CN111215036A - 一种edta改性磁性壳聚糖环糊精吸附剂的制备方法及其应用 - Google Patents

一种edta改性磁性壳聚糖环糊精吸附剂的制备方法及其应用 Download PDF

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CN111215036A
CN111215036A CN202010027570.5A CN202010027570A CN111215036A CN 111215036 A CN111215036 A CN 111215036A CN 202010027570 A CN202010027570 A CN 202010027570A CN 111215036 A CN111215036 A CN 111215036A
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cyclodextrin
edta
magnetic chitosan
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孙治荣
陈欢
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Beijing University of Technology
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Abstract

一种EDTA改性磁性壳聚糖环糊精吸附剂的制备方法及其应用,属于吸附剂制备领域。采用壳聚糖和环糊精为原料,将四氧化三铁加入壳聚糖环糊精溶液中结合,再加入戊二醛,调节酸碱度沉淀,冷却真空干燥后得磁性壳聚糖环糊精。采用称取乙二胺四乙酸二钠于超纯水,加入活化剂和交联剂机械搅拌使溶液澄清达到充分溶解,再加入经制备的磁性壳聚糖环糊精,酰胺化后清洗干净真空烘干待用。该方法制备的复合颗粒具有易分离,吸附容量高,可重复利用的特性,可以作为一种新型的吸附剂应用于水处理工程中。

Description

一种EDTA改性磁性壳聚糖环糊精吸附剂的制备方法及其应用
技术领域
本发明涉及一种EDTA改性磁性壳聚糖环糊精吸附剂的制备方法及应用,属于吸附剂技术领域。
背景技术
随着现代工业技术的快速发展,环境问题日益严峻,而水污染问题更是重中之重,由于冶金、化工、印染、矿业等行业废水的大量排放,重金属和染料污染日益严重,因此,去除水中重金属和染料对保障人体健康具有非常重要的意义。
β-环糊精是一种无臭无毒的白色结晶粉末,具有略呈锥形的中空圆筒立体环状结构,其独特的内部亲水外部疏水结构非常稳定且不易受酶、pH、热等外在条件的影响,这一独特特性使得其可以与很多无机、有机分子结合形成主-客体复合物,并能改变客体分子的理化性质,具有保护、稳定和选择性定向分子的特性,作为吸附剂、改良剂、稳定剂等,在食品、环保、医药等领域都有广泛的应用。
壳聚糖是甲壳素脱乙酰的产物,常温下为白色或灰白色无定型、半透明固体,天然多糖中唯一的碱性多糖,相对分子量在数十万至数百万。壳聚糖分子链上分布着大量羟基、氨基等活性基团,它们能与很多分子相互作用,使其具有良好的生物相容性、可生物降解性、以及无毒无味等,因此在水处理领域受到高度重视和广泛研究,发展迅速。
通过研究具有特定形貌和结构的多种材料对饮用水或废水中有毒离子的去除效果,发现壳聚糖和环糊精具有价格低廉、原料丰富、环境友好等优异点。因此,本发明采用的方法条件温和、制备方法简单、制备周期短,同时加入磁性四氧化三铁,使得吸附剂带有磁性,便于回收利用,重复吸收效果好,且EDTA 的修饰提高了壳聚糖和环糊精的吸附量,使得其在水中可作为一种安全高效的重金属和染料吸附剂。
发明内容
本发明提供一种环境友好、易于回收、重复利用的EDTA改性磁性壳聚糖环糊精吸附剂,具有较好的吸附性能,在常温和酸性条件下对酸性红B的吸附量可达到460.83mg/g。
本发明提供制备EDTA改性磁性壳聚糖环糊精吸附剂的制备方法,包括如下步骤:
(1)磁性壳聚糖环糊精的制备:
将壳聚糖和β-环糊精溶于0.8-1.2mol/L优选1mol/L盐酸溶液中,搅拌 6-10h后加入四氧化三铁,搅拌成均匀溶液,使其完全溶解,加入50%的戊二醛溶液,反应一段时间,用氢氧化钠溶液调节pH值至8-10使其完全沉淀;所得产品冷却,用乙醇和蒸馏水洗涤后在真空干燥烘干箱用60-80℃烘干8-12h,得到磁性壳聚糖环糊精;
(2)EDTA改性磁性壳聚糖环糊精的制备:
称取乙二胺四乙酸二钠盐于超纯水中超声溶解后,加入活化剂和交联剂,机械搅拌0.5-2h使溶液澄清达到充分溶解,再加入经步骤(1)制备的磁性壳聚糖环糊精,继续机械搅拌6h,经外加磁铁磁性分离,超纯水清洗干净后使用 60-80℃真空烘干,得到EDTA改性磁性壳聚糖环糊精。
上述步骤(1)中所述壳聚糖与环糊精的质量比为1:1-1:8,壳聚糖与四氧化三铁的质量比为1:1-5:1。每1gβ-环糊精溶于对应20-30ml盐酸溶液。
上述步骤(1)中所述盐酸与戊二醛的体积比为50:1-100:1,氢氧化钠的物质的量浓度为0.8-1.2mol/L。
步骤(2)所述活化剂为1-3-乙基碳二亚胺(EDC),交联剂为N-羟基琥珀酰亚胺(NHS)。
上述步骤(2)所述乙二胺四乙酸二钠与1-3-乙基碳二亚胺质量比为10:1,乙二胺四乙酸二钠与N-羟基琥珀酰亚胺质量比为5:1。
每10g乙二胺四乙酸二钠盐对应1-5g步骤(1)的磁性壳聚糖环糊精。
本发明得到以壳聚糖-环糊精为主体的吸附剂吸附水中染料和重金属,作为优选,所述染料为酸性红B,所述重金属为六价铬离子。
与现有技术相比,本发明制备的EDTA改性磁性壳聚糖环糊精吸附剂,具有以下优异效果。
本发明采用生物高分子材料壳聚糖和环糊精与四氧化三铁复合,并被EDTA 修饰得到具有三维多孔结构的改性磁性壳聚糖环糊精吸附剂,可以实现以下三方面的优化。一是使用廉价生物材料壳聚糖和环糊精,来源丰富,避免了对环境的二次污染;二是壳聚糖与环糊精复合后,形成三维多孔结构,提高了吸附剂的表面积,同时EDTA的修饰增强了有效基团,增加了对染料和重金属的吸附能力;三是重复实用性好,解吸后重复利用率高,吸附剂带有磁性,利用磁铁可以快速回收再利用。
附图说明
图1为磁性壳聚糖环糊精吸附剂的扫描电镜图。
图2为EDTA改性磁性壳聚糖环糊精吸附剂的扫描电镜图。
图3为实施例1和实施例2中对酸性红B的吸附容量图。
图4为实施例3中不同温度下对酸性红B的吸附等温线图。
图5为实施例4中不同吸附时间下对酸性红B的吸附影响曲线图。
图6为实施例5和实施例6对六价铬离子吸附容量图。
具体实施方式
下面提供本发明制备方法及应用的具体实例,但本发明并不限于以下实施例。
实施例1
将4g的β-环糊精溶于100ml1mol/L盐酸溶液,搅拌溶解,继续加入1.5g的壳聚糖,将上述溶液转移到250ml烧杯中,搅拌一定时间溶解,加入0.6g的四氧化三铁和1.5ml的50%戊二醛,反应1h后用1mol/L氢氧化钠调节pH值至8-10。继续反应使其完全沉淀,所得产品冷却,用乙醇和蒸馏水洗涤后在真空烘干箱 60-80℃烘干,得到磁性壳聚糖环糊精,进行扫描电镜测试,其测试结果如附图 1所示。显示四氧化三铁镶嵌在壳聚糖环糊精表面,形成了具有粗糙表面的均匀尺寸的纳米球颗粒,增强了吸附剂的磁性。
配制初始浓度为50mg/L,100mg/L,200mg/L,300mg/L,400mg/L的酸性红B 溶液,以容积为250ml的锥形瓶为反应器,加入上述不同浓度的200ml酸性红B溶液,再加入0.25g上述制备的磁性壳聚糖环糊精,将锥形瓶密封后放置于恒温振荡培养箱中,调节温度为25℃,转速为200rpm,振荡340min后,测定剩余酸性红 B浓度,得出最大吸附量为155.76mg/g。
实施例2
具体制备过程在实施例1制备的基础上,称取10g的乙二胺四乙酸二钠盐于 150ml超纯水中超声溶解后,加入1g的活化剂(1-3-乙基碳二亚胺,EDC)和2g 的交联剂(N-羟基琥珀酰亚胺,NHS)机械搅拌1h,使溶液澄清达到充分溶解,再加入3g经步骤(1)制备的磁性壳聚糖环糊精,继续机械搅拌6h,经外加磁铁磁性分离,超纯水清洗干净后真空烘干,得到EDTA改性磁性壳聚糖环糊精,进行扫描电镜测试,其测试结果如附图2所示。显示表面更加光滑以及颗粒更加分散,说明EDTA分子结构中的-COOH可以增加吸附剂的亲水性和分散性,有利于对去污染物的去除。
配制初始浓度为50mg/L,100mg/L,200mg/L,300mg/L,400mg/L的酸性红B 溶液,以容积为250ml的锥形瓶为反应器,加入上述不同浓度的200ml酸性红B溶液,再加入0.25g上述制备的EDTA改性磁性壳聚糖环糊精,将锥形瓶密封后放置于恒温振荡培养箱中,调节温度为25℃,转速为200rpm,振荡340min后,测定剩余酸性红B浓度,得出最大吸附量为460.83mg/g。
附图3给出了EDTA改性后的吸附剂和未改性吸附剂的酸性红B吸附容量的对比图,由图可知,EDTA改性后的吸附剂最大吸附量不仅大大高于未改性的吸附剂最大吸附量,而且对不同浓度的酸性红B都有良好的吸附效果。
实施例3
配制初始浓度为50mg/L,100mg/L,200mg/L,300mg/L,400mg/L的酸性红B 溶液,以容积为250ml的锥形瓶为反应器,加入200ml酸性红B溶液,再加入 0.25gEDTA改性磁性壳聚糖环糊精,将锥形瓶密封后放置于恒温振荡培养箱中,调节温度为25℃,35℃,45℃,转速为200rpm,振荡340min后,测定剩余酸性红 B浓度,计算出不同温度下的吸附容量。
附图4给出了实施例3中不同温度的EDTA改性磁性壳聚糖环糊精吸附酸性红 B的吸附等温线,由图可知,随着温度的增加,吸附量越来越大,说明该吸附过程属于放热反应,适合较高温度下吸附试验。
实施例4
配制初始浓度为50mg/L,100mg/L,200mg/L,300mg/L,400mg/L的酸性红B 溶液,以容积为250ml的锥形瓶为反应器,加入200ml酸性红B溶液,再加入 0.25gEDTA改性磁性壳聚糖环糊精,将锥形瓶密封后放置于恒温振荡培养箱中,调节温度为25℃,转速为200rpm,按照一定的时间梯度取样,测定剩余酸性红B 浓度,计算出不同吸附时间下的吸附容量。
附图5给出了实施例4中不同吸附时间的EDTA改性磁性壳聚糖环糊精吸附酸性红B的吸附影响曲线,从图中可以看出吸附初始阶段吸附速率较快,五种浓度的酸性红B溶液在340min后均达到了平衡,说明EDTA改性磁性壳聚糖环糊精吸附剂对酸性红B吸附速率较快,吸附效果较好。
实施例5:
配制初始浓度为20mg/L,50mg/L,70mg/L,100mg/L,120mg/L的六价铬溶液,以容积为250ml的锥形瓶为反应器,加入100ml上述不同浓度六价铬溶液,再加入0.2g实施例1制备的磁性壳聚糖环糊精,将锥形瓶密封后放置于恒温振荡培养箱中,调节温度为25℃,pH=2,转速为200rpm,振荡480min后,测定剩余六价铬离子浓度,得出最大吸附量为36.96mg/g。
实施例6:
配制初始浓度为20mg/L,50mg/L,70mg/L,100mg/L,120mg/L的六价铬溶液,以容积为250ml的锥形瓶为反应器,加入100ml上述不同浓度六价铬溶液,再加入0.2g实施例2制备的EDTA改性磁性壳聚糖环糊精,将锥形瓶密封后放置于恒温振荡培养箱中,调节温度为25℃,pH=2,转速为200rpm,振荡480min 后,测定剩余六价铬离子浓度,得出最大吸附量为58.84mg/g。
附图6给出了EDTA改性后的吸附剂和未改性吸附剂的六价铬吸附容量的对比图,由图可知,EDTA改性后的吸附剂最大吸附量不仅大大高于未改性的吸附剂最大吸附量,而且对不同浓度的六价铬都有良好的吸附效果。

Claims (10)

1.一种EDTA改性磁性壳聚糖环糊精吸附剂的制备方法,其特征在于,包括以下步骤:
(1)磁性壳聚糖环糊精的制备:
将壳聚糖和β-环糊精溶于0.8-1.2mol/L优选1mol/L盐酸溶液中,搅拌6-10h后加入四氧化三铁,搅拌成均匀溶液,使其完全溶解,加入50%的戊二醛溶液,反应一段时间,用氢氧化钠溶液调节pH值至8-10使其完全沉淀;所得产品冷却,用乙醇和蒸馏水洗涤后在真空干燥烘干箱用60-80℃烘干8-12h,得到磁性壳聚糖环糊精;
(2)EDTA改性磁性壳聚糖环糊精的制备:
称取乙二胺四乙酸二钠盐于超纯水中超声溶解后,加入活化剂和交联剂,机械搅拌0.5-2h使溶液澄清达到充分溶解,再加入经步骤(1)制备的磁性壳聚糖环糊精,继续机械搅拌6h,经外加磁铁磁性分离,超纯水清洗干净后使用60-80℃真空烘干,得到EDTA改性磁性壳聚糖环糊精。
2.按照权利要求1所述的一种EDTA改性磁性壳聚糖环糊精吸附剂的制备方法,其特征在于,上述步骤(1)中所述壳聚糖与环糊精的质量比为1:1-1:8,壳聚糖与四氧化三铁的质量比为1:1-5:1。
3.按照权利要求1所述的一种EDTA改性磁性壳聚糖环糊精吸附剂的制备方法,其特征在于,上述步骤(1)中每1gβ-环糊精溶于对应20-30ml盐酸溶液。
4.按照权利要求1所述的一种EDTA改性磁性壳聚糖环糊精吸附剂的制备方法,其特征在于,上述步骤(1)中所述盐酸与戊二醛的体积比为50:1-100:1。
5.按照权利要求1所述的一种EDTA改性磁性壳聚糖环糊精吸附剂的制备方法,其特征在于,步骤(2)所述活化剂为1-3-乙基碳二亚胺(EDC),交联剂为N-羟基琥珀酰亚胺(NHS)。
6.按照权利要求1所述的一种EDTA改性磁性壳聚糖环糊精吸附剂的制备方法,其特征在于,步骤(2)所述乙二胺四乙酸二钠与1-3-乙基碳二亚胺质量比为10:1,乙二胺四乙酸二钠与N-羟基琥珀酰亚胺质量比为5:1。
7.按照权利要求1所述的一种EDTA改性磁性壳聚糖环糊精吸附剂的制备方法,其特征在于,上述步骤(1)中每10g乙二胺四乙酸二钠盐对应1-5g步骤(1)的磁性壳聚糖环糊精。
8.按照权利要求1-7任一项所述的方法制备得到的EDTA改性磁性壳聚糖环糊精吸附剂。
9.按照权利要求1-7任一项所述的方法制备得到的EDTA改性磁性壳聚糖环糊精吸附剂应用,用于吸附水中染料和重金属。
10.按照权利要求9所述的应用,所述染料为酸性红B,所述重金属为六价铬离子。
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