CN110339729A - 一种三价铬离子印迹复合膜的制备方法及应用 - Google Patents
一种三价铬离子印迹复合膜的制备方法及应用 Download PDFInfo
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- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 21
- 239000011636 chromium(III) chloride Substances 0.000 claims description 21
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- 150000002500 ions Chemical class 0.000 abstract description 9
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
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- B01D67/0002—Organic membrane manufacture
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Abstract
本发明公开一种三价铬离子印迹复合膜的制备方法及应用,属于膜分离技术领域。本发明所述离子印迹复合膜经济实用、工艺简单,可用于水体中三价铬离子的选择性吸附与分离。具体方法为:以市售商业膜为支撑膜,三价铬离子为模板离子,2‑乙烯基吡啶为功能单体,将离子印迹技术与膜分离技术相结合,通过热引发方式使功能单体和模板离子在支撑膜表面进行热聚合,然后再洗脱除去模板离子,制备得到三价铬离子印迹复合膜,该印迹复合膜表面具有与三价铬离子形状、大小、尺寸相匹配的印迹孔穴,能够对目标溶液中的三价铬离子进行专一性识别,并能有效吸附溶液中的三价铬离子。
Description
技术领域
本发明涉及一种三价铬离子印迹复合膜的制备方法及应用,属于膜分离技术领域。
背景技术
近年来,由于工业的快速发展,铬及其化合物被广泛用于冶金、钢铁、电镀等工业领域,大量的Cr化合物被排放到环境中,导致土壤、地表和地下水的污染。铬在环境中主要以Cr(III)和Cr(VI)两种价态存在,Cr(III)是新陈代谢所必需的微量营养素,少量的Cr(III)有助于葡萄糖及胆固醇的代谢。而Cr(VI)的毒性远远大于Cr(III),是一种潜在的致癌物质,会导致皮肤、呼吸道、肾脏受损,并增加患肺癌的风险。 由于Cr(III)在一定条件下很容易转换为Cr(VI),对人体健康造成巨大威胁,因此寻找一种高效的三价铬离子处理技术具有极其重要的意义。
膜分离法是一种高效的三价铬离子处理方法,中国专利CN 106179265 A公开了一种用于去除水中三价铬离子的杂化膜吸附剂的制备方法,该方法通过溶胶-凝胶反应得到涂膜液或膜片,对皮革废水中的三价铬离子有较强的吸附脱除能力。但是传统的膜对于具有相似分子量和体积的类似物缺乏对目标物的特异选择性,极大的限制了其在各种领域中的应用。因此,对膜进行修饰,将特异性识别位点建立在膜的表面是解决此问题的有效方法之一。通过离子印迹技术在膜孔壁上涂抹特定的功能聚合物层而得到离子印迹膜,可以提高膜的特异选择性或渗透性。
发明内容
本发明的目的在于提供一种三价铬离子印迹复合膜的制备方法,该方法以市售商业膜为支撑膜,三价铬离子为模板离子,α-甲基丙烯酸为功能单体,在交联剂和引发剂的作用下,利用离子印迹技术并通过热引发方式使功能单体和模板离子在支撑膜表面进行热聚合,制备得到三价铬离子印迹复合膜,具体步骤如下:
(1)将CrCl3溶于有机溶剂和水的混合致孔溶剂中,其中CrCl3浓度为10-100mmol/L,再加入功能单体2-乙烯基吡啶,在室温下置于恒温振荡器中恒温反应2~3h,加入交联剂乙二醇二甲基丙烯酸酯和引发剂偶氮二异丁腈,充分溶解并摇匀,超声脱气除氧10min,形成预聚合溶液。
(2)将支撑膜置于步骤(1)得到的预聚合溶液中,在常温下浸泡1~60min,取出置于两块玻璃板之间,然后于60~80℃下反应12~36h,最后用甲醇和醋酸混合溶液洗脱除去支撑膜上负载的三价铬离子,制备得到三价铬离子印迹复合膜。
优选的,本发明步骤(1)中混合致孔溶剂中有机溶剂和水的体积比为1:1。
优选的,本发明步骤(2)中甲醇和醋酸混合溶液中甲醇和醋酸的体积比为9:1。
优选的,本发明步骤(1)中CrCl3、2-乙烯基吡啶、乙二醇二甲基丙烯酸酯的摩尔比为1: 1~8: 20~50,偶氮二异丁腈与CrCl3的摩尔比为1~6:2~10。
优选的,本发明步骤(1)中的有机溶剂为N-N-二甲基甲酰胺、甲醇、乙醇、异丙醇或乙腈。
优选的,本发明所述支撑膜为Nylon-6膜、聚四氟乙烯膜及聚偏氟乙烯膜。
本发明另一目的在于提供所述方法制备的三价铬离子印迹复合膜用于吸附分离溶液中的三价铬离子。
本发明的有益效果为:
(1)本发明所述采用离子印迹技术与膜分离技术相结合,以商业膜为支撑膜,克服了现行三价铬离子吸附材料制备困难、方法繁琐等缺点。
(2)本发明方法制备的离子印迹复合膜使识别位点暴露在膜表面,不仅能选择性吸附分离三价铬离子,而且能在很大程度上能提高三价铬离子的吸附容量。
(3)本发明所述方法解决了传统三价铬离子印迹材料制备过程中模板离子包埋过深、不易洗脱等问题。
具体实施方式
下面结合具体实施方式,对本发明作进一步说明,但本发明保护范围并不限于所述内容。
实施例1
(1)将10mmol/L CrCl3溶于体积比为1:1的有机溶剂(乙腈)和水的混合致孔溶剂中,再加入功能单体2-乙烯基吡啶,在室温下置于恒温振荡器中恒温反应3h,加入乙二醇二甲基丙烯酸酯和偶氮二异丁腈,充分溶解并摇匀,超声脱气除氧10min,形成预聚合溶液;其中CrCl3、2-乙烯基吡啶和乙二醇二甲基丙烯酸酯摩尔比为1:2:20,偶氮二异丁腈与CrCl3的摩尔比为1:10。
(2)将聚四氟乙膜置于上述步骤的预聚合溶液中,在常温下浸泡3min,取出置于两块玻璃板之间,然后于80℃下反应24h,最后用150mL体积比为9:1的甲醇和醋酸混合溶液洗脱除去聚四氟乙烯膜上负载的三价铬离子,制备得到三价铬离子印迹复合膜。
将本实施例制备得到的5.10g三价铬离子印迹复合膜应用在浓度为54.00mmol/L的三价铬离子溶液中,其吸附量为147.91μmol/g,印迹因子为1.42。
实施例2
(1)将20mmol/L CrCl3溶于体积比为1:1的有机溶剂(甲醇)和水的混合致孔溶剂中,再加入功能单体2-乙烯基吡啶,在室温下置于恒温振荡器中恒温反应2h,加入乙二醇二甲基丙烯酸酯和偶氮二异丁腈,充分溶解并摇匀,超声脱气除氧10min,形成预聚合溶液;其中CrCl3、2-乙烯基吡啶和乙二醇二甲基丙烯酸酯摩尔比为1:4:20,偶氮二异丁腈与CrCl3的摩尔比为5:2。
(2)将Nylon-6膜置于上述步骤的预聚合溶液中,在室温下浸泡1min,取出置于两块玻璃板之间,然后于60℃下反应36h,最后用150mL体积比为9:1的甲醇和醋酸混合溶液洗脱除去Nylon-6膜上负载的三价铬离子,制备得到三价铬离子印迹复合膜。
将本实施例制备得到的4.80g三价铬离子印迹复合膜应用在浓度为54.00mmol/L的三价铬离子溶液中,其吸附量为132.67μmol/g,印迹因子为1.31。
实施例3
(1)将100mmol/L CrCl3溶于体积比为1:1的有机溶剂(N-N-二甲基甲酰胺)和水的混合致孔溶剂中,再加入功能单体2-乙烯基吡啶,在室温下置于摇床中恒温反应2.5h,加入乙二醇二甲基丙烯酸酯和偶氮二异丁腈,充分溶解并摇匀,超声脱气除氧10min,形成预聚合溶液;其中CrCl3、2-乙烯基吡啶和乙二醇二甲基丙烯酸酯摩尔比为1:8:50,偶氮二异丁腈与CrCl3的摩尔比为2:5。
(2)将聚四氟乙烯膜置于上述步骤的预聚合溶液中,在常温下浸泡60min,取出置于两块玻璃板之间,然后于70℃下反应12h,最后用150mL体积比为9:1的甲醇和醋酸混合溶液洗脱除去聚四氟乙烯膜上负载的三价铬离子,制备得到三价铬离子印迹复合膜。
将本实施例制备得到的5.60g三价铬离子印迹复合膜应用在浓度为54.00mmol/L的三价铬离子溶液中,其吸附量为110.64μmol/g,印迹因子为1.51。
实施例4
(1)将45mmol/L CrCl3溶于体积比为1:1的有机溶剂(乙醇)和水的混合致孔溶剂中,再加入2-乙烯基吡啶功能单体,在室温下置于摇床中恒温反应3h,加入乙二醇二甲基丙烯酸酯和偶氮二异丁腈,充分溶解并摇匀,超声脱气除氧10min,形成预聚合溶液;其中CrCl3、2-乙烯基吡啶和乙二醇二甲基丙烯酸酯摩尔比为1:6:30,偶氮二异丁腈与CrCl3的摩尔比为3:4。
(2)将聚偏氟乙烯膜置于上述步骤的预聚合溶液中,在常温下浸泡60 min,取出置于两块玻璃板之间,然后于60℃下反应36h,最后用150mL体积比为9:1的甲醇和醋酸混合溶液洗脱除去聚偏氟乙烯膜上负载的三价铬离子,制备得到三价铬离子印迹复合膜。
将本实施例制备得到的4.80g三价铬离子印迹复合膜应用在浓度为54.00mmol/L的三价铬离子溶液中,其吸附量为140.44μmol/g,印迹因子为1.66。
实施例5
(1)将60mmol/L CrCl3溶于体积比为1:1的有机溶剂(异丙醇)和水的混合致孔溶剂中,再加入功能单体2-乙烯基吡啶,在室温下置于恒温振荡器中恒温反应2h,加入乙二醇二甲基丙烯酸酯和偶氮二异丁腈,充分溶解并摇匀,超声脱气除氧10min,形成预聚合溶液;其中CrCl3、2-乙烯基吡啶和乙二醇二甲基丙烯酸酯摩尔比为1:1:20,偶氮二异丁腈与CrCl3的摩尔比为5:10。
(2)将聚四氟乙烯膜置于上述步骤的预聚合溶液中,在常温下浸泡30min,取出置于两块玻璃板之间,然后于60℃下反应24h,最后用150mL体积比为9:1的甲醇和醋酸混合溶液洗脱除去聚四氟乙烯膜上负载的三价铬离子,制备得到三价铬离子印迹复合膜。
将本实施例制备得到的6.00g三价铬离子印迹复合膜应用在浓度为54.00mmol/L的三价铬离子溶液中,其吸附量为41.33μmol/g,印迹因子为1.39。
Claims (7)
1.一种三价铬离子印迹复合膜的制备方法,其特征在于,具体包括以下步骤:
(1)将CrCl3溶于有机溶剂和水的混合致孔溶剂中,其中CrCl3浓度为10-100mmol/L,再加入功能单体2-乙烯基吡啶,在室温下置于恒温振荡器中恒温反应2~3h,加入交联剂乙二醇二甲基丙烯酸酯和引发剂偶氮二异丁腈,充分溶解并摇匀,超声脱气除氧10min,形成预聚合溶液;
(2)将支撑膜置于步骤(1)得到的预聚合溶液中,在常温下浸泡1~60min,取出置于两块玻璃板之间,然后于60~80℃下反应12~36h,最后用甲醇和醋酸混合溶液洗脱除去支撑膜上负载的三价铬离子,制备得到三价铬离子印迹复合膜。
2.根据权利要求1所述三价铬离子印迹复合膜的制备方法,其特征在于:步骤(1)中混合致孔溶剂中有机溶剂和水的体积比为1:1。
3.根据权利要求1所述三价铬离子印迹复合膜的制备方法,其特征在于:步骤(2)中甲醇和醋酸混合溶液中甲醇和醋酸的体积比为9:1。
4.根据权利要求1所述三价铬离子印迹复合膜的制备方法,其特征在于:步骤(1)中CrCl3、2-乙烯基吡啶、乙二醇二甲基丙烯酸酯的摩尔比为1: 1~8: 20~50,偶氮二异丁腈与CrCl3的摩尔比为1~6:2~10。
5.根据权利要求1所述三价铬离子印迹复合膜的制备方法,其特征在于:步骤(1)中的有机溶剂为N-N-二甲基甲酰胺、甲醇、乙醇、异丙醇或乙腈。
6.根据权利要求1所述三价铬离子印迹复合膜的制备方法,其特征在于:支撑膜为Nylon-6膜、聚四氟乙烯膜及聚偏氟乙烯膜。
7.权利要求1~6任意一项所述方法制备的三价铬离子印迹复合膜用于吸附分离溶液中的三价铬离子。
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