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On the Role of Protonic Acid Sites in Cu Loaded FAU31 Zeolite As a Catalyst for the Catalytic Transformation of Furfural to Furan

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On the Role of Protonic Acid Sites in Cu Loaded FAU31 Zeolite As a Catalyst for the Catalytic Transformation of Furfural to Furan molecules Article On the Role of Protonic Acid Sites in Cu Loaded FAU31 Zeolite as a Catalyst for the Catalytic Transformation of Furfural to Furan Łukasz Kuterasi ´nski* , Małgorzata Smoliło-Utrata , Joanna Kaim, Wojciech Rojek, Jerzy Podobi ´nski, Katarzyna Samson, Dorota Duraczy ´nska,Małgorzata Zimowska , Mariusz Gackowski and Dorota Rutkowska-Zbik * Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Niezapominajek 8, 30-239 Krakow, Poland; [email protected] (M.S.-U.); [email protected] (J.K.); [email protected] (W.R.); [email protected] (J.P.); [email protected] (K.S.); [email protected] (D.D.); [email protected] (M.Z.); [email protected] (M.G.) * Correspondence: [email protected] (Ł.K.); [email protected] (D.R.-Z.); Tel.: +48-12-6395-115 (Ł.K.); +48-12-6395-160 (D.R.-Z.) Abstract: The aim of the present paper is to study the speciation and the role of different active site types (copper species and Brønsted acid sites) in the direct synthesis of furan from furfural catalyzed by copper-exchanged FAU31 zeolite. Four series of samples were prepared by using different conditions of post-synthesis treatment, which exhibit none, one or two types of active sites. Citation: Kuterasi´nski,Ł.; The catalysts were characterized by XRD, low-temperature sorption of nitrogen, SEM, H2-TPR, NMR Smoliło-Utrata, M.; Kaim, J.; Rojek, and by means of IR spectroscopy with ammonia and CO sorption as probe molecules to assess the W.; Podobi´nski,J.; Samson, K.; types of active sites. All catalyst underwent catalytic tests. The performed experiments allowed Duraczy´nska,D.; Zimowska, M.; to propose the relation between the kind of active centers (Cu or Brønsted acid sites) and the type Gackowski, M.; Rutkowska-Zbik, D. of detected products (2-metylfuran and furan) obtained in the studied reaction. It was found that On the Role of Protonic Acid Sites in the production of 2-methylfuran (in trace amounts) is determined by the presence of the redox-type Cu Loaded FAU31 Zeolite as a centers, while the protonic acid sites are mainly responsible for the furan production and catalytic Catalyst for the Catalytic activity in the whole temperature range. All studied catalysts revealed very high susceptibility to Transformation of Furfural to Furan. coking due to polymerization of furfural. Molecules 2021, 26, 2015. https:// doi.org/10.3390/molecules26072015 Keywords: faujasite; Brønsted acidity; copper; furan; furfural Academic Editor: Serena Esposit Received: 15 March 2021 Accepted: 29 March 2021 1. Introduction Published: 1 April 2021 Furan is a heterocyclic organic compound whose molecule consists of a five membered aromatic ring formed by four carbon and one oxygen atoms. It is a precious precursor, Publisher’s Note: MDPI stays neutral mainly used in the production of chemicals such as α-acetylfuran, 2,2-difurylpropane, with regard to jurisdictional claims in pyrrole derivatives and many other compounds [1]. published maps and institutional affil- Furan may be produced using 1,3-butadiene or furfural as substrates. The first op- ◦ iations. tion is a partial oxidation of 1,3-butadiene in the vapor phase at 500 C over MoO3 and WO3 catalysts, nevertheless the obtained furan yields are very poor (10–15%) in spite of utilization of promoters such as Mo, Ni and Co [1]. Production from furfural, which is the second option, can proceed via different routes, Copyright: © 2021 by the authors. employing different classes of catalysts. Originally, furan was produced from furfural Licensee MDPI, Basel, Switzerland. via furoic acid as an intermediate (Cannizzaro reaction), followed by decarboxylation to This article is an open access article produce furan [2]. More straightforward way is a direct decarbonylation of furfural with a distributed under the terms and release of a molecule of carbon monoxide (see Figure1[ 3]), the process that may be treated conditions of the Creative Commons as a side reaction during the hydrogenation of furfural [3,4]. Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/). Molecules 2021, 26, 2015. https://doi.org/10.3390/molecules26072015 https://www.mdpi.com/journal/molecules MoleculesMolecules 20212021, ,2626, ,x 2015 FOR PEER REVIEW 2 2of of 22 22 FigureFigure 1. 1. PossiblePossible pathways pathways of of hydrogenation hydrogenation of of furfural furfural based based on on data data from from [3]. [3]. Most of reports describe the use of precious metals as catalysts. The decomposition of Most of reports describe the use of precious metals as catalysts. The decomposition furfural into furan was investigated over Pd catalysts either in liquid or vapor phase in the of furfural into furan was investigated over Pd catalysts either in liquid or vapor phase in temperature range of 150–250 ◦C[5,6]. Singh et al. [3,7] studied decarbonylation of furfural the temperature range of 150–250 °C [5,6]. Singh et al. [3,7] studied decarbonylation of over Pd/C and Pd/Al2O3, out of which carbon was better carrier than Al2O3. It was found furfural over Pd/C and Pd/Al2O3, out of which carbon was better carrier than Al2O3. It was that the presence of hydrogen enhanced the furan yield and promoted the transport process found that the presence of hydrogen enhanced the furan yield and promoted the transport of the reagents to/from the active sites in catalysts. Furan was also obtained by heating process of the reagents to/from the active sites in catalysts. Furan was also obtained by of furfural at 160 ◦C in the presence of 5% Pd supported on microporous carbon and heating of furfural at 160 °C in the presence of 5% Pd supported on microporous carbon potassium carbonate (furan yields over 98%) [3,8]. In turn, Bhogeswararao and Srinivas [9] and potassium carbonate (furan yields over 98%) [3,8]. In turn, Bhogeswararao◦ and Srini- used Pt/Al2O3 catalyst for which maximum furan yield was 50% at 240 C. vas [9] used Pt/Al2O3 catalyst for which maximum furan yield was 50% at 240 °C. Other, non-noble metal catalysts were tested as well. Wilson [3,10] described the Other, non-noble metal catalysts were tested as well. Wilson [3,10] described the pro- production of furan from furfural over nickel gauze catalyst (yields > 50%). Decomposition ductionof furfural of furan into furanfrom wasfurfural also over studied nickel by gauze Lejemble catalyst et al. (yields [3,11] in> 50%). the presence Decomposition of steam ofover furfural metal into oxide furan catalysts, was also such studied as Zn/Fe by orLej Zn/Mnemble et chromite al. [3,11] at 400in the◦C. presence High temperature of steam overmay metal lead tooxide the ringcatalysts, opening such of as furan Zn/Fe towards or Zn/Mn heavy chromite products at 400 and °C. carbon High deposit temperature on the maysurface lead of to catalyst. the ring Hurd opening et al. of [3 furan,12] reported towards direct heavy production products and of furan carbon from deposit furfural on overthe surfacefused alkali of catalyst. (with yields Hurd upet toal. 60%)[3,12] and report theed pyrolysis direct production of furfural (yieldsof furan ca.16.5%). from furfural over fusedNext, alkali production (with yields of furan up to from 60%) furfural and the was pyrolysis tested of over furfural systems (yields containing ca.16.5%). acid sitesNext, such production as present in of zeolites furan from (at 300–500 furfural◦ waC).s Fanchiangtested over and systems Lin [ 13containing] studied acid H-ZSM-5 sites suchand as Zn/H-ZSM-5-based present in zeolites catalysts(at 300–500 in °C). a continuous Fanchiang fixed and bedLin [13] system. studied The H-ZSM-5 reaction and tem- Zn/H-ZSM-5-basedperature, contact time catalysts and the in a presence continuous of promoters fixed bed system. were crucial The reaction for the manipulationtemperature, contactof final time products and the composition. presence of At promoters 300, 400 andwere 500 crucial◦C, furan for the yields manipulation were 16.5%, of 30.6%final productsand 19.5% composition. respectively. At Doping 300, 400 H-ZSM-5 and 500 with°C, furan 1.5% yields Zn led were to increase 16.5%, 30.6% of furan and yields 19.5% at respectively.lower temperatures Doping andH-ZSM-5 disappearance with 1.5% of Zn furan led to at increase 500 ◦C in of comparison furan yields to at the lower H-ZSM-5 tem- peraturessystem. For and Zn-containing disappearance sample, of furan furan at 500 yields °C in were comparison 30.7%, 45.0% to the and H-ZSM-5 0% at 300,system. 400 For and Zn-containing500 ◦C, respectively. sample, furan yields were 30.7%, 45.0% and 0% at 300, 400 and 500 °C, re- spectively.Finally, catalysts combining acid and metal active sites were also investigated. Seo andFinally, Chon [14 catalysts] tested furfuralcombining hydrogenation acid and metal in a active fixed-bed sites stainless-steel were also investigated. tubular integral Seo andreactor Chon at [14] 160–350 tested◦C furfural in the presence hydrogenation of Pd-HY inand a fixed-bed Pd-LaY. stainless-steel The obtained furan tubular yields integral were reactor50 and at 38%, 160–350 respectively. °C in the Taking presence into of account Pd-HY that and HY Pd-LaY. and LaY The possess obtained strong furan Brønsted yields wereacid sites50 and [15 ,1638%,], it respectively. was postulated Taking that the into presence account of that furan HY resulted and LaY from possess the interaction strong Brønsted acid sites [15,16], it was postulated that the presence of furan resulted from the Molecules 2021, 26, 2015 3 of 22 between polar carbonyl group of furfural and zeolitic acid sites.
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