Permeation properties and regeneration of a ZSM-5 zeolite membrane for bio-oil dehydration

doi:10.11949/0438-1157.20200143

Abstract

Abstract:

A ZSM-5 zeolite membrane was hydrothermally synthesized using a template-free method for bio-oil pervaporation dehydration. The ZSM-5 zeolite membrane showed both excellent chemical stability and selectivity in the highly acidic and multi-component bio-oil system. However, the membrane encountered serious membrane fouling in bio-oil during pervaporation, which resulted in a significant loss in the permeation flux. The membrane regeneration test showed that the permeation flux increased with increasing the regeneration temperature, and the value could be recovered to 88% of the original flux of the fresh ZMS-5 membrane after the membrane was regenerated at 220℃. The membrane regeneration mechanism showed that the intracrystalline pores of the ZSM-5 zeolite membrane were easily fouled in the bio-oil system, which was responsible for the rapid decrease of the permeation flux; while the intercrystalline pores with a relatively larger pore size were difficult to be completely blocked, thus the intercrystalline pores functioned as the main channels for water permeation through the fouled ZSM-5 zeolite membrane. The above results indicate that the bio-oil pervaporation, dehydration performance of a ZSM-5 zeolite membrane can be effectively improved by properly adjusting the number and size of intercrystalline pores of ZSM-5 zeolite membranes.

Key words: zeolite, membrane, separation, pervaporation, bio-oil

摘要：

在水热条件下通过无模板剂法合成了连续的ZSM-5沸石膜，并将其用于生物油的渗透汽化以进行高效脱水分离。ZSM-5沸石膜在强酸性、多组分的生物油体系中保持了很好的化学稳定性和优异的分离选择性，但在分离过程中面临着较强的膜污染问题，导致了膜通量的大幅下降。ZSM-5沸石膜的再生研究表明，膜的渗透通量随着再生温度的升高而逐渐提高。当再生温度为220℃时，ZSM-5沸石膜的渗透通量可以恢复至初始的88%。再生的机理研究表明，ZSM-5沸石膜中大量的晶内孔在生物油体系中极易被污染，从而导致渗透通量迅速下降；而相对较大的晶间孔却难以被完全堵塞，水分子在被污染的ZSM-5沸石膜中主要通过晶间孔进行渗透。上述结果表明，通过合理调控ZSM-5沸石膜的晶间孔的数量和尺寸大小可有效提升ZSM-5沸石膜在生物油中的渗透汽化脱水分离性能。

关键词: 沸石, 膜, 分离, 渗透汽化, 生物油

CLC Number:

TQ 028.8

Shanhong MA, Feng YE, Yanhong WANG, Xuemei LANG, Shuanshi FAN, Gang LI. Permeation properties and regeneration of a ZSM-5 zeolite membrane for bio-oil dehydration[J]. CIESC Journal, 2020, 71(7): 3345-3353.

马珊宏, 叶枫, 王燕鸿, 郎雪梅, 樊栓狮, 李刚. ZSM-5沸石膜用于生物油的脱水分离及其再生过程研究[J]. 化工学报, 2020, 71(7): 3345-3353.

Figures/Tables 9

Fig.1 SEM images of the ZSM-5 seeds (a) and seeded support (b)

Fig.2 XRD patterns of the support (a), ZSM-5 zeolite seeds (b), bio-oil treated ZSM-5 seeds (c), ZSM-5 seeded support (d) and ZSM-5 zeolite membrane (e)

Fig.3 Top-view and cross-sectional SEM images of the ZSM-5 zeolite membrane

Table 1 Time course of the pervaporation performance of the ZSM-5 zeolite membrane for bio-oil dehydration at 30℃

时间/h	渗透通量/(kg·m^-2·h^-1)	渗透侧水含量/% (质量)
1	0.445	97.7
6	0.093	99.0
12	0.038	95.9
18	0.038	99.1
24	0.037	98.2
30	0.036	98.8
36	0.037	99.1

Fig.4 Temperature dependence of pervaporation performance of the fresh and regenerated ZSM-5 membrane for pure water system

Fig.5 Temperature dependence of pervaporation performance of the fresh and regenerated ZSM-5 membrane for bio-oil system

Fig.6 Stability of bio-oil pervaporation performance of the ZSM-5 zeolite membrane regenerated at 220℃

Fig.7 Arrhenius plots of water permeances through the ZSM-5 zeolite membrane

Table 2 Activation energies and pre-exponential factors for water permeation through the fresh and regenerated ZSM-5 membrane for pure water and bio-oil systems

ZSM-5 沸石膜	纯水体系		生物油体系
ZSM-5 沸石膜	k₀_,_水/(mol·Pa^-1·m^-2·s^-1)	E_P_,_水/ (kJ·mol^-1)	k₀_,_水/(mol·Pa^-1·m^-2·s^-1)	E_P_,_水/ (kJ·mol^-1)
新膜	1.14×10^-5	-6.82	1.11×10^-8	-17.99
R-140	1.29×10^-6	-11.47	8.72×10^-10	-23.28
R-180	1.45×10^-6	-11.47	1.65×10^-9	-22.77
R-220	2.89×10^-6	-9.98	4.58×10^-9	-20.16

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