四甲基氢氧化铵辅助合成SSZ-13分子筛及其甲醇制烯烃的催化性能
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摘要
以N,N,N-三甲基金刚烷氢氧化铵(TMAdaOH)为模板剂合成SSZ-13分子筛,探讨有机季铵碱四甲基氢氧化铵(TMAOH)取代体系中的氢氧化钠(NaOH)对SSZ-13分子筛合成的影响,采用X射线衍射(XRD)、扫描电子显微镜(SEM)、傅里叶红外光谱(FT-IR)、热重-微商热重(TG-DTG)、NH_3程序升温脱附(NH_3-TPD)和N_2吸附-脱附等手段对合成样品进行表征,分析合成凝胶的硅/铝比对SSZ-13分子筛的结晶度、比表面积、酸量等的影响,并考察了SSZ-13分子筛在甲醇制烯烃(MTO)反应中的催化性能。结果表明,当有机碱TMAOH完全取代NaOH时,合成样品的结晶度从92.68%提高至108.75%,且合成体系的硅/铝比(n(SiO_2)/n(Al_2O_3))范围可以显著拓宽(33～100),合成产物的硅/铝比也相应提高,比表面积可增大至约800 m~2/g,强酸量减少,SSZ-13分子筛样品在MTO催化反应中表现出了更长的寿命和更高的双烯(乙烯+丙烯)选择性。
Effects of the replacement of NaOH by tetramethylammonium hydroxide(TMAOH) on the synthesis of SSZ-13 molecular sieve were investigated in the presence of the N,N,N-trimethyl-1-adamantanammonium hydroxide(TMAdaOH) as structure-directing agent. The influences of silica/alumina ratios in synthetic gel on the structural, textural and acidic properties of SSZ-13 molecular sieve were investigated. The obtained SSZ-13 molecular sieves were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), Fourier transform infrared(FT-IR), thermogravimetry-derivative thermogravimetry(TG-DTG), NH_3-temperature programmed desorption(NH_3-TPD) and N_2 physisorption techniques. The catalytic performance of the SSZ-13 molecular sieves was evaluated by methanol to olefins(MTO) reaction. Results demonstrate that the crystallinity of the product significantly increases from 92.68% to 108.75% when the organic alkali TMAOH completely take place of the inorganic NaOH. The silica/alumina ratio in synthesis gel ranges from 33 to 100, thus accordingly enhancing the silica/alumina ratio of molecular sieves. Meanwhile, these materials possess large BET surface area of 800 m~2/g and low strong acid amount, therefore exhibit longer catalytic lifetime and higher light olefin(ethylene + propylene) selectivity than conventional SSZ-13 catalysts in MTO reaction.
Effects of the replacement of NaOH by tetramethylammonium hydroxide(TMAOH) on the synthesis of SSZ-13 molecular sieve were investigated in the presence of the N,N,N-trimethyl-1-adamantanammonium hydroxide(TMAdaOH) as structure-directing agent. The influences of silica/alumina ratios in synthetic gel on the structural, textural and acidic properties of SSZ-13 molecular sieve were investigated. The obtained SSZ-13 molecular sieves were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), Fourier transform infrared(FT-IR), thermogravimetry-derivative thermogravimetry(TG-DTG), NH_3-temperature programmed desorption(NH_3-TPD) and N_2 physisorption techniques. The catalytic performance of the SSZ-13 molecular sieves was evaluated by methanol to olefins(MTO) reaction. Results demonstrate that the crystallinity of the product significantly increases from 92.68% to 108.75% when the organic alkali TMAOH completely take place of the inorganic NaOH. The silica/alumina ratio in synthesis gel ranges from 33 to 100, thus accordingly enhancing the silica/alumina ratio of molecular sieves. Meanwhile, these materials possess large BET surface area of 800 m~2/g and low strong acid amount, therefore exhibit longer catalytic lifetime and higher light olefin(ethylene + propylene) selectivity than conventional SSZ-13 catalysts in MTO reaction.
引文
[1]刘中民.甲醇制烯烃[M].北京:科学出版社,2015.
[2]邢爱华,岳国,朱伟平,等.甲醇制烯烃典型技术最新研究进展Ⅰ催化剂开发进展[J].现代化工,2010,30(9):18-24.(XING Aihua,YUE Guo,ZHU Weiping,et al.Latest advances in typical methanol-to-olefins technology I The progress in catalyst development[J].Modern Chemical Industry,2010,30(9):18-24.)
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[12]SHISHKIN A,KANNISTO H,CARLSSON P A,et al.Synthesis and functionalization of SSZ-13as an NH3-SCR catalyst[J].Catalscitechnol,Catalysis Science&Technology,2014,4(11):3917-3926.
[13]ZHU Q,KONDO J N,OHNUMA R,et al.The study of methanol-to-olefin over proton type aluminosilicate CHA zeolites[J].Microporous&Mesoporous Materials,2008,112(1):153-161.
[14]BORODINA E,MEIRER F,LEZCANOGONZLEZ 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,2017,7(8):5268-5281.
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[16]MARTN N,MOLINER M,CORMA A.High yield synthesis of high-silica chabazite by combining the role of zeolite precursors and tetraethylammonium:SCR of NOx[J].Chemical Communications,2015,51(49):9965-9968.
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[19]DELPRATO F,DELMOTTE L,GUTH J L,et al.Synthesis of new silica-rich cubic and hexagonal faujasites using crown-etherbased supramolecules as templates[J].Zeolites,1990,10(6):546-552.
[20]宁永成.有机化合物结构鉴定与有机波谱学[M].第2版.北京:科学出版社,2000.
[21]JAEGER P A J N I.Zeolite Chemistry and Catalysis[M].Washington:American Chemical Society,1991.
[22]VENNA S R,CARREON M A.Synthesis of SAPO-34crystals in the presence of crystal growth inhibitors[J].Journal of Physical Chemistry B,2008,112(51):16261-16265.
[23]BJ?RGEN M,AKYALCIN S,OLSBYE U,et al.Methanol to hydrocarbons over large cavity zeolites:Toward a unified description of catalyst deactivation and the reaction mechanism[J].Journal of Catalysis,2010,275(1):170-180.
[24]陈连璋.沸石分子筛催化[M].大连:大连理工大学出版社,1990.
[25]王桂茹.催化剂与催化作用[M].大连:大连理工大学出版社,2015.
[26]LIU X Z,LIU Q,LU S W.Selenium-catalyzed reduction of 1-nitronaphthalene to 1-naphthylamine with CO/H2O[J].Chinese Journal of Catalysis,2004,25(8):597-598.
[27]李志宏,李晓峰,狄春雨,等.蒸汽相体系下合成SAPO-34分子筛及其MTO催化性能[J].石油学报(石油加工),2017,33(6):1192-1201.(LI Zhihong,LI Xiaofeng,DI Chunyu,et al.Synthesis of SAPO-34molecular sieve by vapor-phase transport and its catalytic performance in methanol to olefin(MTO)reaction[J].Acta Petrolei Sinica(Petroleum Processing Section),2017,33(6):1192-1201.)
[28]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.
[29]GUISNET M,COSTA L,RIBEIRO F R.Prevention of zeolite deactivation by coking[J].Journal of Molecular Catalysis A Chemical,2009,305(1/2):69-83.
[30]DAHL I M,KOLBOE S.On the reaction mechanism for hydrocarbon formation from methanol over SAPO-34I Isotopic labeling studies of the co-reaction of ethene and methanol[J].Journal of Catalysis,1994,149(2):458-464.
[31]XU S,ZHENG D 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,2013,125(44):11564-11568.
[32]LESTHAEGHE D,VANDICHEL M,WAROQUIER D M.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.
[2]邢爱华,岳国,朱伟平,等.甲醇制烯烃典型技术最新研究进展Ⅰ催化剂开发进展[J].现代化工,2010,30(9):18-24.(XING Aihua,YUE Guo,ZHU Weiping,et al.Latest advances in typical methanol-to-olefins technology I The progress in catalyst development[J].Modern Chemical Industry,2010,30(9):18-24.)
[3]CHANG C.Methanol conversion to light olefins[J].Catalysis Reviews,1984,26(3/4):323-345.
[4]CHANG C D,LANG W H,SMITH R L.The conversion of methanol and other O-compounds to hydrocarbons over zeolite catalystsⅡPressure effects[J].Journal of Catalysis,1979,47(2):249-59.
[5]BLEKEN F,BJRGEN M,PALUMBO L,et al.The effect of acid strength on the conversion of methanol to olefins over acidic microporous catalysts with the CHAtopology[J].Topics in Catalysis,2009,52(3):218-228.
[6]HEREIJGERS B P C,BLEKEN F,NILSEN M H,et al.Product shape selectivity dominates the methanolto-olefins(MTO)reaction over H-SAPO-34catalysts[J].Journal of Catalysis,2009,264(1):77-87.
[7]ZHU Q J,KONDO J N,TATSUMI T,et al.A comparative study of methanol to olefin over CHA and MTF zeolites[J].Journal of Physical Chemistry C,2007,111(14):5409-5415.
[8]ZONES S I.Zeolite SSZ-13 and its method of preparation:US 4544538A[P].1985.
[9]赵飞,李渊,王文婷,等.Cu-SSZ-13分子筛的制备及应用进展[J].精细石油化工,2016,33(4):69-75.(ZHAO Fei,LI Yuan,WANG Wenting,et al.Progress in synthesis and applicaton of Cu-SSZ-13molecular sieve[J].Speciality Petrochemicals,2016,33(4):69-75.)
[10]KWAK J H,TONKYN R G,KIM D H,et al.Excellent activity and selectivity of Cu-SSZ-13in the selective catalytic reduction of NOx with NH3[J].Journal of Catalysis,2010,275(2):187-190.
[11]REGLI L,BORDIGA S,BUSCO C,et al.Functionalization of zeolitic cavities:Grafting NH2groups in framework T sites of B-SSZ-13-A way to obtain basic solids catalysts?[J].Journal of the American Chemical Society,2007,129(40):12131-12140.
[12]SHISHKIN A,KANNISTO H,CARLSSON P A,et al.Synthesis and functionalization of SSZ-13as an NH3-SCR catalyst[J].Catalscitechnol,Catalysis Science&Technology,2014,4(11):3917-3926.
[13]ZHU Q,KONDO J N,OHNUMA R,et al.The study of methanol-to-olefin over proton type aluminosilicate CHA zeolites[J].Microporous&Mesoporous Materials,2008,112(1):153-161.
[14]BORODINA E,MEIRER F,LEZCANOGONZLEZ 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,2017,7(8):5268-5281.
[15]POURMAHDI Z,MAGHSOUDI H.Adsorption isotherms of carbon dioxide and methane on CHA-type zeolite synthesized in fluoride medium[J].Adsorption Journal of the International Adsorption Society,2017,23(10):1-9.
[16]MARTN N,MOLINER M,CORMA A.High yield synthesis of high-silica chabazite by combining the role of zeolite precursors and tetraethylammonium:SCR of NOx[J].Chemical Communications,2015,51(49):9965-9968.
[17]SCHMIDT J E,FU D,DEEM M W,et al.Templateframework interactions in tetraethylammonium-directed zeolite synthesis[J].Angewandte Chemie,Angewandte Chemie-International Edition,2016,55(52):16044-16048.
[18]ITAKURA M,INOUE T,TAKAHASHI A,et al.Synthesis of high-silica CHA zeolite from FAU zeolite in the presence of benzyltrimethylammonium hydroxide[J].Chemistry Letters,2008,37(9):908-909.
[19]DELPRATO F,DELMOTTE L,GUTH J L,et al.Synthesis of new silica-rich cubic and hexagonal faujasites using crown-etherbased supramolecules as templates[J].Zeolites,1990,10(6):546-552.
[20]宁永成.有机化合物结构鉴定与有机波谱学[M].第2版.北京:科学出版社,2000.
[21]JAEGER P A J N I.Zeolite Chemistry and Catalysis[M].Washington:American Chemical Society,1991.
[22]VENNA S R,CARREON M A.Synthesis of SAPO-34crystals in the presence of crystal growth inhibitors[J].Journal of Physical Chemistry B,2008,112(51):16261-16265.
[23]BJ?RGEN M,AKYALCIN S,OLSBYE U,et al.Methanol to hydrocarbons over large cavity zeolites:Toward a unified description of catalyst deactivation and the reaction mechanism[J].Journal of Catalysis,2010,275(1):170-180.
[24]陈连璋.沸石分子筛催化[M].大连:大连理工大学出版社,1990.
[25]王桂茹.催化剂与催化作用[M].大连:大连理工大学出版社,2015.
[26]LIU X Z,LIU Q,LU S W.Selenium-catalyzed reduction of 1-nitronaphthalene to 1-naphthylamine with CO/H2O[J].Chinese Journal of Catalysis,2004,25(8):597-598.
[27]李志宏,李晓峰,狄春雨,等.蒸汽相体系下合成SAPO-34分子筛及其MTO催化性能[J].石油学报(石油加工),2017,33(6):1192-1201.(LI Zhihong,LI Xiaofeng,DI Chunyu,et al.Synthesis of SAPO-34molecular sieve by vapor-phase transport and its catalytic performance in methanol to olefin(MTO)reaction[J].Acta Petrolei Sinica(Petroleum Processing Section),2017,33(6):1192-1201.)
[28]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.
[29]GUISNET M,COSTA L,RIBEIRO F R.Prevention of zeolite deactivation by coking[J].Journal of Molecular Catalysis A Chemical,2009,305(1/2):69-83.
[30]DAHL I M,KOLBOE S.On the reaction mechanism for hydrocarbon formation from methanol over SAPO-34I Isotopic labeling studies of the co-reaction of ethene and methanol[J].Journal of Catalysis,1994,149(2):458-464.
[31]XU S,ZHENG D 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,2013,125(44):11564-11568.
[32]LESTHAEGHE D,VANDICHEL M,WAROQUIER D M.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.