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Research progress on modification of SAPO-34 as catalyst for methanol to olefins
Received date: 2022-01-26
Online published: 2022-07-14
Methanol to olefins（MTO） is considered to be the most promising technology route with coal or natural gas to produce olefins by replacing petroleum.SAPO-34 with CHA structure is the most ideal catalyst for MTO reaction to produce ethylene and propylene.However，aromatic hydrocarbon intermediates are limited by the eight membered ring microporous structure of SAPO-34，which blocks the pores of the catalyst and covers its acid sites，resulting in the carbon deposition and deactivation of the catalyst in the process of methanol conversion.In order to improve the life of SAPO-34 catalyst and the selectivity of low-carbon olefins，it is very important to improve mass transfer and delay coke deposition.The research progress on SAPO-34 in MTO reaction was summarized from the three aspects of constructing hierarchical pore structure，reducing the grain size and regulating molecular sieve acidity.Furthermore，the improvement and development direction of catalyst from particle size，pore size，acidity in the future were prospected.
Key words： SAPO-34; methanol to olefin; nanosize; hierarchical pore; catalyst
Chao JI , Luming WU , Bin LI , Jiazhong ZANG , Haibin YU . Research progress on modification of SAPO-34 as catalyst for methanol to olefins[J]. Inorganic Chemicals Industry, 2022 , 54(7) : 1 -9 . DOI: 10.19964/j.issn.1006-4990.2022-0051
| 1 | ST?CKER M.Methanol-to-hydrocarbons：Catalytic materials and their behavior［J］.Microporous and Mesoporous Materials，1999，29（1/2）：3-48. |
| 2 | LEE M K， KIM J， RYU J H，et al.Modeling of reaction and deactivation kinetics in methanol-to-olefins reaction on SAPO-34［J］.Industrial & Engineering Chemistry Research，2019，58（29）： |
| 2 | 13227-13238. |
| 3 | YANG Guoju， HAN Ji， HUANG Yujun，et al.Busting the efficiency of SAPO-34 catalysts for the methanol-to-olefin conversion by post-synthesis methods［J］.Chinese Journal of Chemical Engineering，2020，28（8）：2022-2027. |
| 4 | YANG Miao， FAN Dong， WEI Yingxu，et al.Recent progress in methanol-to-olefins（MTO） catalysts［J］.Advanced Materials，2019，31（50）.Doi：10.1002/adma.201902181 . |
| 5 | LIU Zhongmin， LIANG Juan.Methanol to olefin conversion catalysts［J］.Current Opinion in Solid State and Materials Science，1999，4（1）：80-84. |
| 6 | 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. |
| 7 | 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 Br?nsted acidity［J］.Chemistry：A European Journal，2011，17（10）：2874-2884. |
| 8 | YARULINA I， BAILLEUL S， PUSTOVARENKO A，et al.Suppression of the aromatic cycle in methanol-to-olefins reaction over ZSM- |
| 9 | by post-synthetic modification using calcium［J］.ChemCatChem，2016，8（19）：3057-3063. |
| 10 | VALTCHEV V， MAJANO G， MINTOVA S，et al.Tailored crystalline microporous materials by post-synthesis modification［J］.Che- mical Society Reviews，2013，42（1）：263-290. |
| 11 | BARBERA K， BONINO F， BORDIGA S，et al.Structure-deactivation relationship for ZSM-5 catalysts governed by framework defects［J］.Journal of Catalysis，2011，280（2）：196-205. |
| 12 | SHANG S C， CHEN W B， YANG L，et al.Effect of morphology and acidity control of Ni-SAPO-34 zeolite on catalytic performance of dimethyl ether to olefins［J］.Journal of Solid State Che- mistry，2021，303.Doi：10.1016/j.jssc.2021.122503 . |
| 13 | CHEN D， MOLJORD K， FUGLERUD T，et al.The effect of crystal size of SAPO-34 on the selectivity and deactivation of the MTO reaction［J］.Microporous and Mesoporous Materials，1999，29（1/2）：191-203. |
| 14 | NISHIYAMA N， KAWAGUCHI M， HIROTA Y，et al.Size control |
| 14 | SAPO- of 34 crystals and their catalyst lifetime in the methanol- |
| 14 | to-olefin reaction［J］.Applied Catalysis A：General，2009，362（1/2）：193-199. |
| 15 | JANG H G， MIN H K， LEE J K，et al.SAPO-34 and ZSM-5 nanocrystals′ size effects on their catalysis of methanol-to-olefin reactions［J］.Applied Catalysis A：General，2012，437/438：120- |
| 130 | |
| 17 | YANG Miao， TIAN Peng， WANG Chan，et al.A top-down approach |
| 17 | to prepare silicoaluminophosphate molecular sieve nanocrystals with improved catalytic activity［J］.Chemical Communications，2014，50（15）：1845-1847. |
| 16 | SUN Qiming， XIE Zaiku， YU Jihong.The state-of-the-art synthetic |
| 16 | strategies for SAPO- 34 zeolite catalysts in methanol-to-olefin con- |
| 16 | version［J］.National Science Review，2017，5（4）：542-558. |
| 19 | ZHONG Jiawei， HAN Jingfeng， WEI Yingxu，et al.Recent advan- |
| 19 | ces of the nano-hierarchical SAPO- 34 in the methanol-to-ole- |
| 19 | fin（MTO） reaction and other applications［J］.Catal.Sci.Technol.，2017，7（21）：4905-4923. |
| 18 | LEE Y J， BAEK S C， JUN K W.Methanol conversion on SAPO-34 catalysts prepared by mixed template method［J］.Applied Catalysis A：General，2007，329：130-136. |
| 21 | WANG Pengfei， LV Ailing， HU Jie，et al.The synthesis of SAPO-34 with mixed template and its catalytic performance for methanol to olefins reaction［J］.Microporous and Mesoporous Materials，2012，152：178-184. |
| 20 | MASOUMI S， TOWFIGHI J， MOHAMADALIZADEH A，et al.Tri- |
| 20 | templates synthesis of SAPO- 34 and its performance in MTO reaction by statistical design of experiments［J］.Applied Catalysis A：General，2015，493：103-111. |
| 23 | ASKARI S， SEDIGHI Z， HALLADJ R.Rapid synthesis of SAPO-34 nanocatalyst by dry gel conversion method templated with morphline：Investigating the effects of experimental parameters［J］.Microporous and Mesoporous Materials，2014，197：229-236. |
| 22 | HIROTA Y， MURATA K， TANAKA S，et al.Dry gel conversion synthesis of SAPO-34 nanocrystals［J］.Materials Chemistry and Physics，2010，123（2/3）：507-509. |
| 25 | RIMAZ S， HALLADJ R， ASKARI S.Synthesis of hierarchal SAPO-34 nano catalyst with dry gel conversion method in the presence of carbon nanotubes as a hard template［J］.Journal of Colloid and Interface Science，2016，464：137-146. |
| 24 | SUN Qiming， MA Yanhang， WANG Ning.High performance nano- |
| 24 | sheet-like silicoaluminophosphate molecular sieves：Synthesis，3D EDT structural analysis and MTO catalytic studies［J］.Journal of Materials Chemistry A：Materials for Energy and Sustainability，2014，2（42）：17828-17839. |
| 27 | áLVARO-MUN~OZ T， SASTRE E， MáRQUEZ-áLVAREZ C.Microwave-assisted synthesis of plate-like SAPO-34 nanocrystals with increased catalyst lifetime in the methanol-to-olefin reac- |
| 27 | tion［J］.Catalysis Science & Technology，2014，4：4330-4339. |
| 26 | YANG S T， KIM J Y， CHAE H J，et al.Microwave synthesis of mesoporous SAPO-34 with a hierarchical pore structure［J］.Materials Research Bulletin，2012，47（11）：3888-3892. |
| 29 | ASKARI S， HALLADJ R.Effects of ultrasound-related variables on sonochemically synthesized SAPO-34 nanoparticles［J］.Journal of Solid State Chemistry，2013，201：85-92. |
| 28 | LI Zhibin， MARTíNEZ-TRIGUERO J， CONCEPCIóN P，et al.Methanol to olefins：Activity and stability of nanosized SAPO-34 molecular sieves and control of selectivity by silicon distribu- |
| 28 | tion［J］.Physical Chemistry Chemical Physics：PCCP，2013， |
| 28 | 15（35）：14670-14680. |
| 31 | SUN Chao， WANG Yaquan， ZHAO Aijuan，et al.Synthesis of nano-sized SAPO-34 with morpholine-treated micrometer-seeds and their catalytic performance in methanol-to-olefin reactions［J］.Applied Catalysis A：General，2020，589.Doi：10.1016/j.apcata. 2019.117314 . |
| 30 | SUN Qiming， WANG Ning， GUO Guanqi，et al.Ultrafast synthesis of nano-sized zeolite SAPO-34 with excellent MTO catalytic performance［J］.Chemical Communications（Cambridge，Engla- nd），2015，51（91）：16397-16400. |
| 33 | SUN Qiming， WANG Ning， BAI Risheng，et al.Seeding induced nano-sized hierarchical SAPO-34 zeolites：Cost-effective synthesis and superior MTO performance［J］.Journal of Materials Chemistry A，2016，4（39）：14978-14982. |
| 32 | CHEN Guangrui， SUN Qiming， YU Jihong.Nanoseed-assisted syn- |
| 32 | thesis of nano-sized SAPO- 34 zeolites using morpholine as the sole template with superior MTO performance［J］.Chemical Communications，2017，53（100）：13328-13331. |
| 35 | SCHMIDT F， PAASCH S， BRUNNER E，et al.Carbon templated SAPO-34 with improved adsorption kinetics and catalytic performance in the MTO-reaction［J］.Microporous and Mesoporous Materials，2012，164：214-221. |
| 34 | JUN J W， JEON J， KIM C U，et al.Synthesis of mesoporous SAPO-34 molecular sieves and their applications in dehydration of butanols and ethanol［J］.Journal of Nanoscience and Nanotechnology，2013，13（4）：2782-2788. |
| 37 | SOLTANALI S， DARIAN J T.Synthesis of mesoporous SAPO-34 catalysts in the presence of MWCNT，CNF，and GO as hard templates in MTO process［J］.Powder Technology，2019，355：127- |
| 134 | |
| 36 | SUN Qiming， WANG Ning， XI Dongyang，et al.Organosilane sur- |
| 36 | factant-directed synthesis of hierarchical porous SAPO- 34 catalysts with excellent MTO performance［J］.Chemical Communications（Cambridge，England），2014，50（49）：6502-6505. |
| 40 | WANG Chan， YANG Miao， TIAN Peng，et al.Dual template-directed synthesis of SAPO-34 nanosheet assemblies with impro- |
| 40 | ved stability in the methanol to olefins reaction［J］.Journal of Materials Chemistry A，2015，3（10）：5608-5616. |
| 38 | CHEN Huiyong， WANG Manyun， YANG Mengfei，et al.Organosilane surfactant-directed synthesis of nanosheet-assembled SAPO- |
| 42 | zeolites with improved MTO catalytic performance［J］.Journal of Materials Science，2019，54（11）：8202-8215. |
| 39 | SINGH A K， YADAV R， A.Synthesis SAKTHIVEL，characterization，and catalytic application of mesoporous SAPO- 34 （MESO-SAPO-34） molecular sieves［J］.Microporous and Mesoporous Materials，2013，181：166-174. |
| 44 | KONG Lingtao， JIANG Zhang， ZHAO Jigang，et al.The synthesis of hierarchical SAPO-34 and its enhanced catalytic performance in chloromethane conversion to light olefins［J］.Catalysis Letters，2014，144（9）：1609-1616. |
| 41 | CUI Yu， ZHANG Qiang， HE Jie，et al.Pore-structure-mediated hierarchical SAPO-34：Facile synthesis，tunable nanostructure，and catalysis applications for the conversion of dimethyl ether into olefins［J］.Particuology，2013，11（4）：468-474. |
| 46 | RAZAVIAN M， FATEMI S.Fabrication of SAPO-34 with tuned mesopore structure［J］.Zeitschrift Für Anorganische Und Allgemeine Chemie，2014，640（10）：1855-1859. |
| 43 | WANG Fei， SUN Long， CHEN Chuanling，et al.Polyethyleneimine templated synthesis of hierarchical SAPO-34 zeolites with uniform mesopores［J］.RSC Adv.，2014，4（86）：46093-46096. |
| 48 | REN Shu， LIU Guojuan， WU Xian，et al.Enhanced MTO performance over acid treated hierarchical SAPO-34［J］.Chinese Journal of Catalysis，2017，38（1）：123-130. |
| 45 | JIN Wenlong， WANG Baojie， Pengfei TUO，et al.Selective desilication，mesopores formation，and MTO reaction enhancement via citric acid treatment of zeolite SAPO-34［J］.Industrial & Engineering Chemistry Research，2018，57（12）：4231-4236. |
| 50 | VERBOEKEND D， PéREZ-RAMíREZ J.Design of hierarchical zeolite catalysts by desilication［J］.Catalysis Science & Technology，2011，1（6）：879-890. |
| 47 | ABELLó S， BONILLA A， PéREZ-RAMíREZ J.Mesoporous ZSM-5 zeolite catalysts prepared by desilication with organic hydroxides and comparison with NaOH leaching［J］.Applied Catalysis A：General，2009，364（1/2）：191-198. |
| 52 | VERBOEKEND D， MILINA M， PéREZ-RAMíREZ J.Hierarchical silicoaluminophosphates by postsynthetic modification：Influence of topology，composition，and silicon distribution［J］.Chemistry of Materials，2014，26（15）：4552-4562. |
| 49 | LIU Xiu， REN Shu， ZENG Gaofeng，et al.Coke suppression in MTO over hierarchical SAPO-34 zeolites［J］.RSC Advances，2016，6（34）：28787-28791. |
| 54 | PAN Yingying， CHEN Guangrui， YANG Guoju，et al.Efficient po- |
| 54 | st-synthesis of hierarchical SAPO- 34 zeolites via organic amine etching under hydrothermal conditions and their enhanced MTO performance［J］.Inorganic Chemistry Frontiers，2019，6（5）：1299- |
| 54 | 1303. |
| 51 | VALTCHEV V， BALANZAT E， MAVRODINOVA V，et al.High energy ion irradiation-induced ordered macropores in zeolite crys- |
| 51 | tals［J］.Journal of the American Chemical Society，2011，133（46）：18950-18956. |
| 56 | P?ECH J， BOZHILOV K N， FALLAH J EL，et al.Fluoride etching opens the structure and strengthens the active sites of the layered ZSM-5 zeolite［J］.Microporous and Mesoporous Materials，2019，280：297-305. |
| 53 | QIN Zhengxing， HAFIZ L， SHEN Yanfeng，et al.Defect-engineered |
| 53 | zeolite porosity and accessibility［J］.Journal of Materials Chemistry A，2020，8（7）：3621-3631. |
| 58 | QIN Zhengxing， PINARD L， BENGHALEM M A，et al.Preparation of single-crystal“house-of-cards”-like ZSM-5 and their performance in ethanol-to-hydrocarbon conversion［J］.Chemistry of Materials，2019，31（13）：4639-4648. |
| 55 | CHEN Xiaoxin， VICENTE A， QIN Zhengxing，et al.The preparation of hierarchical SAPO-34 crystals via post-synthesis fluoride etching［J］.Chemical Communications（Cambridge，England），2016，52（17）：3512-3515. |
| 60 | CHEN Xiaoxin， XI Dongyang， SUN Qiming，et al.A top-down approach to hierarchical SAPO-34 zeolites with improved selectivity of olefin［J］.Microporous and Mesoporous Materials，2016，234：401-408. |
| 57 | WU Jinxiong， ZHAO Huiru， LI Niu，et al.Fluorine-free crystallization of triclinic AlPO4-34［J］.CrystEngComm，2012，14（24）：8671-8676. |
| 62 | DAI Weili， CAO Ge， YANG Liu，et al.Insights into the catalytic cycle and activity of methanol-to-olefin conversion over low-silica AlPO-34 zeolites with controllable Br?nsted acid density［J］.Catalysis Science & Technology，2017，7（3）：607-618. |
| 59 | GAO Beibei， YANG Miao， QIAO Yuyan，et al.A low-temperature |
| 59 | approach to synthesize low-silica SAPO- 34 nanocrystals and their |
| 59 | application in the methanol-to-olefins（MTO） reaction［J］.Catalysis Science & Technology，2016，6（20）：7569-7578. |
| 64 | ZHONG Jiawei， HAN Jingfeng， WEI Yingxu，et al.Enhancing ethylene selectivity in MTO reaction by incorporating metal species in the cavity of SAPO-34 catalysts［J］.Chinese Journal of Catalysis，2018，39（11）：1821-1831. |
| 61 | JIANG Zhang， SHEN Benxian， ZHAO Jigang，et al.Enhancement of catalytic performances for the conversion of chloromethane to light olefins over SAPO-34 by modification with metal chlori |
| 61 | de［J］.Industrial & Engineering Chemistry Research，2015， |
| 61 | 54（49）：12293-12302. |
| 66 | MIRZA K， GHADIRI M， HAGHIGHI M，et al.Hydrothermal synthesize of modified Fe，Ag and K-SAPO-34 nanostructured catalysts used in methanol conversion to light olefins［J］.Microporous and Mesoporous Materials，2018，260：155-165. |
| 63 | SALIH H， MURAZA O， ABUSSAUD B，et al.Catalytic enhancement of SAPO-34 for methanol conversion to light olefins using in situ metal incorporation［J］.Industrial & Engineering Chemistry Research，2018，57（19）：6639-6646. |
| 68 | DI Chunyu， LI Xiaofeng， WANG Ping，et al.Green and efficient dry gel conversion synthesis of SAPO-34 catalyst with plate-like morphology［J］.Petroleum Science，2017，14（1）：203-213. |
| 65 | SUN Chao， WANG Yaquan， CHEN Hengbao，et al.Seed-assisted synthesis of hierarchical SAPO-18/34 intergrowth and SAPO-34 zeolites and their catalytic performance for the methanol-to-olefin reaction［J］.Catalysis Today，2020，355：188-198. |
| 70 | HUANG Huiwen， YU Mengyun， ZHANG Qiang，et al.Insights into NH4-SAPO-34 preparation procedure：Effect of the number of ammonium exchange times on catalytic performance of Zn-modified SAPO-34 zeolite for methanol to olefin reaction［J］.Microporous and Mesoporous Materials，2020，295.Doi：10.1016/j.micromeso.2019.109971 . |
| 67 | MA Mingming， ZHAO Xiaoyu， WANG Xiaotong，et al.Synthesis of small-sized SAPO-34 assisted by pluronic F127 nonionic surfactant and its catalytic performance for methanol to olefins （MTO）［J］.Catalysis Communications，2020，133.Doi：10.1016/j.catcom.2019.105839 . |
| 72 | LIU Yuanlin， WANG Lingzhi， ZHANG Jinlong.Preparation of floral mesoporous SAPO-34 with the aid of fluoride ion［J］.Materials Letters，2011，65（14）：2209-2212. |
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