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Effect of Si/Al Ratio on SSZ-13 Crystallization and Its Methanol-To-Olefins Catalytic Properties

Authors: Zhiqiang Xu, Hongfang Ma, Haitao Zhang, Weixin Qian, Weiyong Ying


SSZ-13 materials with different Si/Al ratio were prepared by varying the composition of aluminosilicate precursor solutions upon hydrothermal treatment at 150 °C. The Si/Al ratio of the initial system was systematically changed from 12.5 to infinity in order to study the limits of Al composition in precursor solutions for constructing CHA structure. The intermediates and final products were investigated by complementary techniques such as XRD, HRTEM, FESEM, and chemical analysis. NH3-TPD was used to study the Brønsted acidity of SSZ-13 samples with different Si/Al ratios. The effect of the Si/Al ratio on the precursor species, ultimate crystal size, morphology and yield was investigated. The results revealed that Al species determine the nucleation rate and the number of nuclei, which is tied to the morphology and yield of SSZ-13. The size of SSZ-13 increased and the yield decreased as the Si/Al ratio was improved. Varying Si/Al ratio of the initial system is a facile, commercially viable method of tailoring SSZ-13 crystal size and morphology. Furthermore, SSZ-13 materials with different Si/Al ratio were tested as catalysts for the methanol to olefins (MTO) reaction at 350 °C. SSZ-13 with the Si/Al ratio of 35 shows the best MTO catalytic performance.

Keywords: Crystallization, MTO, Si/Al ratio, SSZ-13.

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[1] P. Tian, Y. Wei, M. Ye, Z. Liu. “Methanol to Olefins (MTO): From Fundamentals to Commercialization,” in ACS Catalysis. vol 5, 2015, pp 1922-38.
[2] M. Stöcker. “Methanol-to-hydrocarbons: catalytic materials and their behavior1,” in Microporous and Mesoporous Materials. vol 29, 1999, pp 3-48.
[3] L. Wu, E. J. M. Hensen. “Comparison of mesoporous SSZ-13 and SAPO-34 zeolite catalysts for the methanol-to-olefins reaction,” in Catalysis Today. vol 235, 2014, pp 160-8.
[4] L. Wu, V. Degirmenci, P. C. M. M. Magusin, N. J. H. G. M. Lousberg, E. J. M. Hensen. “Mesoporous SSZ-13 zeolite prepared by a dual-template method with improved performance in the methanol-to-olefins reaction,” in Journal of Catalysis. vol 298, 2013, pp 27-40.
[5] E. Borodina, F. Meirer, I. Lezcano-González, M. Mokhtar, A. M. Asiri, S. A. Al-Thabaiti, B. M. Weckhuysen. “Influence of the Reaction Temperature on the Nature of the Active and Deactivating Species during Methanol to Olefins Conversion over H-SSZ-13,” in ACS Catalysis. vol 5, 2015, pp 992-1003.
[6] M. A. Deimund, L. Harrison, J. D. Lunn, Y. Liu, A. Malek, R. Shayib, M. E. Davis. “Effect of Heteroatom Concentration in SSZ-13 on the Methanol-to-Olefins Reaction,” in ACS Catalysis. vol 6, 2016, pp 542-50.
[7] C. Gonzalez-Arellano, A. Grau-Atienza, E. Serrano, A. A. Romero, J. Garcia-Martinez, R. Luque. “The role of mesoporosity and Si/Al ratio in the catalytic etherification of glycerol with benzyl alcohol using ZSM-5 zeolites,” in Journal of Molecular Catalysis A: Chemical. vol 406, 2015, pp 40-5.
[8] K. Sato, Y. Nishimura, N. Matsubayashi, M. Imamura, H. Shimada. “Structural changes of Y zeolites during ion exchange treatment: effects of Si/Al ratio of the starting NaY,” in Microporous and Mesoporous Materials. vol 59, 2003, pp 133-46.
[9] L. Shirazi, E. Jamshidi, M. R. Ghasemi. “The effect of Si/Al ratio of ZSM-5 zeolite on its morphology, acidity and crystal size,”in Crystal Research and Technology. vol 43, 2008, pp 1300-6.
[10] A. Simon-Masseron, J. P. Marques, J. M. Lopes, F. R. Ribeiro, I. Gener, M. Guisnet. “Influence of the Si/Al ratio and crystal size on the acidity and activity of HBEA zeolites,” in Applied Catalysis A: General. vol 316, 2007, pp 75-82.
[11] N. Nishiyama, M. Kawaguchi, Y. Hirota, D. Van Vu, Y. Egashira, K. Ueyama. “Size control of SAPO-34 crystals and their catalyst lifetime in the methanol-to-olefin reaction,” in Applied Catalysis A: General. vol 362, 2009, pp 193-9.
[12] S. R. Venna, M. A. Carreon. “Synthesis of SAPO-34 Crystals in the Presence of Crystal Growth Inhibitors,” in The Journal of Physical Chemistry B. vol 112, 2008, pp 16261-5.
[13] P. Wang, D. Yang, J. Hu, J. a. Xu, G. Lu. “Synthesis of SAPO-34 with small and tunable crystallite size by two-step hydrothermal crystallization and its catalytic performance for MTO reaction,” in Catalysis Today. vol 212, 2013, pp 62.e1-.e8.
[14] Z. Li, M. T. Navarro, J. Martínez-Triguero, J. Yu, A. Corma. “Synthesis of nano-SSZ-13 and its application in the reaction of methanol to olefins,” in Catalysis Science & Technology. vol 6, 2016, pp 5856-63.
[15] M. Kumar, H. Luo, Y. Roman-Leshkov, J. D. Rimer. “SSZ-13 Crystallization by Particle Attachment and Deterministic Pathways to Crystal Size Control,” in Journal of the American Chemical Society. vol 137, 2015, pp 13007-17.
[16] S. Bordiga, L. Regli, D. Cocina, C. Lamberti, M. Bjørgen, K. P. Lillerud. “Assessing the Acidity of High Silica Chabazite H−SSZ-13 by FTIR Using CO as Molecular Probe:  Comparison with H−SAPO-34,” in The Journal of Physical Chemistry B. vol 109, 2005, pp 2779-84.
[17] Q. Zhu, J. N. Kondo, R. Ohnuma, Y. Kubota, M. Yamaguchi, T. Tatsumi. “The study of methanol-to-olefin over proton type aluminosilicate CHA zeolites,” in Microporous and Mesoporous Materials. vol 112, 2008, pp 153-61.