Abstract
The possibility of implementing the concept of converting bioglycerin into a blend of oxygenates, potentially applicable as components of gasoline by ketalization with acetone (T = 30–40°C, atmospheric pressure), accompanied by mild hydrogenolysis of ketal [T = 100–140°C, p(H2) = 2 MPa] to obtain a mixture of of glycerol and solketal isopropyl ethers. It was shown that the preferred method of conversion is the separate performing of ketalization and hydrogenolysis, since when these stages are combined, the side reaction of the formation of free isopropyl alcohol is highly selective. The regularities in the influence of the composition of the catalytic system (Pd/C + para-toluenesulfonic acid) on its activity were found in the reaction of catalytic hydrogenation of solketal to a mixture of glycerol and solketal isopropyl ethers (optimal ratio of Pd/para-toluenesulfonic acid = 0.811 mol). It was shown that the addition of 4–5% glycerol to raw materials makes it possible to increase the yield of target hydrogenation products from 25 to 36%. Using a flow unit, the catalytic hydrogenation of solketal was optimized. In the optimal mode [T = 170°C, p(H2) = 4 MPa, v = 0.5 h−1, H2/feedstock = 660 nL L−1], the conversion of solketal to a mixture of target products (glycerol monoisopropyl ether, glycerol diisopropyl ethers, and solketal isopropyl ether) reaches 98%. The possibility of carrying out the reaction on heterogeneous bifunctional catalysts of the Pd/sulfonated coal type is shown.
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Melero, J.A., Vicente, G., Paniagua, M., Morales, G., and Munoz, P., Bioresour. Technol., 2012, vol. 103, pp. 142–151. https://doi.org/10.1016/j.biortech.2011.09.105
Melero, J.A., Vicente, G., Morales, G., and Paniagua, M., Bustamante J. Fuel, 2010, vol. 89, pp. 2011–2018. https://doi.org/10.1016/j.fuel.2010.03.042
Pariente, S., Tanchoux, N., and Fajula, F., Green Chem., 2009, vol. 11, pp. 1256–1261. https://doi.org/10.1039/b905405g
Nandiwale, K.Y., Patil, S.E., and Bokade, V.V., Energy Technol., 2014, vol. 2, pp. 446–452. https://doi.org/10.1002/ente.201300169
Samoilov, V.O., Ramazanov, D.N., Nekhaev, A.I., and Maksimov, A.L., Petrol. Chem., 2016, vol. 56, pp. 125–130. https://doi.org/10.1134/S0965544116010060.
Chang, J.S., Lee, Y.D., Chou, L.C.S., Ling, T.R., and Chou, T.C., Ind. Eng. Chem. Res., 2012, vol. 51, pp. 655–661. https://doi.org/10.1021/ie201612t
Saengarun, C., Petsom, A., and Tungasmita, D.N., Sci. World, J., 2017, pp. 1–11. https://doi.org/10.1155/2017/4089036
Ikizer, B., Oktar, N., and Dogu, T., Fuel Process. Technol., 2015, vol. 138, pp. 570–577. https://doi.org/10.1016/j.fuproc.2015.06.039
Mota, C., J.A., Da Silva, C., X.A., Rosenbach, N., Costa, J., and Da Silva, F., Energy and Fuels, 2010, vol. 24, pp. 2733–2736. https://doi.org/10.1021/ef9015735
Ilgen, O., Yerlikaya, S., and Akyurek, F.O., Period Polytech. Chem. Eng., 2016, vol. 61, pp. 144–148. https://doi.org/10.3311/PPch.8895
Pat. EP0718270A2 (publ. 1995). Verfahren zur Herstellung von Polyalkylethern.
Dmitriev, G.S., Zanaveskin, L.N., Terekhov, A.V., Samoilov, V.O., Kozlovskii, I.A., and Maksimov, A.L., Russ. J. Appl. Chem., 2018, vol. 91, pp. 1478–1485. https://doi.org/10.1134/S1070427218090100
Terekhov, A.V., Dmitriev, G.S., Khadzhiev, S.N., and Zanaveskin, L.N., Russ. J. Appl. Chem., 2016, vol. 89, pp. 639–643. https://doi.org/10.1134/S1070427216040182
Novikov, D.A., Dobryakov, Y.G., and Smirnova, N.A., Russ. J. Appl. Chem., 2013, vol. 86, pp. 398–403. https://doi.org/10.1134/S107042721303018X
Samoilov, V., Onishchenko, M., Ramazanov, D., and Maximov, A., ChemCatChem., 2017, vol. 9, pp. 2839–2849. https://doi.org/10.1002/cctc.201700108
Shi, Y., Dayoub, W., Favre-Réguillon, A., Chen, G.R., and Lemaire, M., Tetrahedron. Lett., 2009, vol. 50, pp. 6891–6893. https://doi.org/10.1016/j.tetlet.2009.09.134
Samoilov, V.O., Ni, D.S., and Maximov, A.L., ChemistrySelect., 2018, vol. 3, pp. 9759–9766. https://doi.org/10.1002/slct.201802135
Bethmont, V., Montassier, C., and Marecot, P., J. Mol. Catal. A: Chemical, 2000, vol. 152, pp. 133–140. https://doi.org/10.1016/S1381-1169(99)00272-1
Lorette, N.B., Howard, W.L., and Brown, J.H., J. Org. Chem., 1959, vol. 24, pp. 1731–1733. https://doi.org/10.1021/jo01093a028
Nanda, M.R., Yuan, Z., Qin, W., Ghaziaskar, H.S., Poirier, M.A., and Xu, C.C., Fuel, 2014, vol. 117, pp. 470–477. https://doi.org/10.1016/j.fuel.2013.09.066
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The study was carried out with financial support from the Russian Foundation for Basic Research in the framework of the scientific project no. 18-33-00533.
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A. L. Maksimov is the chief editor of the Journal of Applied Chemistry. The remaining authors declare that there is no conflict of interest requiring disclosure in this article.
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Russian Text © The Author(s), 2020, published in Zhurnal Prikladnoi Khimii, 2020, Vol. 93, No. 1, pp. 121–131.
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Samoilov, V.O., Ni, D.S., Goncharova, A.V. et al. Catalytic Hydrogenolysis of Solketal on Bifunctional Catalysts with Production of High Octane Components of Motor Fuels. Russ J Appl Chem 93, 108–117 (2020). https://doi.org/10.1134/S1070427220010127
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DOI: https://doi.org/10.1134/S1070427220010127