CN112090406A - 一种聚乙烯亚胺改性壳聚糖磁性复合材料制备方法 - Google Patents
一种聚乙烯亚胺改性壳聚糖磁性复合材料制备方法 Download PDFInfo
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Abstract
本发明属于复合材料领域,具体涉及一种聚乙烯亚胺改性壳聚糖磁性复合材料制备方法,该吸附剂以球形磁性四氧化三铁为核、壳聚糖为壳制备了壳聚糖包覆的四氧化三铁核壳结构,再通过改性制备聚乙烯亚胺改性壳聚糖磁性复合吸附剂。本发明将分子链中含有具有大量氨基的聚乙烯亚胺修饰壳聚糖,并在制备过程中加入三氯化铁,成功制备出易于分离的且能有效去除废水中污染物质的聚乙烯亚胺改性壳聚糖磁性复合材料,解决了传统吸附剂难分离的缺点。
Description
技术领域
本发明属于复合材料领域,具体涉及一种聚乙烯亚胺改性壳聚糖磁性复合材料制备方法。
背景技术
随着人类社会的日益发展,重金属污水因毒性大、难于处理等特点已成为社会各界广泛性关注的难题,如废水中的六价铬离子的毒性是三价铬离子的500倍。因壳聚糖是甲壳素去乙酰基形成的一种环境友好型可再生天然高分子,然因壳聚糖分子内强氢键作用、结晶度高、不溶于水和通常的有机溶剂限制了它的进一步应用,但其分子单体中含有两个活性羟基和一个氨基,它们化学性质相对活泼,为壳聚糖改性提供了可能;将壳聚糖直接用于吸附剂,有限的吸附活性位点不仅限制了其吸附能力,而且难于回收再利用增加了经济成本和回收重金属的目的。
聚乙烯亚胺(PEI)分子链上拥有大量可以和重金属发生螯合作用的给电子氨基N原子,当水溶液pH小于10时,其分子链上处于质子化状态的氨基可以通过静电引力作用去除水中阴离子。然而聚乙烯亚胺具有良好的水溶性,难以实现固/液分离,使得聚乙烯亚胺不能直接用于去除水体环境中的污染物质。
国内已有相关人员公开了一种生活污水处理剂,包括以下组分:聚乙烯亚胺、壳聚糖、聚合三氯化铁、聚合三氯化铝、膨润土、氯化钠、石灰、吸附物、碳酸钠、pH调节剂、三甲基环丙烷基氯化铵、聚丙烯酸钠、苄基三乙基氯化铵、十二烷基苯磺酸钠等14种原料制备而成,其一般用于生活污水处理方面,在含重金属的工业废水中应用较少,且该种修复剂较难回收处理。
基于已有研究,本发明以壳聚糖、三氯化铁、聚乙烯亚胺为原料,制备聚乙烯亚胺改性壳聚糖磁性复合材料(MCMC-PEI),解决了传统吸附剂难于分离再利用以及增加壳聚糖分子链上的吸附活性位点等问题,并用于模拟含Cr(VI)废水处理。
发明内容
本发明的目的是克服现有技术存在的缺陷,提供一种吸附效率高、可分离性能好、可重复利用的具有多活性位点的聚乙烯亚胺改性壳聚糖磁性复合材料制备方法。
实现本发明目的的技术方案是:一种聚乙烯亚胺改性壳聚糖磁性复合吸附剂制备方法;所述吸附剂以球形磁性四氧化三铁为核、壳聚糖为壳制备了壳聚糖包覆的四氧化三铁核壳结构,再通过改性制备聚乙烯亚胺改性壳聚糖磁性复合吸附剂。
上述的聚乙烯亚胺改性壳聚糖磁性复合吸附剂制备方法,包括如下步骤:
(1)首先,将十二烷基苯磺酸钠在室温搅拌下溶于有机溶剂中,待充分溶解后将FeCl3.6H2O和NaAc加入到上述溶液中;
(2)将步骤(1)中所得溶液转入反应釜中于453 K下反应12h,待反应结束后将黑色产物经磁性分离后用去离子水、乙醇洗涤三次,置于真空干燥箱中干燥,制得Fe3O4空心微粒;
(3)随后将壳聚糖溶于2%弱酸溶液中,并加入Fe3O4空心微粒搅拌;
搅拌均匀后加入pH调节剂,调节pH至9时转至盛有液体石蜡的三口烧瓶中,于60℃水浴条件下加入交联剂反应2h;待反应结束经过滤后,采用有机溶剂进行多次洗涤,洗涤后置于真空干燥箱中于60℃干燥24h备用,即得磁性壳聚糖;
(4)将磁性壳聚糖分散于50%(w/v) NaOH溶液中,在搅拌条件
下于40~60℃碱化2h;再将溶有氯乙酸的异丙醇逐滴加入到上述溶液中,在相同温度下反应4h;加入70%(v/v)乙醇终止反应,经磁性分离后用蒸馏水洗涤至中性、再用乙醇洗涤数次后真空干燥24h,即得磁性羧甲基壳聚糖;
(5)将上述磁性羧甲基壳聚糖分散于蒸馏水中并调节pH值为4并加入活化剂在室温搅拌下活化0.5h;然后加入聚乙烯亚胺溶液,并调节pH值为5于室温反应24h;待反应结束经磁性分离后依次用蒸馏水、乙醇洗涤数次后置于真空干燥箱中干燥,即得聚乙烯亚胺改性壳聚糖磁性复合材料。
上述技术方案,所述步骤(1)中十二烷基苯磺酸钠、FeCl3 .6H2O和NaAc的质量比为16:54:(80~100)。
上述技术方案,所述步骤(1)中有机溶剂为乙二醇或水合肼。
上述技术方案,所述步骤(2)中反应釜中压力为162 ~ 170kPa 。
上述技术方案,所述步骤(3)中的弱酸为乙酸或低浓度盐酸;所述pH调节剂为氢氧化钠。
上述技术方案,所述步骤(3)中交联剂为戊二醛,使得壳聚糖和四氧化三铁具备均匀的核壳结构。
上述技术方案,所述步骤(3)采用有机溶剂石油醚和乙醇依次进行洗涤。
上述技术方案,所述步骤(4)中氯乙酸和磁性壳聚糖的质量比为(1~10):1。
上述技术方案,所述步骤(5)中的活化剂为1-(3-二甲氨基丙基)-3-乙基碳二亚胺(EDC)和N-羟基琥珀酰亚胺(NHS),质量比为(1~5):1。
采用上述技术方案后,本发明具有以下积极的效果:
(1)本发明将分子链中含有具有大量氨基的聚乙烯亚胺修饰壳聚糖,并在制备过程中加入三氯化铁,成功制备出易于分离的且能有效去除废水中污染物质的聚乙烯亚胺改性壳聚糖磁性复合材料,解决了传统吸附剂难分离的缺点;
(2)本发明解决了单一壳聚糖作为吸附剂难以分离以及吸附活性位点有限等缺点;
(3)本发明中合成所用的壳聚糖为环境友好型可再生天然高分子,不溶于水和通常的有机溶剂,安全环保;
(4)本发明成本低廉,且本发明合成的聚乙烯亚胺改性壳聚糖磁性复合材料与传统吸附材料相比拥有更好的分离性能及良好的重金属吸附性能,在重金属废水处理领域中有很好的应用前景。
附图说明
为了使本发明的内容更容易被清楚地理解,下面根据具体实施例并结合附图,对本发明作进一步详细的说明,其中
图1为实施例4吸附剂材料的红外光谱图;
图2为磁性Fe3O4和实施例4吸附剂材料的磁滞回线图;
图3为聚乙烯亚胺加入量对实施例1、2、3、4吸附剂材料吸附性能的影响;
图4为实施例4吸附剂材料经历1~4次吸附-脱附循环后对Cr(Ⅵ)的吸附性能图。
具体实施方式
本发明为一种制备聚乙烯亚胺改性壳聚糖磁性复合材料的方法,包括以下步骤:
(1)首先,将0.16 g十二烷基苯磺酸钠在室温搅拌下溶于16 mL乙二醇中,待充分溶解后将0.5 ~ 0.6 g FeCl3 .6H2O和0.90 ~ 0.95g NaAc加入到上述溶液中。本步骤中的乙二醇不仅为溶剂,而且还是还原剂,可以对FeCl3起到还原的作用。
(2)其次,将溶液转入25 mL反应釜中于453 K下反应12h,待反应结束后将黑色产物经磁性分离后用去离子水、乙醇洗涤三次,置于真空干燥箱中干燥。
(3)随后将1 g壳聚糖溶于100 mL 2%的乙酸溶液中,并加入0.4 g Fe3O4空心微粒,搅拌均匀后调节pH值在9左右,然后转至盛有30 mL液体石蜡的三口烧瓶中,于60℃水浴条件下加入一定量的戊二醛反应2h,待反应结束经过滤后,依次用石油醚、无水乙醇洗涤数次后置于真空干燥箱中于60℃干燥24h备用,即得磁性壳聚糖。
本步骤中采用弱酸中的乙酸溶液溶解壳聚糖,使得后续反应更加容易发生和完全,并用石油醚、无水乙醇进行多次洗涤,尽可能的洗净石蜡和多余的有机溶剂。
(4)再将0.7~0.8 g磁性壳聚糖分散于30 mL 50%(w/v) NaOH溶液中,在搅拌条件下于40~60℃碱化2h,再将30 mL溶有一定量氯乙酸的异丙醇逐滴加入到上述溶液中,在相同温度下反应4h,加入70%(v/v)乙醇终止反应,经磁性分离后用蒸馏水洗涤至中性、再用乙醇洗涤数次后真空干燥24h,即得磁性羧甲基壳聚糖。
(5)最后,称取上述0.5 g 磁性羧甲基壳聚糖分散于50 mL蒸馏水中,调节pH值为4,并加入一定量的EDC和NHS在室温搅拌下活化0.5h,然后加入20 mL 1%~10%聚乙烯亚胺溶液,并调节pH值为5于室温反应24h,待反应结束经磁性分离后依次用蒸馏水、乙醇洗涤数次后置于真空干燥箱中干燥,即得聚乙烯亚胺改性壳聚糖磁性复合材料(MCMC-PEI)。
图1为本发明依次对壳聚糖(CS)、磁性羧甲基壳聚糖(MCMC)以及聚乙烯亚胺改性壳聚糖磁性复合材料(MCM-PEI)的傅里叶红外光谱图,由图可知壳聚糖(CS)在3526-3294cm-1附近的特征强宽带对应于-OH的伸缩振动、-NH2的伸缩振动以及多糖的氢键,1610 cm-1处是N-H伸缩振动,1064 cm-1的特征峰是C-O-C的伸缩振动峰;磁性羧甲基壳聚糖(MCMC)在1744 cm-1处是羧基官能团中羰基的特征吸收峰,590 cm-1处的吸收峰是四氧化三铁中Fe-O的伸缩振动;聚乙烯亚胺改性壳聚糖磁性复合材料(MCMC-PEI)在2918、2851 cm-1为饱和C-H伸缩振动峰,1723 cm-1是酰胺与羧基官能团中羰基的伸缩振动吸收峰,以上结果表明成功制备了聚乙烯亚胺改性壳聚糖磁性复合材料。
图2为通过VSM在室温下测试的Fe3O4和MCMC-PEII复合材料的磁性能,其饱和磁化强度分别为74.17 emu/g和59.24 emu/g,剩磁和矫顽力均趋于零,表现出超顺磁性,无滞后圈,表面磁响应性较好。虽然MCMC-PEI复合材料的饱和磁化强度低于Fe3O4,但其优越的磁性能可用于吸附过程的磁性分离。
以下将通过不同实施例中聚乙烯亚胺溶液的加入量不同制得MCMC-PEI,具体实施例如下:
实施例1:
称取上述0.5 g磁性羧甲基壳聚糖分散于50 mL蒸馏水中,调节pH值为4,并加入0.2~0.4 g EDC和0.15~0.25gNHS在室温搅拌下活化0.5h,然后加入20 mL 1%聚乙烯亚胺溶液,并调节pH值为5于室温反应24h,待反应结束经磁性分离后依次用蒸馏水、乙醇洗涤数次后置于真空干燥箱中干燥,即得MCMC-PEI-1。
实施例2:
称取上述0.5 g磁性羧甲基壳聚糖分散于50 mL蒸馏水中,调节pH值为4,并加入0.2~0.4 g EDC和0.15~0.25g NHS在室温搅拌下活化0.5h,然后加入20 mL 3%聚乙烯亚胺溶液,并调节pH值为5于室温反应24h,待反应结束经磁性分离后依次用蒸馏水、乙醇洗涤数次后置于真空干燥箱中干燥,即得MCMC-PEI-2。
实施例3:
称取上述0.5 g磁性羧甲基壳聚糖分散于50 mL蒸馏水中,调节pH值为4,并加入0.2~0.4 g EDC和0.15~0.25gNHS在室温搅拌下活化0.5h,然后加入20 mL 5%聚乙烯亚胺溶液,并调节pH值为5于室温反应24h,待反应结束经磁性分离后依次用蒸馏水、乙醇洗涤数次后置于真空干燥箱中干燥,即得MCMC-PEI-3。
实施例4:
称取上述0.5 g磁性羧甲基壳聚糖分散于50 mL蒸馏水中,调节pH值为4,并加入0.2~0.4 g EDC和0.15~0.25gNHS在室温搅拌下活化0.5h,然后加入20 mL 7%聚乙烯亚胺溶液,并调节pH值为5于室温反应24h,待反应结束经磁性分离后依次用蒸馏水、乙醇洗涤数次后置于真空干燥箱中干燥,即得MCMC-PEI-4。
图3为聚乙烯亚胺加入量对实施例1、2、3、4吸附剂材料吸附性能的影响图。实验结果表明随着聚乙烯亚胺加入量从1%增加到7%,聚乙烯亚胺改性壳聚糖磁性复合材料对Cr(VI)的吸附量也从81.48 mg/g增加到112.94 mg/g ,这是由于随着聚乙烯亚胺含量的增加,复合材料表面的吸附活性位点相继增多,使得Cr(VI)与活性位点结合的几率增加。
应用例1:
称取研磨好的MCMC-PEI-1、MCMC-PEI-2、MCMC-PEI-3和MCMC-PEI-4复合材料0.020 g,加入到盛有50 mL Cr(VI) (100 mg/L)溶液的锥形瓶中,在SHA-C往复式水浴恒温振荡器中常温震荡吸附150 min,用二苯基碳酰二肼分光光度法测定不同吸附剂处理后水溶液中Cr(VI)的质量浓度,并计算吸附量。
应用例2:
准确称取0.020 g MCMC-PEI-4加入到50 mL初始浓度为100 mg/L的Cr(VI)溶液中,将pH调至5,在室温条件下于SHA-C往复式水浴恒温振荡器中常温震荡吸附150 min,吸附饱和后,用磁铁将复合材料移出浸入浓度为0.1 mol/L NaOH溶液中,解吸120min后,用去离子水洗涤至中性,磁性分离后置于60℃真空干燥箱中至恒重,即得经一次吸附-脱附的MCMC-PEI-4(a)。
应用例3:
准确称取0.020 g MCMC-PEI-4(a)加入到50 mL初始浓度为100 mg/L的Cr(VI)溶液中,将pH调至5,在室温条件下于SHA-C往复式水浴恒温振荡器中常温震荡吸附240 min,吸附饱和后,用磁铁将复合材料移出浸入浓度为0.1 mol/L NaOH溶液中,解吸120min后,用去离子水洗涤至中性,磁性分离后置于60℃真空干燥箱中至恒重,即得经两次吸附-脱附的MCMC-PEI-4(b)。
应用例4:
准确称取0.020 g MCMC-PEI-4(b)加入到50 mL初始浓度为100 mg/L的Cr(VI)溶液中,将pH调至5,在室温条件下于SHA-C往复式水浴恒温振荡器中常温震荡吸附240 min,吸附饱和后,用磁铁将复合材料移出浸入浓度为0.1 mol/L NaOH溶液中,解吸120min后,用去离子水洗涤至中性,磁性分离后置于60℃真空干燥箱中至恒重,即得经三次吸附-脱附的MCMC-PEI-4(c)。
应用例5:
准确称取0.020 g MCMC-PEI-4(c)加入到50 mL初始浓度为100 mg/L的Cr(VI)溶液中,将pH调至5,在室温条件下于SHA-C往复式水浴恒温振荡器中常温震荡吸附240 min,吸附饱和后,用磁铁将复合材料移出浸入浓度为0.1 mol/L NaOH溶液中,解吸120min后,用去离子水洗涤至中性,磁性分离后置于60℃真空干燥箱中至恒重,即得经四次吸附-脱附的MCMC-PEI-4(d)。
图4是为实施例4与应用例2、3、4、5吸附剂材料对Cr(Ⅵ)的吸附性能图,采用0.1mol/L NaOH溶液对吸附剂材料进行再生实验,经4次脱吸附后,吸附量仅从110.63 mg/g降到88.94 mg/g,对Cr(VI)的吸附量仍然保持在80.39%,说明本发明吸附材料具有良好的分离性能,可多次进行循环再利用。
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种聚乙烯亚胺改性壳聚糖磁性复合吸附剂制备方法;其特征在于:所述吸附剂以球形磁性四氧化三铁为核、壳聚糖为壳制备了壳聚糖包覆的四氧化三铁核壳结构,再通过改性制备聚乙烯亚胺改性壳聚糖磁性复合吸附剂。
2.如权利要求1所述的聚乙烯亚胺改性壳聚糖磁性复合吸附剂制备方法,其特征在于:包括如下步骤:
(1)首先,将十二烷基苯磺酸钠在室温搅拌下溶于有机溶剂中,待充分溶解后将FeCl3.6H2O和NaAc加入到上述溶液中;
(2)将步骤(1)中所得溶液转入反应釜中于453 K下反应12h,待反应结束后将黑色产物经磁性分离后用去离子水、乙醇洗涤三次,置于真空干燥箱中干燥,制得Fe3O4空心微粒;
(3)随后将壳聚糖溶于2%弱酸溶液中,并加入Fe3O4空心微粒搅拌;
搅拌均匀后加入pH调节剂,调节pH至9时转至盛有液体石蜡的三口烧瓶中,于60℃水浴条件下加入交联剂反应2h;待反应结束经过滤后,采用有机溶剂进行多次洗涤,洗涤后置于真空干燥箱中于60℃干燥24h备用,即得磁性壳聚糖;
(4)将磁性壳聚糖分散于50%(w/v) NaOH溶液中,在搅拌条件
下于40~60℃碱化2h;再将溶有氯乙酸的异丙醇逐滴加入到上述溶液中,在相同温度下反应4h;加入70%(v/v)乙醇终止反应,经磁性分离后用蒸馏水洗涤至中性、再用乙醇洗涤数次后真空干燥24h,即得磁性羧甲基壳聚糖;
(5)将上述磁性羧甲基壳聚糖分散于蒸馏水中并调节pH值为4并加入活化剂在室温搅拌下活化0.5h;然后加入聚乙烯亚胺溶液,并调节pH值为5于室温反应24h;待反应结束经磁性分离后依次用蒸馏水、乙醇洗涤数次后置于真空干燥箱中干燥,即得聚乙烯亚胺改性壳聚糖磁性复合材料。
3.如权利要求2所述的聚乙烯亚胺改性壳聚糖磁性复合吸附剂制备方法,其特征在于:所述步骤(1)中十二烷基苯磺酸钠、FeCl3 .6H2O和NaAc的质量比为16:54:(80~100)。
4.如权利要求2所述的聚乙烯亚胺改性壳聚糖磁性复合吸附剂制备方法,其特征在于:所述步骤(1)中有机溶剂为乙二醇或水合肼。
5.如权利要求2所述的聚乙烯亚胺改性壳聚糖磁性复合吸附剂制备方法,其特征在于:所述步骤(2)中反应釜中压力为162 ~ 170kPa 。
6.如权利要求2所述的聚乙烯亚胺改性壳聚糖磁性复合吸附剂制备方法,其特征在于:所述步骤(3)中的弱酸为乙酸或低浓度盐酸;所述pH调节剂为氢氧化钠。
7.如权利要求2所述的聚乙烯亚胺改性壳聚糖磁性复合吸附剂制备方法,其特征在于:所述步骤(3)中交联剂为戊二醛,使得壳聚糖和四氧化三铁具备均匀的核壳结构。
8.如权利要求2所述的聚乙烯亚胺改性壳聚糖磁性复合吸附剂制备方法,其特征在于:所述步骤(3)采用有机溶剂石油醚和乙醇依次进行洗涤。
9.如权利要求2所述的聚乙烯亚胺改性壳聚糖磁性复合吸附剂制备
方法,其特征在于:所述步骤(4)中氯乙酸和磁性壳聚糖的质量比为(1~10):1。
10.如权利要求2所述的聚乙烯亚胺改性壳聚糖磁性复合吸附剂制备
方法,其特征在于:所述步骤(5)中的活化剂为1-(3-二甲氨基丙基)-3-乙基碳二亚胺(EDC)和N-羟基琥珀酰亚胺(NHS),质量比为(1~5):1。
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