ZIF-L/PDMS混合基质膜蒸气渗透耦合发酵强化乙醇生产效率的研究

doi:10.11949/0438-1157.20210337

摘要/Abstract

摘要：

蒸气渗透（VP）膜分离不存在膜污染风险，在生物乙醇生产中具有广阔的应用前景。将聚二甲基硅氧烷（PDMS）膜和以二维沸石咪唑骨架（ZIF-L）为填充基质制备的PDMS（ZIF-L/PDMS）混合基质膜，分别用于VP膜分离与菊粉水解液发酵制乙醇过程的耦合，分析了二者在耦合过程中的分离性能和发酵性能。探究了不同膜分离方式、不同类型膜及操作条件对膜分离性能的影响。实验结果表明，当料液浓度为5%（质量）、蒸气循环流量为1.5 L·min^-1时，ZIF-L/PDMS混合基质膜的VP性能高于渗透汽化（PV），归一化总通量达到1148.78 g·m^-2·h^-1，分离因子高达19.14，显著提升了乙醇分离性能。ZIF-L/PDMS混合基质膜用于VP耦合发酵，实现了耦合过程的高渗透性和乙醇选择性，与文献报道相比，乙醇移除效果最优，乙醇产率和时空产率分别达到0.421 g·g^-1、3.07 g·L^-1·h^-1，两个指标明显高于单独发酵，极大地提高了乙醇生产效率。因此，ZIF-L/PDMS混合基质膜在原位分离发酵乙醇方面具有很大的应用潜力。

关键词: 聚二甲基硅氧烷, 混合基质膜, 乙醇发酵, 蒸气渗透, 膜分离

Abstract:

Vapor permeation (VP) membrane separation does not have the risk of membrane fouling and has broad application prospects in the production of bioethanol. The polydimethylsiloxane (PDMS) membrane and the novel PDMS mixed matrix membrane (ZIF-L/PDMS) prepared by embedding two-dimensional zeolitic imidazolate framework-L (ZIF-L) into PDMS matrix were used as separate modules to separate ethanol from fermentation of inulin hydrolysate in a VP coupled with fermentation system(VP-fermentation). The separation performance and fermentation performance during coupling process were analyzed. The effects of separation methods, membrane types and operation conditions on the separation performance were explored. The results showed that ZIF-L/PDMS mixed matrix membrane for the separation of 5%(mass) ethanol aqueous solution by VP showed better performance than pervaporation (PV) when vapor cyclic flow was 1.5 L·min^-1, and the normalized total flux and the separation factor reached 1148.78 g·m^-2·h^-1 and 19.14, respectively, suggesting the ethanol separation performance was significantly improved. Furthermore, the ZIF-L/PDMS membrane exhibited an impressive permeability and ethanol selectivity in VP-fermentation process. Compared with the literature reports, it achieved the best ethanol removal effect, which greatly enhanced the ethanol production efficiency. The ethanol yield and productivity reached 0.421 g·g^-1and 3.07 g·L^-1·h^-1, respectively, which were higher than that in independent batch fermentation. Therefore, ZIF-L/PDMS mixed matrix membrane exhibits great application potential in the in-situ removal of ethanol from fermentation.

Key words: polydimethylsiloxane, mixed matrix membrane, ethanol fermentation, vapor permeation, membrane separation

中图分类号:

TQ 028.8

王艳芳,毛恒,蔡玮玮,张傲率,徐李昊,赵之平. ZIF-L/PDMS混合基质膜蒸气渗透耦合发酵强化乙醇生产效率的研究[J]. 化工学报, 2021, 72(10): 5226-5236.

Yanfang WANG,Heng MAO,Weiwei CAI,Aoshuai ZHANG,Lihao XU,Zhiping ZHAO. Enhancing ethanol production efficiency by ZIF-L/PDMS mixed matrix membrane via vapor permeation-fermentation coupling process[J]. CIESC Journal, 2021, 72(10): 5226-5236.

图/表 11

图1 膜渗透分离耦合发酵(VP-ferment、PV-ferment)装置原理图

Fig.1 Schematic diagram of apparatus of membrane separation coupled with fermentation process

图2 PDMS膜表面(a)和截面(b)、ZIF-L/PDMS膜表面[(c)、(d)]和截面[(e)、(f)]的扫描电镜图

Fig.2 SEM images of the surface (a) and cross-section (b) morphologies of pure PDMS membrane and the surface [(c),(d)] and cross-section [(e),(f)] morphologies of ZIF-L/PDMS mixed matrix membrane

图3 PDMS膜和ZIF-L/PDMS混合基质膜的水接触角(a)和乙醇接触角(b)

Fig.3 Water contact angles (a) and ethanol contact angles (b) of PDMS and ZIF-L/PDMS membranes

图4 不同料液浓度对PDMS膜VP分离性能的影响：通量(a)；渗透侧乙醇浓度和分离因子(b)(操作条件:温度35℃,蒸气循环流量1.5 L·min-1,真空度0.095 MPa)

Fig.4 Effect of feed concentration on flux (a), ethanol concentration in permeate and separation factor (b) of VP by PDMS membrane

图5 不同蒸气循环流量对PDMS膜分离性能的影响：通量(a)；渗透侧乙醇浓度和分离因子(b)（操作条件:温度35℃,料液浓度5%(质量),真空度0.095 MPa）

Fig.5 Effect of the vapor cyclic flow on flux (a), ethanol concentration in permeate and separation factor (b) of VP by PDMS membrane

图6 不同膜类型的蒸气渗透(a)和渗透汽化(b)性能（操作条件:温度35℃,料液浓度5%(质量),蒸气循环流量1.5 L·min-1）

Fig.6 Effect of different membrane on membrane performance in PV(a) and VP(b) processes

图7 不同发酵过程中乙醇浓度(a)、还原糖浓度(b)、细胞浓度(c)随发酵时间的变化（操作条件:初始还原糖浓度150 g·L-1,发酵温度35℃,蒸气循环流量1.5 L·min-1）

Fig.7 Variations of ethanol concentration (a), reducing sugar concentration (b) and cell concentration (c) in broth during fermentation processes

表1 不同过程的发酵性能对比

Table 1 Comparation of fermentation performance in different processes

发酵特性参数	单独发酵	VP-ferment-PDMS	VP-ferment-ZIF-L/PDMS
细胞浓度/(g·L^-1)	18.99	26.28	29.81
乙醇总产量/g	23.23	25.01	24.54
乙醇产率/(g·g^-1)	0.418	0.436	0.421
乙醇时空产率/(g·L^-1·h^-1)	1.79	2.61	3.07

图8 VP-ferment-PDMS (a)和VP-ferment-ZIF-L/PDMS (b)中通量随发酵时间的变化

Fig.8 Variations of flux during the VP- fermentation process of PDMS (a) and ZIF-L/PDMS (b)

表2 不同类型膜耦合过程中发酵性能与膜性能的文献对比

Table 2 Comparation of fermentation and membrane performance under different membrane types

膜类型	膜分离方法	发酵温度/ ℃	乙醇产率/ (g·g^-1)	乙醇时空产率/ (g·L^-1·h^-1)	总通量/ (g·m^-2·h^-1)	分离因子	乙醇移除速率^①/(g·h^-1)	文献
PDMS	PV	35	—	—	750	4.83	—	[39]
PDMS	VP	35	0.414	3.33	350	10	0.27	[30]
PDMS	PV	35	0.381	2.67	385	8.8	0.38	[27]
PDMS	PV	35	0.45	3.05	355	6.3	0.47	[38]
CNT-PDMS	PV	30	0.45	2.23	41.4	6.2	—	[40]
PDMS	PV	35	0.38	2.31	370	9.5	—	[27]
PDMS	PV	35	0.42	1.58	417.2	11.7	—	[41]
PDMS/CNT-GO	PV	32	—	—	200	20	—	[42]
Silicalite-1/PDMS	PV	30	0.42	1.6	416	9.8	—	[43]
PDMS	VP	35	0.436	2.61	536	12.3	0.413	本工作
ZIF-L/PDMS	VP	35	0.421	3.07	675	19.5	0.616	本工作

图9 VP-ferment-PDMS和VP-ferment-ZIF-L/PDMS过程中渗透侧乙醇浓度(a)和分离因子随发酵时间的变化(b)

Fig.9 Variations of ethanol concentration in permeate (a) and separation factor (b) during the VP- fermentation process with PDMS membrane and ZIF-L/PDMS membrane

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