Articles
Synthesis and characterization of WO3/ZrO2 and WO3/TiO2 acid systems applied to the hydration of ethylene to ethanol
Published 2018-05-06
Keywords
- ethylene,
- hydration,
- tungsten,
- acid catalysts
How to Cite
Salazar, J. C., Llano, M. A., & Urresta, J. D. (2018). Synthesis and characterization of WO3/ZrO2 and WO3/TiO2 acid systems applied to the hydration of ethylene to ethanol. Revista ION, 30(2), 43–54. https://doi.org/10.18273/revion.v30n2-2017004
Abstract
This work focuses on the synthesis and characterization of two acid systems obtained by the incipient wetness impregnation method, starting from a tungsten salt and using the metal oxides TiO2 and ZrO2 as supports. The two catalyst systems WO3/ZrO2 and WO3/TiO2 were prepared with loads of tungsten of 10, 30 and 40%wt. Surface densities, phase transitions, morphological structure, and thermal stability were determined for each of the tungsten loads used to prepare the catalysts. Additionally, the catalytic activity of these catalysts was evaluated for the hydration of ethylene to ethanol in the presence of a mixture of liquid and gaseous phases, using an equimolar ratio of ethylene to water at pressures from 30 to 40 bar. The results revealed that the catalysts that showed a better performance, reaching a selectivity to ethanol of 98%, were those with a low load of tungsten (10%wt.) at a pressure in the range from 30 to 40 bar.
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References
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[2] Bedia J, Barrionuevo, R, Rodriguez-Mirasol J, Cordero T. Ethanol dehydration to ethylene on acid carbon catalysts. Applied Catalysis B: Environmental. 2011;103:302–10.
[3] Däumer D, Seifert M, Reschetilowski W. Durability improvements of H-ZSM-5 zeolite for ethanol conversion after treatment with chelating agents, Microporous and Mesoporous Materials. 2016;219:66-76.
[4] Li X, Iglesia E. Selective catalytic oxidation of ethanol to acetic acid on dispersed Mo-V-Nb mixed oxides. Chemistry European Journal. 2007;13:9324-30.
[5] Miller SA. Ethylene and its industrial derivatives. Ernest Benn Editors; 1969.
[6] Maki Y, Sato K, Isobe A, Iwasa N, Fujita S, Shimokawabe, M, et al. Structures of H3PO4 / SiO2 catalysts and catalytic performance in the hydration of ethene. Applied Catalysis A: General. 1998;170:269–75.
[7] Fougret CM, Atkins MP, Hölderich WF. Influence of the carrier on the catalytic performance of impregnated phosphoric acid in the hydration of ethylene. Applied Catalysis A: General. 1999;181:145–56.
[8] Fougret CM, Hölderich WF. Ethylene hydration over metal phosphates impregnated with phosphoric acid. Applied Catalysis A: General. 2001;207:295–301.
[9] Mace C, Bonilla CF. Conversion of ethylene to ethanol. Chemical Engineering Progress. 1954;50:385–95.
[10] Isobe A, Yabuuchi Y, Iwasa N, Takezawa N. Gas-phase hydration of ethene over Me ( HPO4)2·n H2O (Me=Ge , Zr , Ti , and Sn). Applied Catalysis A: General. 2000;195:395– 401.
[11] Okuhara T. Water-tolerant solid acid catalysts. Chemical Reviews. 2002;102:3641–66.
[12] Haining GJ. Olefin hydration process. European Patent Application 0955284 A1. 1999.
[13] Onfroy T, Clet G, Bukallah S, Visser T, Houalla, M. Acidity of titania-supported tungsten or niobium oxide catalysts: correlation with catalytic activity. Applied Catalysis A: General. 2006;298:80–87.
[14] Frampton OD, Feldman J. Process for Preparing Ethanol. United States Patent 3,678,118. 1972.
[15] Chu W, Echizen T, Kamiya Y, Okuhara T. Gasphase hydration of ethene over tungstena– zirconia. Applied Catalysis A: General. 2004;259:199–205.
[16] Katada N, Iseki Y, Shichi A, Fujita N, Ishino I, Osaki K, et al. Production of ethanol by vapor phase hydration of ethene over tungsta monolayer catalyst loaded on titania. Applied Catalysis A: General. 2008;349:55–61.
[17] Kolodziej R, Dutt S. Improve direct hydration processes. Hydrocarbon Processing. 2001;80:103–110.
[18] Llano-Restrepo M, Muñoz-Muñoz YM. Combined chemical and phase equilibrium for the hydration of ethylene to ethanol calculated by means of the Peng–Robinson–Stryjek–Vera equation of state and the Wong–Sandler mixing rules. Fluid Phase Equilibria. 2011;307:45–57.
[19] Naito N, Katada N, Niwa M. Tungsten oxide monolayer loaded on zirconia: determination of acidity generated on the monolayer. Journal of Physical Chemistry B. 1999;103:7206–13.
[20] Smukala J, Span R, Wagner W. New equation of state for ethylene covering the fluid region for temperatures from the melting line to 450K at pressures up to 300 MPa. Journal of Physical and Chemical Reference Data. 2000;29:1053121.
[21] Regalbuto J. in Catalyst Preparation: Science and Engineering. Ed. CRC Press; 2007.
[22] Wachs IE, Kim T, Ross EI. Catalysis science of the solid acidity of model supported tungsten oxide catalysts. Catalisis Today. 2006;116:162–8.
[23] Garrido Pedrosa AM, Souza MJB, Marinkovic BA, Melo DMA, Araujo AS. Structure and properties of bifunctional catalysts based on zirconia modified by tungsten oxide obtained by polymeric precursor method. Applied Catalysis A: General. 2008;342:56–62.
[24] Ushikubo T, Kurashige M, Koyanagi T, Ito H, Watanabe Y. Hydration of ethene over W – P mixed metal oxide catalysts. Catalysis Letters. 2000;69:83–7.
[25] Leghari SAK, Sajjad S, Chen F, Zhang J. WO3/TiO2 composite with morphology change via hydrothermal template-free route as an efficient visible light photocatalyst. Chemical Engineering Journal. 2011;166:906–15.
[26] Vaimakis TC. Thermogravimetry (TG) or Thermogravimetric Analysis (TGA). University of Ioannina; 2013.
[27] Park YM, Chung SH, Eom HJ, Lee JS, Lee KY. Tungsten oxide zirconia as solid superacid catalyst for esterification of waste acid oil (dark oil). Bioresource Technology. 2010;101:6589–93.
[28] Barton DG, Soled SL, Iglesia E. Solid acid catalysts based on supported tungsten oxides. Topics in Catalysis. 1998;6:87–99.
[29] Klobes P, Meyer K, Munro RG. Porosity and Specific Surface Area Measurements for Solid Materials. (National Institute of Standars and Thecnology, 2006).
[30] Chu W, Echizen T, Kamiya Y, Okuhara T. Gasphase hydration of ethene over tungstena – zirconia. Applied Catalysis A: General. 2004;259:199–205. [31] Weissermel K, Arpe HJ. in Química orgánica industrial, Editorial Reverté; 1981.