Abstract
Ethanol is an alternative for producing petrochemicals, especially propylene and aromatics (benzene, toluene, and xylenes). To understand ethanol processing routes into olefins and aromatics, it is interesting to use ethylene that is the major primary product of ethanol reaction into hydrocarbons and the intermediate for the formation of olefins and aromatics. In this work, the influence of the operating conditions (ethylene partial pressure, reaction temperature and contact time) in the ethylene conversion into propylene and aromatics, and in the product yield was investigated using HZSM-5 zeolite as catalyst. Lower contact time and ethylene partial pressure, and higher reaction temperature favored propylene yield. Olefin production was based on the formation of carbene species from ethylene that reacts with ethylene to produce propylene and on ethylene dimerization to form butenes. On the other hand, intermediate reaction temperatures and contact times, and higher ethylene partial pressure promote the formation of aromatics, where the dehydrocyclization reaction is favored over hydrogen transfer. The presence of water vapor in long-term reactions deactivated the catalyst. For propylene production, the decrease of ethylene conversion was due to zeolite framework dealumination, while for aromatic formation the reaction mechanism was changed.
Graphic Abstract
Similar content being viewed by others
References
Takahashi A, Xia W, Nakamura I, Shimada H, Fujitani T (2012) Effects of added phosphorus on conversion of ethanol to propylene over ZSM-5 catalysts. Appl Catal A 423–424:162–167
Gayubo A, Alonso A, Valle B, Aguayo A, Olazar M, Bilbao J (2011) Kinetic modelling for the transformation of bioethanol into olefins on a hydrothermally stable Ni–HZSM-5 catalyst considering the deactivation by coke. Chem Eng J 167:262–277
Madeira F, Gnep N, Magnoux P, Maury S, Cadran N (2009) Ethanol transformation over HFAU, HBEA and HMFI zeolites presenting similar Brønsted acidity. Appl Catal A 367:39–46
Song Z, Takahashi A, Mimura N, Fujitani T (2009) Production of propylene from ethanol over ZSM-5 zeolites. Catal Lett 131:364–369
Inaba M, Murata K, Saito M, Takahara I (2006) Ethanol conversion to aromatic hydrocarbons over several zeolite catalysts. React Kinet Catal Lett 88:135–141
Sousa Z, Veloso C, Henriques C, da Silva V (2016) Ethanol conversion into olefins and aromatics over HZSM-5 zeolite: Influence of reaction conditions and surface reaction studies. J Mol Catal A 422:266–274
Aguayo A, Gayubo A, Atutxa A, Olazar M, Bilbao J (2002) Catalyst deactivation by coke in the transformation of aqueous ethanol into hydrocarbons. Kinetic modeling and acidity deterioration of the catalyst. Ind Eng Chem Res 41:4216–4224
Ghashghaee M (2018) Heterogeneous catalysts for gas-phase conversion of ethylene to higher olefins. Rev Chem Eng 34:595–655
Hulea V (2018) Toward platform chemicals from bio-based ethylene: heterogeneous catalysts and processes. ACS Catal 8:3263–3279
Li X, Kant A, He Y, Thakkar H, Atanga M, Rezaei F, Ludlow D, Rownaghi A (2016) Light olefins from renewable resources: selective catalytic dehydration of bioethanol to propylene over zeolite and transition metal oxide catalysts. Catal Today 276:62–77
Epelde E, Aguayo A, Olazar M, Bilbao J, Gayubo A (2014) Modifications in the HZSM-5 zeolite for the selective transformation of ethylene into propylene. Appl Catal A 479:17–25
Batchu R, Galvita V, Alexopoulos K, van der Borght K, Poelman H, Reyniers M-F, Marin G (2017) Role of intermediates in reaction pathways from ethene to hydrocarbons over H-ZSM-5. Appl Catal A 538:207–220
Lin B, Zhang Q, Wang Y (2009) Catalytic conversion of ethylene to propylene and butenes over H − ZSM-5. Ind Eng Chem Res 48:10788–10795
Dai W, Sun X, Tang B, Wu G, Li L, Guan N, Hunger M (2014) Verifying the mechanism of the ethene-to-propene conversion on zeolite H-SSZ-13. J Catal 314:10–20
Takahashi A, Xia W, Wu Q, Furukawa T, Nakamura I, Shimada H, Fujitani T (2013) Difference between the mechanisms of propylene production from methanol and ethanol over ZSM-5 catalysts. Appl Catal A 467:380–385
Gayubo A, Tarrío A, Aguayo A, Olazar M, Bilbao J (2001) Kinetic modelling of the transformation of aqueous ethanol into hydrocarbons on a HZSM-5 zeolite. Ind Eng Chem Res 40:3467–3474
Johansson R, Hruby S, Rass-Hansen J, Christensen C (2009) The hydrocarbon pool in ethanol-to-gasoline over HZSM-5 catalysts. Catal Lett 127:1–6
van der Borght K, Batchu R, Galvita V, Alexopoulos K, Reyniers M-F, Thybaut J, Marin G (2016) Insights into the Reaction Mechanism of ethanol conversion into hydrocarbons on H-ZSM-5. Angew Chem Int Ed 55:12817–12821
Allotta P, Stair P (2012) Time-resolved studies of ethylene and propylene reactions in zeolite H-MFI by in situ fast IR heating and UV raman spectroscopy. ACS Catal 2:2424–2432
Ferreira Madeira F, Gnepa N, Magnoux P, Vezin H, Maury S, Cadran N (2010) Mechanistic insights on the ethanol transformation into hydrocarbons over HZSM-5 zeolite. Chem Eng J 161:403–408
Ferreira Madeira F, Vezin H, Gnep N, Magnoux P, Maury S, Cadran N (2011) Radical species detection and their nature evolution with catalyst deactivation in the ethanol-to-hydrocarbon reaction over HZSM-5 zeolite. ACS Catal 1:417–424
Chang C, Silvestri A (1977) The conversion of methanol and other O-compounds to hydrocarbons over zeolite catalysts. J Catal 47:249–259
Yamazaki H, Shima H, Imai H, Yokoi T, Tatsumi T, Kondo J (2012) Direct production of propene from methoxy species and dimethyl ether over H-ZSM-5. J Phys Chem C 116:24091–24097
Yamazaki H, Shima H, Imai H, Yokoi T, Tatsumi T, Kondo J (2011) Evidence for a “Carbene-like” intermediate during the reaction of methoxy species with light alkenes on H-ZSM-5. Angew Chem Int Ed 50:1853–1856
Costa E, Uguina A, Aguado J, Hernández P (1985) Ethanol to gasoline process: effect of variables, mechanism, and kinetics. Ind Eng Chem Process Des Dev 24:239–244
Derouane E, Nagy J, Dejaifve P, van Hooff J, Spekman B, Vedrine J, Naccache C (1978) Elucidation of the mechanism of conversion of methanol and ethanol to hydrocarbons on a new type of synthetic zeolite. J Catal 53:40–55
Spoto G, Bordiga S, Ricchiardi G, Scarano D, Zecchina A, Borello E (1994) IR study of ethene and propene oligomerization on H-ZSM-5: hydrogen-bonded precursor formation, initiation and propagation mechanisms and structure of the entrapped oligomers. J Chem Soc Faraday Trans 90:2827–2835
Bolis V, Vedrine J, van De Berg J, Wolthuizen J, Derouane E (1980) Adsorption and activation of ethene by zeolite-H-ZSM-5. J Chem Soc Faraday Trans 1(76):1606–1616
Kim H, Kim J-W, Kim N, Kim T-W, Jhung S, Kim C-U (2017) Controlling size and acidity of SAPO-34 catalyst for efficient ethylene to propylene transformation. Mol Catal 438:86–92
Chu Y, Han B, Zheng A, Deng F (2012) Influence of acid strength and confinement effect on the ethylene dimerization reaction over solid acid catalysts: a theoretical calculation study. J Phys Chem C 116:12687–12695
Katada N, Igi H, Kim J-H, Niwa M (1997) Determination of the acidic properties of zeolites by theoretical analysis of temperature-programmed desorption of ammonia based on adsorption equilibrium. J Phys Chem B 101:5969–5977
Katada N, Miyamoto T, Begum H, Naito N, Niwa M, Matsumoto A, Tsutsumi K (2000) Strong acidity of MFI-type ferrisilicate determined by temperature-programmed desorption of ammonia. J Phys Chem B 104:5511–5518
Epelde E, Ibañez M, Aguayo AT, Gayubo AG, Bilbao J, Castaño P (2014) Differences among the deactivation pathway of HZSM-5 zeolite and SAPO-34 in the transformation of ethylene or 1-butene to propylene. Microporous Mesoporous Mater 195:284–293
Blasco T, Corma A, Martínez-Triguero J (2006) Hydrothermal stabilization of ZSM-5 catalytic-cracking additives by phosphorus addition. J Catal 237:267–277
Beran S, Jirú P, Kubelková L (1981) Quantum chemical study of the interaction of ethylene and propylene with the hydroxyl groups of zeolites. J Mol Catal 12:341–349
Oikawa H, Shibata Y, Inazu K, Iwase Y, Murai K, Hyodo S, Kobayashi G, Baba T (2006) Highly selective conversion of ethene to propene over SAPO-34 as a solid acid catalyst. Appl Catal A 312:181–185
Ingram C, Lancashire R (1995) On the formation of C3 hydrocarbons during the conversion of ethanol using H-ZSM-5 catalyst. Catal Lett 31:395–403
Lin L, Qiu C, Zhuo Z, Zhang D, Zhao S, Wu H, Liu Y, He M (2014) Acid strength controlled reaction pathways for the catalytic cracking of 1-butene to propene over ZSM-5. J Catal 309:136–145
Choudhary V, Banerjee S, Panjala D (2002) Influence of temperature on the product selectivity and distribution of aromatics and C8 aromatic isomers in the conversion of dilute ethene over H-Galloaluminosilicate (ZSM-5 type) zeolite. J Catal 205:398–403
Guisnet M, Costa L, Ribeiro F (2009) Prevention of zeolite deactivation by coking. J Mol Catal A 305:69–83
Jun J-W, Khan N, Seo P, Kim C-U, Kim H, Jhung S (2016) Conversion of Y into SSZ-13 zeolites and ethylene-to-propylene reactions over the obtained SSZ-13 zeolites. Chem Eng J 303:667–674
Acknowledgements
Débora S. Fernandes thanks CAPES (Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brazil – Finance Code 001) for M.Sc. scholarship and financial support. Cristiane A. Henriques thanks CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico) and Prociencia program (Universidade do Estado do Rio de Janeiro) for her research scholarship and financial support.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare no conflict of interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Fernandes, D.S., Veloso, C.O. & Henriques, C.A. Ethylene Conversion into Propylene and Aromatics on HZSM-5: Insights on Reaction Routes and Water Influence. Catal Lett 150, 738–752 (2020). https://doi.org/10.1007/s10562-019-02954-w
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10562-019-02954-w