四通道中空纤维MFI分子筛膜用于二甲苯异构体分离

doi:10.11949/0438-1157.20230293

摘要/Abstract

摘要：

采用二次生长法在高机械强度、高装填密度的四通道α-Al₂O₃中空纤维载体（7 cm）上制备MFI分子筛膜，探究了膜合成时间、操作温度、原料分压和吹扫气流量等条件对二甲苯异构体膜分离性能的影响。结果表明，160℃水热合成12 h制得的四通道中空纤维MFI分子筛膜对二甲苯异构体分离性能较优，在150℃、原料分压2 kPa、吹扫气流量20 ml/min时对二甲苯/邻二甲苯分离因子高达878，PX渗透性为2.1×10^-8 mol·m^-2·s^-1·Pa^-1。基于优化的制膜及分离操作条件，进一步将MFI分子筛膜制备于27 cm长的四通道中空纤维载体上，也获得了优异的对二甲苯/邻二甲苯膜分离性能，且所制得的膜材料对该体系的分离可稳定运行100 h以上。为推进中空纤维MFI分子筛膜的批量化制备和传统分离工艺的技术革新奠定了基础。

关键词: MFI分子筛膜, 四通道中空纤维, 二甲苯异构体, 分离, 放大

Abstract:

MFI zeolite membranes were prepared on four-channel α-Al₂O₃ hollow fiber supports (7 cm) with high mechanical strength and high loading density by secondary growth method. The effects of synthetic time, operation temperature, partial pressure of raw material and purge gas flow rate on the membrane separation performance of xylene isomer were investigated. The results showed that the four-channel hollow fiber MFI zeolite membrane prepared by hydrothermal synthesis at 160℃ for 12 h possessed the better separation performance of xylene isomers. The separation factor of p-xylene/o-xylene was up to 878 at 150℃, partial pressure of raw material 2 kPa and purge gas flow rate 20 ml/min. PX permeance was 2.1×10^-8 mol·m^-2·s^-1·Pa^-1. Based on the optimized membrane preparation conditions, the MFI zeolite membranes were further prepared on the 27 cm long four-channel hollow fiber supports. An excellent p-xylene/o-xylene membrane separation performance was obtained, and the as-prepared membrane can run stably for more than 100 h for the separation of xylene isomer mixture. This study laid the foundation for promoting the batch preparation of hollow fiber MFI zeolite membranes and the technical innovation of traditional separation process.

Key words: MFI zeolite membranes, four-channel hollow fiber, xylene isomer, separation, scale-up

中图分类号:

TQ 028.8

韩奎奎, 谭湘龙, 李金芝, 杨婷, 张春, 张永汾, 刘洪全, 于中伟, 顾学红. 四通道中空纤维MFI分子筛膜用于二甲苯异构体分离[J]. 化工学报, 2023, 74(6): 2468-2476.

Kuikui HAN, Xianglong TAN, Jinzhi LI, Ting YANG, Chun ZHANG, Yongfen ZHANG, Hongquan LIU, Zhongwei YU, Xuehong GU. Four-channel hollow fiber MFI zeolite membrane for the separation of xylene isomers[J]. CIESC Journal, 2023, 74(6): 2468-2476.

图/表 13

图1 MFI分子筛膜分离二甲苯异构体示意图

Fig.1 Schematic of the xylene isomer separation by MFI zeolite membrane

图2 膜分离装置示意图

Fig.2 Schematic diagram of membrane separation device

图3 四通道中空纤维载体照片

Fig.3 Photos of four-channel hollow fiber supports

图4 不同水热合成时间所得MFI分子筛膜表面与断面SEM照片

Fig.4 SEM images of MFI zeolite membranes synthesized for different time

表1 不同合成时间制得MFI分子筛膜膜厚及PX/OX分离性能

Table 1 Thickness and PX/OX separation performance of MFI zeolite membranes synthesized with different time

样品	合成时间/h	膜厚/μm	膜性能
样品	合成时间/h	膜厚/μm	PX渗透性/ (10^-8 mol·m^-2·s^-1·Pa^-1)	OX渗透性/ (10^-10 mol·m^-2·s^-1·Pa^-1)	渗透侧PX 摩尔分数/%	PX/OX 分离因子
M1	4	6	3.1	5.8	98.5	53.2
M2	8	10	2.9	0.9	99.7	319
M3	12	12	2.1	0.2	99.9	878
M4	16	18	2.0	1.3	99.5	154

图5 不同操作温度下7 cm长MFI分子筛膜PX/OX分离性能

Fig.5 PX/OX separation performance of 7 cm MFI zeolite membrane at different temperatures

图6 不同原料分压下MFI分子筛膜PX/OX分离性能

Fig.6 PX/OX separation performance of MFI zeolite membrane at different pressures

图7 不同吹扫流量下MFI分子筛膜对PX/OX体系的分离性能

Fig.7 PX/OX separation performance of MFI zeolite membrane at different purge gas flow rates

图8 四通道中纤维MFI分子筛膜照片

Fig.8 Photo of four-channel hollow fiber MFI zeolite membranes

图9 MFI分子筛标准谱图和四通道α-Al2O3中空纤维MFI分子筛膜XRD谱图

Fig.9 XRD patterns of standard MFI zeolites and four-channel α-Al2O3 hollow fiber MFI zeolite membranes

图10 不同操作温度下27 cm长MFI分子筛膜PX/OX分离性能

Fig.10 PX/OX separation performance of 27 cm MFI zeolite membrane at different temperatures

图11 MFI分子筛膜的PX/OX分离稳定性

Fig.11 PX/OX separation stability of MFI zeolite membrane

表2 MFI分子筛膜对二甲苯异构体的分离性能对比

Table 2 Comparisons of the performance of MFI zeolite membranes for xylene isomer separation

载体类型	晶体取向	测试温度/℃	PX渗透性/(10^-8 mol·m^-2·s^-1·Pa^-1)	PX/OX分离因子	文献
α-Al₂O₃片式	b	100	20	600	[8]
SiO₂片式	b	150	29	8000	[9]
SiO₂片式	b	150	23	3990	[25]
SiO₂片式	b	150	14	515	[26]
SiO₂片式	b	150	23	1100	[27]
α-Al₂O₃片式	随机	300	1.02	76	[12]
SiO₂片式	随机	150	4.8	162	[28]
α-Al₂O₃管式（8 cm）	随机	250	0.95	17.8	[29]
不锈钢管式（—）	随机	150	0.66	13.5	[30]
不锈钢管式（2.5 cm）	随机	152	0.26	60	[31]
α-Al₂O₃管式（15 cm）	随机	200	1.1	＞400	[32]
四通道α-Al₂O₃中空纤维（7 cm）	随机	150	2.1	878	本工作
四通道α-Al₂O₃中空纤维（27 cm）	随机	150	1.9	245	本工作

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