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Recent Advances in the Use of Pt-Based Catalysts for Propane Dehydrogenation Reaction

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Recent Advances in the Use of Pt-Based Catalysts for Propane Dehydrogenation Reaction catalysts Review Propylene Synthesis: Recent Advances in the Use of Pt-Based Catalysts for Propane Dehydrogenation Reaction Marco Martino * , Eugenio Meloni , Giovanni Festa and Vincenzo Palma Department of Industrial Engineering, University of Salerno, Via Giovanni Paolo II 132, 84084 Fisciano, SA, Italy; [email protected] (E.M.); [email protected] (G.F.); [email protected] (V.P.) * Correspondence: [email protected]; Tel.: +39-089-964027 Abstract: Propylene is one of the most important feedstocks in the chemical industry, as it is used in the production of widely diffused materials such as polypropylene. Conventionally, propylene is obtained by cracking petroleum-derived naphtha and is a by-product of ethylene production. To ensure adequate propylene production, an alternative is needed, and propane dehydrogenation is considered the most interesting process. In literature, the catalysts that have shown the best performance in the dehydrogenation reaction are Cr-based and Pt-based. Chromium has the non- negligible disadvantage of toxicity; on the other hand, platinum shows several advantages, such as a higher reaction rate and stability. This review article summarizes the latest published results on the use of platinum-based catalysts for the propane dehydrogenation reaction. The manuscript is based on relevant articles from the past three years and mainly focuses on how both promoters and supports may affect the catalytic activity. The published results clearly show the crucial importance Citation: Martino, M.; Meloni, E.; of the choice of the support, as not only the use of promoters but also the use of supports with tuned Festa, G.; Palma, V. Propylene Synthesis: Recent Advances in the acid/base properties and particular shape can suppress the formation of coke and prevent the deep Use of Pt-Based Catalysts for Propane dehydrogenation of propylene. Dehydrogenation Reaction. Catalysts 2021, 11, 1070. https://doi.org/ Keywords: propane dehydrogenation; propylene; platinum; catalysis 10.3390/catal11091070 Academic Editors: Stanisław Wacławek, Dionysios 1. Introduction (Dion) D. Dionysiou, Propylene [1] is the feedstock of strategic materials such as acrolein, polypropylene, Andrzej Kudelski and Jochen acetone, polyacrylonitrile, propylene oxide and other industrial products [2]. The conven- A. Lauterbach tional propylene production industrial processes are the fluid catalytic cracking and the naphtha and light diesel steam cracking [3]. The fast consumption of fossil fuels is making Received: 10 August 2021 conventional propylene production methods unsuitable to meet the growing demand Accepted: 2 September 2021 Published: 3 September 2021 for propylene; therefore, the development of more efficient and economical production methods is a major concern [4]. Innovative methods to produce propylene have been Publisher’s Note: MDPI stays neutral proposed, including the propane dehydrogenation (PDH), the methanol–olefin process with regard to jurisdictional claims in and the Fischer–Tropsch olefin process [2]. The development of shale gas [5] extraction published maps and institutional affil- methods has generated an abundance of light alkanes, therefore making propane dehydro- iations. genation the best candidate for replacing conventional propylene production processes [6]. Several catalysts and propane dehydrogenation processes have been developed, whose representatives are UOP Oleflex, Lummus Catofin, Linde–BASF PDH, Uhde STA and Snamprogetti–Yarsintez FBD [2]. Currently, Lummus Catofin [7] and UOP Oleflex [8] are mainly used in industrialized devices. The Catofin process uses chromium/aluminum- Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. based catalysts, which show good performance, assuring good stability and high propylene This article is an open access article yield and resulting in a propylene selectivity higher than 87% [2]. However, this process distributed under the terms and has low efficiency due to frequent switching to high-temperature conditions [2]; moreover, conditions of the Creative Commons chromium is not considered an environmentally friendly catalyst. The Oleflex process uses Attribution (CC BY) license (https:// platinum/aluminum-based catalysts, and the hydrogen produced together with propylene creativecommons.org/licenses/by/ can be used as fuel in the unit; furthermore, the dehydrogenation unit can be integrated 4.0/). with downstream conversion processes [2]. At the moment, therefore, processes using Catalysts 2021, 11, 1070. https://doi.org/10.3390/catal11091070 https://www.mdpi.com/journal/catalysts Catalysts 2021, 11, x FOR PEER REVIEW 2 of 24 Catalysts 2021, 11, 1070 2 of 26 with propylene can be used as fuel in the unit; furthermore, the dehydrogenation unit can be integrated with downstream conversion processes [2]. At the moment, therefore, pro- cessesplatinum-based using platinum catalysts-based can catalysts provide can the provide highest the propylene highest propylene selectivity, selectivity, high reaction high rate reactionand stability rate and and stability can be and considered can be considered more eco-friendly more eco than‐friendly chromium-based than chromium ones.-based In this ones.review In this article, review a selectionarticle, a ofselection the most of the recent most and recent relevant and relevant articles publishedarticles published in the last in thethree last years three (2019–2021) years (2019 on–2021) platinum-based on platinum catalysts-based catalysts are reviewed, are reviewed, focusing focusing on how on both howpromoters both promoters and supports and supports may affect may the affect catalytic the catalytic activity activity in terms in of terms deactivation of deactivation resistance. resistance.Although Although in most in cases most it cases is difficult it is difficult to make to amake clear a distinction clear distinction between between articles articles dealing dealingwith bimetallicwith bimetallic systems systems and support and support effect, effect, the distribution the distribution of articles of articles between between sections sectionsand paragraphs and paragraphs has been has made been onmade the basison the of basis the main of the conclusions main conclusions reported reported in the articles in thethemselves. articles themselves. Furthermore, Furthermore, at the end at the of end the mainof the sectionsmain sections or paragraphs, or paragraphs, a summary a sum- of marythe of results the results is provided. is provided. Finally, Finally, one section one section focuses focuses exclusively exclusively on theoretical on theoretical studies, studies,while while the last the two last sectionstwo sections focus focus on someon some relevant relevant studies studies on on reactor reactor configuration configuration and andcatalyst catalyst regeneration. regeneration. 2. The2. The Reaction Reaction PropanePropane dehydrogenation dehydrogenation is isan an equil equilibriumibrium endothermic endothermic reaction reaction (1). (1). The The thermo- thermody- dynamicnamic analysis showsshows that thethe equilibriumequilibrium conversionconversion dropsdropsexponentially exponentially with with pressure, pres- sure,so so a reductiona reduction in in hydrocarbon hydrocarbon partial partial pressure pressure can can be be beneficial beneficial to to increaseincrease thethe conver-con- versionsion [[9].]. To To reduce reduce the the hydrocarbon hydrocarbon partial partial pressure, pressure, steam steam or or other other inert inert gases gases can can be be usedused to dilute to dilute the the reacting reacting mixture; mixture; steam steam is preferred is preferred to tocompensate compensate for for the the conversion conversion decrease,decrease, but but an anincrease increase in reaction in reaction temperature temperature is necessary is necessary [9]. [ 9Therefore,]. Therefore, to obtain to obtain high high propanepropane conversions, conversions, high high operating operating temperatures temperatures (80 (800–9500–950 K) K)are are required. required. ◦ CC33HH88 ⇆ C3HH66 ++ H H2,2 ΔH°, DH298K298K = 124.6= 124.6 kJ/mol kJ/mol (1) (1) The reaction conditions therefore result in an increase in side reactions such as ther- The reaction conditions therefore result in an increase in side reactions such as ther- malmal cracking, cracking, deep deep dehydrogenation, dehydrogenation, coke coke formation formation and and the the sintering sintering of the of the supported supported nanoparticles,nanoparticles, limiting limiting the theaverage average life lifeof the of thecatalyst catalyst [6].[ 6To]. Toovercome overcome the the catalyst catalyst deac- deac- tivation,tivation, it is it therefore is therefore mandatory mandatory to toemploy employ a per a periodiciodic regeneration regeneration through through oxidative oxidative cyclescycles to eliminate to eliminate the the coke, coke, followed followed by byreduction reduction;; moreover moreover,, oxygen oxygen–chlorine–chlorine treatment treatment cancan be becarried carried out out to partially to partially redisperse redisperse agglomerated agglomerated Pt Ptparticles particles [10 [].10 ]. TheThe side side reactions reactions are are attributed attributed to the to the persistence persistence of propylene of propylene on onthe the active active site site;; thereforetherefore,, the the geometric geometric and and the the electronic electronic features features of of the the catalysts catalysts play aa crucialcrucial rolerole in in the thesuppressing suppressing of of them them [ 2[2].].
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