HYDROCRACKING OF TETRALIN OVER PHOSPHOROUS AND NICKEL MODIFIED MORDENITE ZEOLITE CATALYSTS

Abstract

Abstract: A series of P, Ni modified mordenite zeolite catalysts were prepared via impregnation, and systematically characterized by using XRD, FT-IR, NH3-TPD, 27Al NMR, 31P NMR, and nitrogen adsorption-desorption techniques. The results demonstrated that P efficiently weakened the acid strength through the coordination with the framework aluminum of zeolites, and simultaneously formed abundant L acid center through dealumination. Meanwhile, the introduction of Ni interacted with framework aluminum to form twisted tetra coordinated aluminum structure, but does not affect significantly the acid properties of zeolites. In the hydrocracking process of tetralin over those modified zeolites, Ni promoter greatly improved the hydrocracking activity of tetralin through H spillover between metal and acid site, while P modified zeolites exhibited better anti-coking ability and catalyst stability. The catalyst modified by the combination of phosphorus and nickel has appropriate hydrogenation function and optimized acid distribution, which improves the conversion rate of tetralin and the selectivity of single cyclic aromatic hydrocarbon, and also improves the operational stability of the catalyst.

Key words: tetralin, hydrocracking, phosphorus, nickel, mordenite sieve

References

[1]Nylén U, Sassu L, Melis S, et al.Catalytic ring opening of naphthenic structures: Part I. From laboratory catalyst screening via pilot unit testing to industrial application for upgrading LCO into a high-quality diesel-blending component[J].Applied Catalysis A: General, 2006, 299(1):1-13 [2]黄新露.重芳烃高效转化生产轻芳烃技术[J].化工进展, 2013, 32(9):2263-2266 [3]李大东.加氢精制与加氢裂化[M]. 石油化学工业出版社, 北京, 1977. [4]蔡新恒, 龙军, 王乃鑫, 等.催化裂化柴油中多环芳烃加氢转化的分子水平表征[J].石油学报石油加工, 2017, 33(3):403-410 [5]高娜.催化柴油对柴油质量升级的影响及相关措施建议[J].当代石油石化, 2016, 24(7):34-40 [6]黄新露, 石培华, 于淼.适应用户需求的催化柴油加氢改质技术[J].当代化工, 2011, 40(7):702-705 [7]王丹, 宋金鹤, 韩志波, 温广明, 张文成.柴油加氢精制催化剂的开发及工业应用[J].石油化工, 2017, 46(2):102-108 [8]Blasco T, Corma A, Martínez-Triguero J.Hydrothermal stabilization of ZSM-5 catalytic-cracking additives by phosphorus addition[J].Journal of catalysis, 2006, 237(2):267-277 [9]Lercher J A, Rumplmayr G.Controlled decrease of acid strength by orthophosphoric acid on ZSM5[J].Applied catalysis, 1986, 25(1-2):215-222 [10]Zhuang J, Ma D, Yang G, et al.Solid-state MAS NMR studies on the hydrothermal stability of the zeolite catalysts for residual oil selective catalytic cracking[J].Journal of catalysis, 2004, 228(1):234-242 [11]Serra J M, Guillon E, Corma A.Optimizing the conversion of heavy reformate streams into xylenes with zeolite catalysts by using knowledge base high-throughput experimentation techniques[J].Journal of Catalysis, 2005, 232(2):342-354 [12]Roldán R, Romero F J, Jiménez C, et al.Transformation of mixtures of benzene and xylenes into toluene by transalkylation on zeolites[J].Applied Catalysis A: General, 2004, 266(2):203-210 [13]Halgeri A B, Das J.Novel catalytic aspects of beta zeolite for alkyl aromatics transformation[J].Applied Catalysis A: General, 1999, 181(2):347-354 [14]Sharma V, Crozier P A, Sharma R, et al.Direct observation of hydrogen spillover in Ni-loaded Pr-doped ceria[J].Catalysis today, 2012, 180(1):2-8 [15]Hincapie B O, Garces L J, Zhang Q, et al.Synthesis of mordenite nanocrystals[J].Microporous and mesoporous materials, 2004, 67(1):19-26 [16]Caeiro G, Magnoux P, Lopes J M, et al.Stabilization effect of phosphorus on steamed H-MFI zeolites[J].Applied Catalysis A: General, 2006, 314(2):160-171 [17]Van Der Bij H E, Weckhuysen B M.Local silico-aluminophosphate interfaces within phosphated H-ZSM-5 zeolites[J].Physical Chemistry Chemical Physics, 2014, 16(21):9892-9903 [18]Xue N, Chen X, Nie L, et al.Understanding the enhancement of catalytic performance for olefin cracking: Hydrothermally stable acids in PHZSM-5[J].Journal of catalysis, 2007, 248(1):20-28 [19]Yan Z, Ma D, Zhuang J, et al.On the acid-dealumination of USY zeolite: a solid state NMR investigation[J].Journal of Molecular Catalysis A: Chemical, 2003, 194(1-2):153-167 [20]Zhang B, Zhang Y, Hu Y, et al.Microexplosion under microwave irradiation: A facile approach to create mesopores in zeolites[J].Chemistry of Materials, 2016, 28(8):2757-2767 [21]Blasco T, Corma A, Martínez-Triguero J.Hydrothermal stabilization of ZSM-5 catalytic-cracking additives by phosphorus addition[J].Journal of catalysis, 2006, 237(2):267-277 [22]Xue N, Olindo R, Lercher J A.Impact of forming and modification with phosphoric acid on the acid sites of HZSM-5[J].The Journal of Physical Chemistry C, 2010, 114(37):15763-15770 [23]Damodaran K, Wiench J W, de Menezes S M C, et al.Modification of H-ZSM-5 zeolites with phosphorus2. Interaction between phosphorus and aluminum studied by solid-state NMR spectroscopy[J].Microporous and mesoporous materials, 2006, 95(1-3):296-305 [24]Caro J, Bülow M, Derewinski M, et al.NMR and IR studies of zeolite H-ZSM-5 modified with orthophosphoric acid[J].Journal of Catalysis, 1990, 124(2):367-375 [25]Decanio E C, Edwards J C, Scalzo T R, et al.FT-IR and solid-state NMR investigation of phosphorus promoted hydrotreating catalyst precursors[J].Journal of catalysis, 1991, 132(2):498-511 [26]Triwahyono S, Jalil A A, Mukti R R, et al.Hydrogen spillover behavior of ZnHZSM-5 showing catalytically active protonic acid sites in the isomerization of n-pentane[J].Applied Catalysis A: General, 2011, 407(1-2):91-99 [27]Occelli M L, Olivier J P, Auroux A.The location and effects of coke deposition in fluid cracking catalysts during gas oil cracking at microactivity test conditions[J].Journal of Catalysis, 2002, 209(2):385-393 [28]Dahl I M, Mostad H, Akporiaye D, et al.Structural and chemical influences on the MTO reaction: a comparison of chabazite and SAPO-34 as MTO catalysts[J].Microporous and Mesoporous Materials, 1999, 29(1-2):185-190 [29]Bibby D M, Milestone N B, Patterson J E, et al.Coke formation in zeolite ZSM-5[J].Journal of Catalysis, 1986, 97(2):493-502