CN109173757B - 一种氯烷季铵化聚吡咯改性阳离子交换膜及其制备与应用 - Google Patents
一种氯烷季铵化聚吡咯改性阳离子交换膜及其制备与应用 Download PDFInfo
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Abstract
本发明公开了一种氯烷季铵化聚吡咯改性阳离子交换膜,所述交换膜将阳离子交换膜依次在碱溶液和酸溶液中浸泡,去离子水清洗,获得酸碱活化后的阳离子交换膜;将活化后的阳离子交换膜浸泡在吡咯溶液中,室温静置至吡咯溶液挥干后,再加入氧化剂水溶液,震荡,取出膜,获得聚吡咯修饰膜;将聚吡咯修饰膜浸入氯烷溶液中1~24h,取出膜,用去离子水清洗,即得氯烷季铵化聚吡咯改性阳离子交换膜。本发明氯烷季铵化聚吡咯改性阳离子交换膜用于阳离子的单价选择性分离,经过季铵化聚吡咯改性后Na+相对Mg2+选择性透过值较未改性的商业膜从0.94增加到4.24。
Description
(一)技术领域
本发明涉及一种单/多价选择性阳离子交换膜及其制备方法,具体涉及一种使用氯丙烷及其部分同系物作为季铵化试剂,基于季铵化聚吡咯的单价选择性阳离子交换膜及制备方法。
(二)背景技术
随着单价选择性阳膜的进一步普及,以单价选择性阳膜为核心的膜分离技术,如选择性电渗析技术已在诸多领域中引起了广泛关注。如,盐湖卤水锂资源的开发,其面临的最主要的难点之一是镁、锂比的数值过高,利用单价选择性阳膜可以实现单价锂离子的浓缩,降低镁、锂比的数值。在工业废水处理领域中,针对同时含有金属离子和H+的废酸液,利用单价选择性阳膜分离单/多价阳离子的性能,可以实现重金属离子和无机酸的高效回收与再利用,大大的降低了生产成本,消除了对环境的二次污染。在皮革生产过程中,同样,利用单价阳离子选择性电渗析技术,可以有效实现Na+/Cr3+分离及Cr3+富集浓缩与回收,这不仅能有效遏制其对环境的污染,还能产生良好的经济效益。单价阳离子选择性电渗析技术在水处理领域拥有诸多方面的优势和巨大的应用前景,但国内外应用实例却相对较少。其主要发展瓶颈在于高性能单价选择性分离膜的缺乏。为了加快选择性电渗析技术从实验室阶段走向规模化市场化的步伐,真正将单价阳离子选择性电渗析的优势体现和发挥出来,开发高性能单价阳离子选择性分离膜刻不容缓。
(三)发明内容
本发明目的是提供一种以氯丙烷及其部分同系物作为季铵化试剂,处理表面修饰的聚吡咯活性皮层,得到季铵化聚吡咯的阳离子交换膜,用于制备单/多价选择性阳离子交换膜,这种膜可以将盐溶液中的单价离子选择性分离,可以应用在盐湖提锂和重金属离子与无机酸的高效回收与再利用等问题。
本发明采用的技术方案是:
本发明提供一种氯烷季铵化聚吡咯改性阳离子交换膜,所述交换膜按如下方法制备:1)室温下,将阳离子交换膜依次在碱溶液(优选氢氧化钠水溶液)和酸溶液(优选盐酸水溶液)中浸泡去除膜表面蜡质材料,去离子水清洗,去掉膜表面多余的碱和酸,获得酸碱活化后的阳离子交换膜;
2)室温下,将步骤1)活化后的阳离子交换膜浸泡在吡咯溶液中,室温静置(2~6h)至吡咯溶液挥干后,再加入氧化剂水溶液,震荡使吡咯聚合(100r/min,1h),取出膜,获得聚吡咯修饰膜;所述氧化剂水溶液中氧化剂为过硫酸钠、氯化铁、过氧化氢、重铬酸钠、铬酸、高锰酸钾或过硫酸铵中的一种;
3)室温下,将步骤2)聚吡咯修饰膜浸入氯烷溶液中1~24h,取出膜,用去离子水清洗,即得氯烷季铵化聚吡咯改性阳离子交换膜。
进一步,步骤1)所述氢氧化钠水溶液和盐酸水溶液浓度均为2mol/L。
进一步,步骤2)所述吡咯溶液浓度为2mol/L,溶剂为水、乙醇、乙醚或苯。
进一步,步骤2)所述氧化剂水溶液浓度为0.5mol/L。
进一步,步骤3)所述溴烷溶液浓度1-20g/L。
进一步,步骤3)所述氯烷溶液中氯烷为1-氯丙烷,2-氯丙烷,1-氯丁烷,2-氯丁烷,1-氯戊烷,2-氯戊烷,1-氯己烷,3-氯己烷,1-氯庚烷,2-氯庚烷,1-氯辛烷,1-氯壬烷或1-氯癸烷中的一种,溶剂为水、乙醇、乙醚或苯。
本发明还提供一种所述氯烷聚吡咯改性阳离子交换膜的制备方法,所述方法按如下步骤进行:1)室温下,将阳离子交换膜在氢氧化钠水溶液(优选2mol/L)浸泡2h,去离子水冲洗去除膜表面的碱,然后用盐酸水溶液(优选2mol/L)浸泡3h,去离子水冲洗去除膜表面的酸,获得酸碱活化后的阳离子交换膜;
2)室温下,将步骤1)活化后的阳离子交换膜浸泡在吡咯溶液(优选2mol/L)中,静置至吡咯溶液挥干后,再加入氧化剂水溶液(优选0.5mol/L),震荡(100r/min,1h),取出膜,获得聚吡咯修饰膜;所述氧化剂水溶液中氧化剂为过硫酸钠,氯化铁,过氧化氢、重铬酸钠、铬酸、高锰酸钾或过硫酸铵中的一种,优选过硫酸钠或氯化铁;
3)室温下,将步骤2)聚吡咯修饰膜浸入1-20g/L氯烷溶液中1-24h,取出膜,用去离子水清洗,即得氯烷季铵化聚吡咯改性阳离子交换膜;所述氯烷溶液中氯烷结构式Cl-(CH2)n-CH3(n=0-12),优选为1-氯丙烷,2-氯丙烷,1-氯丁烷,2-氯丁烷,1-氯戊烷,2-氯戊烷,1-氯己烷,3-氯己烷,1-氯庚烷,2-氯庚烷,1-氯辛烷,1-氯壬烷或1-氯癸烷中的一种,更优选为氯乙烷、1-氯己烷或溴癸烷,溶剂为水、乙醇、乙醚或苯。
进一步,步骤2)所述浸泡在烧杯中进行,所述吡咯溶液加入体积为烧杯总体积的5~30%,所述氧化剂溶液加入体积为烧杯总体积的5~30%。
本发明还提供一种所述氯烷聚吡咯改性阳离子交换膜在制备单价或多价选择性阳离子交换膜中的应用。
本发明所述阳离子交换膜可以为任何商业或自己刮膜制备的阳离子交换膜,优选CM-1Y阳离子交换膜。
本发明所述室温是指25-30℃。
与现有技术相比,本发明有益效果主要体现在:本发明氯烷季铵化聚吡咯改性阳离子交换膜用于阳离子的单价选择性分离,经过季铵化聚吡咯改性后Na+相对Mg2+选择性透过值较未改性的商业膜从0.94增加到4.24。经过本发明改性后的阳离子交换膜,Na+/Mg2+的选择性系数(通量比)相较于改性前最高可以提高4倍,这个选择性系数是市面上出售的日本的两个产品(旭硝子的CSV和Astom的CSO)的选择性系数的1.5倍。
(四)附图说明
图1为本发明氯烷聚吡咯改性阳离子交换膜的制备过程示意图。
图2为改性阳离子交换膜表面(a)、断面(a1)电镜图及未改性阳离子交换膜表面(b)、断面(b1)电镜图。
图3为在1h的单价选择性电渗析实验时,未改性阳离子交换膜与改性阳离子交换膜在浓缩室的钠离子相对镁离子的通量和单价选择性的示意图,其中C-1代表实施例1氯丙烷季铵化聚吡咯改性阳离子交换膜,C-2代表实施例2氯己烷季铵化聚吡咯改性阳离子交换膜,C-3代表实施例3氯癸烷季铵化聚吡咯改性阳离子交换膜(对应实例3),C-4代表未改性阳离子交换膜(即CM-1Y阳离子交换膜)。
(五)具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此:
实施例1
1、单/多价阳离子选择性分离膜
步骤1:室温(25-30℃,下同)下,将一张Tokuyama(日本德山曹达公司)的CM-1Y阳离子交换膜浸泡于2mol/L氢氧化钠水溶液中2h后,将其取出用去离子水反复清洗,去除表面多余的碱,再放入2mol/L盐酸水溶液中浸泡3h,取出后用去离子水反复清洗,去除其表面上多余的酸,获得酸碱活化后的阳离子交换膜。
步骤2:如图1所示,室温下,将活化后的阳离子交换膜浸泡在盛放20ml、2mol/L吡咯乙醇溶液的500ml烧杯中,静置90min至吡咯溶液挥干后,再加入20ml、0.5mol/L氯化铁水溶液,放入振荡器中震荡1h(频率是100次/min),取出膜,获得聚吡咯修饰膜。
步骤3:室温下,将聚吡咯修饰膜放入5g/L氯丙烷的乙醇溶液中,浸泡24h后将膜取出,并用去离子水反复清洗掉表面的氯丙烷溶液,得到氯烷季铵化聚吡咯改性阳离子交换膜,表面电镜图见图2中a所示,断面电镜图见图2中a1所示。同时以CM-1Y阳离子交换膜为对照,表面电镜图见图2中b所示,断面电镜图见图2中b1所示。
从图2中a和图2中b,可以明显看到膜改性和未改性的区别,从图2中a1和图2中b1可以明显看到改性层的存在。
2、一二价阳离子选择性电渗析实验
根据参考文献(Recovery of chemically degraded polyethyleneimine by are-modification method:prolonging the lifetime of cation exchange membranes(DOI:10.1039/C5RA27916J)的测试方法,其中测试体系改为以Na+/Mg2+为测试体系,且初始浓度都为0.05mol/L,其中在1h后取淡化室的溶液利用离子色谱分析Na+和Mg2+的浓度,并计算Na+相对Mg2+选择性透过值。同是以普通阳离子交换膜为对照。结果见图3所示,从图3可以看出经过季铵化聚吡咯改性后Na+相对Mg2+选择性透过值较未改性的商业膜从0.94增加到3.13。
实施例2
将实施例1步骤3中的5g/L氯丙烷乙醇溶液改为20g/L1-氯己烷的乙醇溶液,氧化剂由0.5mol/L FeCl3水溶液改为0.5mol/L过硫酸钠水溶液,其余同实施例1,获得氯烷季铵化聚吡咯改性阳离子交换膜。
用相同方法测得Na+/Mg2+体系的单价选择性,经过氯己烷季铵化聚吡咯改性后Na+相对Mg2+选择性透过值较未改性的商业膜从0.94增加到3.56。
实施例3
将实施例1步骤2中2mol/L吡咯的乙醇溶液改为2mol/L吡咯水溶液,步骤3中的5g/L氯乙烷的乙醇溶液换为1g/L氯癸烷的乙醇溶液,其余同实施例1,制得氯烷季铵化聚吡咯改性阳离子交换膜。
用相同方法测得Na+/Mg2+体系的单价选择性,经过氯癸烷季铵化聚吡咯改性后Na+相对Mg2+选择性透过值较未改性的商业膜从0.94增加到4.24。
Claims (7)
1.一种氯烷季铵化聚吡咯改性阳离子交换膜,其特征在于所述交换膜按如下方法制备:1)将阳离子交换膜依次在碱溶液和酸溶液中浸泡,去离子水清洗,去掉膜表面多余的碱和酸,获得酸碱活化后的阳离子交换膜;
2)将步骤1)活化后的阳离子交换膜浸泡在吡咯溶液中,室温静置至吡咯溶液挥干后,再加入氧化剂水溶液,震荡,取出膜,获得聚吡咯修饰膜;所述氧化剂水溶液中氧化剂为过硫酸钠,氯化铁,过氧化氢、重铬酸钠、铬酸、高锰酸钾或过硫酸铵中的一种;
3)室温下,将步骤2)聚吡咯修饰膜浸入1-20g/L氯烷溶液中1-24h,取出膜,用去离子水清洗,即得氯烷季铵化聚吡咯改性阳离子交换膜;所述氯烷溶液中氯烷为1-氯丙烷,2-氯丙烷,1-氯丁烷,2-氯丁烷,1-氯戊烷,2-氯戊烷,1-氯己烷,3-氯己烷,1-氯庚烷,2-氯庚烷,1-氯辛烷,1-氯壬烷或1-氯癸烷中的一种,溶剂为水、乙醇、乙醚或苯。
2.如权利要求1所述氯烷季铵化聚吡咯改性阳离子交换膜,其特征在于步骤1)所述碱溶液为2mol/L氢氧化钠水溶液,所述酸溶液为2mol/L盐酸水溶液。
3.如权利要求1所述氯烷季铵化聚吡咯改性阳离子交换膜,其特征在于步骤2)所述吡咯溶液浓度为2mol/L,溶剂为水、乙醇、乙醚或苯。
4.如权利要求1所述氯烷季铵化聚吡咯改性阳离子交换膜,其特征在于步骤2)所述氧化剂水溶液浓度为0.5 mol/L。
5.一种权利要求1所述氯烷季铵化聚吡咯改性阳离子交换膜的制备方法,其特征在于所述方法按如下步骤进行:1)室温下,将阳离子交换膜在氢氧化钠水溶液浸泡2h,去离子水冲洗去除膜表面的碱,然后用盐酸水溶液浸泡2h,去离子水冲洗去除膜表面的酸,获得酸碱活化后的阳离子交换膜;
2)室温下,将步骤1)活化后的阳离子交换膜浸泡在吡咯溶液中,静置至吡咯溶液挥干后,再加入氧化剂水溶液,震荡聚合,取出膜,获得聚吡咯修饰膜;所述氧化剂水溶液中氧化剂为过硫酸钠、氯化铁、过氧化氢、重铬酸钠、铬酸、高锰酸钾或过硫酸铵中的一种;
3)室温下,将步骤2)聚吡咯修饰膜浸入1-20g/L氯烷溶液中1-24h,取出膜,用去离子水清洗,即得氯烷季铵化聚吡咯改性阳离子交换膜;所述氯烷溶液中氯烷为1-氯丙烷,2-氯丙烷,1-氯丁烷,2-氯丁烷,1-氯戊烷,2-氯戊烷,1-氯己烷,3-氯己烷,1-氯庚烷,2-氯庚烷,1-氯辛烷,1-氯壬烷或1-氯癸烷中的一种,溶剂为水、乙醇、乙醚或苯。
6.如权利要求5所述的制备方法,其特征在于步骤2)吡咯溶液浓度为2mol/L,溶剂为水、乙醇、乙醚或苯;所述氧化剂水溶液浓度为0.5 mol/L。
7.一种权利要求1所述氯烷季铵化聚吡咯改性阳离子交换膜在单价/多价阳离子选择性分离中的应用。
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