CN114367202B - 一种碱式扩散渗析用磺化聚醚醚酮/磺化介孔氧化硅复合膜材料的制备方法 - Google Patents
一种碱式扩散渗析用磺化聚醚醚酮/磺化介孔氧化硅复合膜材料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种碱式扩散渗析用磺化聚醚醚酮/磺化介孔氧化硅复合膜材料的制备方法,首先通过控制合成过程中溶剂的比例制备出磺化介孔氧化硅微球SMS;然后用浓硫酸对聚醚醚酮进行磺化改性处理,得到SPEEK;随后将SMS超声分散于DMF中,然后加入一定质量比例的SPEEK,混合均匀后成膜,制备出具有高离子通量和选择性的碱式扩散渗析用SPEEK/SMS复合膜。本方法可以在较低的无机粒子添加量下获得分离性能显著提高的SPEEK/SMS复合膜:复合膜的氢氧根渗析系数(UOH)为0.007‑0.018m/h,分离系数为(S)为11.4‑38.6,离子交换容量(IEC)为2.28‑2.38mmol/g。
Description
技术领域
本发明涉及一种复合分离膜的制备方法,具体涉及一种碱式扩散渗析用磺化聚醚醚酮/磺化介孔氧化硅复合膜材料的制备方法。
背景技术
碱性废液在许多工业生产过程中都会产生,如造纸、皮革、印染等,直接排放废物会对环境造成很大的危害。传统工艺中,对碱性废料的处理方法有酸中和法、浓缩法等,但这些方法的副产物盐的处理也会令人头疼,能耗高、操作复杂等缺点阻碍了这些方法的进一步发展。近年来,通过膜法进行碱分离的工艺逐渐发展起来,包括电纳滤,电渗析,扩散渗析等,其中扩散渗析膜分离技术是一种利用浓度梯度的驱动达到离子分离效果的过程,不需要任何的外加电源,其特点是低能耗、环保、操作简单、安装经济成本低等。
在碱回收离子交换膜中,通过结合有机聚合物和无机材料的特性,可以将无机材料分散到有机聚合物中获得所需机械强度和分离性能的复合膜。Mondal等通过溶胶-凝胶法制备了二氧化硅功能化氨基异酞酸交联PVA膜并将其用于扩散渗析碱回收。Liu等采用自由基聚合法合成聚对苯乙烯磺酸钠,与PVA、TEOS以及APTS交联,将其用于碱式扩散渗析过程,分离因子最高为25.7。Ashraf等采用溶胶-凝胶法将两种硅基功能化谷氨酸钠(GMSG和VMSG)/聚乙烯醇(PVA)交联,制备了新型杂化阳离子交换膜(CEMs),进行扩散渗析碱回收时,分离因子为18.2-34.8。
磺化介孔二氧化硅(SMS)材料因为孔径分布窄、比表面积高、性能稳定,且表面磺酸基团的引入增加了其活性,在催化、生物医学、吸附等方面具有潜在的应用前景。磺化聚醚醚酮(SPEEK)具有良好的热稳定性,化学稳定性以及优异的机械性能。基于此,本发明先合成了SMS,然后将其分散在DMF中,将SPEEK溶解于该分散液中,混合均匀后成膜,制备出具有高离子通量和选择性的碱式扩散渗析专用复合膜。SMS表面的磺酸基团和SPEEK带有的磺酸基团在两相界面处通过氢键相互作用,提高了两相之间的界面相容性,并共同构筑了提高离子传递速率与选择性的传递通道。
发明内容
本发明提供了一种碱式扩散渗析用磺化聚醚醚酮/磺化介孔氧化硅复合膜材料的制备方法,从而获得具有良好选择性和分离性能的碱式扩散渗析专用复合膜,磺化聚醚醚酮和磺化介孔氧化硅所带的磺酸基团在两相界面处通过氢键相互作用,提高了两相之间的界面相容性,并共同构筑了提高离子传递速率与选择性的传递通道,能够打破扩散渗析过程中离子通量与选择性之间的“tradeoff”效应。
本发明碱式扩散渗析用磺化聚醚醚酮/磺化介孔氧化硅复合膜材料的制备方法,首先通过控制合成过程中溶剂的比例制备出磺化介孔氧化硅微球(SMS);然后用浓硫酸对450G型号的PEEK进行磺化改性处理,得到SPEEK;随后将SMS超声分散于DMF中,然后加入一定质量比例的SPEEK,混合均匀后成膜,制备出具有高离子通量和选择性的碱式扩散渗析专用复合膜。具体包括如下步骤:
步骤1:磺化介孔氧化硅微球的制备
常温下,将模板及CTAB溶解于水、乙醇、氨水的混合溶剂中,采用TEOS为硅源,以γ-巯丙基三乙氧基硅烷和过氧化氢为表面改性剂,制备磺化介孔氧化硅微球,并利用索氏提取法在乙醇和盐酸的混合溶剂中除去模板;将得到的样品用过氧化氢溶液氧化,将巯基氧化成磺酸基,即得到磺化介孔氧化硅微球。
步骤2:PEEK的磺化
使用浓硫酸同时作为溶剂和磺化剂,将PEEK缓慢溶解于浓硫酸中,通过控制磺化的时间和温度控制磺化度,反应结束后边搅拌边将溶液逐渐倒入冰水浴中终止反应并将SPEEK固体沉淀出来,然后用去离子水洗涤至水呈中性,干燥后即得到SPEEK。
步骤3:SPEEK/SMS复合膜的制备
先将一定质量的SMS微球超声分散在DMF中,然后加入SPEEK,在70℃下磁力搅拌12-24h,得到铸膜液;然后将铸膜液倒在玻璃板上用刮刀刮膜控制膜的厚度,60℃加热固化成型,100℃真空干燥12h,得到SPEEK/SMS复合膜。
步骤1中,乙醇:水:氨水:CTAB的摩尔比为19.9:80-124:10.4:0.3;TEOS在添加时逐滴加入,滴加速率控制在0.4-0.5mL/min;用γ-巯丙基三乙氧基硅烷改性时需在40℃下反应24h,索提时溶剂与样品所用比例为200mL乙醇:1.5gHCl:1g样品。
合成介孔氧化硅时调节溶剂比例,是为了控制介孔氧化硅的形貌,本发明优选乙醇:水:氨水:CTAB的摩尔比为19.9:80:10.4:0.3,在该比例下得到球形介孔氧化硅。
步骤2中,常温下先用浓硫酸将PEEK完全溶解之后再升温磺化,其中聚醚醚酮和浓硫酸的添加比例为1g/10mL,磺化时所用温度为55℃,磺化时间控制在3-5h。
步骤3中,SMS的添加质量为SPEEK质量的2%-10%。
本方法可以在较低的无机粒子添加量下获得分离性能显著提高的SPEEK/SMS复合膜:复合膜的氢氧根渗析系数(UOH)为0.007-0.018m/h,分离系数为(S)为11.4-38.6,离子交换容量(IEC)为2.28-2.38mmol/g。
附图说明
图1为本发明实施例1中所合成的磺化介孔氧化硅的SEM图;
图2为本发明实施例1-4制备的复合膜的离子交换容量性能测试数据;
图3为本发明实施例1-4制备的复合膜的分离性能测试数据。
具体实施方式
以下通过具体的实施例对本发明技术方案作进一步分析说明。
实施例1:
1、磺化介孔氧化硅的制备:常温下,称取18g去离子水、10.94g乙醇、4.45g氨水加入100mL三口烧瓶中混合搅拌均匀,加入1.37gCTAB搅拌至完全溶解,之后逐滴加入2.64gTEOS,用时约5min,在25℃下磁力搅拌2h;然后加入2mLγ-巯丙基三乙氧基硅烷,在40℃下磁力搅拌24h;抽滤、干燥,然后用索提(其中200mL乙醇:1.5gHCl:1g样品)除模板,然后干燥,之后用过氧化氢溶液将巯基氧化成磺酸基,得到磺化介孔氧化硅。
2、PEEK的磺化:将聚醚醚酮提前在烘箱中80℃干燥12h干燥除去水分,量取50mL浓硫酸加入100mL三口烧瓶中,称取5g聚醚醚酮,机械搅拌下逐渐加入聚醚醚酮,常温下搅拌至完全溶解,然后将油浴锅升温至55℃,加热搅拌3.5h。反应结束后,机械搅拌下将反应溶液倒入冰水浴中终止反应同时将固体沉淀出来,然后用去离子水洗涤直至浸泡固体的溶液为中性,然后将所得固体100℃真空干燥12h获得SPEEK,磺化度为82%。
3、复合膜的制备:将质量分数为SPEEK的2%,即0.03g的球形介孔氧化硅加入到10mLDMF中超声分散1h,倒入三口烧瓶中,然后加入1.5g SPEEK,70℃下磁力搅拌24h得到铸膜液,然后将铸膜液倒在玻璃板上用刮刀刮膜控制膜的厚度,将玻璃板放在加热板上60℃加热让膜固化成型,然后将膜100℃真空干燥12h。
4、性能测试:
(1)离子交换容量(IEC)测试:将膜在烘箱中60℃过夜干燥,称重记录质量,将膜泡在1M H2SO4溶液中12h,然后用去离子水清洗直至浸泡膜的水为中性,再将膜放入1M NaCl溶液中浸泡24h,置换出H+,最后用0.02M NaOH溶液滴定浸泡过膜的NaCl溶液。
(2)扩散渗析过程:测试前先将膜浸泡在1M NaOH/Na2WO4混合碱中1h,拿出后将膜冲洗干净测试,其中膜的有效面积为6.0cm2在膜两侧槽室中分别加入100mL去离子水和100mL混合碱溶液,通过机械搅拌避免浓差极化,工作1h将两侧溶液倒出,用0.1M HCl溶液滴定法测定碱侧和水侧的OH-离子浓度得到氢氧根的渗析系数(UOH),用紫外分光光度法测定WO4 2-浓度得到钨酸根的渗析系数(UW),从而得到膜的分离系数(S)。
经测试,本实施例所获得的复合膜的性能参数为:离子交换容量为2.38mmol/g,氢氧根的渗析系数(UOH)为0.0118m/h,分离系数为23.9。
实施例2:
本实施例中复合膜的制备方法以及性能测试同实施例1,区别在于本实例中添加球形介孔氧化硅的质量为0.06g。
经测试,本实施例所获得的复合膜的性能参数为:离子交换容量为2.36mmol/g,氢氧根的渗析系数(UOH)为0.0178m/h,分离系数为38.6。
实施例3:
本实施例中复合膜的制备方法以及性能测试同实施例1,区别在于本实例中添加球形介孔氧化硅的质量为0.09g。
经测试,本实施例所获得的复合膜的性能参数为:离子交换容量为2.35mmol/g,氢氧根的渗析系数(UOH)为0.0137m/h,分离系数为25.7。
实施例4:
本实施例中复合膜的制备方法以及性能测试同实施例1,区别在于本实例中添加球形介孔氧化硅的质量为0.12g。
经测试,本实施例所获得的复合膜的性能参数为:离子交换容量为2.28mmol/g,氢氧根的渗析系数(UOH)为0.0070m/h,分离系数为11.4。
图1为本发明实施例1中所制备的介孔氧化硅的SEM图,可以看出其为球形,且球形直径约为200nm。
图2为实施例1-4制备的复合膜的IEC测试,可以看出当介孔氧化硅的添加量为2%时,IEC最高为2.38,且随着添加量增加,IEC下降。
图3为实施例1-4制备的复合膜的分离性能测试,可以看出随着介孔氧化硅含量的增加,复合膜的分离性能成呈现先增加后降低的趋势。
以上所述的本发明专利实施方式,并不构成对本发明保护范围的限定。任何在本发明的精神和原则之内所作的修改、等同替换和改进等,均应包含在本发明的权利要求保护范围之内。
Claims (5)
1.一种碱式扩散渗析用磺化聚醚醚酮/磺化介孔氧化硅复合膜材料的制备方法,其特征在于:
首先通过控制合成过程中溶剂的比例制备出磺化介孔氧化硅微球SMS;然后用浓硫酸对聚醚醚酮进行磺化改性处理,得到SPEEK;随后将SMS超声分散于DMF中,然后加入一定质量比例的SPEEK,混合均匀后成膜,制备出具有高离子通量和选择性的碱式扩散渗析专用复合膜;包括如下步骤:
步骤1:磺化介孔氧化硅微球的制备
常温下,将模板剂 CTAB溶解于水、乙醇、氨水的混合溶剂中,采用TEOS为硅源,以γ-巯丙基三乙氧基硅烷和过氧化氢为表面改性剂,制备磺化介孔氧化硅微球,并利用索氏提取法在乙醇和盐酸的混合溶剂中除去模板;将得到的样品用过氧化氢溶液氧化,将巯基氧化成磺酸基,即得到磺化介孔氧化硅微球SMS;
步骤2:PEEK的磺化
使用浓硫酸同时作为溶剂和磺化剂,将聚醚醚酮缓慢溶解于浓硫酸中,通过控制磺化的时间和温度控制磺化度,反应结束后边搅拌边将溶液逐渐倒入冰水浴中终止反应并将SPEEK固体沉淀出来,然后用去离子水洗涤至水呈中性,干燥后即得到SPEEK;
步骤3:SPEEK/SMS复合膜的制备
先将一定质量的SMS微球超声分散在DMF中,然后加入SPEEK,在70℃下磁力搅拌12-24h,得到铸膜液;然后将铸膜液倒在玻璃板上用刮刀刮膜控制膜的厚度,60℃加热固化成型,真空干燥,得到SPEEK/SMS复合膜;
步骤1中,乙醇:水:氨水:CTAB的摩尔比为19.9:80-124:10.4:0.3;
步骤3中,SMS的添加质量为SPEEK质量的2%-6%。
2.根据权利要求1所述的制备方法,其特征在于:
步骤1中,TEOS在添加时逐滴加入,滴加速率控制在0.4-0.5mL/min。
3.根据权利要求1所述的制备方法,其特征在于:
步骤1中,添加γ-巯丙基三乙氧基硅烷改性时的反应温度为40℃,反应时间为24h。
4.根据权利要求1所述的制备方法,其特征在于:
步骤1中,索提时溶剂与样品所用比例为200mL乙醇:1.5gHCl:1g样品。
5.根据权利要求1所述的制备方法,其特征在于:
步骤2中,常温下先用浓硫酸将PEEK完全溶解之后再升温磺化,其中聚醚醚酮和浓硫酸的添加比例为1g/10mL,磺化时所用温度为55℃,磺化时间控制在3-5h。
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