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Catalytic Membrane Reactors: the Industrial Applications Perspective catalysts Review Catalytic Membrane Reactors: The Industrial Applications Perspective Catia Algieri 1,*, Gerardo Coppola 2, Debolina Mukherjee 2, Mahaad Issa Shammas 3, Vincenza Calabro 2 , Stefano Curcio 2 and Sudip Chakraborty 2,* 1 Institute on Membrane Technology, National Research Council of Italy (ITM–CNR), Cubo 17C, Via Pietro Bucci, 87036 Rende, Italy 2 Department of DIMES, University of Calabria, Via Pietro Bucci, Cubo 42A, 87036 Rende, Italy; [email protected] (G.C.); [email protected] (D.M.); [email protected] (V.C.); [email protected] (S.C.) 3 Department of Civil & Environmental Engineering at Dhofar University, Salalah 211, Sultanate of Oman; [email protected] * Correspondence: author: [email protected] (C.A.); [email protected] (S.C.) Abstract: Catalytic membrane reactors have been widely used in different production industries around the world. Applying a catalytic membrane reactor (CMR) reduces waste generation from a cleaner process perspective and reduces energy consumption in line with the process intensification strategy. A CMR combines a chemical or biochemical reaction with a membrane separation process in a single unit by improving the performance of the process in terms of conversion and selectivity. The core of the CMR is the membrane which can be polymeric or inorganic depending on the operating conditions of the catalytic process. Besides, the membrane can be inert or catalytically active. The Citation: Algieri, C.; Coppola, G.; number of studies devoted to applying CMR with higher membrane area per unit volume in multi- Mukherjee, D.; Shammas, M.I.; phase reactions remains very limited for both catalytic polymeric and inorganic membranes. The Calabro, V.; Curcio, S.; Chakraborty, S. various bio-based catalytic membrane system is also used in a different commercial application. Catalytic Membrane Reactors: The opportunities and advantages offered by applying catalytic membrane reactors to multi-phase The Industrial Applications systems need to be further explored. In this review, the preparation and the application of inorganic Perspective. Catalysts 2021, 11, 691. https://doi.org/10.3390/ membrane reactors in the different catalytic processes as water gas shift (WGS), Fisher Tropsch catal11060691 synthesis (FTS), selective CO oxidation (CO SeLox), and so on, have been discussed. Academic Editor: Jose Antonio Keywords: catalysis; membrane reactor; process intensification; inorganic catalyst; enzyme; Calles Martín environmental applications Received: 23 April 2021 Accepted: 27 May 2021 Published: 29 May 2021 1. Inorganic Membrane Reactor 1.1. Introduction to Catalytic Inorganic Membrane Reactors Publisher’s Note: MDPI stays neutral Since the conventional methodologies of chemical processes have been successfully with regard to jurisdictional claims in applied to synthesize enormous numbers of sophisticated products, researchers worldwide published maps and institutional affil- have been searching for alternative methods, which are more efficient concerning energy iations. consumption, space reduction, and environmental safety [1]. One of the most promising strategies to achieve these challenging goals is utilizing catalysts. Catalysts play an essential role in numerous environmental transformations with high reaction regioselectivity and stereospecificity. These peculiar characteristics allow scientists to apply them in modern Copyright: © 2021 by the authors. chemistry and organic synthesis processes. Anyway, the rapid growth of the chemical Licensee MDPI, Basel, Switzerland. industries for producing different chemicals requires improving manufacturing and pro- This article is an open access article cessing by reducing the equipment size, energy consumption, and waste production to distributed under the terms and achieve sustainable and cheaper technologies (process intensification strategy) [1]. conditions of the Creative Commons Attribution (CC BY) license (https:// Membrane reactors, a process intensification technology, combine the membrane sepa- creativecommons.org/licenses/by/ ration process with chemical or biochemical reactions in a single unit [2]. This combination 4.0/). determines higher conversion and improved selectivity and a compact and cost-effective Catalysts 2021, 11, 691. https://doi.org/10.3390/catal11060691 https://www.mdpi.com/journal/catalysts Catalysts 2021, 11, x FOR PEER REVIEW 2 of 22 Membrane reactors, a process intensification technology, combine the membrane separation process with chemical or biochemical reactions in a single unit [2]. This combi- nation determines higher conversion and improved selectivity and a compact and cost- effective reactor design [3]. Considering these aspects, membrane reactors (MRs) repre- sent a potential technology in different fields: pharmaceutical, biotechnology, petrochem- Catalysts 2021, 11, 691 ical sectors, energy, and environmental applications, including phase change2 of behavio 22 ur [4]. MRs are categorized as polymeric (or organic) and inorganic depending on the chem- reactorical process design operating [3]. Considering conditions. these aspects,Polymeric membrane membranes reactors can (MRs) operate represent at temperature a poten- s that tialdo not technology exceed in300 different °C [5,6 fields:]. Inorganic pharmaceutical, membranes biotechnology, can be used petrochemical when polymeric sectors, ones fail energy,considering and environmental that they can applications, operate at includinghigher temperatures phase change (300 behaviour–800 °C [4]. and in some case overMRs 1000 are °C) categorized and in the as aggressive polymeric (or chemical organic) environment and inorganic dependingdue to their on thehigh chemi- chemical re- cal process operating conditions. Polymeric membranes can operate at temperatures that sistance [7]. In addition, in polymeric membranes, there is a trade-off between permeabil- do not exceed 300 ◦C[5,6]. Inorganic membranes can be used when polymeric ones fail consideringity and selectivity that they. Generally, can operate glassy at higher polymers temperatures have high (300–800 selectivity◦C and and in somelow permeability, case overwhile1000 rubbery◦C) and polymers in the aggressive show high chemical permeability environment and due low to selectivity their high chemical[8]. Considering resis- this tancedisadvantage, [7]. In addition, inorganic in polymeric membranes membranes, have elicited there is amuch trade-off attention between due permeability to their high per- andmeability selectivity. and selectivity. Generally, glassy The limits polymers in the have inorganic high selectivity membrane and field low are permeability, the high produc- whiletion cost rubbery and the polymers brittleness show [9 high]. Different permeability materials and low have selectivity been used [8]. to Considering fabricate inorganic thismembranes disadvantage, as carbon, inorganic silica membranes, alumina, titania, have elicited zirconia, much zeolite, attention palladium, due to their silver, high and alloy permeability[10,11]. Inorganic and selectivity. membranes The can limits also in be the classified inorganic membraneas dense or field porous are the. P highorous mem- production cost and the brittleness [9]. Different materials have been used to fabricate branes are categorized according to the IUPAC classification into macroporous ( pore di- inorganic membranes as carbon, silica, alumina, titania, zirconia, zeolite, palladium, sil- ver,ameter and (pd) alloy > [1050, 11nm].), Inorganic mesoporous membranes (2 nm< can pd also<50 benm) classified and mi ascroporous dense or ( porous.0.5 nm< pd <2 Porousnm) [11]. membranes These membranes are categorized are self according-standing to or the supported, IUPAC classification the support into being macrop- used to give orousthem mechanical (pore diameter strength(pd) > 50[12 nm]. ), mesoporous (2 nm < pd < 50 nm) and microporous (0.5 nmAccording < pd < 2 nm)to the [11 ]role. These of the membranes membrane are self-standingin the reactor, or three supported, different the support configurations beinghave usedbeen toidentified: give them extractor, mechanical distributor strength [12 and]. contactor and their; these aspects will be deeplyAccording explained to the in roleSection of the 2. membrane In addition, in thethe reactor, inorganic three membranes different configurations used in MR can be haveinert beenor catalyti identified:cally extractor, active. In distributor the first case, and contactor the catalytic and their;particles these are aspects separated will be from the deeply explained in Section2. In addition, the inorganic membranes used in MR can be membrane or are dispersed in its pores, and these configurations are called inert mem- inert or catalytically active. In the first case, the catalytic particles are separated from the membranebrane reactor or are (IMR). dispersed In the in its last pores, case, and the these membrane configurations acts as are both called separator inert membrane and catalysts, reactorand this (IMR). configuration In the last case,is called the membrane catalytic membrane acts as both separatorreactor (CMR) and catalysts,. and this configurationIn this review is called, catalyticthe different membrane methods reactor used (CMR). for the preparation of inorganic mem- branesIn thishave review, been presented. the different The methods application used forof inorganic the preparation membrane of inorganic reactors mem- in different branesinteresting have reactions been presented.
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