One-step aldol condensation of ethyl acetate with formaldehyde over Ce and P modified cesium supported alumina catalyst

Chidchon Sararuk; Dan Yang; Guoliang Zhang; Chunshan Li; Suojiang Zhang

Journal of Industrial and Engineering Chemistry, Vol.46, 342-349, February, 2017

DOI10.1016/j.jiec.2016.11.002 Export Citation

One-step aldol condensation of ethyl acetate with formaldehyde over Ce and P modified cesium supported alumina catalyst

Chidchon Sararuk^{1, 2}, Dan Yang^{1, 3}, Guoliang Zhang^{1, 3}, Chunshan Li^{1, 3, †}, and Suojiang Zhang^{1, 3, †}

¹Key Laboratory of Ionic Liquid Clean Process, State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, PR China
²University of Chinese Academy of Sciences, Beijing 100190, PR China
³, China

E-mail:,

Ethyl acrylate (EA) is synthesized by ethyl acetate (EtOAc) with formaldehyde (FA) through aldol condensation with fixed-bed reactor, and a series of Ce-P-Cs/g-Al2O3 catalyst was developed. The catalysts were characterized with XRD, XPS, SEM-EDS, NH3- and CO2-TPD, BET, and pyridine FTIR. The influence of acidity and basicity on activity was discussed. Catalytic performances were further improved by the addition of small amounts of Ce. Key reaction parameters, such as amount of metal loading, space velocity and reaction temperature, were also optimized. The optimum condition demonstrated a maximum EA yield of 31.38% and 60.03% selectivity toward EA.

Keywords:Aldol condensation;Cesium-supported alumina;Cerium;Phosphorus;Ethyl acetate;Formaldehyde;Ethyl acrylate;Acetic acid;Acid-base bifunctional catalysts;Acidity;Basicity;Pyridine FT-IR;Lewis acid site;Carbon formation;XRD;NH3-TPD;CO2-TPD;BET;XPS;Cerium oxide

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[Referenced By]

[1] The Dow Chemical Company, Ethyl Acrylate, n.d., p. 2.

[2] FINAL Report on Carcinogens Background Document for Ethyl Acrylate, Technology Planning and Management Corporation, Durham, 1998.

[3] O. US EPA, ETHYL ACRYLATE|Technology Transfer Network Air Technical Web Site|US EPA. Available at: https://www3.epa.gov/airtoxics/hlthef/ethylacr. html (Accessed 16 June 2016).

[4] Ethyl Acrylate Market (2014-2019)|Ethyl Acrylate Market Report Trends, Analysis, Forecast-Micro Market Monitor. Available at: http://www.micro-marketmonitor.com/market-report/ethyl-acrylate-reports-3781682822.html (Accessed 20 June 2016).

[5] Campbell WE, McDaniel EL, Reece WH, Williams JE, Young HS, Ind. Eng. Chem. Prod. Res. Dev., 9(3), 325 (1970)

[6] Kaddouri A, Mazzocchia C, Tempesti E, Appl. Catal. A: Gen., 180(1), 271 (1999)

[7] Yu ZX, Zheng W, Xu WL, Zhang YH, Fu HY, Zhang P, Trans. Nonferr. Met. Soc. China, 19, s47 (2009)

[8] Elliott GA, Furbush SA, Preparation of ethyl acrylate, 3,002,016, 1961.

[9] Bhattacharyya SK, Sen AK, Ind. Eng. Chem. Process Des. Dev., 3(2), 169 (1964)

[10] Lin TJ, Meng X, Shi L, Ind. Eng. Chem. Res., 52(39), 14125 (2013)

[11] Rowland DK, Production of ethyl acrylate, 2,980,730, 1961.

[12] Bertram BP, James BF, John BC, Production of ethyl acrylate, 3,337,610, 1967.

[13] Chien IL, Chen K, Kuo CL, J. Process Control, 18(3), 215 (2008)

[14] Vitcha JF, Sims VA, Ind. Eng. Chem. Prod. Res. Dev., 5(1), 50 (1966)

[15] Nebesnyi R, Ivasiv V, Dmytruk Y, Lapychak N, BocΤyΗΟ-EΒpoΠeΠckΠΠ KypHaJI ΠepeΠoBbIX TexΗoJIorΠΠ 6(6) 2013 40.

[16] Yang D, Li D, Yao HY, Zhang GL, Jiao TT, Li ZX, Li CS, Zhang SJ, Ind. Eng. Chem. Res., 54(27), 6865 (2015)

[17] Ai M, Appl. Catal., 63(1), 365 (1990)

[18] Bailey OH, Montag RA, Yoo JS, Appl. Catal. A: Gen., 88(2), 163 (1992)

[19] Yoo JS, Appl. Catal. A: Gen., 102(2), 215 (1993)

[20] Gogate MR, Spivey JJ, Zoeller JR, Catal. Today, 36(3), 243 (1997)

[21] Ai M, Fujihashi H, Hosoi S, Yoshida A, Appl. Catal. A: Gen., 252(1), 185 (2003)

[22] Tai J, Davis RJ, Catal. Today, 123(1), 42 (2007)

[23] Ai M, Appl. Catal. A: Gen., 288(1), 211 (2005)

[24] Ai M, Catal. Today, 111(3), 398 (2006)

[25] Li B, Yan RY, Wang L, Diao YY, Li ZX, Zhang SJ, Catal. Lett., 143(8), 829 (2013)

[26] Li B, Yan RY, Wang L, Diao YY, Li ZX, Zhang SJ, Ind. Eng. Chem. Res., 53(4), 1386 (2014)

[27] Feng XZ, Sun B, Yao Y, Su Q, Ji WJ, Au CT, J. Catal., 314, 132 (2014)

[28] Wang Y, Lang X, Zhao G, Chen H, Fan Y, Yu L, Ma X, Zhu Z, RSC Adv., 5(41), 32826 (2015)

[29] Tanabe K, Holderich WF, Appl. Catal. A: Gen., 181(2), 399 (1999)

[30] Dumitriu E, Hulea V, Chelaru C, Catrinescu C, Tichit D, Durand R, Appl. Catal. A: Gen., 178(2), 145 (1999)

[31] Mullins DR, Surf. Sci. Rep., 70(1), 42 (2015)

[32] Kalita P, Gupta NM, Kumar R, J. Catal., 245(2), 338 (2007)

[33] Liang N, Zhang X, An H, Zhao X, Wang Y, Green Chem., 17(5), 2959 (2015)

[34] Tsoncheva T, Issa G, Blasco T, Concepcion P, Dimitrov M, Hernandez S, Kovacheva D, Atanasova G, Nieto JML, J. Colloid Interface Sci., 404, 155 (2013)

[35] Lin LY, Wang CY, Bai HL, Chem. Eng. J., 264, 835 (2015)

[36] Tang C, Peng J, Fan G, Li X, Pu X, Bai W, Catal. Commun., 43, 231 (2014)

[37] Ayastuy JL, Gurbani A, Gonzalez-Marcos MP, Gutierrez-Ortiz MA, Int. J. Hydrog. Energy, 35(3), 1232 (2010)

[38] Sing KS, Pure Appl. Chem., 57(4), 603 (1985)

[39] Yan J, Zhang C, Ning C, Tang Y, Zhang Y, Chen L, Gao S, Wang Z, Zhang W, J. Ind. Eng. Chem., 25, 344 (2015)

[40] Cheralathan KK, Hayashi T, Ogura M, Microporous Mesoporous Mater., 116(1), 406 (2008)

[41] Emeis CA, J. Catal., 141(2), 347 (1993)

[42] Estevez R, Lopez-Pedrajas S, Blanco-Bonilla F, Luna D, Bautista FM, Chem. Eng. J., 282, 179 (2015)

[43] Larachi F, Pierre J, Adnot A, Bernis A, Appl. Surf. Sci., 195(1), 236 (2002)

[44] Orge CA, Orfao JJM, Pereira MFR, de Farias AMD, Fraga MA, Chem. Eng. J., 200, 499 (2012)

[45] Campbell CT, Peden CH, Science, 309(5735), 713 (2005)

[46] Bampenrat A, Meeyoo V, Kitiyanan B, Rangsunvigit P, Rirksomboon T, Appl. Catal. A: Gen., 373(1), 154 (2010)