Abstract
Copper supported on clay minerals (bentonite and sepiolite) catalysts, with copper loading between 15 and 60 wt%, have been synthesized by precipitation-deposition, calcination and subsequent reduction. The catalysts were characterized by X-ray diffraction, H2 temperature programmed reduction (H2-TPR), N2 adsorption–desorption at −196 °C and X-ray photoelectron spectroscopy, being detected spherical metal Cu-particles with variable size, mainly located on the surface of clays. The evaluation of their catalytic performance in the furfural (FUR) hydrogenation in gas phase has demonstrated that the use of bentonite as support allows attaining conversion values of 83% for 45Cu-Bent, whereas only a 52% is reached by the 45Cu-Sep catalyst. All catalysts were highly selective towards furfuryl alcohol (FOL), reaching yields of 72% for 45Cu-Bent and 45% for 45Cu-Sep after 5 h of time-on-stream (TOS) at 210 °C, by using a H2:FUR molar ratio of 11.5 and a WHSV of 1.5 h−1. However, all catalysts suffer a progressive deactivation with TOS, by deposition of reactants and product (FOL and FUR), as well as the oxidation of the active phase.
Similar content being viewed by others
References
Lange J-P, Van Der Heide E, Buijtenen JV, Price R (2012) Furfural-A promising platform for lignocellulosic biofuels. ChemSusChem 5:150–166
Li X, Jia P, Wang T (2016) Furfural: a promising platform compound for sustainable production of C4 and C5 chemicals. ACS Catal 6:7621–7640
Huber GW, Corma A (2007) Synergies between bio- and oil refineries for the production of fuels from biomass. Angew Chem Int Ed 46:7184–7201
Naik N, Goud VV, Rout PK, Dalai AK (2010) Production of first and second generation biofuels: a comprehensive review. Renew Sust Energy Rev 14:578–597
Alonso DM, Wettsteinab SG, Dumesic JA (2012) Bimetallic catalysts for upgrading of biomass to fuels and chemicals. Chem Soc Rev 41:8075–8098
Zeitsch KJ (2000) The chemistry and technology of furfural and its many by-products. Elsevier, Amsterdam
Hoydonckx HE, van Rhijn WM, van Rhijn W, de Vos DE, Jacobs PA (2016) Furfural and derivatives. Wiley, Weinheim
Wettsteing SG, Alonso DM, Gurbuz EI, Dumesic JA (2012) A roadmap for conversion of lignocellulosic biomass to chemicals and fuels. Curr Opin Chem Eng 1:218–224
Yang Y, Du Z, Huang Y, Lu F, Wang F, Gao J (2013) Conversion of furfural into cyclopentanone over Ni–Cu bimetallic catalysts. Green Chem 15:1932–1940
Hronec M, Fulajtarova K, Micusik M (2013) Influence of furanic polymers on selectivity of furfural rearrangement to cyclopentanone. Appl Catal A 468:426–431
Sitthisa S, Pham T, Prasomsri T, Sooknoi T, Mallinson RG, Resasco DE (2011) Conversion of furfural and 2-methylpentanal on Pd/SiO2 and Pd–Cu/SiO2 catalysts. J Catal 280:17–27
Yan K, Wu G, Lafleur T, Jarvis C (2014) Production, properties and catalytic hydrogenation of furfural to fuel additives and value-added chemicals. Renew Sustain Energy Rev 38:663–676
Brown Ripin DH, Vetelino M (2003) 2-Methyltetrahydrofuran as an alternative to dichlorometane in 2-phase reactions. Synlett 15:2353–2353
Rojas HA, Guerra GB, Murcia JJ, Nuñez PR (2007) Scientia et Technica Año XIII, No 36. Universidad Tecnológica de Pereira ISSN 0122–1701
Kanetaka J, Asano T, Masamune S (1970) New process for production of tetrahydrofuran. Ind Eng Chem 62:24–32
Rao R, Dandekar A, RTK Baker, Vannice MA (1997) Properties of copper chromite catalysts in hydrogenation reactions. J Catal 1171:406–419
Vargas-Hernández D, Rubio-Caballero JM, Mérida-Robles JM, Moreno-Tost R, Santamaría-González J, Maireles-Torres P (2014) Furfuryl alcohol from furfural hydrogenation over copper supported on SBA-15 silica catalysts. J Mol Catal A 383:106–113
Jiménez-Gómez CP, Cecilia JA, Durán-Martín D, Moreno-Tost R, Santamaría-González J, Mérida-Robles J, Mariscal R, Maireles-Torres P (2016) Gas-phase hydrogenation of furfural to furfuryl alcohol over Cu/ZnO catalysts. J Catal 336:107–115
Seo G, Chon H (1981) Hydrogenation of furfural over copper-containing catalysts. J Catal 67:424–429
Sitthisa S, Resasco DE (2011) Hydrodeoxygenation of furfural over supported metal catalysts: a comparative study of Cu, Pd and Ni. Catal Lett 141:784–791
Hronec M, Fulajtarova K (2012) Selective transformation of furfural to cyclopentanone. Catal Commun 24:100–104
Reddy BM, Reddy GK, Rao KN, Khan A, Ganesh I (2007) Synthesis of monophasic Ce0.5Zr0.5O2 solid solution by microwave-induced combustion method. J Mol Catal A 265:276–282
An K, Musselwhite N, Kennedy G, Pushkarev VV, Baker LR, Somorjai GA (2013) Preparation of mesoporous oxides and their support effects on Pt nanoparticle catalysts in catalytic hydrogenation of furfural. J Collid Interf Sci 392:122–128
Vetere V, Merlo AB, Ruggera JF, Casella ML (2010) Transition metal-based bimetallic catalysts for the chemoselective hydrogenation of furfuraldehyde. J Braz Chem Soc 21:914–920
Sitthisa S, An W, Resasco DE (2011) Selective conversion of furfural to methylfuran over silica-supported NiFe bimetallic catalysts. J Catal 284:90–101
Nakagawa Y, Nakazawa H, Watanabe H, Tomishige K (2012) Total hydrogenation of furfural over a silica-supported nickel catalyst prepared by the reduction of a nickel nitrate precursor. ChemCatChem 4:1791–1797
Nagaraja BM, SivaKumar V, Shasikala V, Padmasri AH, Raju BD, Rama Rao KS (2003) A highly efficient Cu/MgO catalyst for vapour phase hydrogenation of furfural to furfuryl alcohol. Catal Commun 4:287–293
Nagaraja BM, Padmasri AH, Raju BD, Rama Rao KS (2007) A highly active Cu–MgO–Cr2O3 catalyst for simultaneous synthesis of furfuryl alcohol and cyclohexanone by a novel coupling route-combination of furfural hydrogenation and cyclohexanol dehydrogenation. J Mol Catal A 265:90–97
Jiménez-Gómez CP, Cecilia JA, Márquez-Rodríguez I, Moreno-Tost R, Santamaría-González J, Mérida-Robles J, Maireles-Torres P (2016) Gas-phase hydrogenation of furfural over Cu/CeO2 catalysts. Catal Today 279:327–338
Hao XY, Zhou W, Wang JW, Zhang YQ, Liu S (2005) A novel catalyst for the selective hydrogenation of furfural to furfuryl alcohol. Chem Lett 34:1000–1001
Sitthisa S, Sooknoi T, Ma Y, Balbuena PB, Resasco DE (2011) Kinetics and mechanism of hydrogenation of furfural on Cu/SiO2 catalysts. J Catal 277:1–13
Dong F, Zhu Y, Zheng H, Zhu Y, Li X, Li YY (2015) Cr-free Cu-catalysts for the selective hydrogenation of biomass-derived furfural to 2-methylfuran: the synergistic effect of metal and acid sites. J Mol Catal A 398:140–148
Vaccari A (1999) Clays and catalysis: a promising future. Appl Catal Sci 14:161–198
Santarén J, Sanz J, Ruiz-Hitzky E (1990) Structural fluorine in sepiolite. Clays Clay Miner 38:63–68
Brauner K, Preisinger A (1956) Structure and formation of the sepiolite. Tscher Miner Petrog 6:120–140
Cecilia JA, García-Sancho C, Franco F (2013) Montmorillonite based porous clay heterostructures: influence of Zr in the structure and acidic properties. Microporous Mesoporous Mater 176:95–102
Caballero E, Reyes E, Linares J, Huertas F (1985) The bentonites of the southern area of Cabo de Gata (Almeria). geochemistry and mineralogy. Miner Petrogr Acta 29:187–196
Williamson GK, Hall WH (1953) X-ray line broadening from filed aluminium and wolfram. Acta Metall 1:22–31
Alcântara ACS, Darder M, Aranda P, Ruíz-Hitzky E (2012) Eur J Inorg Chem 32:5216–5224
Franco F, Pozo M, Cecilia JA, Benítez Guerrero M, Lorenzo M (2016) Effectiveness of microwave assisted acid treatment on dioctahedral and trioctahedral smectites. The influence of octahedral composition. Appl Clay Sci 120:70–80
Franco F, Pozo M, Cecilia JA, Benítez-Guerrero M, Pozo E, Martín Rubí JA (2014) Microwave assisted acid treatment of sepiolite: the role of composition and “crystallinity”. Appl Clay Sci 102:15–27
Thommes M, Kaneko K, Neimark AV, Olivier JP, Rodríguez-Reinoso F, Rouquerol J, Sing SW (2015) Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl Chem 87:1051–1069
Beydoun K, Doucet H (2011) Cyclopentyl methyl ether: an alternative solvent for palladium-catalyzed direct arylation of heteroaromatics. ChemSusChem 4:526–534
Furimsky E, Massoth FE (1999) Deactivation of hydroprocessing catalysts. Catal Today 52:381–495.
Rioux RM, Vannice MA (2003) Hydrogenation/dehydrogenation reactions: isopropanol dehydrogenation over copper catalysts. J Catal 216:362–375
Liu D, Zemlyanov D, Wu T, Lobo-Lapidus RJ, Dumesic JA, Miller JT, Marshall CL (2013) Deactivation mechanistic studies of copper chromite catalyst for selective hydrogenation of 2-furfuraldehyde. J Catal 299:336–345
Mariscal R, Maireles-Torres P, Ojeda M, Sádaba I, López Granados M (2016) Furfural: a renewable and versatile platform molecule for the synthesis of chemicals and fuels. Energy Environ Sci 9:1144–1189
Acknowledgements
The authors are grateful to financial support from the Spanish Ministry of Economy and Competitiveness (CTQ2015-64226-C03-3-R project), Junta de Andalucía (RNM-1565) and FEDER (European Union) funds.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Jiménez-Gómez, C.P., Cecilia, J.A., Moreno-Tost, R. et al. Selective Furfural Hydrogenation to Furfuryl Alcohol Using Cu-Based Catalysts Supported on Clay Minerals. Top Catal 60, 1040–1053 (2017). https://doi.org/10.1007/s11244-017-0804-2
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11244-017-0804-2