Zeolite Catalysis Andreas Martin www.mdpi.com/journal/catalysts Edited by catalysts Printed Edition of the Special Issue Published in Catalysts Andreas Martin (Ed.) Zeolite Catalysis This book is a reprint of the Special Issue that appeared in the online, open access journal, Catalysts (ISSN 2073-4344) from 2015–2016, available at: http://www.mdpi.com/journal/catalysts/special_issues/zeolite-catalysis Guest Editor Andreas Martin Leibniz-Institute for Catalysis Germany Editorial Office MDPI AG St. Alban-Anlage 66 Basel, Switzerland Publisher Shu-Kun Lin Managing Editor Zu Qiu 1. Edition 2016 MDPI • Basel • Beijing • Wuhan • Barcelona • Belgrade ISBN 978-3-03842-264-8 (Hbk) ISBN 978-3-03842-265-5 (PDF) Articles in this volume are Open Access and distributed under the Creative Commons Attribution license (CC BY), which allows users to download, copy and build upon published articles even for commercial purposes, as long as the author and publisher are properly credited, which ensures maximum dissemination and a wider impact of our publications. The book taken as a whole is © 2016 MDPI, Basel, Switzerland, distributed under the terms and conditions of the Creative Commons by Attribution (CC BY-NC-ND) license (http://creativecommons.org/licenses/by-nc-nd/4.0/). III Table of Contents List of Contributors ......................................................................................................... VII About the Guest Editor..................................................................................................... XI Preface to “Zeolite Catalysis” ....................................................................................... XIII Andreas Martin Zeolite Catalysis Reprinted from: Catalysts 2016 , 6 (8), 118 http://www.mdpi.com/2073-4344/6/8/118........................................................................ 1 Radostina Dragomirova and Sebastian Wohlrab Zeolite Membranes in Catalysis—From Separate Units to Particle Coatings Reprinted from: Catalysts 2015 , 5 (4), 2161–2222 http://www.mdpi.com/2073-4344/5/4/2161 ...................................................................... 4 Yong Wang, Toshiyuki Yokoi, Seitaro Namba and Takashi Tatsumi Effects of Dealumination and Desilication of Beta Zeolite on Catalytic Performance in n -Hexane Cracking Reprinted from: Catalysts 2016 , 6 (1), 8 http://www.mdpi.com/2073-4344/6/1/8.......................................................................... 75 Ceri Hammond and Giulia Tarantino Switching off H 2 O 2 Decomposition during TS-1 Catalysed Epoxidation via Post- Synthetic Active Site Modification Reprinted from: Catalysts 2015 , 5 (4), 2309–2323 http://www.mdpi.com/2073-4344/5/4/2309 .................................................................. 100 Gherardo Gliozzi, Sauro Passeri, Francesca Bortolani, Mattia Ardizzi, Patrizia Mangifesta and Fabrizio Cavani Zeolite Catalysts for Phenol Benzoylation with Benzoic Acid: Exploring the Synthesis of Hydroxybenzophenones Reprinted from: Catalysts 2015 , 5 (4), 2223–2243 http://www.mdpi.com/2073-4344/5/4/2223 .................................................................. 117 IV Houbing Zou, Qingli Sun, Dongyu Fan, Weiwei Fu, Lijia Liu and Runwei Wang Facile Synthesis of Yolk/Core-Shell Structured TS-1@Mesosilica Composites for Enhanced Hydroxylation of Phenol Reprinted from: Catalysts 2015 , 5 (4), 2134–2146 http://www.mdpi.com/2073-4344/5/4/2134 .................................................................. 140 Akram Tawari, Wolf-Dietrich Einicke and Roger Gläser Photocatalytic Oxidation of NO over Composites of Titanium Dioxide and Zeolite ZSM-5 Reprinted from: Catalysts 2016 , 6 (2), 31 http://www.mdpi.com/2073-4344/6/2/31...................................................................... 154 Jing Han, Guiyuan Jiang, Shanlei Han, Jia Liu, Yaoyuan Zhang, Yeming Liu, Ruipu Wang, Zhen Zhao, Chunming Xu, Yajun Wang, Aijun Duan, Jian Liu and Yuechang Wei The Fabrication of Ga 2O 3/ZSM-5 Hollow Fibers for Efficient Catalytic Conversion of n -Butane into Light Olefins and Aromatics Reprinted from: Catalysts 2016 , 6 (1), 13 http://www.mdpi.com/2073-4344/6/1/13...................................................................... 177 Xuan Hoan Vu, Sura Nguyen, Tung Thanh Dang, Binh Minh Quoc Phan, Duc Anh Nguyen, Udo Armbruster and Andreas Martin Catalytic Cracking of Triglyceride-Rich Biomass toward Lower Olefins over a Nano-ZSM-5/SBA-15 Analog Composite Reprinted from: Catalysts 2015 , 5 (4), 1692–1703 http://www.mdpi.com/2073-4344/5/4/1692 .................................................................. 193 Guozhu Liu, Yunxia Zhao and Jinhua Guo High Selectively Catalytic Conversion of Lignin-Based Phenols into para -/ m- Xylene over Pt/HZSM-5 Reprinted from: Catalysts 2016 , 6 (2), 19 http://www.mdpi.com/2073-4344/6/2/19...................................................................... 205 V Alessandra V. Silva, Leandro S. M. Miranda, Márcio Nele, Benoit Louis and Marcelo M. Pereira Insights to Achieve a Better Control of Silicon-Aluminum Ratio and ZSM-5 Zeolite Crystal Morphology through the Assistance of Biomass Reprinted from: Catalysts 2016 , 6 (2), 30 http://www.mdpi.com/2073-4344/6/2/30...................................................................... 225 Aixia Song, Jinghong Ma, Duo Xu and Ruifeng Li Adsorption and Diffusion of Xylene Isomers on Mesoporous Beta Zeolite Reprinted from: Catalysts 2015 , 5 (4), 2098–2114 http://www.mdpi.com/2073-4344/5/4/2098 .................................................................. 239 VII List of Contributors Mattia Ardizzi Dipartimento di Chimica Industriale “Toso Montanari”, Viale Risorgimento 4, Università di Bologna, 40136 Bologna, Italy. Udo Armbruster Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Straße 29a, 18059 Rostock, Germany. Francesca Bortolani Dipartimento di Chimica Industriale “Toso Montanari”, Viale Risorgimento 4, Università di Bologna, 40136 Bologna, Italy. Fabrizio Cavani Dipartimento di Chimica Industriale “Toso Montanari”, Viale Risorgimento 4, Università di Bologna, 40136 Bologna, Italy. Tung Thanh Dang Vietnam Petroleum Institute, 167 Trung Kinh, Yen Hoa, Cau Giay, Hanoi 10000, Vietnam. Radostina Dragomirova Leibniz Institute for Catalysis, University of Rostock (LIKAT Rostock), Albert-Einstein-Str. 29a, 18059 Rostock, Germany. Aijun Duan State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China. Wolf-Dietrich Einicke Institute of Chemical Technology, Universität Leipzig, Linnéstraβe 3, 04103 Leipzig, Germany. Dongyu Fan School of Science, Beijing University of Posts and Telecommunications, No. 10, Xitucheng Road, Haidian District, Beijing 100876, China. Weiwei Fu College of Chemistry, Experimental Center of Shenyang Normal University, Shenyang 110034, China ǀ State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China. Roger Gläser Institute of Chemical Technology, Universität Leipzig, Linnéstraβe 3, 04103 Leipzig, Germany. Gherardo Gliozzi Dipartimento di Chimica Industriale “Toso Montanari”, Viale Risorgimento 4, Università di Bologna, 40136 Bologna, Italy. Jinhua Guo Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin University, Tianjin 300072, China. Ceri Hammond Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff CF10 3AT, UK. VIII Jing Han State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China. Shanlei Han State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China. Guiyuan Jiang State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China. Ruifeng Li Institute of Special Chemicals, School of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China. Guozhu Liu Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin University, Tianjin 300072, China. Jia Liu State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China. Jian Liu State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China. Lijia Liu State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China. Yeming Liu State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China. Benoit Louis Institute of Chemistry, UMR 7177, University of Strasbourg, 1 rue Blaise Pascal, 67000 Strasbourg Cedex, France. Jinghong Ma Institute of Special Chemicals, School of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China. Patrizia Mangifesta Dipartimento di Chimica Industriale “Toso Montanari”, Viale Risorgimento 4, Università di Bologna, 40136 Bologna, Italy. Andreas Martin Leibniz-Institute for Catalysis, Albert-Einstein-Str. 29a, 18059 Rostock, Germany. Leandro S. M. Miranda Instituto de Química, Universidade Federal do Rio de Janeiro, Av. Athos da Silveira Ramos 149, CT Bloco A, Cidade Universitária, 21941-909 Rio de Janeiro, Brazil. Seitaro Namba Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan. IX Márcio Nele Universidade Federal do Rio de Janeiro, Escola de Química Av. Athos da Silveira Ramos 149, CT Bloco E, Cidade Universitária, 21941-909 Rio de Janeiro, Brazil. Duc Anh Nguyen Vietnam Petroleum Institute, 167 Trung Kinh, Yen Hoa, Cau Giay, Hanoi 10000, Vietnam. Sura Nguyen Vietnam Petroleum Institute, 167 Trung Kinh, Yen Hoa, Cau Giay, Hanoi 10000, Vietnam. Sauro Passeri Dipartimento di Chimica Industriale “Toso Montanari”, Viale Risorgimento 4, Università di Bologna, 40136 Bologna, Italy. Marcelo M. Pereira Instituto de Química, Universidade Federal do Rio de Janeiro, Av. Athos da Silveira Ramos 149, CT Bloco A, Cidade Universitária, 21941-909 Rio de Janeiro, Brazil. Binh Minh Quoc Phan Vietnam Petroleum Institute, 167 Trung Kinh, Yen Hoa, Cau Giay, Hanoi 10000, Vietnam. Alessandra V. Silva Instituto de Química, Universidade Federal do Rio de Janeiro, Av. Athos da Silveira Ramos 149, CT Bloco A, Cidade Universitária, 21941-909 Rio de Janeiro, Brazil. Aixia Song Institute of Special Chemicals, School of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China. Qingli Sun State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China. Giulia Tarantino Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff CF10 3AT, UK. Takashi Tatsumi Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan. Akram Tawari Institute of Chemical Technology, Universität Leipzig, Linnés traβe 3, 04103 Leipzig, Germany. Xuan Hoan Vu Vietnam Petroleum Institute, 167 Trung Kinh, Yen Hoa, Cau Giay, Hanoi 10000, Vietnam. Ruipu Wang State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China. Runwei Wang State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China. X Yajun Wang State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China. Yong Wang Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan. Yuechang Wei State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China. Sebastian Wohlrab Leibniz Institute for Catalysis, University of Rostock (LIKAT Rostock), Albert-Einstein-Str. 29a, D-18059 Rostock, Germany. Chunming Xu State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China. Duo Xu Institute of Special Chemicals, School of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China. Toshiyuki Yokoi Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan. Yaoyuan Zhang State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China. Yunxia Zhao Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin University, Tianjin 300072, China. Zhen Zhao State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China. Houbing Zou State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China ǀ School of Science, Beijing University of Posts and Telecommunications, No. 10, Xitucheng Road, Haidian District, Beijing 100876, China. XI About the Guest Editor Andreas Martin was born in Wilkau-Haßlau, East-Germany (1955) and received his M.Sc. degree from Dresden University of Technology (TU Dresden), Germany (1980) and his Ph.D. (1986) from the “Academy of Sciences”, Berlin, Germany. He received postdoctoral qualification (2005) and “venia legendi” from the University of Jena, Germany. Since 1980 he has been working as a researcher at the Academy of Sciences and since 1993 as project leader at the „Institute of Applied Chemistry” (ACA), Berlin. He had several research stays at the German Universities of Darmstadt, Karlsruhe and Bremen. He was Head of the “Catalytic Processes” Department at ACA from 2002–2005. From 2006 to date he is the Head of “Heterogeneously Catalyzed Processes” Department at Leibniz-Institute for Catalysis (LIKAT), Rostock, Germany. At present he is also an associate professor at the Leibniz-Institute for Catalysis (LIKAT) and University of Rostock. He is the author and co-author of over 250 peer-reviewed publications and holds over 40 German and international patents. XIII Preface to “Zeolite Catalysis” The term zeolite is based on the Greek words for “to boil” and “stone” and has been known for more than 250 years. At that time, the Swedish mineralogist, A.F. Cronstedt (1722–1765), observed the formation of a large amount of steam when heating the material Stilbite, pointing to its porous character and adsorption capacity. At present, over 200 different zeolite frameworks have been identified. In general, zeolites are crystalline aluminosilicates with a defined micropore structure. Within zeolites, a good number of elements can be isomorphously incorporated and many more elements or their oxides can be hosted by zeolites. In addition, zeolites display a large variety of pore-mouths sizes, channels, crossings, etc. which has led to their designation as molecular sieves and uses in membrane applications. Nowadays, various hierarchical and composite materials are available offering further interesting properties, e.g., by introduction of mesopores or generation of fibers. Zeolites reveal Brønsted and Lewis acidic properties that can be highly varied as well, thereby justifying the name “solid acids”. Zeolites are immensely important in diverse industrial applications such as catalysts and adsorbents, for example in the refinery industry, chemical industry, detergent sector or for solar thermal collectors and adsorption refrigeration. This Special Issue collection focusses on new developments and recent progress with respect to zeolite-catalyzed chemical reactions, adsorption applications and membrane uses, as well as improved synthesis strategies and characterization techniques. It brought together the recent research of well-known research teams from all over the world. The editor thanks MDPI and Keith Hohn as Editor-in-Chief of Catalysts —the open access catalysis journal—and Mary Fan, as the Senior Assistant Editor, for the opportunity to organize this Special Issue on “Zeolite Catalysis” and for their immense support, and significant encouragement and patience. I would also like to thank the contributing authors and colleagues acting as peer reviewers for their efforts in preparing high quality manuscripts, and in further improving the manuscripts several times following comments and suggestions of the reviewers. Andreas Martin Guest Editor Zeolite Catalysis Andreas Martin Reprinted from Catalysts . Cite as: Martin, A. Zeolite Catalysis. Catalysts 2016 , 6 , 118. 1. Background The Special Issue “Zeolite Catalysis” published in the online journal Catalysts was recently successfully completed. A good number of peer-reviewed publications were published reflecting the broadness of the zeolite syntheses, characterizations and various application fields. This issue brought together recent research of well-known research teams from all over the world. The term “zeolite” is based on the Greek words for “to boil” and “stone” and it has been known since 250 years ago. At that time, the Swedish mineralogist, A.F. Cronstedt (1722–1765), observed the formation of a large amount of steam when heating the material Stilbite which indicated its porous character and adsorption capacity. At present, over 200 different zeolite frameworks have been identified. In general, zeolites are crystalline aluminosilicates with a defined micropore structure. Within zeolites, a good number of elements can be isomorphously incorporated and much more elements or their oxides can be hosted by zeolites. In addition, zeolites comprise a large variety in size of pore mouths, channels, crossings, etc. leading also to their designation as molecular sieves and use in membrane applications. Nowadays, various hierarchical and composite materials are designed offering further interesting properties, e.g., by the introduction of mesopores or generation of fibers. Zeolites reveal Brønsted and Lewis acidic properties that can be varied in wide limits as well. Thus, they deserve the name “solid acids”. Zeolites have an immense importance in diverse industrial applications such as catalysts and adsorbents, for example in the refinery industry, chemical industry, detergent sector or for solar thermal collectors and adsorption refrigeration. 2. This Special Issue The aim of the Special Issue was directed to new developments and recent progress with respect to zeolite-catalyzed chemical reactions, adsorption applications and membrane uses, as well as improved syntheses strategies and characterization techniques. Xuan Hoan Vu and colleagues [ 1 ] reported on the synthesis of novel ZSM-5 containing hierarchical composites and their use in catalytic cracking of triglyceride-rich biomass to lower olefins. It could be proven that the yield for propene and butenes can be increased using such composites. Aixia Song et al. [ 2 ] studied the adsorption and diffusion properties of zeolite Beta using three xylene isomers. Adsorption isotherms from microporous and mesoporous zeolite 1 Beta were recorded showing the impact of mesopores on adsorption properties. Houbing Zou and co-workers [ 3 ] reported on facile synthesis of yolk/core-shell structured TS1@mesosilica composites, catalytic properties were checked in the challenging hydroxylation of phenol. The catalyst characterizations showed a high surface area of 560–700 m 2 /g and a hierarchical pore structure with mesochannels and micropores. In comparison to well-known TS-1, the synthesized solids reveal enhanced activity at comparable selectivity. The research group of Fabrizio Cavani [ 4 ] contributed to the Special Issue with an article on the use of zeolite catalysts for phenol benzoylation with benzoic acid. The aim of this work was the synthesis of hydroxybenzophenons which are important intermediates in the chemical industry. H-Beta zeolites offer superior performance compared to H-Y solid. The studies were supported by various mechanistic insights. Radostina Dragomirova and Sebastian Wohlrab [ 5 ] extensively summarized the application of zeolite membranes in catalysis. The detailed review is backed by ca. 300 references on zeolite membrane preparation, separation principles as well as basic considerations on membrane reactors. The given classification according to membrane location considers: (i) membranes spatially decoupled from the reaction zone; (ii) packed bed membrane reactors; (iii) catalytic membrane reactors; and (iv) zeolite capsuled catalyst particles. Ceri Hammond and Giulia Tarantino [ 6 ] reported on post-synthesis modifications of TS-1 to suppress undesirable H 2 O 2 decomposition in hydroxylations. Ti site speciation changes were observed by in-situ spectroscopic techniques. Takashi Tatsumi and colleagues [ 7 ] in their contribution described effects of dealumination and desilication of Beta zeolite and the consequences for their catalytic performance in n -hexane cracking to propene. Dealumination was carried out by HNO 3 treatment; desilication was obtained by alkali treatment. The propene selectivity at high n -hexane conversions was increased after alkali treatment followed by acid treatment. This is due to: (i) the decrease in number of acidic sites; and (ii) by an increase in number of mesopores which are beneficial to the diffusion of coke precursor compounds. Jing Han et al. [ 8 ] reported on the manufacture of Ga 2 O 3 /ZSM-5 hollow fibers for use as efficient dehydrogenation catalysts for n -butane conversion. Light olefin yields could be increased significantly compared to Ga 2 O 3 , ZSM-5 fibers and GaO 3 supported on ZSM-5. Guozhu Liu and coworkers [ 9 ] in their article showed the catalytic properties of Pt/H-ZSM-5 in the conversion of lignin-based phenols into xylene isomers. The addition of methanol to the reaction mixtures leads to increased xylene yields. The impact of MeOH addition is attributed to the combined action in both the reaction pathways: methylation of m-cresol into xylenols followed by hydrodeoxygenation to form p-/m-xylene, and hydrodeoxygenation of m-cresol into toluene followed by methylation into p-/m-xylene. Alessandra Silva et al. [ 10 ] reported on the synthesis of ZSM-5 zeolites using biomass such as sugar cane bagasse as structure directing agent. MFI crystals with different morphologies were obtained that were different 2 from the pristine zeolite formed in the absence of biomass. The research team of Roger Gläser [ 11 ] contributed to the Special Issue with a report on photocatalytic oxidation of NO over TiO 2 /ZSM-5 composites. Various composites were synthesized using different TiO 2 sources. The highest NO conversion of ca. 40% was obtained with a catalyst from sol–gel synthesis with equal amounts of the two components after calcination at 250 ̋ C. This short survey proves the potential of zeolites and zeolite-based materials in modern catalysis and related research areas. I have no doubt that further articles on the above mentioned topics will be published in Catalysts soon. Conflicts of Interest: The author declares no conflict of interest. References 1. Vu, X.H.; Nguyen, S.; Dang, T.T.; Phan, B.M.Q.; Nguyen, D.A.; Armbruster, U.; Martin, A. Catalytic Cracking of Triglyceride-Rich Biomass toward Lower Olefins over a Nano-ZSM-5/SBA-15 Analog Composite. Catalysts 2015 , 5 , 1692–1703. 2. Song, A.; Ma, J.; Xu, D.; Li, R. Adsorption and Diffusion of Xylene Isomers on Mesoporous Beta Zeolite. Catalysts 2015 , 5 , 2098–2114. 3. Zou, H.; Sun, Q.; Fan, D.; Fu, W.; Liu, L.; Wang, R. Facile Synthesis of Yolk/Core-Shell Structured TS-1@Mesosilica Composites for Enhanced Hydroxylation of Phenol. Catalysts 2015 , 5 , 2134–2146. 4. Gliozzi, G.; Passeri, S.; Bortolani, F.; Ardizzi, M.; Mangifesta, P.; Cavani, F. Zeolite Catalysts for Phenol Benzoylation with Benzoic Acid: Exploring the Synthesis of Hydroxybenzophenones. Catalysts 2015 , 5 , 2223–2243. 5. Dragomirova, R.; Wohlrab, S. Zeolite Membranes in Catalysis—From Separate Units to Particle Coatings. Catalysts 2015 , 5 , 2161–2222. 6. Hammond, C.; Tarantino, G. Switching off H 2 O 2 Decomposition during TS-1 Catalysed Epoxidation via Post-Synthetic Active Site Modification. Catalysts 2015 , 5 , 2309–2323. 7. Wang, Y.; Yokoi, T.; Namba, S.; Tatsumi, T. Effects of Dealumination and Desilication of Beta Zeolite on Catalytic Performance in n-Hexane Cracking. Catalysts 2016 , 6 , 8. 8. Han, J.; Jiang, G.; Han, S.; Liu, J.; Zhang, Y.; Liu, Y.; Wang, R.; Zhao, Z.; Xu, C.; Wang, Y.; et al. The Fabrication of Ga 2 O 3 /ZSM-5 Hollow Fibers for Efficient Catalytic Conversion of n-Butane into Light Olefins and Aromatics. Catalysts 2016 , 6 , 13. 9. Liu, G.; Zhao, Y.; Guo, J. High Selectively Catalytic Conversion of Lignin-Based Phenols into para-/m-Xylene over Pt/HZSM-5. Catalysts 2016 , 6 , 19. 10. Silva, A.V.; Miranda, L.S.M.; Nele, M.; Louis, B.; Pereira, M.M. Insights to Achieve a Better Control of Silicon-Aluminum Ratio and ZSM-5 Zeolite Crystal Morphology through the Assistance of Biomass. Catalysts 2016 , 6 , 30. 11. Tawari, A.; Einicke, W.-D.; Gläser, R. Photocatalytic Oxidation of NO over Composites of Titanium Dioxide and Zeolite ZSM-5. Catalysts 2016 , 6 , 31. 3 Zeolite Membranes in Catalysis—From Separate Units to Particle Coatings Radostina Dragomirova and Sebastian Wohlrab Abstract: Literature on zeolite membranes in catalytic reactions is reviewed and categorized according to membrane location. From this perspective, the classification is as follows: (i) membranes spatially decoupled from the reaction zone; (ii) packed bed membrane reactors; (iii) catalytic membrane reactors and (iv) zeolite capsuled catalyst particles. Each of the resulting four chapters is subdivided by the kind of reactions performed. Over the whole sum of references, the advantage of zeolite membranes in catalytic reactions in terms of conversion, selectivity or yield is evident. Furthermore, zeolite membrane preparation, separation principles as well as basic considerations on membrane reactors are discussed. Reprinted from Catalysts . Cite as: Dragomirova, R.; Wohlrab, S. Zeolite Membranes in Catalysis—From Separate Units to Particle Coatings. Catalysts 2015 , 5 , 2161–2222. 1. Introduction It is not possible to imagine industrial catalysis without zeolites. Over the years, zeolites gained that importance owing to their outstanding properties which are (i) high surface area; (ii) pore sizes in the molecular range; (iii) adsorption capacity; (iv) controllable adsorption properties; (v) inherent active sites; (vi) shape selectivity and (vii) stability [ 1 , 2 ]. Certainly, due to these unique features the application of zeolites is not only restricted to catalysis. Their potential to serve as highly selective sorption materials make zeolites also indispensable for industrial separation tasks [ 3 ]. Highlighting, separation and purification of gases [ 4 ], especially swing adsorption techniques [ 5 – 7 ], as well as water and waste water treatment [ 8 , 9 ] are also not imaginable without zeolitic materials. To run separation processes continuously and without recurring regeneration steps zeolite membranes have been developed and studied over the last decades [ 10 – 20 ]. With this development, the utilization of zeolite membranes was progressively investigated for catalytic reactions [ 21 – 32 ]. The special interest in membranes for catalysis science lies in the possibilities of equilibrium shifts, improved yields and selectivities as well as more compact operations compared to conventional processes. Nevertheless, no industrial commercialization of zeolite membrane reactors has been occurring until now. However, recent pioneering developments towards sub- μ m membranes [ 33 – 38 ] or the reduction of defects [ 39 – 41 ] promise a revival of zeolite 4 membrane applications. Furthermore, novel cost reduction concepts [ 42 ] will make zeolite membranes more attractive for industry. However, a first application of zeolite membranes in industry already exists. It is the use of hydrophilic zeolite membranes in the dehydration of organic solvents. In detail, NaA membranes have been used in a large-scale pervaporation plant mainly for alcohols by BNRI (Mitsui Holding) [ 43 ], and further progress on LTA membranes in the pervaporation separation of water was achieved over the years [ 44 – 47 ]. An important consideration on the way for industrial application might be the availability of membranes characterized by suitable performances at reasonable prices. On the one hand, a 10,000 m 2 /year production line for LTA membranes was established [ 48 ]. In this context, the further up-scaling also of other membrane types will be of significant importance whether zeolite membranes will be applied in industrial catalysis or not. On the other hand, over the last years, membrane coatings on catalyst particles have been successfully developed and applied as micro membrane reactors [ 24 ]. Perhaps, these zeolite capsuled catalysts will be the final breakthrough for zeolite membrane reactors in industry? A review of the state of the art of permselective zeolite membranes in reaction processing is given in the following for anyone who is already engaged with the matter and for those who want to start with. In particular, the application of zeolite membranes for a bunch of different possible reactions is presented. In the first part, a short overview on zeolite membrane synthesis will be given, followed by discussion on the transport mechanisms in a zeolite membrane. Afterwards, the application of zeolite membrane reactors in diverse configurations will be presented and discussed for the different reaction types. Starting with zeolite membranes apart from the reaction zone over packed bed membrane reactors and catalytic membrane reactors, zeolite coatings on catalyst particles are finally covered. 2. Separation by Zeolite Membranes 2.1. Synthesis of Zeolite Membranes Over the last decades a great research effort is allocated in the preparation of zeolite membranes applying different synthesis techniques. Generally, for the synthesis of zeolite membranes two procedure routes are followed. On the one hand, one-step techniques referred to as direct in situ crystallization are applied. Thereby, the surface of the untreated either tubular or disc support is brought in a direct contact with an aluminosilicate precursor solution and the membrane crystallization is performed under hydrothermal conditions as shown exemplarily in the following references [ 49 – 55 ]. Alternatively, Caro et al. proposed a seeding-free synthesis strategy for the preparation of dense and phase-pure zeolite LTA and FAU membranes using 3-aminopropyltriethoxysilane (APTES) as covalent linker 5