Abstract
In this study, a novel heterogeneous catalyst based on silicotungstic acid (STA) has been synthesised using hydrothermal and wet-impregnation methods for methanol–acetic acid esterification. Active compound STA was loaded on MCM-48 support material to compose proposed catalysis. Tungsten (W) to silica (Si) molar ratios were set as 5%, 10%, 20% and 40%. Characterizations of MCM-48 and STA/MCM-48 catalysts were performed using BET, XRD, FT-IR, DRIFT, TGA/DTA, SEM, and EDX mapping analysis. Results showed successful synthesis of the novel catalyst with good thermal stability and formation of both Brønsted acid and Lewis acid sites. The catalytic activity was also investigated in methyl acetate esterification reaction and it was shown that temperature, reaction time and the molar ratio of the reactants had significant effect on conversion rate. The highest catalytic activity was obtained as 84% with 20% catalyst at feed ratio of 1:3 (metanol:acetic acid, 353 K, 27 h).
Similar content being viewed by others
References
F. Rajabi, M. Abdollahi, R. Luque, Solvent-free esterification of carboxylic acids using supported iron oxide nanoparticles as an efficient and recoverable catalyst. Materials (Basel, Switzerland) 9(7), 557 (2016)
I. Sádaba, M. López Granados, A. Riisager, E. Taarning, Deactivation of solid catalysts in liquid media: the case of leaching of active sites in biomass conversion reactions. Green Chem. 17(8), 4133–4145 (2015)
Y. Liu, E. Lotero, J.G. Goodwin Jr., A comparison of the esterification of acetic acid with methanol using heterogeneous versus homogeneous acid catalysis. J. Catal. 242(2), 278–286 (2006)
R.M. de Almeida, F.T. Souza, M.A. Júnior, N.J. Albuquerque, S.M. Meneghetti, M.R. Meneghetti, Improvements in acidity for TiO2 and SnO2 via impregnation with MoO3 for the esterification of fatty acids. Catal. Commun. 46, 179–182 (2014)
R. Sirsam, D. Hansora, G.A. Usmani, A mini-review on solid acid catalysts for esterification reactions. J. Inst. Eng (India) Ser. E 97(2), 167–181 (2016)
M.R. Abukhadra, M.A. Sayed, K + trapped kaolinite (Kaol/K +) as low cost and eco-friendly basic heterogeneous catalyst in the transesterification of commercial waste cooking oil into biodiesel. Energy Convers. Manage. 177, 468–476 (2018)
A. Hykkerud, J.M. Marchetti, Esterification of oleic acid with ethanol in the presence of Amberlyst 15. Biomass Bioenerg. 95, 340–343 (2016)
V.N. Mutlu, S. Yilmaz, Esterification of cetyl alcohol with palmitic acid over WO3/Zr-SBA-15 and Zr-SBA-15 catalysts. Appl. Catal. A 522, 194–200 (2016)
J. Bedard, H. Chiang, A. Bhan, Kinetics and mechanism of acetic acid esterification with ethanol on zeolites. J. Catal. 290, 210–219 (2012)
S. Veli, A. Pinar, Characterization and catalytic performance of modified sba-16 in liquid phase reaction. Int. J. Chem. Reactor Eng. (2018). https://doi.org/10.1515/ijcre-2017-0246
M. Mekala, V.R. Goli, Kinetics of esterification of methanol and acetic acid with mineral homogeneous acid catalyst. Chin. J. Chem. Eng. 23(1), 100–105 (2015)
R. Koster, B. van der Linden, E. Poels, A. Bliek, The mechanism of the gas-phase esterification of acetic acid and ethanol over MCM-41. J. Catal. 204(2), 333–338 (2001)
J.H. Sepúlveda, C.R. Vera, J.C. Yori, J.M. Badano, D. Santarosa, D. Mandelli, H3PW12O40 (HPA), an efficient and reusable catalyst for biodiesel production related reactions: esterification of oleic acid and etherification of glycerol. Quim. Nova 34(4), 601–606 (2011)
M.A. Hanif, S. Nisar, U. Rashid, Supported solid and heteropoly acid catalysts for production of biodiesel. Catal. Rev. 59(2), 165–188 (2017)
G. Øye, J. Sjöblom, M. Stöcker, Synthesis, characterization and potential applications of new materials in the mesoporous range. Adv. Coll. Interface. Sci. 89, 439–466 (2001)
W. Qian, H. Wang, J. Chen, Y. Kong, Spherical V-Fe-MCM-48: the synthesis, characterization and hydrothermal stability. Materials 8(4), 1752–1765 (2015)
K. Bachari, R. Guerroudj, M. Lamouchi, Catalytic behavior of gallium-containing mesoporous silicas. Arab. J. Chem. 10, S301–S305 (2017)
S. Zhang, S. Muratsugu, N. Ishiguro, M. Tada, Ceria-doped Ni/SBA-16 catalysts for dry reforming of methane. ACS Catal. 3(8), 1855–1864 (2013)
R. Ouargli, R. Hamacha, N. Benharrats, A. Boos, A. Bengueddach, β-diketone functionalized SBA-15 and SBA-16 for rapid liquid–solid extraction of copper. J. Porous Mater. 22(2), 511–520 (2015)
Y. Ueno, A. Tate, O. Niwa, H.-S. Zhou, T. Yamada, I. Honma, High benzene selectivity of mesoporous silicate for BTX gas sensing microfluidic devices. Anal. Bioanal. Chem. 382(3), 804–809 (2005)
J. Tu, R. Wang, W. Geng, X. Lai, T. Zhang, N. Li, N. Yue, X. Li, Humidity sensitive property of Li-doped 3D periodic mesoporous silica SBA-16. Sens. Actuat. B Chem. 136(2), 392–398 (2009)
B. Boukoussa, R. Hamacha, A. Morsli, A. Bengueddach, Adsorption of yellow dye on calcined or uncalcined Al-MCM-41 mesoporous materials. Arab. J. Chem. 10, S2160–S2169 (2017)
M.M.M. Abd El-Wahab, A.A. Said, Phosphomolybdic acid supported on silica gel and promoted with alkali metal ions as catalysts for the esterification of acetic acid by ethanol. J. Mol. Catal. A Chem. 240(1), 109–118 (2005)
V. Brahmkhatri, A. Patel, Esterification of lauric acid with butanol-1 over H3PW12O40 supported on MCM-41. Fuel 102, 72–77 (2012)
W. Trakarnpruk, Platinum/phosphotungstic acid/(Zr)MCM-41 catalysts in glycerol dehydration. Mendeleev Commun. 24(3), 167–169 (2014)
D.J. Thompson, Y. Zhang, T. Ren, Polyoxometalate [γ-SiW10O34(H2O)2]4—on MCM-41 as catalysts for sulfide oxygenation with hydrogen peroxide. J. Mol. Catal. A Chem. 392, 188–193 (2014)
N.M. Deraz, The comparative jurisprudence of catalysts preparation methods: I. Precipitation and impregnation methods. J. Ind. Environ. Chem. 2(2), 19–21 (2018)
A. Ciftci, D. Varisli, K. Cem Tokay, N. Aslı Sezgi, T. Dogu, Dimethyl ether, diethyl ether & ethylene from alcohols over tungstophosphoric acid based mesoporous catalysts. Chem. Eng. J. 207–208, 85–93 (2012)
P.E. JagadeeshBabu, K. Sandesh, M.B. Saidutta, Kinetics of esterification of acetic acid with methanol in the presence of ion exchange resin catalysts. Ind. Eng. Chem. Res. 50(12), 7155–7160 (2011)
R. Rönnback, T. Salmi, A. Vuori, H. Haario, J. Lehtonen, A. Sundqvist, E. Tirronen, Development of a kinetic model for the esterification of acetic acid with methanol in the presence of a homogeneous acid catalyst. Chem. Eng. Sci. 52(19), 3369–3381 (1997)
M.R. Altıokka, A. Çıtak, Kinetics study of esterification of acetic acid with isobutanol in the presence of amberlite catalyst. Appl. Catal. A 239(1), 141–148 (2003)
H. Li, S. Wang, F. Ling, J. Li, Studies on MCM-48 supported cobalt catalyst for Fischer-Tropsch synthesis. J. Mol. Catal. A: Chem. 244(1–2), 33–40 (2006)
P. Solanki, A. Patel, In vitro release of l-arginine and cysteine from MCM-48: a study on effect of size of active biomolecules on release rate. J. Porous Mater. 25(5), 1489–1498 (2018)
M. Shaban, M.R. Abukhadra, A. Hamd, Recycling of glass in synthesis of MCM-48 mesoporous silica as catalyst support for Ni2O3 photocatalyst for Congo red dye removal. Clean Technol. Environ. Policy 20(1), 13–28 (2018)
H. Uhlig, T. Muenster, G. Kloess, S.G. Ebbinghaus, W.-D. Einicke, R. Gläser, D. Enke, Synthesis of MCM-48 granules with bimodal pore systems via pseudomorphic transformation of porous glass. Microporous Mesoporous Mater. 257, 185–192 (2018)
Q.-Y. Liu, W.-L. Wu, J. Wang, X.-Q. Ren, Y.-R. Wang, Characterization of 12-tungstophosphoric acid impregnated on mesoporous silica SBA-15 and its catalytic performance in isopropylation of naphthalene with isopropanol. Microporous Mesoporous Mater. 76(1), 51–60 (2004)
F.J. Méndez, A. Llanos, M. Echeverría, R. Jáuregui, Y. Villasana, Y. Díaz, G. Liendo-Polanco, M.A. Ramos-García, T. Zoltan, J.L. Brito, Mesoporous catalysts based on Keggin-type heteropolyacids supported on MCM-41 and their application in thiophene hydrodesulfurization. Fuel 110, 249–258 (2013)
Y. Duan, D. Zhai, X. Zhang, J. Zheng, C. Li, Synthesis of CuO/Ti-MCM-48 photocatalyst for the degradation of organic pollutions under solar-simulated irradiation. Catal. Lett. 148(1), 51–61 (2018)
C. Sangwichien, G. Aranovich, M. Donohue, Density functional theory predictions of adsorption isotherms with hysteresis loops. Colloids Surf. A 206(1–3), 313–320 (2002)
O.C. Gobin, SBA-16 materials: synthesis, diffusion and sorption properties (Laval University, Quebec, 2006), p. 80
C. Sener, T. Dogu, G. Dogu, Effects of synthesis conditions on the structure of Pd incorporated MCM-41 type mesoporous nanocomposite catalytic materials with high Pd/Si ratios. Microporous Mesoporous Mater. 94(1), 89–98 (2006)
K. Schumacher, P.I. Ravikovitch, A. Du Chesne, A.V. Neimark, K.K. Unger, Characterization of MCM-48 materials. Langmuir 16(10), 4648–4654 (2000)
V. Zeleňák, D. Halamová, M. Almáši, L. Žid, A. Zeleňáková, O. Kapusta, Ordered cubic nanoporous silica support MCM-48 for delivery of poorly soluble drug indomethacin. Appl. Surf. Sci. 443, 525–534 (2018)
V. Şimşek, K. Mürtezaoğlu, Characterizations and catalytic activities investigation of synthesized solid-based heterogeneous catalysts in the esterification reaction. Anadolu Üniversitesi Bilim Ve Teknoloji Dergisi A-Uygulamalı Bilimler ve Mühendislik. 19(2), 422–432 (2018)
J.A. Wang, L.F. Chen, L.E. Noreña, J. Navarrete, M.E. Llanos, J.L. Contreras, O. Novaro, Mesoporous structure, surface acidity and catalytic properties of Pt/Zr–MCM-41 catalysts promoted with 12-tungstophosphoric acid. Microporous Mesoporous Mater. 112(1), 61–76 (2008)
B. Torabi, E. Ameri, Methyl acetate production by coupled esterification-reaction process using synthesized cross-linked PVA/silica nanocomposite membranes. Chem. Eng. J. 288, 461–472 (2016)
P. Verma, K. Kaur, R.K. Wanchoo, A.P. Toor, Esterification of acetic acid to methyl acetate using activated TiO2 under UV light irradiation at ambient temperature. J. Photochem. Photobiol. A 336, 170–175 (2017)
Author information
Authors and Affiliations
Corresponding authors
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Şimşek, V., Şahin, S. Characterization and catalytic performance evaluation of a novel heterogeneous mesoporous catalyst for methanol–acetic acid esterification. J Porous Mater 26, 1657–1665 (2019). https://doi.org/10.1007/s10934-019-00764-4
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10934-019-00764-4