壳聚糖的应用范围。
(3)循环再生性能
为了评价新型壳聚糖凝胶吸附材料的吸附稳定性和循环再生性能,选择0.1MNaOH溶液作为解吸剂,甲基蓝初始浓度为450mg/L进行循环实验。达到吸附平衡后,用解吸剂对饱和吸附的实施例3制备的新型壳聚糖凝胶材料进行解吸,用去离子水洗净再进行下一次循环实验。测试结果如图4所示,经过11次吸附/解吸循环后,新型壳聚糖凝胶材料对甲基蓝的吸附容量仍然保持在800mg/g左右,去除率保持在90%左右,说明新型壳聚糖凝胶吸附材料是一种非常稳定、可再生且高效的吸附剂。
(4)与壳聚糖/戊二醛凝胶材料吸附性能对比
为了探究对比新型壳聚糖凝胶材料与壳聚糖/戊二醛凝胶材料吸附性能,测试了实施例4制备的壳聚糖/戊二醛凝胶材料在0~420min内对甲基蓝染料的吸附容量(甲基蓝溶液初始浓度为400mg/L,反应溶液pH值为6,反应温度为308K)。测试结果如图5所示,吸附量在前10min内急剧增加。随着反应的进行,染料分子在吸附剂表面的有效吸附位点逐渐减少,反应时间持续到30min时吸附速率也有所降低,120min后吸附量基本保持不变,说明基本达到吸附平衡。相较于新型壳聚糖凝胶吸附材料(A/CS),壳聚糖/戊二醛凝胶吸附材料(G/CS)的吸附容量和去除率均有所降低,新型壳聚糖凝胶吸附材料对于甲基蓝染料具备更加优异的吸附性能。
本发明采用的丙烯醛的高反应活性源于羰基与乙烯基的共轭,并且由于醛基的强诱导效应,使丙烯醛的双键极易被引发离子聚合。壳聚糖是一类具有大量活性氨基和羟基的生物大分子,其中的氨基能够有效引发丙烯醛中碳碳双键的聚合反应,并且丙烯醛的羰基在反应过程中也容易被打开参与主链的构建从而留下双键在侧链之上,这些双键可以发生进一步的交联反应。传统壳聚糖凝胶的制备方法多使用戊二醛等作为交联剂,所生成的C=N键酸性条件下不稳定,并且交联度不够高。
Claims (8)
1.一种高吸附型壳聚糖气凝胶的制备方法,其特征在于,包括如下过程:
(1)将壳聚糖溶于酸性水溶液中,搅拌至壳聚糖完全溶解;
(2)将稀释后的α,β-不饱和醛加入(1)中的壳聚糖溶液中,机械搅拌均匀,静置成水凝胶;
(3)用去离子水多次浸泡、洗涤(2)中的水凝胶,然后进行冷冻干燥,得到壳聚糖气凝胶材料。
2.根据权利要求1所述的方法,其特征在于,步骤(1)中,所述酸性水溶液包括冰醋酸水溶液、甲酸水溶液、盐酸水溶液、硝酸水溶液或硫酸水溶液。
3.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,所述酸性水溶液的体积浓度为0.01%~10%。
4.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,所述每100mL酸性水溶液中掺杂壳聚糖为0.1g~10g。
5.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,所述每100mL壳聚糖溶液中掺杂α,β-不饱和醛为0.1mL~5mL。
6.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,所述α,β-不饱和醛包括丙烯醛、反式丁烯醛和苯丙烯醛。
7.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,所述温度范围为0~80℃。
8.根据权利要求1所述的制备方法,其特征在于,步骤(3)中,用纯水浸泡洗涤0.1h~48h。
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