High-performance 19-channel monolithic CHA zeolite membranes for vapor-permeation dehydration of acetic acid

doi:10.1016/j.cjche.2025.04.021

中国化学工程学报 ›› 2025, Vol. 87 ›› Issue (11): 252-261.DOI: 10.1016/j.cjche.2025.04.021

High-performance 19-channel monolithic CHA zeolite membranes for vapor-permeation dehydration of acetic acid

Hong Xiao, Shilei Yu, Yuhan Yan, Junjing Zhou, Rongfei Zhou, Weihong Xing

State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 210009, China

收稿日期:2025-03-11 修回日期:2025-04-22 接受日期:2025-04-24 出版日期:2025-11-28 发布日期:2025-07-01
通讯作者: Rongfei Zhou,E-mail:rf-zhou@njtech.edu.cn
基金资助:
This work was financially supported by the National Key Research and Development Program of China (2023YFB3810700), the National Natural Science Foundation of China (22378189, U22A20414 and 22378188), the Natural Science Foundation of Jiangsu Provincial Department of Science and Technology (BK20232010 and BG2024018), and National State Key Laboratory of Material-oriented Chemical Engineering (SKL-MCE-22A02 and SKL-MCE23B14).

High-performance 19-channel monolithic CHA zeolite membranes for vapor-permeation dehydration of acetic acid

Hong Xiao, Shilei Yu, Yuhan Yan, Junjing Zhou, Rongfei Zhou, Weihong Xing

State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 210009, China

Received:2025-03-11 Revised:2025-04-22 Accepted:2025-04-24 Online:2025-11-28 Published:2025-07-01
Contact: Rongfei Zhou,E-mail:rf-zhou@njtech.edu.cn
Supported by:
This work was financially supported by the National Key Research and Development Program of China (2023YFB3810700), the National Natural Science Foundation of China (22378189, U22A20414 and 22378188), the Natural Science Foundation of Jiangsu Provincial Department of Science and Technology (BK20232010 and BG2024018), and National State Key Laboratory of Material-oriented Chemical Engineering (SKL-MCE-22A02 and SKL-MCE23B14).

摘要/Abstract

摘要： Membrane-based vapor permeation (VP) is regarded as a highly efficient technology, featuring low energy consumption and free salt fouling. In this study, we have demonstrated upscaling chabazite (CHA) zeolite membranes on the 19-channel α-Al₂O₃ monolithic supports synthesized from high-silica gel (SiO₂/Al₂O₃ ratio of 200) for the dehydration of acetic acid by VP. The monolithic membrane presents higher surface-to-volume ratio and a-tenfold greater mechanical strength compared to tubular ones. The micromorphology and crystallinity of the monolithic CHA zeolite membranes were characterized by scanning electron micrographs and X-ray diffraction analysis. The single-gas permeation test and the effects of temperature, feed water content and feed flow rate on the VP separation performance of monolithic CHA zeolite membrane for dehydration of acetic acid were investigated. Moreover, the stability test of monolithic CHA zeolite membranes was carried out. The 19-channel monolithic membrane achieved a comparable separation performance (water flux of 0.63 kg m^-2·h^-1 and selectivity of 369 at 393 K) with the reported small-area zeolite membranes in water/acetic acid mixtures. It is demonstrated that the monolithic CHA zeolite membranes could be transformative candidates for industrial dehydration of acetic acid under harsh environments.

关键词: Zeolite membrane, Monolithic, Chabazite, Acetic acid, Vapor permeation

Abstract: Membrane-based vapor permeation (VP) is regarded as a highly efficient technology, featuring low energy consumption and free salt fouling. In this study, we have demonstrated upscaling chabazite (CHA) zeolite membranes on the 19-channel α-Al₂O₃ monolithic supports synthesized from high-silica gel (SiO₂/Al₂O₃ ratio of 200) for the dehydration of acetic acid by VP. The monolithic membrane presents higher surface-to-volume ratio and a-tenfold greater mechanical strength compared to tubular ones. The micromorphology and crystallinity of the monolithic CHA zeolite membranes were characterized by scanning electron micrographs and X-ray diffraction analysis. The single-gas permeation test and the effects of temperature, feed water content and feed flow rate on the VP separation performance of monolithic CHA zeolite membrane for dehydration of acetic acid were investigated. Moreover, the stability test of monolithic CHA zeolite membranes was carried out. The 19-channel monolithic membrane achieved a comparable separation performance (water flux of 0.63 kg m^-2·h^-1 and selectivity of 369 at 393 K) with the reported small-area zeolite membranes in water/acetic acid mixtures. It is demonstrated that the monolithic CHA zeolite membranes could be transformative candidates for industrial dehydration of acetic acid under harsh environments.

Key words: Zeolite membrane, Monolithic, Chabazite, Acetic acid, Vapor permeation

Hong Xiao, Shilei Yu, Yuhan Yan, Junjing Zhou, Rongfei Zhou, Weihong Xing. High-performance 19-channel monolithic CHA zeolite membranes for vapor-permeation dehydration of acetic acid[J]. 中国化学工程学报, 2025, 87(11): 252-261.

参考文献

[1] G. Merli, A. Becci, A. Amato, F. Beolchini, Acetic acid bioproduction: The technological innovation change, Sci. Total Environ. 798 (2021) 149292.
[2] G. Deshmukh, H. Manyar, Production pathways of acetic acid and its versatile applications in the food industry. Biotechnological Applications of Biomass. IntechOpen, (2021), pp.
[3] J.L. Martin-Espejo, J. Gandara-Loe, J.A. Odriozola, T.R. Reina, L. Pastor-Perez, Sustainable routes for acetic acid production: Traditional processes vs a low-carbon, biogas-based strategy, Sci. Total Environ. 840 (2022) 156663.
[4] G.J. Sunley, D.J. Watson, High productivity methanol carbonylation catalysis using iridium The Cativa^TM process for the manufacture of acetic acid, Catal. Today 58 (4) (2000) 293-307.
[5] T. Tsuru, T. Shibata, J.H. Wang, H.R. Lee, M. Kanezashi, T. Yoshioka, Pervaporation of acetic acid aqueous solutions by organosilica membranes, J. Membr. Sci. 421 (2012) 25-31.
[6] N. Jullok, P. Luis, J. Degreve, B. Van der Bruggen, A cascaded pervaporation process for dehydration of acetic acid, Chem. Eng. Sci. 105 (2014) 208-212.
[7] G.P. Liu, W.Q. Jin, Pervaporation membrane materials: Recent trends and perspectives, J. Membr. Sci. 636 (2021) 119557.
[8] L.Q. Li, J.J. Li, L.J. Cheng, J.X. Wang, J.H. Yang, Microwave synthesis of high-quality mordenite membrane by a two-stage varying heating-rate procedure, J. Membr. Sci. 612 (2020) 118479.
[9] F.Z. Charik, B. Achiou, A. Belgada, Z.C. Elidrissi, M. Ouammou, M. Rabiller-Baudry, S.A. Younssi, Optimal preparation of low-cost and high-permeation NaA zeolite membrane for effective ethanol dehydration, Microporous Mesoporous Mater. 344 (2022) 112229.
[10] K.I. Okamoto, H. Kita, K. Horii, K.T. Kondo, Zeolite NaA membrane: preparation, single-gas permeation, and pervaporation and vapor permeation of water/organic liquid mixtures, Ind. Eng. Chem. Res. 40 (1) (2001) 163-175.
[11] H. Kita, K. Horii, Y. Ohtoshi, K. Tanaka, K.I. Okamoto, Synthesis of a zeolite NaA membrane for pervaporation of water/organic liquid mixtures, J. Mater. Sci. Lett. 14 (3) (1995) 206-208.
[12] L.Z. Li, Y. Lu, L.Q. Li, J.H. Yang, W.J. Fu, Y.W. Luo, J.M. Lu, Y. Zhang, L. Zhou, Highly selective zeolite T membranes with different ERI stacking faults for pervaporative dehydration of ethanol, J. Membr. Sci. 638 (2021) 119701.
[13] J. Kuhn, K. Yajima, T. Tomita, J. Gross, F. Kapteijn, Dehydration performance of a hydrophobic DD3R zeolite membrane, J. Membr. Sci. 321 (2) (2008) 344-349.
[14] X. Lin, E. Kikuchi, M. Matsukata, Preparation of mordenite membranes on α-alumina tubular supports for pervaporation of water-isopropyl alcohol mixtures, Chem. Commun. (11) (2000) 957-958.
[15] Q. Wang, C. Qian, C.X. Guo, N. Xu, Q. Liu, B. Wang, L. Fan, K.H. Hu, Pervaporation dehydration mechanism and performance of high-aluminum ZSM-5 zeolite membranes for organic solvents, Int. J. Mol. Sci. 25 (14) (2024) 7723.
[16] X. Lin, H. Kita, K.I. Okamoto, Silicalite membrane preparation, characterization, and separation performance, Ind. Eng. Chem. Res. 40 (19) (2001) 4069-4078.
[17] Q. Liu, R.D. Noble, J.L. Falconer, H.H. Funke, Organics/water separation by pervaporation with a zeolite membrane, J. Membr. Sci. 117 (1-2) (1996) 163-174.
[18] T. Sano, H. Yanagishita, Y. Kiyozumi, F. Mizukami, K. Haraya, Separation of ethanol/water mixture by silicalite membrane on pervaporation, J. Membr. Sci. 95 (3) (1994) 221-228.
[19] Y. Cui, H. Kita, K.I. Okamoto, Zeolite T membrane: preparation, characterization, pervaporation of water/organic liquid mixtures and acid stability, J. Membr. Sci. 236 (1-2) (2004) 17-27.
[20] J. Jiang, L. Peng, X.R. Wang, H. Qiu, M.M. Ji, X.H. Gu, Effect of Si/Al ratio in the framework on the pervaporation properties of hollow fiber CHA zeolite membranes, Microporous Mesoporous Mater. 273 (2019) 196-202.
[21] Y. Hasegawa, H. Hotta, K. Sato, T. Nagase, F. Mizukami, Preparation of novel chabazite (CHA)-type zeolite layer on porous α-Al₂O₃ tube using template-free solution, J. Membr. Sci. 347 (1-2) (2010) 193-196.
[22] H. Qiu, J. Jiang, L. Peng, H. Liu, X.H. Gu, Choline chloride templated CHA zeolite membranes for solvents dehydration with improved acid stability, Microporous Mesoporous Mater. 284 (2019) 170-176.
[23] S. Imasaka, M. Itakura, K. Yano, S. Fujita, M. Okada, Y. Hasegawa, C. Abe, S. Araki, H. Yamamoto, Rapid preparation of high-silica CHA-type zeolite membranes and their separation properties, Sep. Purif. Technol. 199 (2018) 298-303.
[24] H.L. Hong, K.L. Yu, H.B. Liu, R.F. Zhou, W.H. Xing, Industrial-scale 61-channel monolithic silicalite-1 membranes for butane isomer separation, Adv. Membr. 4 (2024) 100096.
[25] Z.G. Xue, Y. Shen, L. Chen, B. Liu, N. Hu, R.F. Zhou, W.H. Xing, High-performance 19-channel monolithic chabazite membranes for efficient separation of water/ethanol and water/isopropanol mixtures by pervaporation and vapor permeation, J. Membr. Sci. 713 (2025) 123353.
[26] B. Liu, R. Zhang, Y. Du, F. Gao, J.J. Zhou, R.F. Zhou, Highly selective high-silica SSZ-13 zeolite membranes for H₂ production from syngas, Int. J. Hydrog. Energy 45 (32) (2020) 16210-16218.
[27] L. Yu, M.S. Nobandegani, A. Holmgren, J. Hedlund, Highly permeable and selective tubular zeolite CHA membranes, J. Membr. Sci. 588 (2019) 117224.
[28] D. Korelskiy, T. Leppajarvi, H. Zhou, M. Grahn, J. Tanskanen, J. Hedlund, High flux MFI membranes for pervaporation, J. Membr. Sci. 427 (2013) 381-389.
[29] M. Pera-Titus, J. Llorens, F. Cunill, R. Mallada, J. Santamaria, Preparation of zeolite NaA membranes on the inner side of tubular supports by means of a controlled seeding technique, Catal. Today 104 (2-4) (2005) 281-287.
[30] X.Q. Mo, H.B. Liu, Y.L. Li, Q.L. Gu, B. Wang, R.F. Zhou, W.H. Xing, SSZ-13 membranes on novel silica carbide monoliths for efficient CO₂ separation, J. Membr. Sci. 699 (2024) 122642.
[31] J.J. Zhou, S.J. Wu, B. Liu, R.F. Zhou, W.H. Xing, Scalable fabrication of highly selective SSZ-13 membranes on 19-channel monolithic supports for efficient CO₂ capture, Sep. Purif. Technol. 293 (2022) 121122.
[32] Y.M. Li, Y.L. Wang, M.Y. Guo, B. Liu, R.F. Zhou, Z.P. Lai, High-performance 7-channel monolith supported SSZ-13 membranes for high-pressure CO₂/CH₄ separations, J. Membr. Sci. 629 (2021) 119277.
[33] S. Kobuchi, K. Takakura, S. Yonezawa, K. Fukuchi, Y. Arai, Correlation of vapor-liquid equilibria of binary systems containing carboxylic acid by using Wilson equation with parameters estimated from pure-component properties, J. Chem. Eng. Japan / JCEJ 46 (2) (2013) 100-106.
[34] D.H. Olson, M.A. Camblor, L.A. Villaescusa, G.H. Kuehl, Light hydrocarbon sorption properties of pure silica Si-CHA and ITQ-3 and high silica ZSM-58, Microporous Mesoporous Mater. 67 (1) (2004) 27-33.
[35] N.N. Wang, N. Liu, J.J. Zhou, Q. Wang, N. Hu, R.F. Zhou, Large-area, high-permeance and acid-resistant zeolite SSZ-13 membranes for efficient pervaporative separation of water/acetic acid mixtures, J. Membr. Sci. 691 (2024) 122251.
[36] Y.T. Zhang, X.F. Zhu, S.Z. Chen, J.Y. Liu, Z. Hong, J.C. Wang, Z. Li, X.C. Gao, R. Xu, X.H. Gu, TiO₂-decorated NaA zeolite membranes with improved separation stability for pervaporation dehydration of N, N-Dimethylacetamide, J. Membr. Sci. 634 (2021) 119398.
[37] Y.T. Zhang, S.Z. Chen, R. Shi, P. Du, X.F. Qiu, X.H. Gu, Pervaporation dehydration of acetic acid through hollow fiber supported DD3R zeolite membrane, Sep. Purif. Technol. 204 (2018) 234-242.
[38] R.W. Baker, J.G. Wijmans, Y. Huang, Permeability, permeance and selectivity: a preferred way of reporting pervaporation performance data, J. Membr. Sci. 348 (1-2) (2010) 346-352.
[39] J.H. Chen, J.Z. Zheng, Q.L. Liu, H.X. Guo, W. Weng, S.X. Li, Pervaporation dehydration of acetic acid using polyelectrolytes complex (PEC)/11-phosphotungstic acid hydrate (PW11) hybrid membrane (PEC/PW11), J. Membr. Sci. 429 (2013) 206-213.
[40] Y.Q. Li, M.H. Zhu, N. Hu, F. Zhang, T. Wu, X.S. Chen, H. Kita, Scale-up of high performance mordenite membranes for dehydration of water-acetic acid mixtures, J. Membr. Sci. 564 (2018) 174-183.
[41] T. Nagase, Y. Kiyozumi, Y. Hasegawa, T. Inoue, T. Ikeda, F. Mizukami, Dehydration of concentrated acetic acid solutions by pervaporation using novel MER zeolite membranes, Chem. Lett. 36 (5) (2007) 594-595.
[42] K. Xu, Z.Q. Jiang, B. Feng, A.S. Huang, A graphene oxide layer as an acid-resisting barrier deposited on a zeolite LTA membrane for dehydration of acetic acid, RSC Adv. 6 (28) (2016) 23354-23359.
[43] D.Y. Si, M.H. Zhu, X.M. Sun, M. Xue, Y.Q. Li, T. Wu, T. Gui, I. Kumakiri, X.S. Chen, H. Kita, Formation process and pervaporation of high aluminum ZSM-5 zeolite membrane with fluoride-containing and organic template-free gel, Sep. Purif. Technol. 257 (2021) 117963.
[44] M.H. Zhu, I. Kumakiri, K. Tanaka, H. Kita, Dehydration of acetic acid and esterification product by acid-stable ZSM-5 membrane, Microporous Mesoporous Mater. 181 (2013) 47-53.
[45] R. Yao, Y. Peng, H.L. Song, C.Y. Zhu, P.Y. Wang, L. Kun, W.S. Yang, Rational design and fabrication of a novel acid-resistant UZM-5 zeolite membrane for pervaporation dehydration processes, Chem. Commun. 57 (75) (2021) 9574-9577.

High-performance 19-channel monolithic CHA zeolite membranes for vapor-permeation dehydration of acetic acid

High-performance 19-channel monolithic CHA zeolite membranes for vapor-permeation dehydration of acetic acid

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	Xiangli Liu, Yiqing Zeng, Jiahao Chen, Zhaoxiang Zhong, Weihong Xing. Research progress on the monolithic catalyst for hydrogenation of CO₂ to methane[J]. 中国化学工程学报, 2025, 80(4): 184-197.
[2]	Jiayi Zhang, Jiali He, Guibing Wang, Yu Zhao, Huairong Zhou, Dongliang Wang, Dongqiang Zhang. Study on the recovery of NMP waste liquid in lithium battery production by coupled pervaporation–adsorption process and evaluation of technical and economic performances[J]. 中国化学工程学报, 2025, 78(2): 273-283.
[3]	Mohammad Sohrabi, Reza Alizadeh, S. Majid Abdoli. Boron-modified ZSM-5 coated on honeycomb monolith surface for selective production of propylene from methanol[J]. 中国化学工程学报, 2025, 88(12): 21-33.
[4]	Xiangli Liu, Fei Gao, Jingyang Huang, Yiqing Zeng, Zhaoxiang Zhong, Weihong Xing. Insights on the effect of Si-Al interaction on Ni/Al₂O₃/SiC monolithic catalysts for CO₂ methanation[J]. 中国化学工程学报, 2025, 87(11): 171-181.
[5]	Liqin Tang, Xiang Jin, Bing Gao, Xuechao Gao, Xuehong Gu. CPAM-assisted synthesis of NaA zeolite membrane on macroporous mullite hollow fiber for ethanol dehydration by pervaporation[J]. 中国化学工程学报, 2025, 77(1): 66-80.
[6]	Huanxu Teng, Ronghui You, Huanyi Li, Siqi Shao, Qi Zhou, Ying Yang, Ting Wu, Meihua Zhu, Xiangshu Chen, Hidetoshi Kita. Pervaporation performance and characterization of hydrophilic ZSM-5 zeolite membranes for high inorganic acid and inorganic salts[J]. 中国化学工程学报, 2024, 73(9): 27-33.
[7]	Omama Rehman, Youduo Wu, Quan Zhang, Jin Guo, Cuihuan Sun, Huipeng Gao, Yaqing Xu, Rui Xu, Ayesha Shahid, Chuang Xue. Acetic acid- and furfural-based adaptive evolution of Saccharomyces cerevisiae strains for improving stress tolerance and lignocellulosic ethanol production[J]. 中国化学工程学报, 2024, 72(8): 26-33.
[8]	Yunyu Guo, Yiran Wang, Shu Zhang, Yi Wang, Song Hu, Jun Xiang, Walid Nabgan, Xun Hu. Steam reforming of acetic acid over Ni/biochar of low metal-loading: Involvement of biochar in tailoring reaction intermediates renders superior catalytic performance[J]. 中国化学工程学报, 2024, 68(4): 241-252.
[9]	Meihua Zhu, Xingguo An, Tian Gui, Ting Wu, Yuqin Li, Xiangshu Chen. Effects of ion-exchange on the pervaporation performance and microstructure of NaY zeolite membrane[J]. 中国化学工程学报, 2023, 59(7): 176-181.
[10]	Xingzhong Li, Kunlin Yu, Zibo He, Bo Liu, Rongfei Zhou, Weihong Xing. Improved SSZ-13 thin membranes fabricated by seeded-gel approach for efficient CO₂ capture[J]. 中国化学工程学报, 2023, 56(4): 273-280.
[11]	Huan Xiang, Huiping Zhang, Pengfei Liu, Ying Yan. Adsorption dynamics of ethane from air in structured fixed beds with different microfibrous composites[J]. 中国化学工程学报, 2023, 53(1): 14-24.
[12]	Xueting Liu, Chunhui Hu, Jingjing Wu, Peng Cui, Fengyu Wei. Defective NH₂-UiO-66 (Zr) effectively converting CO₂ into cyclic carbonate under ambient pressure, solvent-free and co-catalyst-free conditions[J]. 中国化学工程学报, 2022, 43(3): 222-229.
[13]	Hai-Long Liao, Bao-Ju Wang, Ya-Zhao Liu, Yong Luo, Jie-Xin Wang, Guang-Wen Chu, Jian-Feng Chen. Preparation of Pd/γ-Al₂O₃/nickel foam monolithic catalyst and its performance for selective hydrogenation in a rotating packed bed reactor[J]. 中国化学工程学报, 2022, 41(1): 311-319.
[14]	Xiaopan Chen, Meihua Zhu, Sitong Xiang, Tian Gui, Ting Wu, Yuqin Li, Na Hu, Izumi Kumakiri, Xiangshu Chen, Hidetoshi Kita. Growth process and short chain alcohol separation performance of fluoride-containing NaY zeolite membrane[J]. 中国化学工程学报, 2021, 29(1): 154-159.
[15]	Lijuan Zhang, Peng Hu, Jiang Pan, Huilei Yu, Jianhe Xu. Immobilization of trophic anaerobic acetogen for semi-continuous syngas fermentation[J]. 中国化学工程学报, 2021, 29(1): 311-316.