CN111068626B - 一种磁性二硫代氨基甲酸改性壳聚糖微球及制备方法和应用 - Google Patents
一种磁性二硫代氨基甲酸改性壳聚糖微球及制备方法和应用 Download PDFInfo
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Abstract
本发明公开一种磁性二硫代氨基甲酸改性壳聚糖微球及其制备方法,本发明以壳聚糖为原料,四氧化三铁纳米颗粒为磁核先制备磁性壳聚糖微球,再以二硫化碳为改性剂制备得到磁性二硫代氨基甲酸改性壳聚糖微球。通过对壳聚糖磁性微球进行二硫代氨基甲酸改性,不仅可以增加壳聚糖磁性微球在酸性介质中的稳定性,同时引入的巯基中的大量S配位原子能与金属离子形成稳定的配合物,提高对金属离子的吸附性能,尤其增加对废水中Cr(VI)的吸附能力。
Description
技术领域
本发明环境工程应用领域,具体涉及一种磁性二硫代氨基甲酸改性壳聚糖微球和制备方法,以及所述磁性二硫代氨基甲酸改性壳聚糖微球在吸附废水中Cr(VI)的应用。
背景技术
水是生命之源,是人类及一切生物赖以生存发展,不可或缺的自然资源。但是近年来,随着科技进步,全球工业农业的迅猛发展,需水量也在日益增加,与之相应的是大量废水排放,日益严峻的水体污染问题俨然成为了人类发展所面临的重要挑战之一。
铬是自然界中广泛存在的元素之一,铬及其化合物广泛应用于电镀、制革即涂料等行业,因此,在生产过程中不可避免得产生大量含铬废水。铬的存在形式以Cr(III)和Cr(VI)为主,其中Cr(VI)是最常见的重金属污染物之一,其氧化性强,毒性强,会随着河流或地下水而转移,继而污染水和土壤资源,危害动物和植物的生活环境,进而影响人类生活,危害人类健康。
Cr(VI)化合物不能自然降解,目前处理Cr(VI)废水的主要技术包括化学沉淀法、离子交换法、生物法、吸附法、生物法。吸附法是利用固体吸附剂将废水中的重金属物质吸附于表面,再将溶质解析,以达到分离和富集金属的目的。吸附法具有设备简单、方便操作、成本低、无二次污染、处理效果好等特点,使其在快速处理含Cr(VI)废水方法具有应用价值。目前利用吸附法处理含Cr(VI)废水技术核心是开发一种吸附效率高且成本低的吸附材料,既能有效的吸附废水中Cr(VI)元素,还能降低废水处理成本。
壳聚糖是由甲壳素经脱乙酰氨基而得到的一种天然碱性氨基多糖,是一种生物相容性好、易生物降解、无毒、廉价易得的天然高分子生物材料。壳聚糖分子中含有大量的氨基和羟基,这些基团中存在孤对电子,与重金属离子可形成稳定的螯合物。但壳聚糖水溶性差,仅溶于稀酸溶液,在酸性条件下,壳聚糖C2位上的-NH2易形成-NH3 +,不利于重金属的吸附,使得吸附效果差,限制了其应用。同时,仅以壳聚糖作为重金属吸附剂还存在吸附剂回收率低,不利于吸附剂的重复使用,由此导致处理成本增加。
二硫代氨基甲酸含有S、N等配位原子,可以和许多重金属离子形成稳定常数很高的螯合物。为此,本发明在碱性条件下将二硫化碳与壳聚糖微球反应得到二硫代氨基甲酸改性的壳聚糖微球。通过对壳聚糖磁性微球进行二硫代氨基甲酸改性,不仅可以增加壳聚糖磁性微球在酸性介质中的稳定性,同时引入的巯基中的大量S配位原子能与金属离子形成稳定的配合物,提高壳聚糖对金属离子的吸附性能。
磁性四氧化三铁纳米颗粒具有良好的兼容性和顺磁性,毒性低,且易从液相中分离。本发明技术人员以壳聚糖为原料,四氧化三铁纳米颗粒为磁核制备磁性壳聚糖微球,再以二硫化碳为改性剂对磁性壳聚糖微球进行改性,制备得到一种磁性二硫代氨基甲酸改性壳聚糖微球,并将其应用于废水中Cr(VI)的吸附处理。
发明内容
本发明的一个目的是提供一种磁性二硫代氨基甲酸改性壳聚糖微球及其制备方法,本发明的另一个目的是提供一种磁性二硫代氨基甲酸改性壳聚糖微球在吸附废水中Cr(VI)的应用。
本发明的目的是通过以下技术方案实现的:
第一方面,本发明提供一种磁性二硫代氨基甲酸改性壳聚糖微球的制备方法,包括如下步骤:
(1)制备水基Fe3O4纳米磁性材料:将含铁化合物溶于聚乙二醇溶液中,滴加浓氨水至pH≥10,熟化反应1-2h,再用酸中和至pH=7.0,磁场分离得到水基Fe3O4纳米磁性材料;
(2)制备磁性壳聚糖微球:向壳聚糖溶液中加入步骤(1)制备的Fe3O4纳米磁性材料,超声混匀,通过乳化交联法制备得到磁性壳聚糖微球;
(3)制备磁性二硫代氨基甲酸改性壳聚糖微球:将步骤(2)制备的磁性壳聚糖微球悬浮于甲醇中得到浓度为10-30mg/mL的悬浮液,超声混匀,加入二硫化碳,超声反应0.5-2h,磁场分离,得到磁性二硫代氨基甲酸改性壳聚糖微球。
步骤(1)中所述含铁化合物包括但不限于水合氯化铁(FeCl3·6H2O)、水合氯化亚铁(FeCl2·4H2O)、水合硫酸铁(Fe2(SO4)3·9H2O)、水合硫酸亚铁(FeSO4·7H2O)中的一种或两种以上的组合。
在本发明最优选实施方式中,所述含铁化合物为水合硫酸铁和水合硫酸亚铁的组合,水合硫酸铁与水合硫酸亚铁的质量比为4-10:1。
优选的,所述步骤(1)中用于调节体系pH的酸选自乙酸或盐酸,在本发明中使用质量百分比浓度为25%的乙酸。
优选的,所述步骤(1)中磁场分离具体为将反应体系置于吸铁石正上方静置1-3h,倾倒上层液体和浮渣,再用蒸馏水洗涤微球3-5次,得到乌黑发亮的水基Fe3O4纳米磁性材料。
优选的,步骤(2)中壳聚糖溶液为壳聚糖溶于质量百分比为2.5%乙酸中形成的溶液,壳聚糖与Fe3O4纳米磁性材料加入质量比为1-5:1;更优选的,壳聚糖与Fe3O4纳米磁性材料加入质量比为1-3:1;在本发明最优选实施方式中,壳聚糖与Fe3O4纳米磁性材料加入质量比为3:1。
所述乳化交联法具体为:壳聚糖与Fe3O4纳米磁性材料混合液少量多次加入到含3%乳化剂斯盘-80的液体石蜡中,在35℃恒温下以3000转/min转速搅拌乳化,完毕,加入质量百分比浓度为25%的戊二醛溶液进行固化,磁场分离得到目标产物。
优选的,所述步骤(2)还包括采用磁过滤方式将产物用***洗涤微球表面3-5次,再用蒸馏水洗涤3-5次,随后在真空烘箱中60℃下干燥1-3h。
优选的,所述步骤(3)中加入二硫化碳后超声反应0.5-1h,最优选的,超声反应1h,加入二硫化碳的体积百分比为6%。
优选的,所述步骤(3)还包括采用磁过滤方式将产物用无水乙醇洗涤微球表面3-5次,再用蒸馏水洗涤3-5次,随后在真空烘箱中60℃下干燥1-3h。
第二方面,本发明提供一种磁性二硫代氨基甲酸改性壳聚糖微球,所述微球通过上述方法制备得到。
第三方面,本发明还提供一种磁性二硫代氨基甲酸改性壳聚糖微球在吸附废水中Cr(VI)的应用。
优选的,所述废水中Cr(VI)的浓度为100-200mg/L。
磁性二硫代氨基甲酸改性壳聚糖微球作为吸附剂吸附重金属离子后,采用磁场分离,再用碱性溶液浸泡和/或洗涤解吸,可以反复利用。
优选的,所述碱性溶液选自体积分数为10-20%的氨水,或浓度为0.1-0.5%的氢氧化钠溶液。
在本发明的优选实施方式中,所述碱性溶液是体积分数为10%的氨水。
本发明制备的磁性二硫代氨基甲酸改性壳聚糖微球可反复利用3-5次,优选利用3次。
本发明的有益效果是:壳聚糖大分子链上活泼的氨基在氢氧化钠的催化作用下,与二硫化碳进行非均相反应,氨基上的氢原子被取代,生成壳聚糖的二硫代氨基甲酸盐。二硫化碳将二硫代氨基甲酸基团引入到壳聚糖分子结构中,而二硫代氨基甲酸基团上的巯基(-SH)S原子具有比-NH2、-OH上的N、O配位原子与金属离子更强的配位能力,因而对金属离子的吸附能力更强。同时交联反应通过壳聚糖分子中的氨基和戊二醛的醛基发生加成消除反应,把线性壳聚糖分子交联成网状大分子,由此增强了壳聚糖在酸性介质中易溶解损失的问题。磁性Fe3O4纳米颗粒具有良好的兼容性和磁响应性,在废水处理后,磁性Fe3O4纳米材料负载的二硫代氨基甲酸改性壳聚糖微球可与治理后水体的快速分离,且分离后的磁性二硫代氨基甲酸改性壳聚糖微球还能够再生与重复利用。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅是本发明的部分实施例,而不是全部。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
S1:将5g聚乙二醇4000溶于100mL蒸馏水中,按质量比为1:4加入FeSO4·7H2O和Fe2(SO4)3·9H2O共11.12g充分溶解,在搅拌和50℃保温条件下,滴加浓氨水至pH≥10.0,再继续熟化反应2h后用质量百分比浓度为25%乙酸中和至pH=7.0,磁场分离,倾倒上层液体和浮渣后,用蒸馏水洗涤除杂质,即得到乌黑发亮的水基Fe3O4纳米磁性材料;
S2:准确称取0.3g壳聚糖溶于质量百分比为2.5%的10mL乙酸溶液中,按壳聚糖:Fe3O4纳米磁性材料=3:1的质量比例加入0.1g步骤S1制备的Fe3O4纳米磁性材料,超声5-10min使混匀;
S3:取5g混合液少量多次加入到含3%乳化剂斯盘-80的60mL液体石蜡中,在35℃恒温下以3000转/min转速搅拌乳化1h,乳化完毕,加入质量百分比浓度为25%的戊二醛溶液0.15mL固化6h,之后将反应物转移至小烧杯中,磁场分层,弃去上清液,用***少量分3次洗涤微球表面的有机容积,再用蒸馏水洗涤三次,磁过滤后,产品在真空烘箱中于60℃干燥得到磁性壳聚糖微球;
S4:称取1g磁性壳聚糖微球,悬浮于50mL甲醇中,搅拌下滴加50mL质量百分比为8%的氢氧化钠溶液,超声均匀后静置脱气泡,加入体积百分比为6%的二硫化碳,超声反应1h,反应完成后,将产物用磁场分离,弃去上清液,分别用无水乙醇和蒸馏水洗涤三次,磁过滤后,产品在真空烘箱中于60℃干燥得到磁性二硫代氨基甲酸改性壳聚糖微球。
实施例2
制备方法与制备原料同实施例1,区别仅在于步骤S4中加入二硫化碳后超声反应0.5h。
实施例3
制备方法与制备原料同实施例1,区别仅在于步骤S2中壳聚糖:Fe3O4纳米磁性材料=1:1,加入的Fe3O4纳米磁性材料为0.3g。
对比实施例1
制备方法与制备原料同实施例1,区别仅在于步骤S4中不添加二硫化碳。
效果例1
实验目的:检测本发明制备的磁性二硫代氨基甲酸改性壳聚糖微球吸附Cr(VI)的能力;
实验方法:向250mL具塞锥形瓶中加入100mL Cr(VI)浓度为100mg/L的重铬酸钾溶液,调节pH为5.0,分别向溶液中加入100mg实施例1-3制备的磁性二硫代氨基甲酸改性壳聚糖微球和对比实施例1制备的磁性壳聚糖微球,将具塞锥形瓶放入恒温震荡器中,在25℃、180转/min条件下进行吸附,60min时取样,采用国家水质监测标准分析方法中规定的二苯碳酰二肼分光光度法测定Cr(VI)浓度,计算得吸附剂的吸附容量;
实验结果:实验结果如下表所示。
表1磁性二硫代氨基甲酸改性壳聚糖微球对Cr(VI)的吸附容量
实施例1制备的壳聚糖微球为二硫代氨基甲酸改性的磁性壳聚糖微球,对比实施例1是没有经过改性的磁性壳聚糖微球,实施例1微球的吸附容量(585mg/g)是对比实施例1微球吸附容量(142.6mg/g)的4倍还多,说明经过二硫代氨基甲酸改性后的磁性壳聚糖微球对水中Cr(VI)的吸附能力有显著提升。实施例1与实施例2吸附容量数据对比说明,在加入二硫化碳后超声反应1小时的效果比超声0.5小时效果更好一些。实施例1与实施例3数据对比说明,在制备磁性壳聚糖微球过程中,壳聚糖与Fe3O4纳米磁性材料最佳质量比为3:1。
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (6)
1.一种用于吸附废水中Cr(VI)的磁性二硫代氨基甲酸改性壳聚糖微球的制备方法,包括如下步骤:
(1)制备水基Fe3O4纳米磁性材料:将含铁化合物溶于聚乙二醇溶液中,滴加浓氨水至pH≥10,熟化反应1-2h,再用酸中和至pH=7.0,磁场分离得到水基Fe3O4纳米磁性材料;
(2)制备磁性壳聚糖微球:向壳聚糖溶液中加入步骤(1)制备的Fe3O4纳米磁性材料,超声混匀,通过乳化交联法制备得到磁性壳聚糖微球,壳聚糖溶液为壳聚糖溶于质量百分比为2.5%乙酸中形成的溶液,壳聚糖与Fe3O4纳米磁性材料加入质量比为3:1;
(3)制备磁性二硫代氨基甲酸改性壳聚糖微球:将步骤(2)制备的磁性壳聚糖微球悬浮于甲醇中得到浓度为10-30mg/mL的悬浮液,超声混匀,加入二硫化碳,二硫化碳的体积百分比为6%,超声反应1h,磁场分离,得到磁性二硫代氨基甲酸改性壳聚糖微球,所述废水中Cr(VI)的浓度为100-200mg/L。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中所述含铁化合物包括但不限于水合氯化铁、水合氯化亚铁、水合硫酸铁、水合硫酸亚铁中的一种或两种以上的组合。
3.根据权利要求2所述的制备方法,其特征在于,所述含铁化合物为水合硫酸铁和水合硫酸亚铁的组合,水合硫酸铁与水合硫酸亚铁的质量比为4-10:1,步骤(1)中用于调节体系pH的酸选自乙酸或盐酸。
4.根据权利要求1所述的制备方法,其特征在于,所述步骤(1)中磁场分离具体为将反应体系置于吸铁石正上方静置1-3h,倾倒上层液体和浮渣,再用蒸馏水洗涤3-5次,得到水基Fe3O4纳米磁性材料。
5.根据权利要求1所述的制备方法,其特征在于,所述步骤(2)和(3)还包括采用磁过滤方式将产物用无水乙醇洗涤微球表面3-5次,再用蒸馏水洗涤3-5次,随后在真空烘箱中60℃下干燥1-3h。
6.一种磁性二硫代氨基甲酸改性壳聚糖微球,所述微球由权利要求1-5任一项所述的方法制备得到。
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