CN112892502A - 含聚多巴胺的离子螯合剂的制备方法及所得产品 - Google Patents
含聚多巴胺的离子螯合剂的制备方法及所得产品 Download PDFInfo
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Abstract
本发明公开了一种含聚多巴胺的离子螯合剂的制备方法及所得产品,该方法以磁性四氧化三铁微球为芯材,通过表面修饰、多巴胺单体聚合形成聚合物核壳结构,再在磁性核壳微球聚合物上引入具有强重金属离子吸附螯合性能的二硫代氨基甲酸盐。所得离子螯合剂具备磁性和强吸附作用螯合位点,吸附容量高,耐酸/碱性好,操作方便,对重金属离子分离效果好,能够实现对重金属离子污染领域的快速治理,具有巨大的应用潜力。
Description
技术领域
本发明涉及一种含聚多巴胺的离子螯合剂的制备方法及所得产品,还涉及该含聚多巴胺的离子螯合剂在去除污水中的重金属离子的应用。
背景技术
重金属废水主要来源于矿石加工、建材加工、电镀、机械制造、金属和钢材冶炼和一些化工生产等行业,一般含有铜、铅、镍、汞等,去除重金属显得尤为重要。
目前,世界各国重金属废水处理方法主要有三类:第一类是废水中重金属离子通过发生化学反应除去,包括中和沉淀法、硫化物沉淀法、铁氧体共沉淀法、化学还原法、电化学还原法和高分子重金属捕集剂法等。化学法是目前应用较广、技术成熟的水处理方法,但它适用于高浓度重金属废水的处理,且易产生大量污泥。第二类是使废水中的重金属在不改变其化学形态的条件下进行吸附、浓缩、分离的方法。第三类是借助微生物或植物的絮凝、吸收、积累、富集等作用去除废水中重金属。
对于现阶段磁性重金属捕获剂来说,主要是通过硅烷偶联剂对Fe3O4粉体表面进行修饰后再修饰SiO2壳层,再在SiO2表面修饰螯合位点。通过SiO2壳层来提高芯材Fe3O4稳定性,但在修饰SiO2壳层时需要大量的溶剂来保证微胶囊的粒径。该反应会产生大量的废溶剂,实际合成意义不大。因此研发一种合成简单、稳定性好、吸附容量大、应用方便的重金属螯合剂成为研究的重点。
发明内容
针对现有技术存在的不足,本发明提供了一种含聚多巴胺的离子螯合剂的制备方法,该方法合成工艺简单、不会产生大量废水,重现性好,符合绿色环保的工艺要求。
本发明具体技术方案如下:
一种含聚多巴胺的离子螯合剂的制备方法,包括以下步骤:
(1)在四氧化三铁微球表面修饰抗坏血酸(AA),得到Fe3O4@AA微球;
(2)用多巴胺(DA)对Fe3O4@AA微球进行表面改性,得到Fe3O4@AAPDA微球;
(3)将Fe3O4@AAPDA微球分散到氢氧化钠水溶液中,滴加二硫化碳进行反应,反应后分离微球,得到含聚多巴胺的离子螯合剂。该含聚多巴胺的离子螯合剂的合成反应的方程式如下所示:
进一步的,本发明以四氧化三铁微球为基材,四氧化三铁微球具有磁性,在后续使用过程中便于回收,操作便捷。所用四氧化三铁微球的粒径为10 nm-50 um。优选的,四氧化三铁微球的粒径为10-100nm,在此范围内,微球具有较好的比表面积,便于修饰,吸附性能好。
进一步的,步骤(1)中,四氧化三铁微球和抗坏血酸的质量比为1:(0.5~1)。
进一步的,步骤(1)中,将四氧化三铁微球和抗坏血酸在溶剂中进行回流反应,将稳定剂抗坏血酸修饰到四氧化三铁微球表面,得到Fe3O4@AA微球。回流反应的时间一般为3~5h。反应所用的溶剂为水,水的用量为四氧化三铁微球质量的40~100倍。
进一步的,步骤(2)中,Fe3O4@AA微球和多巴胺的质量比为1:(0.2~2)。
进一步的,步骤(2)中,将Fe3O4@AA微球、多巴胺和溶剂混合均匀,然后加入PBS缓冲溶液使体系为弱碱性,充分反应,得到Fe3O4@AAPDA微球。Fe3O4@AA微球、多巴胺和溶剂可以在超声下进行分散混合。加入PBS缓冲溶液后,反应3-4h。反应所用的溶剂为水,所用的PBS缓冲溶液即为磷酸缓冲盐溶液,其pH为7.4。溶剂用量为Fe3O4@AA微球质量的1000~1500倍,PBS缓冲溶液与溶剂的质量比为1:0.9-1.1,优选为1:1。
进一步的,步骤(3)中,Fe3O4@AAPDA微球上的NH与NaOH、二硫化碳进行反应形成二硫代氨基甲酸钠,CS2与Fe3O4@AAPDA微球的质量比为1:1~2,CS2与NaOH按照理论摩尔量加入,或者CS2过量加入, NaOH与CS2的摩尔比优选为1:1-2。
进一步的,步骤(3)中,在室温下滴加二硫化碳,滴完后保持该温度继续反应2-5h。反应所用的NaOH溶液的浓度为1-5 mol/L。
本发明还提供了按此方法制得的含聚多巴胺的离子螯合剂,该离子螯合剂具有磁性,对多种重金属离子有很好的吸附效果,稳定性好,吸附容量大,吸附操作简单,便于回收。其结构式如下所示:
本发明含聚多巴胺的离子螯合剂是一种新型的磁性捕集重金属材料,以具有磁性的四氧化三铁作为基材,便于吸附分离操作,用抗坏血酸来稳定Fe3O4,用聚多巴胺和二硫代氨基甲酸钠(DTC)进行表面修饰,使Fe3O4表面富含稳定剂抗坏血酸和聚多巴胺,聚多巴胺表面富含螯合位点,增加了螯合剂的吸附容量。该螯合剂可以实现大部分重金属离子的吸附去除,分离操作简单易行,是一种吸附操作便捷的高性能吸附材料。
本发明还提供了该含聚多巴胺的离子螯合剂在吸附重金属离子中的应用,所述重金属离子可以为Cu2+,Cd2+,Ni2+,Pb2+,Hg2+等重金属离子。
进一步的,本发明还提供了一种废水中重金属的处理方法,该处理方法为:用上述含聚多巴胺的离子螯合剂作为重金属吸附剂吸附废水中的重金属离子。所述重金属离子包括Cu2+,Cd2+,Ni2+,Pb2+,Hg2+等重金属离子。
进一步的,上述处理方法中,所述废水为含有重金属离子的废水,主要为工业废水。
本发明具有以下有益效果:
1、本发明含聚多巴胺的离子螯合剂由四氧化三铁、抗坏血酸、多巴胺、氢氧化钠和二硫化碳反应得到,原料易得,合成工艺简单,操作简易,合成过程不会产生大量废水,环保性更高,在实际应用中可实施性高。
2、本发明含聚多巴胺的离子螯合剂以磁性四氧化三铁为基材,先在磁性微球表面修饰稳定剂抗坏血酸和聚多巴胺,然后再引入具有强吸附螯合性能的二硫代氨基甲酸钠,通过二硫代氨基甲酸钠与重金属离子配位螯合,从而实现对废水中重金属离子的去除。该含聚多巴胺的离子螯合剂吸附效能高,可以实现大部分重金属离子的吸附去除,吸附重离子后分离操作简单易行,是一种吸附操作便捷的高性能吸附材料。
3、本发明含聚多巴胺的离子螯合剂兼备磁性和强吸附作用螯合位点,耐酸/碱性好,能够方便的进行操作和在较短的时间内对重金属离子Cu2+,Cd2+,Ni2+,Pb2+,Hg2+等实现吸附分离,能够实现对含重金属离子的废水的快速治理,便于回收,操作方便快捷,具有巨大的应用潜力。
具体实施方式
下面通过具体实施例进一步说明本发明,但本发明并不限于此,具体保护范围见权利要求。
实施例1
1、将1g粒径500 nm的四氧化三铁微球分散在100 mL去离子水中,加入0.5 g抗坏血酸,加热回流3 h。反应结束后用强磁铁对产物进行分离,用20 mL去离子水洗涤三次,真空干燥得到抗坏血酸修饰的Fe3O4@AA微球。
2、将1g上述制备的Fe3O4@AA微球均匀分散在1000 mL去离子水中,加入0.5 g多巴胺,超声分散1 h,加入1000 mL PBS缓冲溶液(pH7.4)反应3 h。反应结束后用高强磁铁对产物进行分离,用去离子水、乙醇交替洗涤三次(20 mL/次),真空干燥得到Fe3O4@AAPDA微球。
3、将1g Fe3O4@AAPDA微球分散在10 mL 1 mol/L的NaOH水溶液中,慢慢滴加1 g二硫化碳,滴完后室温搅拌反应3小时,然后用强磁铁对产物进行分离,去离子水20 mL洗涤三次后,真空干燥,得到含聚多巴胺的离子螯合剂。
实施例2
1、将2 g粒径100 nm的四氧化三铁微球均匀分散在150 mL去离子水中,加入1.5 g抗坏血酸,加热回流5 h。反应结束后用强磁铁对产物进行分离,用20 mL去离子水洗涤三次,真空干燥得到抗坏血酸修饰的Fe3O4@AA。
2、将1 g上述制备的Fe3O4@AA微球均匀分散在1100 mL去离子水中,加入1 g多巴胺,超声分散1 h,加入1100 mL PBS缓冲溶液(pH7.4)反应3 h。反应结束后用高强磁铁对产物进行分离,用去离子水、乙醇交替洗涤三次(20 mL/次),真空干燥得到Fe3O4@AAPDA微球。
3、将1g Fe3O4@AAPDA微球分散在5 mL 2 mol/L的NaOH水溶液中,慢慢滴加1 g二硫化碳,滴完后室温搅拌反应3小时,然后用强磁铁对产物进行分离,去离子水10 mL洗涤三次后,真空干燥,得到含聚多巴胺的离子螯合剂。
实施例3
1、将1g粒径50 nm的四氧化三铁微球分散在100 mL去离子水中,加入1 g抗坏血酸,加热回流4 h。反应结束后用强磁铁对产物进行分离,用20 mL去离子水洗涤三次,真空干燥得到抗坏血酸修饰的Fe3O4@AA微球。
2、将1g上述制备的Fe3O4@AA微球均匀分散在1500 mL去离子水中,加入1 g多巴胺,超声分散1 h,加入1500 mL PBS缓冲溶液(pH7.4)反应3 h。反应结束后用高强磁铁对产物进行分离,用去离子水、乙醇交替洗涤三次(20 mL/次),真空干燥得到Fe3O4@AAPDA微球。
3、将1g Fe3O4@AAPDA微球分散在8 mL 1 mol/L的NaOH水溶液中,慢慢滴加1 g二硫化碳,滴完后室温搅拌反应3小时,然后用强磁铁对产物进行分离,去离子水20 mL洗涤三次后,真空干燥,得到含聚多巴胺的离子螯合剂。
实施例4
1、将2 g粒径10 nm的四氧化三铁微球均匀分散在100 mL去离子水中,加入1 g抗坏血酸,加热回流5 h。反应结束后用强磁铁对产物进行分离,用20 mL去离子水洗涤三次,真空干燥得到抗坏血酸修饰的Fe3O4@AA。
2、将1 g上述制备的Fe3O4@AA微球均匀分散在1500 mL去离子水中,加入2 g多巴胺,超声分散1 h,加入1500 mL PBS缓冲溶液(pH7.4)反应3 h。反应结束后用高强磁铁对产物进行分离,用去离子水、乙醇交替洗涤三次(20 mL/次),真空干燥得到Fe3O4@AAPDA微球。
3、将1 g Fe3O4@AAPDA微球分散在10mL 1 mol/L的NaOH水溶液中,慢慢滴加1 g二硫化碳,滴完后室温搅拌反应3小时,然后用强磁铁对产物进行分离,去离子水10 mL洗涤三次后,真空干燥,得到含聚多巴胺的离子螯合剂。
实施例5
1、将2 g粒径50 um的四氧化三铁微球均匀分散在80 mL去离子水中,加入1 g抗坏血酸,加热回流5 h。反应结束后用强磁铁对产物进行分离,用20 mL去离子水洗涤三次,真空干燥得到抗坏血酸修饰的Fe3O4@AA。
2、将1 g上述制备的Fe3O4@AA微球均匀分散在1000 mL去离子水中,加入0.5 g多巴胺,超声分散1 h,加入1000 mL PBS缓冲溶液(pH7.4)反应3 h。反应结束后用高强磁铁对产物进行分离,用去离子水、乙醇交替洗涤三次(20 mL/次),真空干燥得到Fe3O4@AAPDA微球。
3、将1 g Fe3O4@AAPDA微球分散在7 mL 1 mol/L的NaOH水溶液中,慢慢滴加1 g二硫化碳,滴完后室温搅拌反应3小时,然后用强磁铁对产物进行分离,去离子水10 mL洗涤三次后,真空干燥,得到含聚多巴胺的离子螯合剂。
应用例
对上述实施例制得的含聚多巴胺的离子螯合剂对重金属的吸附性能进行测试,方法如下:
准确称量一定量的上述实施例制备的离子螯合剂(m),加入到一定体积(V)、一定浓度(C0)的重金属离子溶液中(pH为5)。在室温振荡摇床中充分吸收,直至吸收饱和,用强磁铁对螯合剂进行分离。采用电感耦合原子发射光谱测得吸收饱和后溶液中重金属离子的浓度(Ce)。
含聚多巴胺的离子螯合剂对贵金属离子的吸附容量Qe按下式进行计算:
Qe = (C0-Ce)V/m
其中,C0单位 mol/L;Ce单位 mol/L;V单位 ml;m单位 g。
各重金属离子螯合剂对各重金属离子的吸附容量如下表1所示:
Claims (10)
1.一种含聚多巴胺的离子螯合剂的制备方法,其特征是包括以下步骤:
(1)在四氧化三铁微球表面修饰抗坏血酸,得到Fe3O4@AA微球;
(2)用多巴胺对Fe3O4@AA微球进行表面改性,得到Fe3O4@AAPDA微球;
(3)将Fe3O4@AAPDA微球分散到氢氧化钠水溶液中,滴加二硫化碳进行反应,反应后分离微球,得到含聚多巴胺的离子螯合剂。
2.根据权利要求1所述的制备方法,其特征是:步骤(1)中,四氧化三铁微球的粒径为10nm-50 um,优选为10-100nm。
3.根据权利要求1或2所述的制备方法,其特征是:步骤(1)中,四氧化三铁微球和抗坏血酸的质量比为1:0.5~1;步骤(2)中,Fe3O4@AA微球和多巴胺的质量比为1:0.2~2;步骤(3)中,CS2与Fe3O4@AAPDA微球的质量比为1:1-2,NaOH与CS2的摩尔比为1:1-2。
4.根据权利要求1或2所述的制备方法,其特征是:步骤(1)中,将四氧化三铁微球和抗坏血酸在溶剂中进行回流反应,得到Fe3O4@AA微球。
5.根据权利要求1或2所述的制备方法,其特征是:步骤(1)中,反应时间为3-5h;反应溶剂为水,水的用量为四氧化三铁微球质量的40~100倍。
6.根据权利要求4所述的制备方法,其特征是:步骤(2)中,将Fe3O4@AA微球、多巴胺和溶剂混合均匀,然后加入PBS缓冲溶液,充分反应,得到Fe3O4@AAPDA微球。
7.根据权利要求6所述的制备方法,其特征是:步骤(2)中,PBS缓冲溶液的pH为7.4,所述溶剂为水。
8.根据权利要求6或7所述的制备方法,其特征是:步骤(2)中,溶剂用量为Fe3O4@AA微球质量的1000~1500倍,PBS缓冲溶液与溶剂的质量比为1:0.9-1.1;加入PBS缓冲溶液后反应3-4h。
9.根据权利要求1所述的制备方法,其特征是:步骤(3)中,在室温下滴加二硫化碳,滴完后保持该温度继续反应2-5 h;NaOH溶液的浓度为1-5 mol/L。
10.按照权利要求1-9中任一项所述的含聚多巴胺的离子螯合剂的制备方法制得的含聚多巴胺的离子螯合剂。
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