Furfural Acetalization with Ethanol over Hierarchical vs. Conventional Beta Zeolites

Kopa, Ivan; Yevdokimova, Olha; Martínez‐Klimov, Mark E.; Kurmach, Mykhailo; Murzin, Dmitry Yu.; Shcherban, Nataliya

doi:10.1002/slct.202304754

Title: Furfural Acetalization with Ethanol over Hierarchical vs. Conventional Beta Zeolites

Journal Article · 14 April 2024 · Chemistry Select

DOI: https://doi.org/10.1002/slct.202304754 · OSTI ID:2350762

Kopa, Ivan ^[1]; Yevdokimova, Olha ^[2]; Martínez‐Klimov, Mark E. ^[2]; Kurmach, Mykhailo ^[3]; Murzin, Dmitry Yu. ^[2];

^[4]

National Academy of Sciences of Ukraine, Kyiv (Ukraine); University of Massachusetts Amherst
Åbo Akademi University (Finland)
National Academy of Sciences of Ukraine, Kyiv (Ukraine)
National Academy of Sciences of Ukraine, Kyiv (Ukraine); Åbo Akademi University (Finland)

A set of hierarchical Beta zeolites was synthesized using concentrated reaction mixtures and compared to conventional materials with a similar composition. The obtained zeolite catalysts were investigated in acetalization of furfural with ethanol at room temperature yielding a commercially valuable fuel additive (furfural diethyl acetal). The highest yield of the desired product (91 %) was achieved over a zeolite catalyst possessing developed mesoporosity (V_meso 0.75 cm³/g) and a high external surface area (280 m²/g). Here, the concentration of accessible acid sites was found to be responsible for high catalytic performance of the tested zeolitic catalysts.

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Research Organization:: University of Massachusetts, Amherst, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0021041

OSTI ID:: 2350762

Journal Information:: Chemistry Select, Journal Name: Chemistry Select Journal Issue: 15 Vol. 9; ISSN 2365-6549

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (41)

Advances and challenges in zeolite synthesis and catalysis Čejka, Jiří; Millini, Roberto; Opanasenko, Maksym Catalysis Today, Vol. 345 https://doi.org/10.1016/j.cattod.2019.10.021	journal	April 2020
Hierarchical Beta zeolites as catalysts in a one-pot three-component cascade Prins–Friedel–Crafts reaction Barakov, Roman; Shcherban, Nataliya; Yaremov, Pavel Green Chemistry, Vol. 22, Issue 20 https://doi.org/10.1039/D0GC01787F	journal	January 2020
Hierarchical nanofabrication of microporous crystals with ordered mesoporosity Fan, Wei; Snyder, Mark A.; Kumar, Sandeep Nature Materials, Vol. 7, Issue 12 https://doi.org/10.1038/nmat2302	journal	October 2008
An Efficient Acetalization Method for Biomass‐Derived Furfural with Ethanol Using γ‐Al₂O₃‐Supported Catalysts Castellanos‐Blanco, Nahury; Taborda, Gonzalo; Cobo, Martha ChemistrySelect, Vol. 5, Issue 11 https://doi.org/10.1002/slct.202000410	journal	March 2020
Validity of the t-plot Method to Assess Microporosity in Hierarchical Micro/Mesoporous Materials Galarneau, Anne; Villemot, François; Rodriguez, Jeremy Langmuir, Vol. 30, Issue 44 https://doi.org/10.1021/la5026679	journal	October 2014
Design of hierarchical zeolite catalysts by desilication Verboekend, Danny; Pérez-Ramírez, Javier Catalysis Science & Technology, Vol. 1, Issue 6 https://doi.org/10.1039/c1cy00150g	journal	January 2011
A kinetic study of heteropolyacid-catalyzed furfural acetalization with methanol at room temperature via ultraviolet spectroscopy Teixeira, Milena Galdino; Natalino, Ricardo; da Silva, Márcio José Catalysis Today, Vol. 344 https://doi.org/10.1016/j.cattod.2018.11.071	journal	March 2020
Production, properties and catalytic hydrogenation of furfural to fuel additives and value-added chemicals Yan, Kai; Wu, Guosheng; Lafleur, Todd Renewable and Sustainable Energy Reviews, Vol. 38 https://doi.org/10.1016/j.rser.2014.07.003	journal	October 2014
Solvent-Free Methods for Making Acetals Derived from Glycerol and Furfural and Their Use as a Biodiesel Fuel Component Wegenhart, Benjamin L.; Liu, Shuo; Thom, Melanie ACS Catalysis, Vol. 2, Issue 12 https://doi.org/10.1021/cs300562e	journal	October 2012
Amphiphilic organosilane-directed synthesis of crystalline zeolite with tunable mesoporosity Choi, Minkee; Cho, Hae Sung; Srivastava, Rajendra Nature Materials, Vol. 5, Issue 9 https://doi.org/10.1038/nmat1705	journal	August 2006
Bismuth Subnitrate as an Efficient Heterogeneous Catalyst for Acetalization and Ketalization of Carbonyl Compounds with Diols Wu, Shuisheng; Dai, Weili; Yin, Shuangfeng Catalysis Letters, Vol. 124, Issue 1-2 https://doi.org/10.1007/s10562-008-9435-3	journal	February 2008
Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts Choi, Minkee; Na, Kyungsu; Kim, Jeongnam Nature, Vol. 461, Issue 7261, p. 246-249 https://doi.org/10.1038/nature08288	journal	September 2009
Hierarchically Structured Zeolites: From Design to Application Chen, Li-Hua; Sun, Ming-Hui; Wang, Zhao Chemical Reviews, Vol. 120, Issue 20 https://doi.org/10.1021/acs.chemrev.0c00016	journal	September 2020
Aluminosilicate mesostructures with improved acidity and hydrothermal stability Liu, Yu; Pinnavaia, Thomas J. Journal of Materials Chemistry, Vol. 12, Issue 11 https://doi.org/10.1039/b204094h	journal	October 2002
Zeolite-catalyzed acetalization reaction of furfural with alcohol under solvent-free conditions Song, Heyuan; Jin, Fuxiang; Liu, Qiao Molecular Catalysis, Vol. 513 https://doi.org/10.1016/j.mcat.2021.111752	journal	August 2021
Nanofusion: Mesoporous Zeolites Made Easy Möller, Karin; Yilmaz, Bilge; Müller, Ulrich Chemistry - A European Journal, Vol. 18, Issue 25 https://doi.org/10.1002/chem.201200544	journal	May 2012
Specific Surface Area Determination for Microporous/Mesoporous Materials: The Case of Mesoporous FAU-Y Zeolites Galarneau, Anne; Mehlhorn, Dirk; Guenneau, Flavien Langmuir, Vol. 34, Issue 47 https://doi.org/10.1021/acs.langmuir.8b02144	journal	October 2018
One-Step Synthesis of Hierarchical Zeolite Beta via Network Formation of Uniform Nanocrystals Möller, Karin; Yilmaz, Bilge; Jacubinas, Richard M. Journal of the American Chemical Society, Vol. 133, Issue 14 https://doi.org/10.1021/ja108698s	journal	April 2011
Probing the acid sites of zeolites with pyridine: Quantitative AGIR measurements of the molar absorption coefficients Zholobenko, Vladimir; Freitas, Cátia; Jendrlin, Martin Journal of Catalysis, Vol. 385, p. 52-60 https://doi.org/10.1016/j.jcat.2020.03.003	journal	May 2020
Catalytic activity of hierarchical beta zeolites in the Prins cyclization of (−)-isopulegol with acetone Laluc, Mathias; Barakov, Roman; Mäki-Arvela, Päivi Applied Catalysis A: General, Vol. 618 https://doi.org/10.1016/j.apcata.2021.118131	journal	May 2021
Alkylation of aromatics with ethylene and propylene: recent developments in commercial processes Degnan, Thomas F.; Smith, C. Morris; Venkat, Chaya R. Applied Catalysis A: General, Vol. 221, Issue 1-2, p. 283-294 https://doi.org/10.1016/S0926-860X(01)00807-9	journal	November 2001
Efficient valorization of biomass-derived furfural to fuel bio-additive over aluminum phosphate Fang, Wenting; Riisager, Anders Applied Catalysis B: Environmental, Vol. 298 https://doi.org/10.1016/j.apcatb.2021.120575	journal	December 2021
How Reproducible are Surface Areas Calculated from the BET Equation? Osterrieth, Johannes W. M.; Rampersad, James; Madden, David Advanced Materials, Vol. 34, Issue 27 https://doi.org/10.1002/adma.202201502	journal	May 2022
Hierarchical Beta Zeolites As Catalysts in α-Pinene Oxide Isomerization Barakov, Roman; Shcherban, Nataliya; Mäki-Arvela, Päivi ACS Sustainable Chemistry & Engineering, Vol. 10, Issue 20 https://doi.org/10.1021/acssuschemeng.2c00441	journal	May 2022
Characterization of nanocrystalline zeolite Beta Camblor, M. A.; Corma, A.; Valencia, S. Microporous and Mesoporous Materials, Vol. 25, Issue 1-3 https://doi.org/10.1016/S1387-1811(98)00172-3	journal	December 1998
Conversion of biomass platform molecules into fuel additives and liquid hydrocarbon fuels Climent, Maria J.; Corma, Avelino; Iborra, Sara Green Chemistry, Vol. 16, Issue 2 https://doi.org/10.1039/c3gc41492b	journal	January 2014
Determination of Microporous and Mesoporous Surface Areas and Volumes of Mesoporous Zeolites by Corrected t‐Plot Analysis Desmurs, Lucie; Galarneau, Anne; Cammarano, Claudia ChemNanoMat, Vol. 8, Issue 4 https://doi.org/10.1002/cnma.202200051	journal	March 2022
Highly selective synthesis under benign reaction conditions of furfural dialkyl acetal using SnCl₂ as a recyclable catalyst da Silva, Márcio José; Teixeira, Milena Galdino; Natalino, Ricardo New Journal of Chemistry, Vol. 43, Issue 22 https://doi.org/10.1039/C9NJ01284B	journal	January 2019
Synthesis of BEA by dry gel conversion and its characterization Hari Prasad Rao, P. R.; Leon y. Leon, C. A.; Ueyama, K. Microporous and Mesoporous Materials, Vol. 21, Issue 4-6 https://doi.org/10.1016/S1387-1811(98)00033-X	journal	May 1998
Progress in the design of zeolite catalysts for biomass conversion into biofuels and bio-based chemicals Serrano, David P.; Melero, Juan A.; Morales, Gabriel Catalysis Reviews, Vol. 60, Issue 1 https://doi.org/10.1080/01614940.2017.1389109	journal	October 2017
Industrial application of solid acid–base catalysts Tanabe, K. Applied Catalysis A: General, Vol. 181, Issue 2 https://doi.org/10.1016/S0926-860X(98)00397-4	journal	May 1999
Hierarchy concepts: classification and preparation strategies for zeolite containing materials with hierarchical porosity Schwieger, Wilhelm; Machoke, Albert Gonche; Weissenberger, Tobias Chemical Society Reviews, Vol. 45, Issue 12 https://doi.org/10.1039/C5CS00599J	journal	January 2016
Direct synthesis of hierarchical zeolites with oriented nanocrystals without adding extra templates Wang, Xuan; Li, Yingxia; Luo, Can RSC Advances, Vol. 3, Issue 18 https://doi.org/10.1039/c3ra21913e	journal	January 2013
Hierarchically‐Ordered Zeolites: A Critical Assessment Hartmann, Martin; Thommes, Matthias; Schwieger, Wilhelm Advanced Materials Interfaces, Vol. 8, Issue 4 https://doi.org/10.1002/admi.202001841	journal	February 2021
Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report) Thommes, Matthias; Kaneko, Katsumi; Neimark, Alexander V. Pure and Applied Chemistry, Vol. 87, Issue 9-10 https://doi.org/10.1515/pac-2014-1117	journal	October 2015
Hierarchical Beta zeolites obtained in concentrated reaction mixtures as catalysts in tetrahydropyranylation of alcohols Barakov, Roman; Shcherban, Nataliya; Yaremov, Pavel Applied Catalysis A: General, Vol. 594 https://doi.org/10.1016/j.apcata.2019.117380	journal	March 2020
Acetalization of furfural with zeolites under benign reaction conditions Rubio-Caballero, Juan Miguel; Saravanamurugan, Shunmugavel; Maireles-Torres, Pedro Catalysis Today, Vol. 234 https://doi.org/10.1016/j.cattod.2014.03.004	journal	October 2014
Effect of the organic moiety nature on the synthesis of hierarchical ZSM-5 from silanized protozeolitic units Serrano, D. P.; Aguado, J.; Escola, J. M. Journal of Materials Chemistry, Vol. 18, Issue 35 https://doi.org/10.1039/b805502e	journal	January 2008
Florol synthesis via Prins cyclization over hierarchical beta zeolites Shcherban, Nataliya; Barakov, Roman; Lasne, Basile Molecular Catalysis, Vol. 531 https://doi.org/10.1016/j.mcat.2022.112683	journal	October 2022
Furfural acetalization with ethanol over conventional and hierarchical beta zeolites Kopa, I. D.; Barakov, R. Yu; Sotnik, S. O. Materials Today: Proceedings, Vol. 62 https://doi.org/10.1016/j.matpr.2022.03.146	journal	January 2022
The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms Barrett, Elliott P.; Joyner, Leslie G.; Halenda, Paul P. Journal of the American Chemical Society, Vol. 73, Issue 1 https://doi.org/10.1021/ja01145a126	journal	January 1951

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
hierarchical zeolite
acetalization of furfural
mesoporosity
external surface area
accessible acid sites

Title: Furfural Acetalization with Ethanol over Hierarchical vs. Conventional Beta Zeolites

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References (41)

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