CN114716612A - 一种聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂及其制备方法与应用 - Google Patents
一种聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂及其制备方法与应用 Download PDFInfo
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Abstract
本发明属于重金属废水处理的技术领域,公开了一种聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂及其制备方法与应用。方法:(1)将壳聚糖溶于衣康酸溶液中,获得壳聚糖溶液;(2)在保护性氛围下,将聚乙烯吡咯烷酮、衣康酸、引发剂与步骤(1)的壳聚糖溶液混合,加热反应,加入沉淀剂进行沉淀,获得聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂。本发明的方法简单,所制备的吸附剂对对重金属离子汞具有较高的选择性吸收能力,且吸附量大,易分离。本发明的吸附剂用于去除水中重金属离子。
Description
技术领域
本发明属于重金属废水处理技术领域,具体涉及一种聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂及其制备方法与应用。
背景技术
随着工业化、城市化的发展,重金属污染问题日趋严重。重金属不可被生物降解,易累积在生物链中,通过生物链传播,对现有动植物及人类产生巨大危害。除此之外,长期过量摄入重金属离子会损害肾脏、肝脏、大脑功能和神经系统。目前已经开发了大量重金属处理技术,如化学沉淀法、混凝絮凝法、浮选法、离子交换法和膜分离法。但是,吸附法由于操作简单、效率高、便于回收、成本低等优点,受到广泛关注且具有广阔应用前景。
活性炭是最常用的吸附剂之一,但由于其对重金属离子吸附不具有选择性且吸附后难以再生,其应用受到了限制。壳聚糖由甲壳素的酰氨基脱乙酰制备而成,壳聚糖仅从少数甲壳类动物(螃蟹、小龙虾)中获得,每年获得数百万吨,然而其中约50%的壳聚糖作为贝壳废物被丢弃。壳聚糖成本低、无毒性、良好的生物相容性和生物降解性,并且壳聚糖含有氨基和羟基,能够与金属离子螯合,因此,近年来引起了人们的极大兴趣,成为重金属废水处理的有效工具。但是,纯壳聚糖存在着不溶于水、不溶于有机物、选择性差、吸附性能差等缺点,需要对其进行改性。
目前人们对壳聚糖的改性吸附材料已进行了一些研究。如:专利申请CN113289588A以亚磷酸、磷酸、三亿烯四胺的至少一种作为壳聚糖的改性材料,以甲醛为交联剂制得重金属螯合剂。但该专利申请使用有毒且易挥发得甲醛试剂作为交联剂,不利于环保。专利CN20171040781.4将壳聚糖和海藻酸钠溶解后加入磁性纳米粒子制备成混合溶液,然后利用静电液滴法及冷凝固浴的方法制备壳聚糖/海藻酸钠磁性复合微球,但该方法制备复杂,需要用到特殊设备,难以实现大规模生产。专利CN201110042318.2将壳聚糖和海藻酸钠分别溶于水中混合均匀,加入氯化钙溶液,边滴加边搅拌,滴加完成并充分搅拌,调节溶液pH值,待出现固体絮状物后,过滤烘干凝胶得到改性壳聚糖材料。但该专利不具有对金属离子的选择性吸附能力,且吸附能力较弱。专利CN109999909A,制备了一种壳聚糖/硅藻土/氧化石墨烯复合材料,然而该材料的制备过程亦需要较低和较高温度,且制备过程步骤较繁复。专利申请CN201811279939.0选用碳酸钾溶液、碳酸钠溶液、硫酸钾溶液、硫酸钠溶液、碳酸氢钠溶液、碳酸氢钾溶液、碳酸铵溶液、碳酸氢铵溶液中的任一种加入到壳聚糖醋酸溶液中,通过乙醇沉淀,得到水溶性壳聚糖材料。但该专利申请制备的材料易溶于水,不利于材料分离并反复利用。专利申请CN202011600805.1先用水热法合成二氧化钛纳米花,再与硅烷偶联剂反应,得到氨基化二氧化钛,将其与丁二酸酐反应,氨基与丁二酸酐开环,从而在其表面引入活性羧基,在催化剂作用下,壳聚糖交联微球与羧基化二氧化钛反应,得到TiO2纳米花负载壳聚糖微球。但该方法步骤繁复,反应条件不温和,不利于大规模推广。
本发明采用衣康酸和聚乙烯吡咯烷酮为改性剂,通过一锅法制备了一种聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂。本发明的方法所需原料少,制备过程简单,材料成本低。所制备的吸附剂吸附能力强,对重金属离子选择性高、吸附量大,而且稳定性好。
发明内容
为了克服现有技术的缺点和不足,本发明的首要目的是提供一种聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂及其制备方法。本发明解决了现有壳聚糖吸附剂制备过程复杂、选择性低、吸附量不高等缺点。本发明的壳聚糖吸附剂合成简单、选择性高、成本低、可重复利用、吸附量、稳定性好。
本发明的另一目的在于提供上述吸附剂的应用。所述吸附剂用于含有重金属离子的废水处理,用于去除重金属离子。
本发明的目的通过以下技术方案实现:
一种聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂的制备方法,包括以下步骤:
(1)将壳聚糖溶于衣康酸溶液中,获得壳聚糖溶液;
(2)在保护性氛围下,将聚乙烯吡咯烷酮、衣康酸、引发剂与步骤(1)的壳聚糖溶液混合,加热反应,加入沉淀剂进行沉淀,获得聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂。
步骤(1)中所述衣康酸溶液中衣康酸与水的质量体积比为(1~5)g:100mL。所述衣康酸溶液中衣康酸与壳聚糖的质量比为(1~5):(0.5~1)。
步骤(2)中聚乙烯吡咯烷酮与壳聚糖的质量比为(0.2~0.5):(0.5~1)。
所述乙烯吡咯烷酮的平均分子量为3000-5000,优选K-30级别。
步骤(2)中所述引发剂与衣康酸的质量比为0.002-0.004:1。
所述引发剂为过硫酸钾。
步骤(2)中所述聚乙烯吡咯烷酮与衣康酸的质量比为(0.2~0.8):1。
步骤(2)中加热反应的温度为50-70℃;加热反应的时间为6-12小时。所述保护性气氛为氮气。
步骤(2)中所述沉淀剂为氢氧化钠溶液;沉淀完后进行离心,洗涤,干燥。氢氧化钠溶液浓度为0.5-2mol/L;离心转速为8000-12000rpm。
所述洗涤是指采用水和无水乙醇分别进行洗涤。
所述洗涤是指洗涤至溶液的PH为6-7。
所述干燥的温度为50-70℃;干燥的时间为6-12h。
一种聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂通过上述所述方法制得到。
本发明制备的吸附剂可以应用到重金属废水的处理过程中。
优选地,上述重金属废水为含Hg2+废水。
本发明选用衣康酸作为改性剂,不仅可以引入有利于吸附的基团,还可不使用其他酸溶解壳聚糖,降低成本并改善吸附效果。本发明使用聚乙烯吡咯烷酮作为改性剂,不仅与壳聚糖结合能力强,还引入了吡咯环和碳氧双键,可大大增强其吸附能力。需要特别指出的是,根据实际效果验证,该材料对Hg2+有较强选择性吸附能力。
由于极性壳聚糖和极性聚乙烯吡咯烷酮之间的强分子内相互作用,壳聚糖和聚乙烯吡咯烷酮共混物是相容的,这归因于聚乙烯吡咯烷酮的质子受体碳氧双键和壳聚糖的质子供体基团之间形成的氢键。衣康酸能够在壳聚糖存在下聚合,聚衣康酸在一个单体中含有两个羧基,能够与金属离子螯合,从而提高壳聚糖的吸附能力,同时羧基也能提供质子供体,与聚乙烯吡咯烷酮形成牢固的氢键,提高材料的稳定性,以减少吸附过程中材料的损失。
本发明采用的原材料有如下特点:壳聚糖是从虾、螃蟹和龙虾等提取的几丁质中获得的部分脱乙酰聚合物,具有良好的生物降解性、生物相容性、成本低、无毒的特点;壳聚糖表面含有大量胺基、羟基,可作为有效的吸附位点;聚乙烯吡咯烷酮具有生物相容性、生物降解性,能与壳聚糖相容,可提供重金属吸附位点;衣康酸可以减少酸性溶剂的使用量,提供大量含氧羧基作为重金属吸附位点。
与现有技术相比,本发明具有以下优点和有益效果:
1)本发明的方法简单,反应条件温和,采用一锅法将聚乙烯吡咯烷酮、壳聚糖、衣康酸单体和引发剂混合,在氢键和分子间作用力下,两种高分子聚合物与壳聚糖充分包埋,引入大量含氧、氮的吸附位点,提高材料重金属吸附量和选择性。
2)本发明的吸附材料对重金属离子汞具有较高的选择性吸收能力,吸附量大,明显高于改性前的壳聚糖,在溶液PH为6、298K时达到886.61mg/g。
3)改性后的壳聚糖相比改性前,表面粗糙程度大大提升,比表面积增加,有利于重金属的吸附;经过五次循环利用后,吸附剂的吸附量依旧可以达到初始值的65%以上。
附图说明
图1为本发明的吸附剂的制备流程示意图;
图2为改姓前后壳聚糖的电镜图;(a)和(b)为改性前壳聚糖的不同放大倍数的扫描电镜图;(c)和(d)为实施例1中改性后的壳聚糖(即吸附剂)的不同放大倍数的扫描电镜图。
具体实施方式
以下结合实例对本发明的具体实施作进一步说明,但本发明的实施和保护不限于此。需指出的是,以下若有未特别详细说明之过程,均是本领域技术人员可参照现有技术实现或理解的。所用试剂或仪器未注明生产厂商者,视为可以通过市售购买得到的常规产品
图1为本发明的吸附剂的制备流程示意图;
图2为改姓前后壳聚糖的电镜图;(a)和(b)为改性前壳聚糖的不同放大倍数的扫描电镜图;(c)和(d)为实施例1中改性后的壳聚糖(即吸附剂)的不同放大倍数的扫描电镜图。
实施例1
一种聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂的制备方法,包括以下步骤:
1)将1g衣康酸单体与100ml水,使用磁力搅拌搅拌均匀,获得衣康酸溶液;将1g壳聚糖加入衣康酸溶液中使用磁力搅拌搅拌均匀,获得壳聚糖溶液;
2)将0.4g聚乙烯吡咯烷酮(乙烯吡咯烷酮的平均分子量为K-30级别)、1g衣康酸、0.002g引发剂(过硫酸钾)先后加入步骤1)的壳聚糖溶液中,通入氮气,开启加热到70℃,连续搅拌12h;
3)向步骤2)所得的溶液中加入1mol/L的氢氧化钠溶液,直到完全沉淀,离心(10000rpm)分离1min,倒出上层清液,所得沉淀物用纯水和无水乙醇分别离心-清洗沉淀物3次,最后在60℃烘箱中烘干12h,获得聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂。
效果验证:称取20mg上述吸附剂于容器中,加入50ml含0.01mol/L的PH为5的Hg2+、Zn2+、Cd2+、Co2+、Pb2+在298k的条件下吸附1h。最后,采用EDTA滴定法滴定重金属溶液浓度,计算吸附量,Hg2+吸附量为886.61mg/g;Zn2+吸附量为142.35mg/g;Cd2+吸附量为171.97mg/g;Co2+吸附量为150.45mg/g;Pb2+与吸附剂强烈作用,使吸附剂溶解在水中。
本实施例中经过五次循环利用后,吸附剂的吸附量依旧可以达到初始值的65%以上。
实施例2
一种聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂的制备方法,包括以下步骤:
1)将1g衣康酸单体与100ml水,使用磁力搅拌搅拌均匀,获得衣康酸溶液;将1g壳聚糖加入衣康酸溶液中使用磁力搅拌搅拌均匀,获得壳聚糖溶液;
2)将0.2g聚乙烯吡咯烷酮、1g衣康酸、0.002g引发剂(过硫酸钾)先后加入步骤1)的壳聚糖溶液中,通入氮气,开启加热到70℃,连续搅拌12h;乙烯吡咯烷酮的平均分子量为K-30级别;
3)向步骤2)所得的溶液中加入1mol/L的氢氧化钠溶液,直到完全沉淀,使用50ml离心管在10000rpm中离心分离1min,倒出上层清液,所得沉淀物用纯水和无水乙醇分别离心-清洗沉淀物3次,最后在60℃烘箱中烘干12h,获得聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂。
效果验证:称取20mg上述吸附剂于容器中,加入50ml含0.01mol/L的PH为5的Hg2+在298k的条件下吸附1h。最后,采用EDTA滴定法滴定重金属溶液浓度,计算吸附量,Hg2+吸附量为786.61mg/g。
实施例3
一种聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂的制备方法,包括以下步骤:
1)将1g衣康酸单体与100ml水,使用磁力搅拌搅拌均匀,获得衣康酸溶液;将1g壳聚糖加入衣康酸溶液中使用磁力搅拌搅拌均匀,获得壳聚糖溶液;
2)将0.5g聚乙烯吡咯烷酮、1g衣康酸、0.002g引发剂(过硫酸钾)先后加入步骤1)的壳聚糖溶液中,通入氮气,开启加热到70℃,连续搅拌12h;乙烯吡咯烷酮的平均分子量为K-30级别;
3)向步骤2)所得的溶液中加入1mol/L的氢氧化钠溶液,直到完全沉淀,在10000rpm条件下离心分离1min,倒出上层清液,所得沉淀物用纯水和无水乙醇分别离心-清洗沉淀物3次,最后在60℃烘箱中烘干12h,获得聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂。
效果验证:称取20mg上述吸附剂于容器中,加入50ml含0.01mol/L的PH为5的Hg2+在298k的条件下吸附1h。最后,采用EDTA滴定法滴定重金属溶液浓度,计算吸附量,Hg2+吸附量为786.61mg/g。
实施例4
一种聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂的制备方法,包括以下步骤:
1)将1g衣康酸单体与100ml水,使用磁力搅拌搅拌均匀,获得衣康酸溶液;将1g壳聚糖加入衣康酸溶液中使用磁力搅拌搅拌均匀,获得壳聚糖溶液;
2)将0.4g聚乙烯吡咯烷酮、0.5g衣康酸、0.001g引发剂(过硫酸钾)先后加入步骤1)的壳聚糖溶液中,通入氮气,开启加热到70℃,连续搅拌12h;乙烯吡咯烷酮的平均分子量为K-30级别;
3)向步骤2)所得的溶液中加入1mol/L的氢氧化钠溶液,直到完全沉淀,在10000rpm条件下离心分离1min,倒出上层清液,所得沉淀物用纯水和无水乙醇分别离心-清洗沉淀物3次,最后在60℃烘箱中烘干12h,获得聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂。
效果验证:称取20mg上述吸附剂于容器中,加入50ml含0.01mol/L的PH为5的Hg2+在298k的条件下吸附1h。最后,采用EDTA滴定法滴定重金属溶液浓度,计算吸附量,Hg2+吸附量为686.61mg/g。
实施例5
一种聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂的制备方法,包括以下步骤:
1)将1g衣康酸单体与100ml水,使用磁力搅拌搅拌均匀,获得衣康酸溶液;将1g壳聚糖加入衣康酸溶液中使用磁力搅拌搅拌均匀,获得壳聚糖溶液;
2)将0.4g聚乙烯吡咯烷酮、0.5g衣康酸、0.001g引发剂(过硫酸钾)先后加入步骤1)的壳聚糖溶液中,通入氮气,开启加热到70℃,连续搅拌12h;乙烯吡咯烷酮的平均分子量为K-30级别;
3)向步骤2)所得的溶液中加入1mol/L的氢氧化钠溶液,直到完全沉淀,在10000rpm条件下离心分离1min,倒出上层清液,所得沉淀物用纯水和无水乙醇分别离心-清洗沉淀物3次,最后在60℃烘箱中烘干12h,获得聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂。
效果验证:称取20mg上述吸附剂于容器中,加入50ml含0.01mol/L的PH为5的Hg2+在298k的条件下吸附1h。最后,采用EDTA滴定法滴定重金属溶液浓度,计算吸附量,Hg2+吸附量为686.61mg/g。
实施例6
一种聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂的制备方法,包括以下步骤:
1)将1g衣康酸单体与100ml水,使用磁力搅拌搅拌均匀,获得衣康酸溶液;将1g壳聚糖加入衣康酸溶液中使用磁力搅拌搅拌均匀,获得壳聚糖溶液;
2)将0.4g聚乙烯吡咯烷酮、0.5g衣康酸、0.002g引发剂(过硫酸钾)先后加入步骤1)的壳聚糖溶液中,通入氮气,开启加热到70℃,连续搅拌12h;乙烯吡咯烷酮的平均分子量为K-30级别;
3)向步骤2)所得的溶液中加入1mol/L的氢氧化钠溶液,直到完全沉淀,在10000rpm条件下离心分离1min,倒出上层清液,所得沉淀物用纯水和无水乙醇分别离心-清洗沉淀物3次,最后在60℃烘箱中烘干12h,获得聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂。
效果验证:称取20mg上述吸附剂于容器中,加入50ml含0.01mol/L的PH为5的Hg2+在298k的条件下吸附1h。最后,采用EDTA滴定法滴定重金属溶液浓度,计算吸附量,Hg2+吸附量为686.61mg/g。
以上实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂的制备方法,其特征在于:包括以下步骤:
(1)将壳聚糖溶于衣康酸溶液中,获得壳聚糖溶液;
(2)在保护性氛围下,将聚乙烯吡咯烷酮、衣康酸、引发剂与步骤(1)的壳聚糖溶液混合,加热反应,加入沉淀剂进行沉淀,获得聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂。
2.根据权利要求1所述聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂的制备方法,其特征在于:步骤(2)中聚乙烯吡咯烷酮与壳聚糖的质量比为(0.2~0.5):(0.5~1);
步骤(2)中所述聚乙烯吡咯烷酮与衣康酸的质量比为(0.2~0.8):1。
3.根据权利要求1所述聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂的制备方法,其特征在于:步骤(2)中加热反应的温度为50-70℃;加热反应的时间为6-12小时。
4.根据权利要求1所述聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂的制备方法,其特征在于:
步骤(2)中所述聚乙烯吡咯烷酮的平均分子量为3000-5000;
步骤(2)中所述引发剂与衣康酸的质量比为0.002-0.004:1。
5.根据权利要求1所述聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂的制备方法,其特征在于:步骤(1)中所述衣康酸溶液中衣康酸与水的质量体积比为(1~5)g:100mL;所述衣康酸溶液中衣康酸与壳聚糖的质量比为(1~5):(0.5~1);
步骤(2)中所述引发剂为过硫酸钾。
6.根据权利要求1所述聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂的制备方法,其特征在于:步骤(2)中所述沉淀剂为氢氧化钠溶液;沉淀完后进行离心,洗涤,干燥。
7.根据权利要求6所述聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂的制备方法,其特征在于:氢氧化钠溶液浓度为0.5-2mol/L;离心转速为8000-12000rpm;
所述洗涤是指采用水和无水乙醇分别进行洗涤;
所述洗涤是指洗涤至溶液的PH为6-7;
所述干燥的温度为50-70℃;干燥的时间为6-12h。
8.一种由权利要求1~7任一项所述制备方法得到的聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂。
9.根据权利要求8所述聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂的应用,其特征在于:所述聚乙烯吡咯烷酮/聚衣康酸功能化壳聚糖吸附剂用于重金属废水处理,去除重金属离子。
10.根据权利要求9所述的应用,其特征在于:所述重金属离子为Hg2+。
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