基于聚异丁烯胺改性的耐甲醇溶胀新型薄膜复合膜

doi:10.16085/j.issn.1000-6613.2021-2667

摘要/Abstract

摘要：

聚合物膜可以在甲醇/染料废液处理中发挥重要作用。为了保证膜在甲醇处理过程中的高性能，提高膜的耐甲醇溶胀性是必要的。然而，关于耐甲醇溶胀膜的研究相对较少。在此，提出将活性聚合物（聚异丁烯胺，PIBA）引入分离层，制备新型耐甲醇溶胀聚酰胺（PA）薄膜复合（TFC）膜。PIBA的掺入增加了膜的表面粗糙度、活性层厚度和活性层背面的致密性。PIBA提高了膜的耐甲醇溶胀性能：当PIBA的添加量从0增加到1g/L时，溶胀率从46.81%下降到15.00%。因此，PA/PIBA膜表现出比PA膜更高的染料（藏红T）截留率（99.53%与94.62%）。此外，在20bar（1bar=0.1MPa）的操作压力下，PA/PIBA膜保持了高通量[84.62L/(m²·h)]和良好的长期运行稳定性。最后，由于聚异丁烯（PIB）在先前的工作中同样用于提高膜的耐甲醇溶胀性，本工作将PIBA与PIB进行了比较，得出PIBA优于PIB。这项工作为开发一种用于甲醇流出物处理的分离膜提供了新途径。

关键词: 分离, 膜, 聚合物, 耐甲醇溶胀, 聚异丁烯胺

Abstract:

Polymer membrane can play a big role for methanol/dye effluent treatment. For guaranteeing a high performance, enhancing the methanol swelling resistance of membrane is necessary. However, works on organic solvent-resistant membranes for methanol are relatively few. Herein, an active polymer (polyisobutenamine, PIBA) is proposed to be introduced into the separation layer for preparing a novel methanol swelling-resistant polyamide (PA) thin film composite (TFC) membrane. The incorporation of PIBA was confirmed. PIBA increased the membrane surface roughness, active layer thickness and backside compactness of active layer. The methanol swelling resistance of membrane was enhanced obviously by PIBA. The swelling rate dropped from 46.81% to 15.00% when the addition amount of PIBA increased from 0 to 1g/L. Because of this, PA/PIBA TFC membrane exhibited a far higher dye (Safranine T) rejection than PA TFC membrane (99.53% vs. 94.62%). Besides, the PA/PIBA TFC membrane maintained a high flux [84.62L/(m²•h)] and a satisfactory long-term operation stability at an operating pressure of 20bar. Finally, since polyisobutylene (PIB) was also used in previous work to improve the methanol swelling resistance of the membrane, and thus PIBA and PIB were compared. By comparison, PIBA was superior to PIB. This work provided a new avenue for developing a separation membrane for methanol effluent treatment. As a result, PIBA is superior to polyisobutylene. This work provides a novel pathway for developing separation membranes toward methanol effluent treatment.

Key words: separation, membranes, polymers, methanol swelling resistance, polyisobuteneamine

中图分类号:

TQ028

丁俊毅, 陈营东, 王书浩, 严文韬, 周勇, 高从堦. 基于聚异丁烯胺改性的耐甲醇溶胀新型薄膜复合膜[J]. 化工进展, 2022, 41(10): 5530-5540.

DING Junyi, CHEN Yingdong, WANG Shuhao, YAN Wentao, ZHOU Yong, GAO Congjie. Methanol swelling-resistant novel TFC membrane based on polyisobutylene amine modification[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5530-5540.

图/表 12

图1 PIB与PIBA的结构式以及相关反应方程

表1 不同活性PA层样品的制备参数

膜样品	水相溶液			有机相溶液
膜样品	MPD浓度 /g·L^-1	CSA浓度 /g·L^-1	pH（TEA）	TMC浓度 /g·L^-1	PIBA浓度 /g·L^-1
P0	20	40	10	1	0
P1	20	40	10	1	0.2
P2	20	40	10	1	0.4
P3	20	40	10	1	0.6
P4	20	40	10	1	0.8
P5	20	40	10	1	1

图2 死端过滤装置1—高压氮气瓶；2—压力调节阀；3—止回阀；4—高压胶管；5—HP4750型号搅拌池；6—Heidolph MR Hei-Tec型电磁搅拌器

图3 机械强度试验装置

图4 PIBA和TMC反应生成产物的红外光谱

图5 膜的静态甲醇接触角测量

图6 P0和P3膜的SEM和AFM图像

表2 P0膜和P3膜背面孔结构参数

膜	表面平均孔径/nm	表面孔隙密度/个·μm^-2	表面孔隙率/%
P0	19.9±8.5	153±23	5.40±0.14
P3	18.2±7.6	109±11	2.77±0.25

图7 膜的溶胀度分析

图8 膜的分离性能

图9 PA/PIBA TFC和PA/PIB TFC膜的性能比较0.6g/L PIB和3g/L PIB—使用0.6g/L PIB和3g/L PIB制备的PA/PIB TFC膜；0.6g/L PIBA—使用0.6g/L PIBA制备的PA/PIBA TFC膜

表3 PIB与PIBA的结构式与价格对比

名称	价格/USD·g^-1	结构式
PIB	1.876
PIBA	0.1705

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