CN112973654A - 一种双浓度区间水凝胶吸附剂的制备方法 - Google Patents

一种双浓度区间水凝胶吸附剂的制备方法 Download PDF

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CN112973654A
CN112973654A CN202110251508.9A CN202110251508A CN112973654A CN 112973654 A CN112973654 A CN 112973654A CN 202110251508 A CN202110251508 A CN 202110251508A CN 112973654 A CN112973654 A CN 112973654A
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孙健
王宏
伞影
王吉洋
高华晶
金朝辉
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Abstract

本发明属于污水吸附剂水凝胶制备技术领域,具体涉及一种双浓度区间水凝胶吸附剂的制备方法。本发明以离子液体做为交联剂,在N2保护下,将单体、氢氧化钠和水加入反应瓶中,然后加入交联剂和引发剂,60‑80℃聚合6‑8h,反应完毕,洗涤,干燥至恒重,粉碎、筛分,得水凝胶。本发明采用离子液体为交联剂,由于离子液体的阴阳离子之间存在很强大静电力,当水凝胶在低浓度吸附时,主要依靠离子液体的静电力来吸附,在高浓度时,依靠水凝胶内部的单体螯合基团来对金属离子进行吸附,因此实现了对低高浓度金属离子的吸附。

Description

一种双浓度区间水凝胶吸附剂的制备方法
技术领域
本发明属于污水吸附剂水凝胶制备技术领域,具体涉及一种双浓度区间水凝胶吸附剂的制备方法。
背景技术
随着工业化的大力发展,水污染问题日益严重。其中重金属离子污染尤为严重,给动植物的生存环境、人类健康以及生产生活带来了巨大威胁。目前处理水中重金属离子的方法主要有过滤法、离子交换法、氧化还原法、化学沉淀法等。但上述处理方法存在去除效率低、增加废水组分复杂性、成本高、污泥量大、易造成二次污染等问题。水凝胶由于其结构可设计、成本低、可生物降解等优点,将其作为重金属离子的吸附剂,具有广阔的应用前景。
2015年,Zahra合成了聚乙烯醇/羧甲基淀粉-g-聚乙烯醇咪唑磁性水凝胶,其对铜离子和铬离子的去除率分别为93.2%和62.5%。在重金属离子浓度为20ppm时,水凝胶对重金属离子具有较高的去除率,但随着重金属离子浓度的增加,去除率在逐渐降低。2018年,Shah合成了PAA/PAM高吸水性聚合物水凝胶,水凝胶对铬离子、镍离子和铜离子的去除率均达到75%以上。在重金属离子浓度为100ppm时,水凝胶的RR(%)值较高,当重金属离子浓度较低时,去除率是极低的。目前已报道的水凝胶仅单一的在低浓度或高浓度对重金属离子具有极佳的去除率,因此,对低、高浓度的重金属离子均具有较高的去除率的水凝胶制备是热点问题。
发明内容
针对上述问题,本发明提出了一种双浓度区间水凝胶吸附剂的制备方法,采用本发明获得的水凝胶可以作为吸附剂来吸附重金属离子,在低、高浓度对重金属离子(镍、锌、铜、铬)都具有极佳的去除效果。
本发明所述一种双浓度区间水凝胶吸附剂的制备方法,以离子液体做为交联剂,在N2保护下,将单体、氢氧化钠和水加入反应瓶中,然后加入交联剂和引发剂,60-80℃聚合6-8h,反应完毕,洗涤,干燥至恒重,粉碎、筛分,得水凝胶。氢氧化钠由于提高水凝胶内部的渗透压。
所述的离子液体化合物采用以下结构:
Figure BDA0002966260760000021
所述离子液体化合物的合成过程为:在N2保护下,将原料A溶解于有机溶剂中,滴入原料B,20℃~100℃搅拌反应2h~48h,得离子液体;
所述的原料A为1,2-二溴乙烷或1,6-二溴已烷或1,10-二溴癸烷;所述的原料B为1-乙烯基咪唑。
所述单体为丙烯酸和丙烯酰胺,以质量比计,丙烯酸:丙烯酰胺=100:1-1:100。
所述有机溶剂选自四氢呋喃或甲苯或丙酮或乙腈或甲醇或乙醇或N,N-二甲基甲酰胺或1,4-二氧六环;以质量比计,有机溶剂:原料A=2:1。
引发剂添加量为单体总质量的0.2%~0.8%,交联剂的添加量为单体总质量的0.2%~0.8%。
以摩尔比计,丙烯酸:氢氧化钠=1:0.5-0.8。
干燥温度为30℃~80℃,干燥时间为0.5h~4h。
本发明采用离子液体化合物为交联剂,由于离子液体的阴阳离子之间存在很强大静电力,当水凝胶在低浓度吸附时,主要依靠离子液体的静电力来吸附,在高浓度时,依靠水凝胶内部的单体螯合基团来对金属离子进行吸附,因此实现了对低高浓度金属离子的吸附。
附图说明
图1是实施例1中离子液体化合物的1H核磁谱图。
图2是实施例2水凝胶的红外谱图。
图3是实施例3中水凝胶作为吸附剂对不同浓度的镍、铜、锌、铬离子的去除率效果图。
图4是实施例2中水凝胶溶胀后的表面形貌图。
具体实施方式
本发明是通过将单体、溶剂、引发剂及离子液体化合物混合,通过一步法合成水凝胶,并将其用作吸附剂,实现对低、高浓度的重金属离子均具有较高的去除效果。由于水凝胶具有合成简单、去除性能好、经济环保等优点,具有很好的应用前景。
下面结合具体实施例,进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。在本领域内的技术人员对本发明所做的简单替换或改进均属于本发明所保护的技术方案之内。
实施例1:1-乙烯基咪唑和1,2-二溴乙烷合成离子液体化合物
在N2保护下,将1,2-二溴乙烷(3.76g,0.02mol)溶解于10ml甲醇中,滴入1-乙烯基咪唑(0.94g,0.01mol)。搅拌反应混合物,加热至50℃加热24h。
反应结束后,缓慢释放出氮气,将反应液转移至100ml单口烧瓶中,放入到旋转蒸发器上,设置温度为60℃,直至蒸出所有甲醇溶剂为止,得到黄色粉末粗产品。粗品用乙醚洗涤3次,真空50℃烘干2h,得到黄色粉状产品。此反应收率为89%。采用核磁共振仪对实施例1中的离子液体结构进行表征,结果见图1。
实施例2:丙烯酸、丙烯酰胺、1-乙烯基咪唑溴盐和过硫酸铵合成水凝胶
将丙烯酸(7g,0.097mol)、丙烯酰胺(3g,0.042mol)、氢氧化钠和(2.3g,0.057mol)和3ml蒸馏水混合搅拌,冷却至室温。然后加入1-乙烯基咪唑溴盐(0.08g,0.00021mol),室温磁搅拌30min,引入N2排出烧瓶中的氧气,加入过硫酸铵(0.04g,0.00017mol)并密封。在60℃水浴中聚合6h。水凝胶用蒸馏水反复洗涤以去除未反应的单体,在60℃下干燥至恒重,粉碎、筛分和备用。水凝胶的红外谱图如图2所示。
实施例3:丙烯酸、丙烯酰胺、1-乙烯基咪唑溴盐和过硫酸铵合成水凝胶
将丙烯酸(7g,0.097mol)、丙烯酰胺(7g,0.098mol)、氢氧化钠和(2.7g,0.068mol)和5ml蒸馏水混合搅拌,冷却至室温。然后加入1-乙烯基咪唑溴盐(0.03g,0.00008mol),室温磁搅拌30min,引入N2排出烧瓶中的氧气,加入过硫酸铵(0.04g,0.00017mol)并密封。在70℃水浴中聚合8h。水凝胶用蒸馏水反复洗涤以去除未反应的单体,在60℃下干燥至恒重,粉碎、筛分和备用。
实施例4:丙烯酸、丙烯酰胺、1-乙烯基咪唑溴盐和过硫酸铵合成水凝胶
将丙烯酸(7g,0.097mol)、丙烯酰胺(3g,0.042mol)、氢氧化钠和(3.0g,0.077mol)和3ml蒸馏水混合搅拌,冷却至室温。然后加入1-乙烯基咪唑溴盐(0.06g,0.00020mol),室温磁搅拌30min,引入N2排出烧瓶中的氧气,加入过硫酸铵(0.04g,0.00017mol)并密封。在80℃水浴中聚合7h。水凝胶用蒸馏水反复洗涤以去除未反应的单体,在60℃下干燥至恒重,粉碎、筛分和备用。
实施例5:水凝胶对四重金属离子的吸附实验
将实施例2中的水凝胶作为吸附剂,对不同浓度(20ppm-150ppm)的四重金属离子进行吸附,水凝胶对不同浓度的重金属离子去除率结果如图3所示。
实施例6:
将实施例2中的水凝胶作为吸附剂,将其放入蒸馏水中溶胀24h,取出后去除水凝胶外表面水分,干燥。用扫描电子显微镜扫描溶胀后水凝胶的表面形貌,结果如图4所示。

Claims (6)

1.一种双浓度区间水凝胶吸附剂的制备方法,其特征在于,以离子液体化合物做为交联剂,在N2保护下,将单体、氢氧化钠和水加入反应瓶中,然后加入交联剂和引发剂,60-80℃聚合6-8h,反应完毕,洗涤,干燥至恒重,粉碎、筛分,得水凝胶;
所述的离子液体化合物采用以下结构:
Figure FDA0002966260750000011
2.根据权利要求1所述的一种双浓度区间水凝胶吸附剂的制备方法,其特征在于:所述离子液体化合物的合成过程为:在N2保护下,将原料A溶解于有机溶剂中,滴入原料B,20℃~100℃搅拌反应2h~48h,后处理,得离子液体;
所述的原料A为1,2-二溴乙烷或1,6-二溴已烷或1,10-二溴癸烷;所述的原料B为1-乙烯基咪唑。
3.根据权利要求1所述的一种双浓度区间水凝胶吸附剂的制备方法,其特征在于:所述单体为丙烯酸和丙烯酰胺,以质量比计,丙烯酸:丙烯酰胺=100:1-1:100。
4.根据权利要求2所述的一种双浓度区间水凝胶吸附剂的制备方法,其特征在于:所述有机溶剂选自四氢呋喃或甲苯或丙酮或乙腈或甲醇或乙醇或N,N-二甲基甲酰胺或1,4-二氧六环;以质量比计,有机溶剂:原料A=2:1。
5.根据权利要求1所述的一种双浓度区间水凝胶吸附剂的制备方法,其特征在于:所述引发剂添加量为单体总质量的0.2%~0.8%,交联剂的添加量为单体总质量的0.2%~0.8%。
6.根据权利要求3所述的一种双浓度区间水凝胶吸附剂的制备方法,其特征在于:以摩尔比计,丙烯酸:氢氧化钠=1:0.5-0.8。
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