Mixed Oxide Catalyst for the Oxidation of Glycerol to Lactic Acid: Influence of the Preparation Method and Calcination Temperature


Noraini Razali(1*), Ahmad Zuhairi Abdullah(2)

(1) Faculty of Chemical Engineering, Universiti Teknologi MARA, Cawangan Terengganu, Bukit Besi Campus, 23200, Dungun, Terengganu, Malaysia
(2) School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, 14300 Nibong Tebal, Penang, Malaysia
(*) Corresponding Author


The selective oxidation reaction of glycerol to produce lactic acid is a high-temperature reaction, and requiring a catalyst with high thermal stability. The mixed metal oxide is one of the potential catalysts to be explored. In this study, prepared CaCe supported on ZrO2 catalyst with two preparation methods (co-precipitation and impregnation), and calcination temperatures (800 and 600 °C) were investigated. The oxidation reaction of glycerol to lactic acid was carried out at 250 °C for 2 h in a base-free condition using pure glycerol as a reactant. The catalysts were characterized using XRD, TGA, XPS, SEM and basicity test to evaluate and correlate the physical and chemical properties with their catalytic performance. It was found that the catalyst prepared by co-precipitation and calcined at 800 °C exhibited the highest catalytic performance. The high lactic acid yield of 38.8 and 95% glycerol conversion were achieved. The catalyst was successfully developed with sufficient porosity and high intensity of mixed metal structure that contributed to the desired high performance. Improvement in the basicity and formation of surface oxygen vacancies was attributed to cationic Ce4+/Ce3+ elements leading to the promotion of lactic acid yield and high glycerol conversion.


mixed metal oxide catalyst; oxidation; impregnation; co-precipitation; calcination

Full Text:

Full Text PDF


[1] Quispe, C.A.G., Coronado, C.J.R., and Carvalho, J.A., 2013, Glycerol: Production, consumption, prices, characterization and new trends in combustion, Renewable Sustainable Energy Rev., 27, 475–493.

[2] Zhao, Z., Arentz, J., Pretzer, L.A., Limpornpipat, P., Clomburg, J.M., Gonzalez, R., Schweitzer, N.M., Wu, T., Miller, J.T., and Wong, M.S., 2014, Volcano-shape glycerol oxidation activity of palladium-decorated gold nanoparticles, Chem. Sci., 5 (10), 3715–3728.

[3] Dimitratos, N., Lopez-Sanchez, J.A., Anthonykutty, J.M., Brett, G., Carley, A.F., Tiruvalam, R.C., Herzing, A.A., Kiely, C.J., Knight, D.W., and Hutchings, G.J., 2009, Oxidation of glycerol using gold–palladium alloy-supported nanocrystals, Phys. Chem. Chem. Phys., 11 (25), 4952–4961.

[4] Chieregato, A., Basile, F., Concepción, P., Guidetti, S., Liosi, G., Soriano, M.D., Trevisanut, C., Cavani, F., and López, J.M.L., 2012, Glycerol oxidehydration into acrolein and acrylic acid over W–V–Nb–O bronzes with hexagonal structure, Catal. Today, 197 (1), 58–65.

[5] Zeng, S., Zhang, X., Fu, X., Zhang, L., Su, H., and Pan, H., 2013, Co/CexZr1-xO2 solid-solution catalysts with cubic fluorite structure for carbon dioxide reforming of methane, Appl. Catal., B, 136-137, 308–316.

[6] Kambolis, A., Matralis, H., Trovarelli, A., and Papadopoulou, C., 2010, Ni/CeO2-ZrO2 catalysts for the dry reforming of methane, Appl. Catal., A, 377 (1-2), 16–26.

[7] Maciel, C.G., Silva, T.F., Hirooka, M.I., Belgacem, M.N., and Assaf, J.M., 2012, Effect of nature of ceria support in CuO/CeO2 catalyst for PROX-CO reaction, Fuel, 97, 245–252.

[8] Kim, M., DiMaggio, C., Yan, S., Salley, S.O., and Ng, K.Y.S., 2011, The effect of support material on the transesterification activity of CaO–La2O3 and CaO–CeO2 supported catalysts, Green Chem., 13 (2), 334–339.

[9] Kim, Y.H., Hwang, S.K., Kim, J.W., and Lee, Y.S., 2014, Zirconia-supported ruthenium catalyst for efficient aerobic oxidation of alcohols to aldehydes, Ind. Eng. Chem. Res., 53 (31), 12548–12552.

[10] He, Y., Ford, M.E., Zhu, M., Liu, Q., Wu, Z., and Wachs, I.E., 2016, Selective catalytic reduction of NO by NH3 with WO3-TiO2 catalysts: Influence of catalyst synthesis method, Appl. Catal., B, 188, 123–133.

[11] Yang, G.Y., Ke, Y.H., Ren, H.F., Liu, C.L., Yang, R.Z., and Dong, W.S., 2016, The conversion of glycerol to lactic acid catalyzed by ZrO2-supported CuO catalysts, Chem. Eng. J., 283, 759–767.

[12] Kouzu, M., Kasuno, T., Tajika, M., Sugimoto, Y., Yamanaka, S., and Hidaka, J., 2008, Calcium oxide as a solid base catalyst for transesterification of soybean oil and its application to biodiesel production, Fuel, 87 (12), 2798–2806.

[13] Huaping, Z., Zongbin, W., Yuanxiong, C., Ping, Z., Shijie, D., Xiaohua, L., and Zongqiang, M., 2006, Preparation of biodiesel catalyzed by solid super base of calcium oxide and its refining process, Chin. J. Catal., 27 (5), 391–396.

[14] Al-Fatesh, A.S., Fakeeha, A.H., Ibrahim, A.A., Khan, W.U., Atia, H., Eckelt, R., Seshan, K., and Chowdhury, B., 2016, Decomposition of methane over alumina supported Fe and Ni–Fe bimetallic catalyst: Effect of preparation procedure and calcination temperature, J. Saudi Chem. Soc., 22 (2), 239–247.

[15] Ozawa, M., Takahashi-Morita, M., Kobayashi, K., and Haneda, M., 2017, Core-shell type ceria zirconia support for platinum and rhodium three way catalysts, Catal. Today, 281, 482–489.

[16] Piumetti, M., Bensaid, S., Fino, D., and Russo, N., 2016, Nanostructured ceria-zirconia catalysts for CO oxidation: Study on surface properties and reactivity, Appl. Catal., B, 197, 35–46.

[17] Purushothaman, R.K.P., van Haveren, J., van Es, D.S., Melián-Cabrera, I., Meeldijk, J.D., and Heeres, H.J., 2014, An efficient one pot conversion of glycerol to lactic acid using bimetallic gold-platinum catalysts on nanocrystalline CeO2 support, Appl. Catal., B, 147, 92–100.

[18] Reddy, B.M., and Khan, A., 2003, Structural characterization of CeO2-TiO2 and V2O5/CeO2-TiO2 catalysts by Raman and XPS techniques, J. Phys. Chem. B, 107 (22), 5162–5167.

[19] Atia, H., Armbruster, U., and Martin, A., 2011, Influence of alkaline metal on the performance of supported silicotungstic acid catalysts in glycerol dehydration towards acrolein, Appl. Catal., A, 393 (1-2), 331–339.

[20] Chen, L., Ren, S., and Ye, X.P., 2014, Lactic acid production from glycerol using CaO as a solid base catalyst, Fuel Process. Technol., 120, 40–47.

[21] Sietsma, J.R.A., Friedrich, H., Broersma, A., Versluijs-Helder, M., van Dillen,  A.J., de Jongh, P.E., and de Jong, K.P., 2008, How nitric oxide affects the decomposition of supported nickel nitrate to arrive at highly dispersed catalysts, J. Catal., 260 (2), 227–235.

[22] Al-Fatesh, A.S., and Fakeeha, A.H., 2012, Effects of calcination and activation temperature on dry reforming catalysts, J. Saudi Chem. Soc., 16 (1), 55–61.

[23] Xu, W., Haarberg, G.M. Sunde, S., Seland, F., Ratvik, A.P, Zimmerman, E., Shimamune, T., Gustavsson, J., and Åkre, T., 2017, Calcination temperature dependent catalytic activity and stability of IrO2–Ta2O5 anodes for oxygen evolution reaction in aqueous sulfate electrolytes, J. Electrochem. Soc., 164 (9), 895–900.

DOI: https://doi.org/10.22146/ijc.44137

Article Metrics

Abstract views : 28 | views : 50

Copyright (c) 2019 Indonesian Journal of Chemistry

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.


Indonesian Journal of Chemisty (ISSN 1411-9420 / 2460-1578) - Chemistry Department, Universitas Gadjah Mada, Indonesia.

Analytics View The Statistics of Indones. J. Chem.