Propane Dehydrogenation over Pt-Sn Supported on Magnesium Aluminate Material
Pt-Sn catalysts have been prepared using magnesium aluminate as a support with two different Mg/Al ratio. The supports/catalysts have been characterized by N2-adsorption, XRD, and temperature programmed desorption of NH3 and thermogravimetry analysis (TGA). The catalysts have been evaluated at 595 0C for the propane dehydrogenation reaction at 0.5 barg pressure using a feed containing pure propane with steam to hydrocarbon ratio of 1 mol/mol and weight hourly space velocity (WHSV) 0.9 h-1. Chlorine quantification studies have been developed using Carbon-Hydrogen-Nitrogen-Sulphur (CHNS) analyzer. The dechlorinated catalyst with higher alumina content showed better performance (38-43% propane conversion, 91-94% propylene selectivity) in propane conversion and propylene selectivity than Pt-Sn-MG-AL-DC-1 (30-18% propane conversion, 83-90% propylene selectivity).
Digital Object Identifier (DOI): doi.org/10.5281/zenodo.3669218Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 619
 N.A. Pakhomov, V.N. Kashkin, E.I. Nemykina, V.V. Molchanov, V.I. Nadtochiy, A.S. Noskov, “Dehydrogenation of C3–C4 paraffins on Cr2O3/Al2O3 catalysts in fluidized and fixed bed reactors”, Chem. Eng. J., vol. 154, pp.185–188, 2009.
 M.A. Chen, J. Xu, Y. Cao, H.Y. He, K.N. Fan, J.H. Zhuang, “Dehydrogenation of propane over In2O3–Al2O3 mixed oxide in the presence of carbon dioxide”, J. Catal., vol. 272, pp.101–108, 2010..
 S. Pisduangdaw, J. Panpranot, C. Methastidsook, C. Chaisuk, K. Faungnawakij, P. Praserthdam, O. Mekasuwandumrong, “Characteristics and catalytic properties of Pt-Sn/Al2O3 nanoparticles synthesized by one-step flame spray pyrolysis in the dehydrogenation of propane”, Appl. Catal. A: Gen., vol. 370, pp. 1–6, 2009.
 B. S.A. Bocanegra, A.A. Castro, O.A. Scelza, S.R. de Miguel, “Characterization and catalytic behavior in the n-butane dehydrogenation of trimetallic InPtSn/MgAl2O4 catalysts”, Appl. Catal A:Gen., vol.333, pp.49–56, 2007.
 S.A. Bocanegra, A. Guerrero-Ruiz, S.R. de Miguel, O.A. Scelza, “Performance of PtSn catalysts supported on MAl2O4 (M: Mg or Zn) in n-butane dehydrogenation: characterization of the metallic phase”, Appl. Catal. A: Gen., vol.277, pp.11–22, 2004.
 R.D. Cortright, J.M. Hill, J.A. Dumesic, “Selective dehydrogenation of isobutane over supported Pt/Sn catalysts”, Catal. Today, vol.55, pp.213–223, 2000.
 M. Tasbihi, F. Feyzi, M.A. Amlashi, A.Z. Abdullah, A.R. Mohamed, “Effect of the addition of potassium and lithium in Pt–Sn/Al2O3 catalysts for the dehydrogenation of isobutene”, Fuel Proc. Tech., vol.88, pp. 883–889, 2007.
 Y. Zhang, Y. Zhou, A. Qiu, Y. Wang, Y. Xu, P. Wu, “Propane dehydrogenation on PtSn/ZSM-5 catalyst: Effect of tin as a promoter”, Catal. Comm., vol.7, pp. 860–866, 2006.
 T. Waku, J.A. Biscardi, E. Iglesia, “Catalytic dehydrogenation of alkanes on Pt/Na-(Fe)ZSM5 and staged O2 introduction for selective H2 removal”, J. Catal., vol. 222, pp.481–492, 2004.
 S.R. Vatcha, F. Trifiro, F. Cavani, in: D. Helius (Ed.), Oxidative Dehydrogenation and Alternative Dehydrogenation Processes, Catalytic study number 4992, OD, CA, USA, 1993.
 R.J. Rennard, J. Freel, “The role of sulfur in deactivation for propane dehydrogenation,” J. Catal., vol. 98, pp- 235, 1986.
 G. Aguilar-R´ıos, M.A. Valenzuela, H. Armendáriz, P. Salas, J.M. Dominguez, D. Acosta, I. Schifter, “Influence of vanadium on the physicochemical and catalytic properties of USHY zeolite and FCC catalyst”, Appl. Catal. A, Vol. 90, pp. 35, 1992.
 G. Aguilar-R´ıos, M.A. Valenzuela, P. Salas, H. Armendáriz, P. Bosch, G. Del Toro, R. Silva, V. Bert´ın, S. Castillo, A. Ramirez-Solis, I. Schifter, “Hydrogen interactions and catalytic properties of platinum-tin supported on zinc aluminate ,” Appl. Catal., vol. 127, pp.65, 1995.
 D. Roth, P. Gelin, M. Primet, E. Tena. “Catalytic behaviour of Cl-free and Cl-containing Pd/Al2O3 catalysts in the total oxidation of methane at low temperature,” Appl. Catal. A. Gen., vol. 203, pp.37-45, 2003.
 S. S. Peri, C. R. F. Lund, “The Role of Chlorine in Induction Periods During the Oxidation of Methane over Pd/SiO2”, J. Catal., vol.152, pp.410-414, 1995..
 E. Marceau, M. Che, J. Saint-Just, J. M. Tatibou, “Influence of chlorine ions in Pt/A12O3 catalysts for methane total oxidation”, Catal. Today, vol. 29, pp.415-419, 1996.
 N. W. Cant, D. E. Angove, M. J. Patterson, “In situ FT-IR study of NH3 formation during the reduction of NOx with propane on H/Cu-ZSM-5 in excess oxygen”, Catal. Today, vol. 44, pp.93-140, 1998.
 Application Report (Elementar Analyse system GmbH Germany) – Detection of chlorine in combination with traditional elemental analysis (AB-S-261012-E-01).
 M. Paulis, H. Peyrard, M. Montes, “Influence of Chlorine on the Activity and Stability of Pt/Al2O3 Catalysts in the Complete Oxidation of Toluene”, J. Catal., vol.199, pp.30-40, 2001.
 G. J. Arteaga, J. A. Anderson, C. H. Rochester, “Effects of Catalyst Regeneration with and without Chlorine on Heptane Reforming Reactions over Pt/Al2O3 and Pt–Sn/Al2O3”, J. Catal., vol. 187, pp.219-229, 1999.
 J. Salmones, J.A. Galicia, O. Mart´ınez, M.A. Valenzuela and G.Aguilar-R´ıos, “Propane dehydrogenation activity of Pt and Pt–Sn catalysts supported on magnesium aluminate: influence of steam and hydrogen”, n: Acta XVI Simp. Iberoam. Catal., vol. 1, pp. 277-282, 1998.
 E.J.W. Verwey, E.L. Heilmann, “Physical Properties and Cation Arrangement of Oxides with Spinel Structures I. Cation Arrangement in Spinels”, J. Chem. Phys., vol. 15, pp.174, 1947.
 Y.-L. Shan, Yu-Ling Shan, Ting Wang, Zhi-Jun Sui, Yi-An Zhu, Xing-Gui Zhou, “Hierarchical MgAl2O4 supported Pt-Sn as a highly thermostable catalyst for propane dehydrogenation”, Catal. Comm. vol. 84, pp.85–88, 2016.
 B. Li, Z. Xu, F. Jing, S.Luo, Wei Chu, Facile one-pot synthesized ordered mesoporous Mg-SBA-15 supported PtSn catalysts for propane dehydrogenation, Appl. Catal. A: Gen. vol. 533, pp.17-27, 2017.
 C. Dai, Y. Li, C. Ning, W.Zhang, X. Wang, C. Zhang, The influence of alumina phases on the performance of Pd/Al2O3 catalyst in selective hydrogenation of benzonitrile to benzylamine, Appl. Catal. A, Gen. vol. 545, pp.97–103, 2017.
 Z. Yiwei, Z.Yuming, S. Junjun, “Comparative study of bimetallic Pt-Sn catalysts supported on different supports for propane dehydrogenation”, 2014.
 Yu Shi, X.Li, Xin Rong, Bin Gu, H. Wei and C. Sun, Influence of support on the catalytic properties of Pt–Sn–K/q-Al2O3 for propane dehydrogenation, RSC Adv., vol. 7, pp. 1, 2017.
 S. Won Choi, W.G. Kim, J.S. So, J.S. Moore, Y. Liu, R.S. Dixit, J.G. Pendergast, C. Sievers, D.S. Sholl, S. Nair, and C. W. Jones, “Propane dehydrogenation catalyzed by gallosilicate MFI zeolites with perturbed acidity”, J.Catal., vol. 345, pp.113–123, 2017.
 T. Gjervan, R. Prestvik, B. Tøtdal, C. E. Lyman, A. Holmen. “The influence of the chlorine content on the bimetallic particle formation in Pt–Re/Al2O3 studied by STEM/EDX, TPR, H2 chemisorption and model reaction studies”, Catal. Today, vol. 65, pp.163-169, 2001.
 W.M.H. Sachtler, “Selectivity and rate of activity decline of bimetallic catalysts,” J.Mol.Catal., vol. 25, pp. 1-12, 1984.
 M. Sheintucha, O. Lirona, A. Riccab, V. Palma,” Propane dehydrogenation kinetics on supported Pt catalyst”, Appl. Catal. A: Gen., vol. 516, pp.17–29, 2016.
 W.Z. Li, L. Kovarik, D. Mei, et al., “Stable platinum nanoparticles on specific MgAl2O4 spinel facets at high temperatures in oxidizing atmospheres”, Nat. Comm., vol. 4, pp.2481, 2013.
 Y.L. Shan, Y.A. Zhu, Z.J. Sui, et al., “Insights into the effects of steam on propane dehydrogenation over a Pt/Al2O3 catalyst”, Catal. Sci. Technol., vol. 5, pp.399-4000, 2015.
 M. Fattahi, F. Khorasheh, S. Sahebdelfar, F.T. Zangeneh, K. Ganji, M. Saeedizad, “The effect of oxygenate additives on the performance of Pt–Sn/γ - Al2O3 catalyst in the propane dehydrogenation process”, Scientia Iranica, Vol.18, pp.1377– 1383, 2011.
 H. Armend´ariz A. Guzmán, J.AToledo, M.E Llanos, AVázquez, G Aguilar-Rı́os., “Isopentane dehydrogenation on Pt-Sn catalysts supported on Al-Mg-O mixed oxides: effect of Al/Mg atomic ratio”, App. Catal A: Gen., vol. 211, vol.69–80, 2001.
 Stepanova, L.N., Belskaya, O.B., Leont’eva, N.N., and Likholobov, V.A., Use of Platinum Carbonyl Complexes in the Synthesis of Pt/MgAlOx Catalysts, Kin. Catal., vol.54, pp.505-510, 2013.
 Belskaya, O.B., Gulyaeva, T.I., Talsi, V.P., Kazakov, M.O.,Nizovskii, A.I., Kalinkin, A.V., Bukhtiyarov, V.I., and Likholobov, V.A., “Formation of platinum sites on layered double hydroxide type basic supports: III. Effect of the mechanism of (PtCl6)2− complex binding to aluminum-magnesium layered double hydroxides on the properties of supported platinum in Pt/MgAlO x catalysts” Kinet. Catal., vol. 55, pp. 786. 2014.
 Mironenko, R.M., Belskaya, O.B., Talsi, V.P., Gulyaeva, T.I., Kazakov, M.O., Nizovskii, A.I.,Kalinkin, A.V., Bukhtiyarov, V.I., Lavrenov, A.V., and Likholobov, V.A., “Effect of γ-Al2O3 hydrothermal treatment on the formation and properties of platinum sites in Pt/γ-Al2O3 catalysts”., Appl. Catal., A, vol. 469, pp. 472, 2014.