膜科学与技术

位置：首页 >> 期刊内容阅读

聚二甲基硅氧烷膜蒸汽渗透分离乙醇/二氧化碳的研究

作者：石新宇，谢纹纹，毛恒，王涛，陈欣如，齐昊，胡晓雪，赵之平

单位：北京理工大学化学与化工学院，北京 102488

关键词：蒸汽渗透；聚二甲基硅氧烷；复合膜；发酵尾气；乙醇回收

DOI号：

分类号： TQ028；O634.4+1

出版年,卷(期):页码： 2024,44(2):29-36

摘要：

生物质发酵制乙醇过程中，发酵尾气的产生与排放对生态环境有极大影响。本文以聚偏氟乙烯（PVDF）多孔膜为基底，聚二甲基硅氧烷（PDMS）为分离层基质，制备出适用于发酵尾气乙醇/CO2分离的PDMS/PVDF复合膜。通过红外光谱、X射线衍射、扫描电子显微镜等手段对PDMS/PVDF复合膜进行了系统表征，探究了热交联时间、进料压力、进料乙醇浓度、进料温度、吹扫气流量对PDMS/PVDF复合膜渗透分离性能的影响。结果表明，在PVDF基底上成功制备出薄约10.5 μm、致密且均质的PDMS分离层。热交联时间越长，膜的选择性越低而渗透性升高；随着进料压力增加，膜的渗透性和选择性均升高；随着进料乙醇浓度升高，膜的渗透性和选择性均呈先升后降的趋势；随着进料温度升高，膜的渗透性和选择性均下降；随吹扫气流量的增加，膜的渗透性和选择性先升高后下降。在进料温度35℃，进料压力0.15 MPa（表压），乙醇蒸汽体积分数0.1 %时，所制PDMS/PVDF复合膜的乙醇渗透性高达33052.2 Barrer，乙醇/CO2选择性为17.1。此外，在连续测试60 h中，所制复合膜性能保持稳定，在生物乙醇发酵尾气处理方面具有应用前景。

During the production of bioethanol, the generation and emission of fermentation tail gas have a significant impact on ecological environment. In this study, the PDMS/PVDF composite membranes suitable for the vapor permeation (VP) separation of ethanol from CO2 were prepared by casting the polydimethylsiloxane (PDMS) separation layer upon the polyvinylidene fluoride (PVDF) porous substrate. The microstructures of PDMS/PVDF composite membranes were systematically characterized by FTIR, XRD, and SEM. The effects of thermal crosslinking time, feed pressure, ethanol concentration, feed temperature, and sweep gas flow rate on the separation performance of the PDMS/PVDF composite membranes were explored. The results showed that the dense and homogeneous PDMS separation layer about 10.5 μm was successfully prepared. Longer thermal crosslinking time led to lower selectivity and higher ethanol permeability. The higher feed pressure resulted in higher ethanol permeability and membrane selectivity. As the feed ethanol concentration increased, the ethanol permeability and selectivity first increased and then decreased. Higher feed temperature resulted in lower ethanol permeability and selectivity. Higher sweep gas flow rate led to a trend of first increased and then decreased of ethanol permeability and selectivity. The as-prepared PDMS/PVDF composite membrane achieved an ethanol permeability of 33052.2 Barrer and the selectivity of 17.1 in separating 0.1 %(volume fraction) ethanol/CO2 system under 0.15 MPa (gauge pressure) at 35℃, and remained a stable separation performance after 60 hours of testing. Therefore, the PDMS/PVDF composite membrane exhibits great application potential in the treatment of tail gas from bioethanol fermentation.

基金项目：

国家重点研发计划课题（2021YFC2101203）、国家自然科学基金项目（21736001和22008008）及北京理工大学青年教师学术启动计划资助

作者简介：

石新宇（1999- ），男，河北邢台人，硕士研究生，主要从事气体分离膜与膜组件研究

参考文献：

[1] Xu G Y, Schwarz P, Yang H L. Adjusting energy consumption structure to achieve China's CO2 emissions peak[J]. Renewable and Sustainable Energy Reviews, 2020, 122: 109737.
[2] Zabed H, Sahu J N, Suely A, et al. Bioethanol production from renewable sources: Current perspectives and technological progress[J]. Renewable and Sustainable Energy Reviews, 2017, 71: 475-501.
[3] Wu B, Wang Y W, Dai Y H, et al. Current status and future prospective of bio-ethanol industry in China[J]. Renewable and Sustainable Energy Reviews, 2021, 145: 111079.
[4] Zhao S, Gao Y, Mao G, et al. Synthesis of azo-linked porous polymers as fillers to enhance the performance of mixed-matrix membranes for the separation of bioethanol fermentation tail gas[J]. Chemical Engineering Journal, 2023, 456: 141141.
[5] Hegely L, Lang P. Reduction of the energy demand of a second-generation bioethanol plant by heat integration and vapour recompression between different columns[J]. Energy, 2020, 208: 118443.
[6] Vane L M. Review: Membrane materials for the removal of water from industrial solvents by pervaporation and vapor permeation[J]. Journal of Chemical Technology and Biotechnology, 2019, 94(2): 343-365.
[7] Chen Z, Qin P Y, Chen C X. Research, application situation and development of pervaporation and vapor permeation technology[J]. Membr Sci Technol, 2003, 23(4): 103-109.
[8] Belaissaoui B, Le Moullec Y, Favre E. Energy efficiency of a hybrid membrane/condensation process for VOC (Volatile Organic Compounds) recovery from air: A generic approach[J]. Energy, 2016, 95: 291-302.
[9] Vane L M, Alvarez F R. Effect of membrane and process characteristics on cost and energy usage for separating alcohol-water mixtures using a hybrid vapor stripping-vapor permeation process[J]. Journal of Chemical Technology and Biotechnology, 2015, 90(8): 1380-1390.
[10] 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.
[11] 李洪深, 李十中. 蒸汽渗透技术在燃料乙醇生产中的应用研究进展[J]. 化工进展, 2020, 39(05): 1620-1631.
[12] 张芯, 金华峰, 赵振志. 聚二甲基硅氧烷渗透汽化膜的研究进展[J]. 当代化工, 2020, 49(5)：1001-1004．
[13] 由涛, 陈龙祥, 张庆文, 等. 聚二甲基硅氧烷膜在渗透汽化技术中的研究进展[J]. 化工新型材料, 2009, 37(9)：1-4.
[14] Qian K, Bruggen B, Dewil R, et al. Hybrid operation of the bio-ethanol fermentation[J]. Separation and Purification Technology, 2015, 149: 322-330.
[15] Zhang F, Zhang W, Yu Y, et al. Sol-gel preparation of PAA-g-PVDF/TiO2 nanocomposite hollow fiber membranes with extremely high water flux and improved antifouling property[J]. J Membr Sci, 2013, 432: 25-32.
[16] Cai D, Neyer A, Kuckuk R, et al. Raman, mid-infrared, near-infrared and ultraviolet–visible spectroscopy of PDMS silicone rubber for characterization of polymer optical waveguide materials[J]. Journal of Molecular Structure, 2010, 976(1-3): 274-281.
[17] Mao H, Zhen H, Ahmad A, et al. In situ fabrication of MOF nanoparticles in PDMS membrane via interfacial synthesis for enhanced ethanol permselective pervaporation[J]. J Membr Sci, 2019, 573: 344-358.
[18] 霍宏达. 聚酰胺反渗透膜交联结构的调控与脱盐性能构效关系的研究[D]. 北京化工大学, 2023.
[19] Ma Y N, He X Y, Tang S H, et al. Enhanced 2-D MOFs nanosheets/PIM-PMDA-OH mixed matrix membrane for efficient CO2 separation[J]. Journal of Environmental Chemical Engineering, 2022, 10(2): 107274.
[20] 唐俏瑜, 王莉, 展侠等. 高选择性PDMS/PVDF复合膜渗透汽化分离乙醇/水混合物[J]. 膜科学与技术, 2011, 31(6): 1-5.
[21] Gan G, Fan S, Li X, et al. Adsorption and membrane separation for removal and recovery of volatile organic compounds[J]. Journal of Environmental Sciences, 2023, 123(01): 96-115.
[22] Yang W, Zhou H, Zong C, Li Y, Jin W. Study on membrane performance in vapor permeation of VOC/N2 mixtures via modified constant volume/variable pressure method[J]. Sep Purif Technol, 2018, 200: 273–283.
[23] Zong C, Yang X, Chen D, Chen Y, Zhou H, Jin W. Rational tuning of the viscosity of membrane solution for the preparation of sub-micron thick PDMS composite membrane for pervaporation of ethanol-water solution[J]. Sep Purif Technol, 2021, 255:117729.
[24] Yang W P, Su X, Zheng T C, et al. Fabricating a ZIF-8@Polydimethylsiloxane(PDMS)/PVDF mixed matrix composite membrane for separation of ethanol from aqueous solution via vapor permeation[J]. Zeitschrift Fur Anorganische Und Allgemeine Chemie, 2022, 648(7): e202100379.

服务与反馈：

【文章下载】【加入收藏】

《膜科学与技术》编辑部地址：北京市朝阳区北三环东路19号蓝星大厦邮政编码：100029 电话：010-64426130/64433466 传真：010-80485372邮箱：mkxyjs@163.com