基于多巴胺亲水改性下Janus膜的制备及其油水乳液分离

doi:10.16085/j.issn.1000-6613.2022-0268

摘要/Abstract

摘要：

目前用于处理含油废水的特殊润湿材料通常分为去油型和去水型，其仅局限分离单一乳液。本文基于多巴胺改性的聚偏氟乙烯（PVDF）膜，通过交替浸渍工艺和无纺布剥离，制备了具有不对称润湿性的Janus膜。通过调整交替次数以及剥离无纺布，可分别获得超亲水/水下超疏油的表面以及超疏水/超亲油的底面，水/水下油接触角（CA）差异高达150°。基于Janus膜的非对称润湿性，仅通过切换跨膜方向，对表面活性剂稳定的水包油（O/W）和油包水（W/O）乳液渗透通量高达367L/(m²·h)和1729L/(m²·h)，其中水包油渗透液化学需氧量（COD）符合石油化工排放标准，油包水渗透液中水含量小于80mg/L，实现了对O/W和W/O乳液的高效分离。此外，Janus膜在牛血清蛋白（BSA）溶液分离过程中表现出理想的防污性能和可重复使用性。

关键词: 聚偏氟乙烯, Janus膜, 不对称润湿性, 交替浸渍, 油水乳液分离

Abstract:

Current special wetting materials used for treating oily wastewater are usually divided into the oil-removing type or the water-removing type, which are limited to separating single emulsion. In this paper, Janus membranes with asymmetric wettability were fabricated by alternating soaking process and non-woven peeling upon dopamine-modified PVDF membranes. By facilely adjusting the number of alternating soaking and peeling the nonwoven fabric, superhydrophilic/underwater superoleophobic surface and superhydrophobic/superoleophobic bottom surface could be respectively obtained, where the discrepancy in water contact angle between these two surfaces water contact angle was up to 150°. Based on the asymmetric wettability of Janus membranes, high permeate flux of 367L/(m²·h) and 1729L/(m²·h) were achieved for surfactant-stabilized oil-in-water (O/W) and water-in-oil (W/O) emulsions by simply switching the transmembrane direction, where the COD in the permeate of oil-in-water fulfilled the petrochemical discharge standard and the water content in the permeate of water-in-oil was less than 80mg/L, achieving efficient separation of O/W and W/O emulsions. Moreover, Janus membranes exhibited ideal antifouling property and reusability during BSA solution separation process.

Key words: poly(vinylidenefluoride) (PVDF), Janus membrane, asymmetric wettability, alternating soaking, oil/water emulsion separation

中图分类号:

TQ028.8

山林娜, 杨振生, 燕国飞, 李春利, 李浩, 王志英. 基于多巴胺亲水改性下Janus膜的制备及其油水乳液分离[J]. 化工进展, 2022, 41(12): 6500-6510.

SHAN Linna, YANG Zhensheng, YAN Guofei, LI Chunli, LI Hao, WANG Zhiying. Asymmetric Janus membranes based on hydrophilic modification of dopamine for efficient oil/water separation[J]. Chemical Industry and Engineering Progress, 2022, 41(12): 6500-6510.

图/表 20

图1 Janus膜分离油水乳液示意图

图2 实验流程图

图3 基于静电吸引作用的CaSiO3自组装过程示意图

图4 BSA标准曲线

图5 PVDF微孔膜的SEM图M-0—PVDF基膜；M-P45—多巴胺改性膜；M-P45-5c—交替循环5次；M-P45-10c—交替循环10次；M-P45-15c—交替循环15次；M-P45-20c—交替循环20次；D1、D2—膜底面Janus-B侧；D3—膜断面；D4—M-P45-15c高倍数SEM图

图6 M-0、M-P45膜与M-P45-15c膜Janus-T面XPS图

表1 M-0、M-P45膜与M-P45-15c膜Janus-T面元素组成

膜样品	膜表面元素含量/%						原子比/%
膜样品	C	F	O	N	Ca	Si	F/C	O/C
M-0	53.99	46.01	0	0	0	0	85.82	0
M-P45	74.3	3.15	17.99	4.56	0	0	4.24	24.2
M-P45-15c	56.29	2.31	26.19	2.58	2.84	9.79	4.1	46.53

图7 M-P45膜实拍图和EDS图

图8 M-P45-15c膜的EDS表面扫描图

图9 不同浸渍次数下Janus-T侧水接触角

图10 Janus-T侧水下油接触角

图11 Janus-B侧亲油图

图12 M-0、M-P45、M-P45-15c膜Janus-B侧对二氯乙烷包水乳液的分离性能

图13 Janus-T侧对无表面活性剂水包油乳化液的分离性能

图14 Janus-T侧对含表面活性剂水包油乳化液的分离性能

图15 二氯乙烷包水乳化液分离前后粒径及显微镜图

表2 用于处理表面活性剂稳定的O/W和W/O乳液的Janus膜

膜材料	O/W乳液			W/O乳液
膜材料	渗透通量 /L·m^-2·h^-1	滤液含油量TOC /mg·L^-1	分离效率 /%	渗透通量 /L·m^-2·h^-1	滤液含油量 /μL·L^-1	分离效率 /%
PVDF/PVP-VTES膜^［21］	T/W 3700	—	97.5	W/T 1650	—	97
HDTMS/Al₂O₃陶瓷膜^［22］	H/W 90	—	95	W/H 927	—	98.6
F/P-SiO₂/PVDF膜^［20］	H/W 4500	20	99.8	W/H 6800	105	99
聚(N-异丙基丙烯酰胺)/尼龙膜^[23]	T/W 2100	125	98.5	W/T 1300	170	97.8
SiO₂-PVDF/PVDF膜^［24］	P/W 88	25	97.5	W/P 880	60	94.2
PFDS/TiO₂、PPS膜^［25］	T/W 470	152	98.4	W/T 290	160	98.3

图16 M-P45膜和M-P45-15c膜通量变化

图17 M-P45膜和M-P45-15c膜截留率变化

图18 M-P45膜和M-P45-15c膜污染指数图

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