High-performance phosphate supported on HZSM-5 catalyst for dehydration of glycerol to acrolein

doi:10.1016/j.cjche.2018.01.005

摘要/Abstract

摘要： The purpose of this study is to increase acrolein yield and capability of coking resistance in the reaction of glycerol dehydration to acrolein by assembling metal phosphate supported on HZSM-5 catalyst. The as-prepared catalysts were characterized by XRD, SEM, EDS, BET, NH₃-TPD, CO₂-TPD and Py-IR techniques. It was found that metal phosphate species were incorporated into the porous structure of HZSM-5 zeolites, thus influencing the surface and textural physico-chemical properties of the supporters. The alkaline-treated HZSM-5 catalyst promoted the dispersion of phosphate species on the carriers. Moreover, the amount of strong acidity was tremendously improved by adding the different metal hydrophosphates and the catalysts show high catalytic activity. In this present work, the Sn_1/4H₂PO₄/HZSM-5 catalyst exhibited good performance in the catalytic activity and coking resistant ability, which resulted in a high acrolein yield of 83% initially and acrolein yield of 68% after 30 h. The acidity, especially the ratio of strong to weak acid, plays an important role in promoting acrolein yield and stability simultaneously.

关键词: HZSM-5, Metal hydrophosphate, Glycerol dehydration, Coking resistance

Abstract: The purpose of this study is to increase acrolein yield and capability of coking resistance in the reaction of glycerol dehydration to acrolein by assembling metal phosphate supported on HZSM-5 catalyst. The as-prepared catalysts were characterized by XRD, SEM, EDS, BET, NH₃-TPD, CO₂-TPD and Py-IR techniques. It was found that metal phosphate species were incorporated into the porous structure of HZSM-5 zeolites, thus influencing the surface and textural physico-chemical properties of the supporters. The alkaline-treated HZSM-5 catalyst promoted the dispersion of phosphate species on the carriers. Moreover, the amount of strong acidity was tremendously improved by adding the different metal hydrophosphates and the catalysts show high catalytic activity. In this present work, the Sn_1/4H₂PO₄/HZSM-5 catalyst exhibited good performance in the catalytic activity and coking resistant ability, which resulted in a high acrolein yield of 83% initially and acrolein yield of 68% after 30 h. The acidity, especially the ratio of strong to weak acid, plays an important role in promoting acrolein yield and stability simultaneously.

Key words: HZSM-5, Metal hydrophosphate, Glycerol dehydration, Coking resistance

Feng Zhang, Xin Ren, He Huang, Jun Huang, Medak Sudhakar, Licheng Liu. High-performance phosphate supported on HZSM-5 catalyst for dehydration of glycerol to acrolein[J]. Chinese Journal of Chemical Engineering, 2018, 26(5): 1031-1040.

参考文献

[1] A. Behr, J. Eilting, K. Irawadi, J. Leschinski, F. Lindner, Improved utilisation of renewable resources:New important derivatives of glycerol, Green Chem. 10(2008) 13-30.

[2] B. Katryniok, S. Paul, M. Capron, F. Dumeignil, Towards the sustainable production of acrolein by glycerol dehydration, ChemSusChem 2(2009) 719-730.

[3] K.H. Bowmer, G.H. Smith, Herbicides for injection into flowing water:Acrolein and endothal-amine, Weed Res. 24(1984) 201-211.

[4] M. Pagliaro, R. Ciriminna, H. Kimura, M. Rossi, C. Della Pina, From glycerol to valueadded products, Angew. Chem. Int. Ed. 46(2007) 4434-4440.

[5] D. Stosic, S. Bennici, S. Sirotin, P. Stelmachowski, J.-L. Couturier, J.-L. Dubois, A. Travert, A. Auroux, Examination of acid-base properties of solid catalysts for gas phase dehydration of glycerol:FTIR and adsorption microcalorimetry studies, Catal. Today 226(2014) 167-175.

[6] M.H. Haider, N.F. Dummer, D. Zhang, P. Miedziak, T.E. Davies, S.H. Taylor, D.J. Willock, D.W. Knight, D. Chadwick, G.J. Hutchings, Rubidium-and caesium-doped silicotungstic acid catalysts supported on alumina for the catalytic dehydration of glycerol to acrolein, J. Catal. 286(2012) 206-213.

[7] W. Yan, G.J. Suppes, Low-pressure packed-bed gas-phase dehydration of glycerol to acrolein, Ind. Eng. Chem. Res. 48(2009) 3279-3283.

[8] M. Massa, A. Andersson, E. Finocchio, G. Busca, F. Lenrick, L.R. Wallenberg, Performance of ZrO₂-supported Nb-and W-oxide in the gas-phase dehydration of glycerol to acrolein, J. Catal. 297(2013) 93-109.

[9] J.A. Cecilia, C. Garcia-Sancho, J.M. Merida-Robles, J. Santamaria-Gonzalez, R. MorenoTost, P. Maireles-Torres, V and V-P containing Zr-SBA-15 catalysts for dehydration of glycerol to acrolein, Catal. Today 254(2015) 43-52.

[10] T. Ma, Z. Yun, W. Xu, L. Chen, L. Li, J. Ding, R. Shao, Pd-H₃PW₁₂O₄₀/Zr-MCM-41:An efficient catalyst for the sustainable dehydration of glycerol to acrolein, Chem. Eng. J. 294(2016) 343-352.

[11] A.S. de Oliveira, S.J.S. Vasconcelos, J.R. de Sousa, F.F. de Sousa, J.M. Filho, A.C. Oliveira, Catalytic conversion of glycerol to acrolein over modified molecular sieves:Activity and deactivation studies, Chem. Eng. J. 168(2011) 765-774.

[12] L.G. Possato, R.N. Diniz, T. Garetto, S.H. Pulcinelli, C.V. Santilli, L. Martins, A comparative study of glycerol dehydration catalyzed by micro/mesoporous MFI zeolites, J. Catal. 300(2013) 102-112.

[13] A. Corma, From microporous to mesoporous molecular sieve materials and their use in catalysis, Chem. Rev. 97(1997) 2373-2419.

[14] D. Kubicka, I. Kubickova, J. Cejka, Application of molecular sieves in transformations of biomass and biomass-derived feedstocks, Catal. Rev. Sci. Eng. 55(2013) 1-78.

[15] C.S. Carrico, F.T. Cruz, M.B. Santos, H.O. Pastore, H.M.C. Andrade, A.J.S. Mascarenhas, Efficiency of zeolite MCM-22 with different SiO₂/Al₂O₃ molar ratios in gas phase glycerol dehydration to acrolein, Microporous Mesoporous Mater. 181(2013) 74-82.

[16] T. Ma, J. Ding, R. Shao, W. Xu, Z. Yun, Dehydration of glycerol to acrolein over Wells-Dawson and Keggin type phosphotungstic acids supported on MCM-41 catalysts, Chem. Eng. J. 316(2017) 797-806.

[17] H. Zhang, Z. Hu, L. Huang, H. Zhang, K. Song, L. Wang, Z. Shi, J. Ma, Y. Zhuang, W. Shen, Y. Zhang, H. Xu, Y. Tang, Dehydration of glycerol to acrolein over hierarchical ZSM-5 zeolites:Effects of mesoporosity and acidity, ACS Catal. 5(2015) 2548-2558.

[18] C.-J. Yue, M.-M. Gan, L.-P. Gu, Y.-F. Zhuang, In situ synthesized nano-copper over ZSM-5 for the catalytic dehydration of glycerol under mild conditions, J. Taiwan Inst. Chem. Eng. 45(2014) 1443-1448.

[19] S. Erfle, U. Armbruster, U. Bentrup, A. Martin, A. Bruckner, Impact of redox properties on dehydration of glycerol to acrolein over heteropolyacids assessed by operando-EPR spectroscopy, Appl. Catal. A Gen. 391(2011) 102-109.

[20] W. Suprun, M. Lutecki, T. Haber, H. Papp, Acidic catalysts for the dehydration of glycerol:Activity and deactivation, J. Mol. Catal. A Chem. 309(2009) 71-78.

[21] S.-H. Chai, H.-P. Wang, Y. Liang, B.-Q. Xu, Sustainable production of acrolein:investigation of solid acid-base catalysts for gas-phase dehydration of glycerol, Green Chem. 9(2007) 1130-1136.

[22] B. Katryniok, S. Paul, V. Belliere-Baca, P. Rey, F. Dumeignil, Glycerol dehydration to acrolein in the context of new uses of glycerol, Green Chem. 12(2010) 2079.

[23] D.J. Jones, J. Jimenez-Jimenez, A. Jimenez-Lopez, P. Maireles-Torres, P. Olivera-Pastor, E. Rodriguez-Castellon, J. Roziere, Surface characterisation of zirconium-doped mesoporous silica, Chem. Commun. (1997) 431-432.

[24] A. Vinu, D.P. Sawant, K. Ariga, K.Z. Hossain, S.B. Halligudi, M. Hartmann, M. Nomura, Direct synthesis of well-ordered and unusually reactive FeSBA-15 mesoporous molecular sieves, Chem. Mater. 17(2005) 5339-5345.

[25] S.-Y. Chen, C.-Y. Tang, J.-F. Lee, L.-Y. Jang, T. Tatsumi, S. Cheng, Effect of calcination on the structure and catalytic activities of titanium incorporated SBA-15, J. Mater. Chem. 21(2011) 2255-2265.

[26] R. Liu, T. Wang, Y. Jin, Catalytic dehydration of glycerol to acrolein over HPW supported on Cs+ modified SBA-15, Catal. Today 233(2014) 127-132.

[27] L. Huang, F. Qin, Z. Huang, Y. Zhuang, J. Ma, H. Xu, W. Shen, Hierarchical ZSM-5 zeolite synthesized by an ultrasound-assisted method as a long-life catalyst for dehydration of glycerol to acrolein, Ind. Eng. Chem. Res. 55(2016) 7318-7327.

[28] J.A. Cecilia, C. Garcia-Sancho, J.M. Merida-Robles, J. Santamaria Gonzalez, R. Moreno-Tost, P. Maireles-Torres, WO₃ supported on Zr doped mesoporous SBA-15 silica for glycerol dehydration to acrolein, Appl. Catal. A Gen. 516(2016) 30-40.

[29] A. Alhanash, E.F. Kozhevnikova, I.V. Kozhevnikov, Gas-phase dehydration of glycerol to acrolein catalysed by caesium heteropoly salt, Appl. Catal. A Gen. 378(2010) 11-18.

[30] G.S. Foo, D. Wei, D.S. Sholl, C. Sievers, Role of Lewis and Bronsted acid sites in the dehydration of glycerol over niobia, ACS Catal. 4(2014) 3180-3192.

[31] J. Mohd Ekhsan, S.L. Lee, H. Nur, Niobium oxide and phosphoric acid impregnated silica-titania as oxidative-acidic bifunctional catalyst, Appl. Catal. A Gen. 471(2014) 142-148.

[32] Y.Y. Lee, K.A. Lee, N.C. Park, Y.C. Kim, The effect of PO₄ to Nb₂O₅ catalyst on the dehydration of glycerol, Catal. Today 232(2014) 114-118.

[33] T.H. Peterson, A.H. Zacher, M.J. Gray, J.F. White, J.E. Holladay, T.A. Werpy, Chemical Production Process, System, and Catalyst Compositions, US, 2009.

[34] Y.T. Kim, K.D. Jung, E.D. Park, Gas-phase dehydration of glycerol over ZSM-5 catalysts, Microporous Mesoporous Mater. 131(2010) 28-36.

[35] H.P. Decolatti, B.O. Dalla Costa, C.A. Querini, Dehydration of glycerol to acrolein using H-ZSM5 zeolite modified by alkali treatment with NaOH, Microporous Mesoporous Mater. 204(2015) 180-189.

[36] C.J. Zhou, C.J. Huang, W.G. Zhang, H.S. Zhai, C.J. Huang, H.L. Wu, Z.S. Chao, Synthesis of micro-and mesoporous ZSM-5 composites and their catalytic application in glycerol dehydration to acrolein, Stud. Surf. Sci. Catal. 165(2007) 527-530.

[37] Z.X. Yang, Y.D. Xia, R. Mokaya, Zeolite ZSM-5 with unique supermicropores synthesized using mesoporous carbon as a template, Adv. Mater. 16(2004) 727-732.

[38] K. Suzuki, Y. Aoyagi, N. Katada, M. Choi, R. Ryoo, M. Niwa, Acidity and catalytic activity of mesoporous ZSM-5 in comparison with zeolite ZSM-5, Al-MCM-41 and silica-alumina, Catal. Today 132(2008) 38-45.

[39] M.I. Zaki, M.A. Hasan, F.A. Al-Sagheer, L. Pasupulety, In situ FTIR spectra of pyridine adsorbed on SiO₂-Al₂O₃, TiO₂, ZrO₂ and CeO₂:General considerations for the identification of acid sites on surfaces of finely divided metal oxides, Colloids Surf. A Physicochem. Eng. Asp. 190(2001) 261-274.

[40] O. Kikhtyanin, Y. Ganjkhanlou, D. Kubicka, R. Bulanek, J. Cejka, Characterization of potassium-modified FAU zeolites and their performance in aldol condensation of furfural and acetone, Appl. Catal. A Gen. 549(2018) 8-18.

[41] S. Deng, H. Li, S. Li, Y. Zhang, Activity and characterization of modified Cr₂O₃/ZrO₂ nano-composite catalysts for oxidative dehydrogenation of ethane to ethylene with CO₂, J. Mol. Catal. A Chem. 268(2007) 169-175.

[42] S. Thanasilp, J.W. Schwank, V. Meeyoo, S. Pengpanich, M. Hunsom, One-pot oxydehydration of glycerol to value-added compounds over metal-doped SiW/HZSM-5 catalysts:Effect of metal type and loading, Chem. Eng. J. 275(2015) 113-124.

[43] H. Gan, X. Zhao, B. Song, L. Guo, R. Zhang, C. Chen, J. Chen, W. Zhu, Z. Hou, Gas phase dehydration of glycerol to acrolein catalyzed by zirconium phosphate, Chin. J. Catal. 35(2014) 1148-1156.

[44] N.P. Rajan, G.S. Rao, V. Pavankumar, K.V.R. Chary, Vapour phase dehydration of glycerol over VPO catalyst supported on zirconium phosphate, Catal. Sci. Technol. 4(2014) 81-92.