Glycerol Acetylation with Propionic Acid Using Iron and Cobalt Oxides in Al-MCM-41 Catalysts

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In this work, Al-MCM-41 molecular sieves were synthesized, containing iron and/or cobalt oxides, impregnated by incipient wetness method, characterized and applied as catalysts in the acetylation reaction of glycerol with propionic acid to produce green glyceryl propionate molecules of high commercial value. According to this, X-ray Diffraction (XRD), X-ray Fluorescence (XRF), Fourier Transform Infra Red (FT-IR), adsorption/desorption N2 isotherms, textural analysis, and Scanning Electron Microscope (SEM) analysis were recorded to evaluate the main characteristics of materials. The presence of Lewis and Brønsted acidic sites and catalysts surface area were observed as important key points to functionalize acetylation reaction. Thus, time reaction, temperature, and glycerol / propionic acid ratio varied to improve the most suitable reaction conditions and behaviors. As a result, glycerol conversion was above 96%, followed by 68% of selectivity to glyceryl monopropionate as well as the formation of glyceryl di- and tri- propionate and a small amount of ethylene glycol dipropionate as an undesired product. Copyright © 2020 BCREC Group. All rights reserved
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- Faria, R.P.V., Pereira, C.S.M., Silva, V.M.T.M., Loureiro, J.M., Rodrigues, A.E. (2013). Glycerol valorisation as biofuels: Selection of a suitable solvent for an innovative process for the synthesis of GEA. Chemical Engineering Journal, 233, 159–167. DOI: 10.1016/j.cej.2013.08.035
- Nakagawa, Y., Tomishige, K. (2011). Heterogeneous catalysis of the glycerol hydrogenolysis. Catalysis Science & Technology, 1, 179–190. DOI: 10.1039/c0cy00054j
- Sudarsanam, P., Mallesham, B., Prasad, A. N., Reddy, P.S., Reddy, B.M. (2013). Synthesis of bio – additive fuels from acetalization of glycerol with benzaldehyde over molybdenum promoted green solid acid catalysts. Fuel Processing Technology, 106, 539–545. DOI: 10.1016/j.fuproc.2012.09.025
- Bagnato, G., Iulianelli, A., Sanna, A., Basile, A. (2017). Glycerol Production and Transformation: A Critical Review with Particular Emphasis on Glycerol Reforming Reaction for Producing Hydrogen in Conventional and Membrane Reactors. Membranes, 7(2), 1–17. DOI: 10.3390/membranes7020017
- Christy, S., Noschese, A., Lomelí-Rodriguez, M., Greeves, N., Lopez-Sanchez, J.A. (2018). Recent progress in the synthesis and applications of glycerol carbonate. Current Opinion in Green and Sustainable Chemistry, 14, 99–107. DOI: 10.1016/j.cogsc.2018.09.003
- Katryniok, B., Dumeignil, F. (2013). Recent developments in the field of catalytic dehydration of glycerol to acrolein. ACS Catalysis, 3, 1819–1834. DOI: 10.1021/cs400354p
- Cornejo, A., Barrio, I., Campoy, M., Lázaro, J., Navarrete, B. (2017). Oxygenated fuel additives from glycerol valorization. Main production pathways and effects on fuel properties and engine performance: A critical review. Renewable and Sustainable Energy Reviews, 79, 1400–1413. DOI: 10.1016/j.rser.2017.04.005
- Silva, C.X.A., Gonçalves, V.L.C., Mota, C.J.A. (2009). Water-tolerant zeolite catalyst for the acetalisation of glycerol. Green Chemistry, 11(1), 38–41. DOI: 10.1039/b813564a
- Rahmat, N., Abdullah, A.Z., Mohamed, A.R. (2010). Recent progress on innovative and potential technologies for glycerol transformation into fuel additives: A critical review. Renewable and Sustainable Energy Reviews, 14, 987–1000. DOI: 10.1016/j.rser.2009.11.010
- Pham, T.T., Crossley, S.P., Sooknoi, T., Lobban, L.L., Resasco, D.E., Mallinson, R.G. (2010). Etherification of aldehydes, alcohols and their mixtures on Pd / SiO2 catalysts. Applied Catalysis A, General, 379(1–2), 135–140. DOI: 10.1016/j.apcata.2010.03.014
- Gu, Y., Azzouzi, A., Pouilloux, Y. (2008). Heterogeneously catalyzed etherification of glycerol: new pathways for transformation of glycerol to more valuable chemicals. Green Chemistry, 10, 164–167. DOI: 10.1039/b715802e
- Silva, C.R.B., Gonçalves, V.L.C., Lachter, E.R., Mota, C.J.A. (2009). Etherification of Glycerol with Benzyl Alcohol Catalyzed by Solid Acids. Journal of the Brazilian Chemical Society, 20(2), 201–204. DOI: 10.1590/S0103-50532009000200002
- Gupta, M., Kumar, N. (2012). Scope and opportunities of using glycerol as an energy source. Renewable and Sustainable Energy Reviews, 16(7), 4551–4556. DOI: 10.1016/j.rser.2012.04.001
- Sun, D., Yamada, Y., Sato, S., Ueda, W. (2016). Glycerol hydrogenolysis into useful C3 chemicals. Applied Catalysis B: Environmental, 193, 75–92. DOI: 10.1016/j.apcatb.2016.04.013
- Yamamoto, K., Kiyan, A.M., Bagio, J.C., Rossi, K.A.B., Delabio Berezuk, F., Berezuk, M.E. (2019). Green cyclic acetals production by glycerol etherification reaction with benzaldehyde using cationic acidic resin. Green Processing and Synthesis, 8(1), 183-190. DOI: 10.1515/gps-2018-0059
- Khayoon, M.S., Hameed, B.H. (2011). Acetylation of glycerol to biofuel additives over sulfated activated carbon catalyst. Bioresource Technology, 102(19), 9229–9235. DOI: 10.1016/j.biortech.2011.07.035
- Gonçalves, M., Rodrigues, R., Galhardo, T.S., Carvalho, W.A. (2016). Highly selective acetalization of glycerol with acetone to solketal over acidic carbon-based catalysts from biodiesel waste. Fuel, 181, 46–54. DOI: 10.1016/j.fuel.2016.04.083
- Ekinci, E.K., Oktar, N. (2019). Production of value-added chemicals from esterification of waste glycerol over MCM-41 supported catalysts. Green Processing and Synthesis, 8(1), 128–134. DOI: 10.1515/gps-2018-0034
- De Canck, E., Dosuna-Rodríguez, I., Gaigneaux, E.M., Van Der Voort, P. (2013). Periodic mesoporous organosilica functionalized with sulfonic acid groups as acid catalyst for glycerol acetylation. Materials, 6(8), 3556–3570. DOI: 10.3390/ma6083556
- Sánchez, J.A., Hernández, D.L., Moreno, J.A., Mondragón, F., Fernández, J.J. (2011). Alternative carbon based acid catalyst for selective esterification of glycerol to acetylglycerols. Applied Catalysis A: General, 405(1–2), 55–60. DOI: 10.1016/j.apcata.2011.07.027
- Gonzalez-Arellano, C., De, S., Luque, R. (2014). Selective glycerol transformations to high value-added products catalysed by aluminosilicate-supported iron oxide nanoparticles. Catalysis Science and Technology, 4(12), 4242–4249. DOI: 10.1039/c4cy00714j
- Khayoon, M.S., Triwahyono, S., Hameed, B.H., Jalil, A.A. (2014). Improved production of fuel oxygenates via glycerol acetylation with acetic acid. Chemical Engineering Journal, 243, 473–484. DOI: 10.1016/j.cej.2014.01.027
- Gonçalves, C.E., Laier, L.O., Cardoso, A.L., José, M. (2012). Bioadditive synthesis from H3PW12O40-catalyzed glycerol esterification with HOAc under mild reaction conditions. Fuel Processing Technology, 102, 46–52. DOI: 10.1016/j.fuproc.2012.04.027
- Wang, L., Liu, Q., Zhou, M., Xiao, G. (2012). Synthesis of glycerin triacetate over molding zirconia-loaded sulfuric acid catalyst. Journal of Natural Gas Chemistry, 21(1), 25–28. DOI: 10.1016/S1003-9953(11)60328-9
- Zhu, S., Zhu, Y., Gao, X., Mo, T., Zhu, Y., Li, Y. (2013). Production of bioadditives from glycerol esterification over zirconia supported heteropolyacids. Bioresource Technology, 130, 45–51. DOI: 10.1016/j.biortech.2012.12.011
- Dhakshinamoorthy, A., Alvaro, M., Garcia, H. (2012). Commercial metal–organic frameworks as heterogeneous catalysts. Chemical Communications, 48(92), 11275–11288. DOI: 10.1039/c2cc34329k
- Zhou, C.H., Beltramini, J.N., Lu, G.Q. (2008). Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals. Chemical Society Reviews, 37(3), 527–549. DOI: 10.1039/b707343g
- Trifoi, A.R., Agachi, P.Ş., Pap, T. (2016). Glycerol acetals and ketals as possible diesel additives. A review of their synthesis protocols. Renewable and Sustainable Energy Reviews, 62, 804–814. DOI: 10.1016/j.rser.2016.05.013
- Cai, Q., Lin, W.Y., Xiao, F.S., Pang, W.Q., Chen, X.H., Zou, B.S. (1999). The preparation of highly ordered MCM-41 with extremely low surfactant concentration. Microporous and Mesoporous Materials, 32(1–2), 1–15. DOI: 10.1016/S1387-1811(99)00082-7
- Corma, A., Fornés, V., Navarro, M.T., Pérez-Pariente, J. (1994). Acidity and stability of MCM-41 crystalline aluminosilicates. Journal of Catalysis, 148(2), 569–574. DOI: 10.1006/jcat.1994.1243
- Heravi, M.M., Hosseini, M., Oskooie, H.A., Baghernejad, B. (2011). Fe/Al-MCM-41: An efficient and reusable catalyst for the synthesis of quinoxaline derivatives. Journal of the Korean Chemical Society, 55(2), 235–239. DOI: 10.5012/jkcs.2011.55.2.235
- Oprescu, E.E., Stepan, E., Dragomir, R.E., Radu, A., Rosca, P. (2013). Synthesis and testing of glycerol ketals as components for diesel fuel. Fuel Processing Technology, 110, 214–217. DOI: 10.1016/j.fuproc.2012.12.017
- Kim, I., Kim, J., Lee, D. (2014). A comparative study on catalytic properties of solid acid catalysts for glycerol acetylation at low temperatures. Applied Catalysis B: Environmental, 148–149, 295–303. DOI: 10.1016/j.apcatb.2013.11.008
- Mallesham, B., Govinda Rao, B., Reddy, B.M. (2016). Production of biofuel additives by esterification and acetalization of bioglycerol. Comptes Rendus Chimie, 19(10), 1194–1202. DOI: 10.1016/j.crci.2015.09.011
- Li, X., Zheng, L., Hou, Z. (2018). Acetalization of glycerol with acetone over Co[II](Co[III]xAl2−x)O4 derived from layered double hydroxide. Fuel, 233, 565–571. DOI: 10.1016/j.fuel.2018.06.096
- Zhang, S., Zhao, Z., Ao, Y. (2015). Design of highly efficient Zn-, Cu-, Ni- and Co-promoted M-AlPO4 solid acids: The acetalization of glycerol with acetone. Applied Catalysis A: General, 496, 32–39. DOI: 10.1016/j.apcata.2015.02.006
- Schuette, H.A., Hale, J.T. (1930). Some physical constants of monacetin, monopropin and mono-normal-butyrin. Journal of the American Chemical Society, 52(5), 1978–1981. DOI: 10.1021/ja01368a033
- Gilchrist, P.G., Schuette, H.A. (1931). Monoglycerides of the lower fatty acids. Journal of the American Chemical Society, 53(9), 3480–3484. DOI: 10.1021/ja01360a038
- Cho, G.H.P., Yeong, S.K., Ooi, T.L., Chuah, C.H. (2006). Glycerol esters from the reaction of glycerol with dicarboxylic acid esters. Journal of Surfactants and Detergents, 9(2), 147–152. DOI: 10.1007/s11743-006-0384-9
- Rathod, A.P., Wasewar, K.L., Sonawane, S.S. (2014). Enhancement of esterification of propionic acid with ethanol by pervaporation reactor. Research Journal of Chemistry and Environment, 18(5), 41–44. DOI: 10.1155/2014/539341
- Saengarun, C., Petsom, A., Tungasmita, D.N. (2017). Etherification of glycerol with propylene or 1-butene for fuel additives. Scientific World Journal, 2017, 1-11. DOI: 10.1155/2017/4089036
- Preethi, E.L., Revathi, S., Sivakumar, T., Manikandan, D., Divakar, D., Valentine-Rupa, A., Palanichami, M. (2008). Phenol hydroxylation using Fe/Al-MCM-41 catalysts. Catalysis Letters, 120(1–2), 56–64. DOI: 10.1007/s10562-007-9249-8
- Decyk, P., Trejda, M., Ziolek, M., Kujawa, J., Głaszczka, K., Bettahar, M., Monteverdi, S., Mercy, M. (2003). Physicochemical and catalytic properties of iron-doped silica - The effect of preparation and pretreatment methods. Journal of Catalysis, 219(1), 146–155. DOI: 10.1016/S0021-9517(03)00186-6
- Missen, R.W., Mims, C.A., Saville, B.A. (1999). Introduction to Chemical Reaction Engineering and Kinetics, New York, John Wiley & Sons.
- Silva, C., Mota, C.J.A., Pinto, B.P. (2008). Acetylation of glycerol catalyzed by different solid acids. Catalysis Today, 133-135, 673–677. DOI: 10.1016/j.cattod.2007.12.037
- Beck, J.S., Vartuli, J.C., Roth, W.J., Leonowicz, M.E., Kresge, C.T., Schmitt, K.D., Chu, C.T.W., Olson, D.H., Sheppard, E.W., McCullen, S.B., Higgins, J.B., Schlenker, J.L. (1992). A New Family of Mesoporous Molecular Sieves Prepared with Liquid Crystal Templates. Journal of the American Chemical Society, 114(27), 10834–10843. DOI: 10.1021/ja00053a020
- Ajaikumar, S., Pandurangan, A. (2008). Reaction of benzaldehyde with various aliphatic glycols in the presence of hydrophobic Al-MCM-41: A convenient synthesis of cyclic acetals. Journal of Molecular Catalysis A: Chemical, 290(1–2), 35–43. DOI: 10.1016/j.molcata.2008.04.008
- Mate, V.R., Shirai, M., Rode, C.V. (2013). Heterogeneous Co3O4 catalyst for selective oxidation of aqueous veratryl alcohol using molecular oxygen. Catalysis Communications, 33(3), 66–69. DOI: 10.1016/j.catcom.2012.12.015
- Abdelkader, A., Daly, H., Saih, Y., Morgan, K., Mohamed, M.A., Halawy, S.A., Hardacre, C. (2013). Steam reforming of ethanol over Co3O4-Fe2O3 mixed oxides. International Journal of Hydrogen Energy, 38(20), 8263–8275. DOI: 10.1016/j.ijhydene.2013.04.009
- Alves, I.C.B., Santos, J.R.N., Viégas, D.S.S., Marques, E.P., Lacerda, C.A., Zhang, L., Zhang, J., Marques, A.L.B. (2019). Nanoparticles of Fe2O3 and Co3O4 as efficient electrocatalysts for oxygen reduction reaction in acid medium. Journal of the Brazilian Chemical Society, 30(12), 2681–2690. DOI: 10.21577/0103-5053.20190195
- Ertl, G., Knözinger, H., Schülf, F, Weitkamp, J. (1997). Handbook of Heterogeneous Catalysis, Germany, Wiley-VCH.
- Fontes, M.S.B., Melo, D.M.A., Costa, C.C., Melo, M.A.F., Alvez, J.A.B.L.R., Silva, M.L.P. (2016). Effect of different silica sources on textural parameters of molecular sieve MCM-41. Ceramica, 62, 85-90. DOI: 10.1590/0366-69132016623611966
- Selvaraj, M., Pandurangan, A., Seshadri, K.S., Sinha, P.K., Lal, K.B. (2003). Synthesis, characterization and catalytic application of MCM-41 mesoporous molecular sieves containing Zn and Al. Applied Catalysis A: General, i(2), 347–364. DOI: 10.1016/S0926-860X(02)00527-6
- Camblor, M.A., Corma, A., Pérez-Pariente, J. (1993). Infrared spectroscopic investigation of titanium in zeolites. A new assignment of the 960 cm–1 band. Journal of the Chemical Society, Chemical Communications, 6, 557–559. DOI: 10.1039/C39930000557
- Vidya, K., Gupta, N.M., Selvam, P. (2004). Influence of pH on the sorption behaviour of uranyl ions in mesoporous MCM-41 and MCM-48 molecular sieves. Materials Research Bulletin, 39(13), 2035–2048. Doi: 10.1016/j.materresbull.2004.07.013
- Alves, I.C.B., Santos, J.R.N., Viégas, D.S.S., Marques, E.P., Lacerda, C.A., Zhang, L., Zhang, J, Marques, A.L.B. (2019). Nanoparticles of Fe2O3 and Co3O4 as efficient electrocatalysts for oxygen reduction reaction in acid medium. Journal of the Brazilian Chemical Society, 30, 2681-2690. DOI: 10.21577/0103-5053.20190195
- Sahoo, S., Agarwal, K., Singh, A., Polke, B., Raha, K. (2011). Characterization of g- and α-Fe2O3 nano powders synthesized by emulsion precipitation-calcination route and rheological behaviour of α-Fe2O3. International Journal of Engineering, Science and Technology, 2(8), 118–126. DOI: 10.4314/ijest.v2i8.63841
- Varghese, S., Cutrufello, M.G., Rombi, E., Cannas, C., Monaci, R., Ferino, I. (2012). CO oxidation and preferential oxidation of CO in the presence of hydrogen over SBA-15-templated CuO-Co3O4 catalysts. Applied Catalysis A: General, 443–444, 161–170. DOI: 10.1016/j.apcata.2012.07.038
- Borade, R.B., Clearfield, A. (1995). Synthesis of aluminum rich MCM-41. Catalysis Letters, 31(2–3), 267–272. DOI: 10.1007/BF00808839
- Savidha, R, Pandurangan, A. (2004) Isopropylation of toluene: a comparative study of microporous zeolites and mesoporous MCM-41 materials. Applied Catalysis A: General, 276, 39–50. DOI: 10.1016/j.apcata.2004.04.015
- Carmo Jr, A.C., Souza, L.K.C., Costa, C.E.F., Longo, E., Zamina, J.R., Rocha-Filho, G.N. (2009) Production of biodiesel by esterification of palmitic acid over mesoporous aluminosilicate Al-MCM-41. Fuel, 88, 461-468. DOI: 10.1016/j.fuel.2008.10.007
- Samanta, S., Giri, S., Sastry, P.U., Mal, N.K., Manna, A., Bhaumik, A. (2003). Synthesis and characterization of iron-rich highly ordered mesoporous Fe-MCM-41. Industrial and Engineering Chemistry Research, 42(13), 3012–3018. DOI: 10.1021/ie020905g
- Tran, N.T.T., Uemura, Y., Ramli, A. (2016). Hydrodeoxygenation of Guaiacol over Al-MCM-41 Supported Metal Catalysts: A Comparative Study of Co and Ni. Procedia Engineering, 148, 1252–1258. DOI: 10.1016/j.proeng.2016.06.488
- Udayakumar, S., Ajaikumar, S., Pandurangan, A. (2006). Synthesis of commercial important diethyl phthalate over Al-, Fe- and Al, Zn-MCM-41 molecular sieves. Applied Catalysis A: General, 307(2), 245–256. DOI: 10.1016/j.apcata.2006.03.059
- Fletcher, R.E., Ling, S., Slater, B. (2017). Violations of Löwenstein’s rule in zeolites. Chemical Science, 8(11), 7483–7491. DOI: 10.1039/c7sc02531a
- Uytterhoeven, J.B., Christner, L.G., Hall, W.K. (1965). Studies of the hydrogen held by solids. VIII. The decationated zeolites. Journal of Physical Chemistry, 69(6), 2117–2126. DOI: 10.1021/j100890a052
- Pearson, R.G. (1963). Hard and Soft Acids and Bases. Journal of the American Chemical Society, 85(22), 3533–3539. DOI: 10.1021/ja00905a001
- Vasconcellos, M.L.A.A. (2014) A Teoria de Pearson para a disciplina de química orgânica: um exercício prático e teórico aplicado em sala de aula. Química Nova, 37, 171–175. DOI: 10.1590/S0100-40422014000100029
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