对比SSZ-13和SAPO-34分子筛在甲醇制烯烃中的研究进展

doi:10.16085/j.issn.1000-6613.2017.01.021

摘要/Abstract

摘要： SSZ-13和SAPO-34是性能优异的甲醇制烯烃（methanol to olefins，MTO）催化剂。本文从酸性、积炭、烃池物种及其反应途径等方面介绍了SSZ-13和SAPO-34的酸强度和酸中心密度的差异及其对MTO反应催化性能的影响，综述了SSZ-13和SAPO-34在MTO中的催化反应机理和失活机理的研究进展。总结显示，尽管SSZ-13和SAPO-34都是CHA型拓扑结构，但SSZ-13的酸性强于SAPO-34，更有利于碳正离子的生成；与修边机理相比，侧链烷基化机理是更主要的反应途径，且SSZ-13的甲基化速率比SAPO-34高3个数量级；SSZ-13和SAPO-34的积炭速率和积炭物种存在差异，积炭行为受温度影响较大。从催化剂的角度，指出合理调控酸强度和酸中心密度、研制出能够抑制反应失活的催化剂结构、发展高产乙烯或者丙烯的特色MTO催化剂是以后的研究方向；从反应机理的角度，认为SSZ-13和SAPO-34在MTO反应中活性中间体的形成以及转化途径、活性物种到积炭物种的演变有待进一步研究。此外，如何在MTO反应过程中观察到高活性的反应中间体是今后研究的难点。

关键词: SSZ-13, SAPO-34, 分子筛, 甲醇制烯烃

Abstract: SSZ-13 and SAPO-34 are excellent zeolites for the catalyzation of MTO(methanol to olefins,MTO). From the respects of acidity,coke deposition,hydrocarbon pool species and the MTO reaction pathway,the differences of acid strength and acid site density between SSZ-13 and SAPO-34 and their effects on catalytic performance in MTO process are discussed. The catalyzation mechanism and the deactivation mechanism of SSZ-13 and SAPO-34 are also reviewed. It is found that although SSZ-13 and SAPO-34 have the same CHA framework topology,the acidity of SSZ-13 is stronger than that of SAPO-34,which is more favorable to produce carbonium ions. Compared with the paring mechanism,the side-chain methylation mechanism is more predominant and the methylation rate for SSZ-13 is approximately 3 orders of magnitude higher than that for SAPO-34. There are also some differences in the rate and nature of coke formation,which are influenced greatly by temperature. Therefore,from the perspective of the catalysts,controlling the acid strength and acid site density reasonably,developing a new type of structure that can prevent catalyst deactivation and preparing a typical catalyst of high yield of ethylene or propylene will be the future trend of research. Regarding the reaction mechanism,for SSZ-13 and SAPO-34,the formation of active intermediate compounds, their further transformation and the evolution of active species to coke species should be further studied. In addition,direct observation of the carbonium ions of high reactivity during the reaction of MTO is a great challenge.

Key words: SSZ-13, SAPO-34, molecular sieves, methanol to olefins(MTO)

中图分类号:

O643.36

赵飞, 李渊, 张岩, 谭小耀. 对比SSZ-13和SAPO-34分子筛在甲醇制烯烃中的研究进展[J]. 化工进展, 2017, 36(01): 166-173.

ZHAO Fei, LI Yuan, ZHANG Yan, TAN Xiaoyao. Research progress of SSZ-13 and SAPO-34 zeolites for methanol to olefins[J]. Chemical Industry and Engineering Progree, 2017, 36(01): 166-173.

参考文献

[1] STÖCKER M. Methanol-to-hydrocarbons:catalytic materials and their behavior[J]. Microporous and Mesoporous Materials,1999,29(1):3-48.
[2] HEMELSOET K,MYNSBRUGGE J V D,WISPELAERE K D,et al. Unraveling the reaction mechanisms governing methanol-to-olefins catalysis by theory and experiment[J]. ChemPhysChem,2013,14(8):1526-1545.
[3] LOK B M,MESSINA C A,PATTON R L,et al. Silicoaluminophosphate molecular sieves:another new class of microporous crystalline inorganic solids[J]. Journal of the American Chemical Society,1984,106(20):6092-6093.
[4] TIAN P,WEI Y,YE M,et al. Methanol to olefins (MTO):from fundamentals to commercialization[J]. ACS Catalysis,2015,5(3):1922-1938.
[5] ZONES S I. Zeolite SSZ-13 and its method of preparation:US4544538[P]. 1985-10-01.
[6] 杨博,郭翠梨,程景耀. SSZ-13分子筛的合成及应用进展[J]. 化工进展,2014,33(2):368-373. YANG B,GUO C L,CHENG J Y. Progress in synthesis and application of SSZ-13 zeolite[J]. Chemical Industry and Engineering Progress,2014,33(2):368-373.
[7] 代跃利,王磊,刘德阳. 用于催化甲醇制烯烃的SAPO-34分子筛合成的研究进展[J]. 化工进展,2015,34(3):731-737. DAI Y L,WANG L,LIU D Y. Progress in the synthesis of SAPO-34 molecular sieve for the conversion of methanol to olefins[J]. Chemical Industry and Engineering Progress,2015,34(3):731-737.
[8] WANG C M,WANG Y D,DU Y J,et al. Similarities and differences between aromatic-based and olefin-based cycles in H-SAPO-34 and H-SSZ-13 for methanol-to-olefins conversion:insights from energetic span model[J]. Catalysis Science & Technology,2015,5(9):4354-4364.
[9] LIU X Z,LIU Q,LU S W. Selenium-catalyzed reduction of 1-nitronaphthalene to 1-naphthylamine with CO/H₂O[J]. Journal of Catalysis,2004,25(8):597-598.
[10] YUEN L T,ZONES S,HARRIS T,et al. Product selectivity in methanol to hydrocarbon conversion for isostructural compositions of AFI and CHA molecular sieves[J]. Microporous Materials,1994,2(2):105-117.
[11] BLEKEN F,BJØRGEN M,PALUMBO L,et al. The effect of acid strength on the conversion of methanol to olefins over acidic microporous catalysts with the CHA topology[J]. Topics in Catalysis,2009,52(3):218-228.
[12] MARTINS G,BERLIER G,COLUCCIA S,et al. Revisiting the nature of the acidity in chabazite-related silicoaluminophosphates:combined FTIR and 29Si MAS NMR study[J]. The Journal of Physical Chemistry C,2007,111(1):330-339.
[13] QIAN Q,RUIZ-MARTíNEZ J,MOKHTAR M,et al. Single-catalyst particle spectroscopy of alcohol-to-olefins conversions:comparison between SAPO-34 and SSZ-13[J]. Catalysis today,2014,226:14-24.
[14] ZHU Q,KONDO J N,OHNUMA R,et al. The study of methanol-to-olefin over proton type aluminosilicate CHA zeolites[J]. Microporous and Mesoporous Materials,2008,112(1):153-161.
[15] DAHL I M,KOLBOE S. On the reaction mechanism for hydrocarbon formation from methanol over SAPO-34:Ⅰ. Isotopic labeling studies of the co-reaction of ethene and methanol[J]. Journal of Catalysis,1994,149(2):458-464.
[16] DAHL I M,KOLBOE S. On the reaction mechanism for hydrocarbon formation from methanol over SAPO-34:2. Isotopic labeling studies of the co-reaction of propene and methanol[J]. Journal of Catalysis,1996,161(1):304-309.
[17] ARSTAD B,KOLBOE S. The reactivity of molecules trapped within the SAPO-34 cavities in the methanol-to-hydrocarbons reaction[J]. Journal of the American Chemical Society,2001,123(33):8137-8138.
[18] SONG W,HAW J F,NICHOLAS J B,et al. Methylbenzenes are the organic reaction centers for methanol-to-olefin catalysis on HSAPO-34[J]. Journal of the American Chemical Society,2000,122(43):10726-10727.
[19] BJØRGEN M,BONINO F,KOLBOE S,et al. Spectroscopic evidence for a persistent benzenium cation in zeolite H-beta[J]. Journal of the American Chemical Society,2003,125(51):15863-15868.
[20] SVELLE S,JOENSEN F,NERLOV J,et al. Conversion of methanol into hydrocarbons over zeolite H-ZSM-5:ethene formation is mechanistically separated from the formation of higher alkenes[J]. Journal of the American Chemical Society,2006,128(46):14770-14771.
[21] CUI Z M,LIU Q,SONG W G,et al. Insights into the mechanism of methanol-to-olefin conversion at zeolites with systematically selected framework structures[J]. Angewandte Chemie(International Edition),2006,45(39):6512-6515.
[22] CUI Z M,LIU Q,MA Z,et al. Direct observation of olefin homologations on zeolite ZSM-22 and its implications to methanol to olefin conversion[J]. Journal of Catalysis,2008,258(1):83-86.
[23] SONG W,FU H,HAW J F. Selective synthesis of methylnaphthalenes in HSAPO-34 cages and their function as reaction centers in methanol-to-olefin catalysis[J]. The Journal of Physical Chemistry B,2001,105(51):12839-12843.
[24] DEIMUND M A,HARRISON L,LUNN J D,et al. Effect of heteroatom concentration in SSZ-13 on the methanol-to-olefins reaction[J]. ACS Catalysis,2015,6:542-550.
[25] SEO G,KIM J H,JANG H G. Methanol-to-olefin conversion over zeolite catalysts:active intermediates and deactivation[J]. Catalysis Surveys from Asia,2013,17(3/4):103-118.
[26] HEREIJGERS B P,BLEKEN F,NILSEN M H,et al. Product shape selectivity dominates the methanol-to-olefins(MTO)reaction over H-SAPO-34 catalysts[J]. Journal of Catalysis,2009,264(1):77-87.
[27] 陈景润. 笼结构小孔分子筛催化甲醇制烯烃反应机理研究[D]. 大连:中国科学院大连化学物理研究所,2014. CHEN Jingrun. The mechanism of methanol to olefins reaction catalyzed by small hole in cage structure[D]. Dalian:Dalian Institute of Chemical Physics,Chinese Academy of Sciences,2014.
[28] WANG C M,WANG Y D,XIE Z K. Insights into the reaction mechanism of methanol-to-olefins conversion in HSAPO-34 from first principles:are olefins themselves the dominating hydrocarbon pool species?[J]. Journal of Catalysis,2013,301:8-19.
[29] XU S,ZHENG A,WEI Y,et al. Direct observation of cyclic carbenium ions and their role in the catalytic cycle of the methanol-to-olefin reaction over chabazite zeolites[J]. Angewandte Chemie(International Edition),2013,52(44):11564-11568.
[30] HAW J F,SONG W,MARCUS D M,et al. The mechanism of methanol to hydrocarbon catalysis[J]. Accounts of Chemical Research,2003,36(5):317-326.
[31] WANG C M,WANG Y D,XIE Z K,et al. Methanol to olefin conversion on HSAPO-34 zeolite from periodic density functional theory calculations:a complete cycle of side chain hydrocarbon pool mechanism[J]. The Journal of Physical Chemistry C,2009,113(11):4584-4591.
[32] RUIZ-MARTÍNEZ J. Reaction temperature influences the nature of the active and deactivating species during methanol-to-olefins conversion over H-SSZ-13[C]//24th North American Catalysis Society Meeting,2015.
[33] BJØRGEN M,SVELLE S,JOENSEN F,et al. Conversion of methanol to hydrocarbons over zeolite H-ZSM-5:on the origin of the olefinic species[J]. Journal of Catalysis,2007,249(2):195-207.
[34] SVELLE S,OLSBYE U,JOENSEN F,et al. Conversion of methanol to alkenes over medium-and large-pore acidic zeolites:steric manipulation of the reaction intermediates governs the ethene/propene product selectivity[J]. The Journal of Physical Chemistry C,2007,111(49):17981-17984.
[35] MCCANN D M,LESTHAEGHE D,KLETNIEKS P W,et al. A complete catalytic cycle for supramolecular methanol-to-olefins conversion by linking theory with experiment[J]. Angewandte Chemie,2008,120(28):5257-5260.
[36] LESTHAEGHE D,MYNSBRUGGE J V D,VICHEL M,et al. Full theoretical cycle for both ethene and propene formation during methanol-to-olefin conversion in H-ZSM-5[J]. ChemCatChem,2011,3(1):208-212.
[37] HWANG A,PRIETO-CENTURION D,BHAN A. Isotopic tracer studies of methanol-to-olefins conversion over HSAPO-34:the role of the olefins-based catalytic cycle[J]. Journal of Catalysis,2016,337:52-56.
[38] SUN S,LI J. Kinetics of the entire methanol to olefins process over SAPO-34 catalyst[J]. Progress in Reaction Kinetics and Mechanism,2015,40(1):22-34.
[39] VAN SPEYBROECK V,HEMELSOET K,DE WISPELAERE K,et al. Mechanistic studies on chabazite-type methanol-to-olefin catalysts:insights from time-resolved UV/vis microspectroscopy combined with theoretical simulations[J]. ChemCatChem,2013,5(1):173-184.
[40] DAI W,WANG C,DYBALLA M,et al. Understanding the early stages of the methanol-to-olefin conversion on H-SAPO-34[J]. ACS Catalysis,2014,5(1):317-326.
[41] QI G,XIE Z,YANG W,et al. Behaviors of coke deposition on SAPO-34 catalyst during methanol conversion to light olefins[J]. Fuel Processing Technology,2007,88(5):437-441.
[42] CHEN D,MOLJORD K,HOLMEN A. A methanol to olefins review:diffusion,coke formation and deactivation on SAPO type catalysts[J]. Microporous and Mesoporous Materials,2012,164:239-250.
[43] LI J,WEI Y,CHEN J,et al. Observation of heptamethylbenzenium cation over SAPO-type molecular sieve DNL-6 under real MTO conversion conditions[J]. Journal of the American Chemical Society,2011,134(2):836-839.
[44] 胡浩,叶丽萍,应卫勇,等. SAPO-34分子筛催化剂上甲醇制烯烃反应的本征动力学[J]. 华东理工大学学报:社会科学版,2009(5):655-660. HU H,YE L P,YING W Y,et al. Intrinsic kinetics for methanol-to-olefin reaction based on SAPO-34 catalyst[J]. Journal of East China University of Science and Technology(Natural Science Edition)2009(5):655-660.
[45] MORES D,KORNATOWSKI J,OLSBYE U,et al. Coke formation during the methanol-to-olefin conversion:in situ microspectroscopy on individual H-ZSM-5 crystals with different Brønsted acidity[J]. Chemistry:A European Journal,2011,17(10):2874-2884.
[46] 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):185-190.
[47] GUISNET M,COSTA L,RIBEIRO F R. Prevention of zeolite deactivation by coking[J]. Journal of Molecular Catalysis A:Chemical,2009,305(1):69-83.
[48] DAI W,WANG X,WU G,et al. Methanol-to-olefin conversion on silicoaluminophosphate catalysts:effect of Brønsted acid sites and framework structures[J]. ACS catalysis,2011,1(4):292-299.
[49] DAI W,LI N,LI L,et al. Unexpected methanol-to-olefin conversion activity of low-silica aluminophosphate molecular sieves[J]. Catalysis Communications,2011,16(1):124-127.
[50] DAI W,WANG X,WU G,et al. Methanol-to-olefin conversion catalyzed by low-silica AlPO-34 with traces of Brønsted acid sites:combined catalytic and spectroscopic investigations[J]. ChemCatChem,2012,4(9):1428-1435.
[51] YING L,YE M,CHENG Y,et al. Characteristics of coke deposition over a SAPO-34 catalyst in the methanol-to-olefins reaction[J]. Petroleum Science and Technology,2015,33(9):984-991.
[52] BORODINA E,MEIRER F,LEZCANO-GONZÁLEZ I,et al. Influence of the reaction temperature on the nature of the active and deactivating species during methanol to olefins conversion over H-SSZ-13[J]. ACS Catalysis,2015,5(2):992-1003.
[53] ROSTAMI R B,GHAVIPOUR M,DI Z,et al. Study of coke deposition phenomena on the SAPO-34 catalyst and its effects on light olefin selectivity during the methanol to olefin reaction[J]. RSC Advances,2015,5(100):81965-81980.
[54] ZHU X. On the role of defect sites in the premature deactivation of SSZ-13 zeolite in the methanol-to-olefins reaction[C]//24th North American Catalysis Society Meeting,2015.
[55] ZHAO H,SHI S,WU J,et al. Charge compensation dominates the distribution of silica in SAPO-34[J]. Chinese Journal of Catalysis,2016,37(2):227-233.