随着低碳烯烃需求量的增加,甲醇制烯烃(MTO)成为由非石油资源制取低碳烯烃的关键技术,其中沸石由于具有可调节的酸度、有序的微孔结构和较好的择型性能而被广泛用作MTO反应催化剂.ITQ-13沸石(ITH拓扑结构)由于其独特的九元环结构在MTO...随着低碳烯烃需求量的增加,甲醇制烯烃(MTO)成为由非石油资源制取低碳烯烃的关键技术,其中沸石由于具有可调节的酸度、有序的微孔结构和较好的择型性能而被广泛用作MTO反应催化剂.ITQ-13沸石(ITH拓扑结构)由于其独特的九元环结构在MTO反应中表现出较好的丙烯选择性和反应寿命,引起了广泛关注.研究表明,分子筛的酸中心分布与MTO反应性能密切相关,因此,研究ITQ-13沸石中铝分布与MTO反应性能的关系,对进一步提升其MTO催化性能具有重要意义.本文分别以与ITH具有共同基本结构单元(双四元环,D4Rs)的LTA沸石(LTA-ITH)和薄水铝石(C-ITH)为铝源,合成了两类铝硅酸盐ITH沸石.X射线衍射、扫描电子显微镜以及氮气吸脱附表征结果表明,这两类分子筛具有相似的片状形貌和微孔性质.氨气程序升温脱附结果表明,具有相近硅铝比的两类ITH沸石具有相近的酸量.进一步采用27Al魔角旋转核磁共振(MAS NMR)、密度泛函理论计算和1-己烯裂解反应对两类ITH分子筛的铝分布进行研究.结果表明,两类分子筛具有不同的铝分布,LTA-ITH中有更多的铝进入ITH的正弦孔道与直孔道,而C-ITH中有更多的铝分布在交叉孔道.当前,研究者普遍认为MTO反应过程遵循双循环烃池机理,ITH交叉孔道由于具有较大的空间,相比于正弦孔道和直孔道,更有利于芳烃循环中间体的产生,从而有利于形成芳烃循环产物(乙烯),而正弦孔道和直孔道却更有利于烯烃循环过程,导致产生更多的丙烯.对两类ITH进行了MTO催化性能测试,结果表明,LTA-ITH比C-ITH表现出更高的丙烯选择性,并且表现出更高的丙烯与乙烯的比率,表明其烯烃循环过程得到加强,这与^(27)Al MAS NMR以及1-己烯裂解反应得到的结论一致,进一步证明ITH分子筛的铝分布得到有效调控.综上,本文阐明了ITH沸石中铝分布与其反应性能的关系,为调整沸石骨架中的Al位点提供一种新策略,为未来制备高效的MTO沸石基催化剂提供参考.展开更多
Oxide-Zeolite(OX-ZEO) bifunctional catalyst design concept has been exemplified in several processes to direct conversion syngas to value-added chemicals and fuels such as mixed light olefins, ethylene, aromatics and ...Oxide-Zeolite(OX-ZEO) bifunctional catalyst design concept has been exemplified in several processes to direct conversion syngas to value-added chemicals and fuels such as mixed light olefins, ethylene, aromatics and gasoline.Herein we demonstrate that the product can be steered toward liquefied petroleum gas(LPG) with a selectivity up to 89% in hydrocarbons especially propane selectivity reaching 80% at CO conversion of 63% using ZnCrOx-H-SSZ-39 catalyst.Interestingly, the quantity of the acid sites of SSZ-39 does not influence obviously the hydrocarbon distribution but the strength is crucial for selective formation of propane.This finding provides an alternative route of LPG synthesis from a variety of carbon resources via syngas.展开更多
SSZ-39 zeolite with AEI framework structure is a good catalyst candidate for the methanol-to-olefins(MTO)reaction.However,the diffusion limitation and coke formation often results in fast deactivation of the SSZ-39 ze...SSZ-39 zeolite with AEI framework structure is a good catalyst candidate for the methanol-to-olefins(MTO)reaction.However,the diffusion limitation and coke formation often results in fast deactivation of the SSZ-39 zeolite catalyst.One solution for this challenge is to introduce mesoporosity in the SSZ-39 zeolite.Herein,we report the synthesis of mesoporous SSZ-39 zeolite using an organosilane surfactant,,-dimethyl--(3-(trimethoxysilyl)propyl)octan-1-aminium chloride,as a mesopore template and,-dimethyl--2,6-dimethylpiperidinium as a micropore template.The obtained zeolites were characterized by X-ray diffraction,N sorption,scanning electron microscopy,temperature programmed desorption of ammonia,and magic angle spinning nuclear magnetic resonance of Al.The results show that the mesoporous SSZ-39 zeolite has high crystallinity,meso/microporosity,high surface area,cuboid morphology,and abundant acidic sites.More importantly,this mesoporous SSZ-39 zeolite exhibits enhanced catalyst lifetime in the MTO reaction due to the presence of mesoporosity for fast mass transfer,compared with a conventional SSZ-39 zeolite without mesoporosity.展开更多
文摘随着低碳烯烃需求量的增加,甲醇制烯烃(MTO)成为由非石油资源制取低碳烯烃的关键技术,其中沸石由于具有可调节的酸度、有序的微孔结构和较好的择型性能而被广泛用作MTO反应催化剂.ITQ-13沸石(ITH拓扑结构)由于其独特的九元环结构在MTO反应中表现出较好的丙烯选择性和反应寿命,引起了广泛关注.研究表明,分子筛的酸中心分布与MTO反应性能密切相关,因此,研究ITQ-13沸石中铝分布与MTO反应性能的关系,对进一步提升其MTO催化性能具有重要意义.本文分别以与ITH具有共同基本结构单元(双四元环,D4Rs)的LTA沸石(LTA-ITH)和薄水铝石(C-ITH)为铝源,合成了两类铝硅酸盐ITH沸石.X射线衍射、扫描电子显微镜以及氮气吸脱附表征结果表明,这两类分子筛具有相似的片状形貌和微孔性质.氨气程序升温脱附结果表明,具有相近硅铝比的两类ITH沸石具有相近的酸量.进一步采用27Al魔角旋转核磁共振(MAS NMR)、密度泛函理论计算和1-己烯裂解反应对两类ITH分子筛的铝分布进行研究.结果表明,两类分子筛具有不同的铝分布,LTA-ITH中有更多的铝进入ITH的正弦孔道与直孔道,而C-ITH中有更多的铝分布在交叉孔道.当前,研究者普遍认为MTO反应过程遵循双循环烃池机理,ITH交叉孔道由于具有较大的空间,相比于正弦孔道和直孔道,更有利于芳烃循环中间体的产生,从而有利于形成芳烃循环产物(乙烯),而正弦孔道和直孔道却更有利于烯烃循环过程,导致产生更多的丙烯.对两类ITH进行了MTO催化性能测试,结果表明,LTA-ITH比C-ITH表现出更高的丙烯选择性,并且表现出更高的丙烯与乙烯的比率,表明其烯烃循环过程得到加强,这与^(27)Al MAS NMR以及1-己烯裂解反应得到的结论一致,进一步证明ITH分子筛的铝分布得到有效调控.综上,本文阐明了ITH沸石中铝分布与其反应性能的关系,为调整沸石骨架中的Al位点提供一种新策略,为未来制备高效的MTO沸石基催化剂提供参考.
基金supported by the Ministry of Science and Technology of China (No.2017YFB0602201)the Chinese Academy of Sciences (XDA21020400)+2 种基金the National Natural Science Foundation of China (Grant nos.91645204, 21425312 and 21621063)the Youth Innovation Promotion Association of Chinese Academy of Sciences (2019184)the INCOE (International Network of Centers of Excellence) project coordinated by BASF SE
文摘Oxide-Zeolite(OX-ZEO) bifunctional catalyst design concept has been exemplified in several processes to direct conversion syngas to value-added chemicals and fuels such as mixed light olefins, ethylene, aromatics and gasoline.Herein we demonstrate that the product can be steered toward liquefied petroleum gas(LPG) with a selectivity up to 89% in hydrocarbons especially propane selectivity reaching 80% at CO conversion of 63% using ZnCrOx-H-SSZ-39 catalyst.Interestingly, the quantity of the acid sites of SSZ-39 does not influence obviously the hydrocarbon distribution but the strength is crucial for selective formation of propane.This finding provides an alternative route of LPG synthesis from a variety of carbon resources via syngas.
基金the National Key Research and Development Program of China(Grant No.2017YFC0211101)the National Natural Science Foundation of China(Grant Nos.21333009,21703203 and 21673205).
文摘SSZ-39 zeolite with AEI framework structure is a good catalyst candidate for the methanol-to-olefins(MTO)reaction.However,the diffusion limitation and coke formation often results in fast deactivation of the SSZ-39 zeolite catalyst.One solution for this challenge is to introduce mesoporosity in the SSZ-39 zeolite.Herein,we report the synthesis of mesoporous SSZ-39 zeolite using an organosilane surfactant,,-dimethyl--(3-(trimethoxysilyl)propyl)octan-1-aminium chloride,as a mesopore template and,-dimethyl--2,6-dimethylpiperidinium as a micropore template.The obtained zeolites were characterized by X-ray diffraction,N sorption,scanning electron microscopy,temperature programmed desorption of ammonia,and magic angle spinning nuclear magnetic resonance of Al.The results show that the mesoporous SSZ-39 zeolite has high crystallinity,meso/microporosity,high surface area,cuboid morphology,and abundant acidic sites.More importantly,this mesoporous SSZ-39 zeolite exhibits enhanced catalyst lifetime in the MTO reaction due to the presence of mesoporosity for fast mass transfer,compared with a conventional SSZ-39 zeolite without mesoporosity.
