SSZ-13分子筛合成研究进展

综述了SSZ-13分子筛合成及其性能优化的研究近况。介绍了模板剂、晶种、矿化剂和晶化原料等因素对SSZ-13分子筛合成的影响,以及SSZ-13分子筛孔径、晶粒尺寸、骨架稳定性、酸性等性能优化的方法和效果。指出开发价格低廉的模板剂体系,完善合成及性能优化工艺路线,是SSZ-13分子筛研发的重要方向。     

混合模板法低成本合成SSZ-13分子筛的研究

以硅溶胶、硫酸铝、氢氧化钠和去离子水为原料,以N,N,N-三甲基金刚烷氢氧化铵和三乙胺为模板剂,采用传统的水热法快速合成了SSZ-13分子筛。采用X射线荧光光谱（XRF）、X射线衍射（XRD）和扫描电镜（SEM）表征产物。综合考察了碱度、水量、模板剂和晶种等因素对合成SSZ-13分子筛的影响,确定了最佳合成条件。在有晶种或无晶种条件下,通过引入辅助模板剂三乙胺,晶化2 d即可得到SSZ-13分子筛。该方法缩短了生产周期,降低了生产成本,具有广泛的工业应用前景。     

SSZ-13分子筛合成及应用进展

对SSZ-13分子筛及SSZ-13分子筛膜的制备进行了综述,介绍了SSZ-13分子筛在应用领域的研究进展,对SSZ-13分子筛的发展趋势做了展望。通过低成本模板剂替代或开发无有机模板剂的高效合成路线,是实现SSZ-13分子筛工业应用的基础。在应用领域,SSZ-13分子筛的未来研发方向应集中于反应机理的研究。     

SSZ-13分子筛的水热合成及应用研究

以硅溶胶、氢氧化铝为原料,N,N,N-三甲基-1-金钢烷基氢氧化铵为模板剂,采用水热法合成出较高结晶度的SSZ-13分子筛。采用低廉的铜胺配合物为辅助模板剂合成出较高结晶度的Cu-SSZ-13分子筛。采用离子交换法和浸渍法对SSZ-13分子筛制备出Cu/SSZ-13催化剂。相比Cu/ZSM-5催化剂,Cu/SSZ-13催化剂具有更优异的脱硝活性和更宽的活性窗口。用SSZ-13和Cu-SSZ-13分子筛制备的催化剂样品(29)90%NO_x转化率的高活性温度窗口分别为220~480℃、280~460℃。     

SSZ-13分子筛的合成及应用进展

由于微孔分子筛SSZ-13具有独特的物理化学性质,使其在越来越多的领域显示出广阔的应用前景,近年来成为研究的热点。本文综述了利用不同模板剂制备SSZ-13分子筛的研究进展,并评价了这些方法的优缺点,从而为降低N,N,N-三甲基金刚烷铵(TMADa+)的用量或者完全替换为廉价模板剂,最终实现SSZ-13分子筛的工业化生产提供思路;总结了SSZ-13分子筛在脱除汽车尾气NOx、甲醇制低碳烯烃(MTO)以及气体分离吸附过程中的应用研究进展,尽管SSZ-13分子筛在这些领域显示出很好的性能,但仍存在SCR高温催化活性有待进一步提高、MTO反应中易积碳等问题。最后指出,对SSZ-13负载双金属、降低酸性中心强度以及进行机理研究等将成为SSZ-13分子筛今后研究的重点。     

干胶转化法合成整体式SSZ-13分子筛

采用干胶转化法合成了整体式SSZ-13分子筛,先成型后晶化,系统地考察了物料配比及晶化条件对合成结果的影响,通过X射线衍射(XRD)、X射线荧光(XRF)、热重-差热分析仪(TG-DTA)、扫描电子显微镜(SEM)、氨气的程序升温吸附-脱附(NH_3-TPD)、傅里叶红外光谱仪(FI-IR)、液体核磁共振谱(NMR)对产物进行表征分析,并讨论了混合模板剂N,N,N-三甲基-1-金刚烷氢氧化铵和氯化胆碱在晶化过程中起的作用。结果表明,合成的整体式SSZ-13分子筛具有典型的介孔堆积孔、较大的比表面积,在空气中热稳定性良好。氯化胆碱加速了分子筛晶化,缩短了晶化时间,提高产物的结晶度,明显降低了N,N,N-三甲基-1-金刚烷氢氧化铵的使用量,起到了辅助结构导向的作用,且混合模板剂均填充产物孔道。     

干胶转化法合成整体式SSZ-13分子筛

采用干胶转化法合成了整体式SSZ-13分子筛,先成型后晶化,系统地考察了物料配比及晶化条件对合成结果的影响,通过X射线衍射（XRD）、X射线荧光（XRF）、热重-差热分析仪（TG-DTA）、扫描电子显微镜（SEM）、氨气的程序升温吸附-脱附（NH₃-TPD）、傅里叶红外光谱仪（FI-IR）、液体核磁共振谱（NMR）对产物进行表征分析,并讨论了混合模板剂N,N,N-三甲基-1-金刚烷氢氧化铵和氯化胆碱在晶化过程中起的作用。结果表明,合成的整体式SSZ-13分子筛具有典型的介孔堆积孔、较大的比表面积,在空气中热稳定性良好。氯化胆碱加速了分子筛晶化,缩短了晶化时间,提高产物的结晶度,明显降低了N,N,N-三甲基-1-金刚烷氢氧化铵的使用量,起到了辅助结构导向的作用,且混合模板剂均填充产物孔道。     

纳米Y型分子筛的合成研究进展

综述了近年来纳米Y型分子筛的合成方法,包括无导向剂合成法、晶种辅助晶化法、硬模板剂法、软模版剂法和有机添加剂法,并对这些方法的优缺点进行了评价。讨论了纳米Y分子筛合成目前存在的问题,对纳米Y分子筛未来发展进行了展望,指出深入研究纳米Y分子筛的晶化机理、提高纳米Y分子筛的结晶度和骨架硅铝比是今后的研究重点。     

SAPO-34分子筛的合成与Ce改性

本论文主要研究了SAPO-34分子筛的合成与改性,阐述了当下SAPO-34分子筛的主要合成方法并通过水热合成法将稀土金属Ce引入SAPO-34分子骨架中制备出CeSAPO-34分子筛。考察了反应温度、晶化时间、模板剂、Ce金属改性等因素对SAPO-34分子筛结构的影响,优化制备工艺得出最佳的反应条件。     

微波辅助双模板剂体系快速合成纳米SSZ-13分子筛及NH3-SCR脱硝性能研究

采用硅溶胶为硅源、偏铝酸钠为铝源、四甲基氢氧化铵(TMAOH)和N,N,N-三甲基金刚烷氢氧化铵(TMAdaOH)为混合模板剂，通过微波加热方式在8 h内快速合成结晶度良好的纳米SSZ-13分子筛。结合XRD和SEM理化性质表征，考察了微波辅助晶化时间、晶化温度、初始凝胶中TMAdaOH用量、硅源和铝源类型等因素对合成SSZ-13分子筛的影响，进一步通过离子交换的方式负载铜离子制备Cu-SSZ-13催化剂。结果表明，在中低温(175～350℃)区域NO_x转化率达99%,NH₃-SCR脱硝性能满足中低温脱硝催化剂的要求。     

SSZ-13沸石粒径及硅铝比对甲醇制烯烃反应性能的影响

通过调控合成配方,以水热合成法制备一系列不同粒径及硅铝比的SSZ-13沸石,考察沸石孔道结构、酸性质与催化性能之间的关系。采用XRD、SEM、XRF、N₂吸附-脱附以及²⁷Al MAS NMR对沸石样品进行详细的表征,并评价其甲醇制烯烃反应(MTO)催化性能。结果表明,小晶粒SSZ-13沸石相对结晶度高、晶粒尺寸均一;在MTO中,小晶粒SSZ-13沸石的MTO催化寿命大幅高于大晶粒SSZ-13沸石;减小晶粒尺寸可改善分子扩散效率,在此基础上提高沸石的酸密度可增加其活性稳定性。     

Investigation of Small-Pore Zeolites via Vapor-Phase Adsorption of n-Hexane

Cage-based small-pore zeolites are promising catalysts for catalytic applications such as methanol-to-olefins to produce light olefins and selective catalytic reduction to mitigate NO_x emissions. The present paper reports our recent studies on vapor-phase adsorption of n-hexane in a series of small-pore zeolites with cages such as 3A, 4A, 5A, ITQ-29, SSZ-13, SSZ-16, SSZ-17, SSZ-36, SSZ-50, ITQ-12, ZK-5, and Rho. The effects of zeolite compositions and crystal sizes on the adsorption kinetics and capacity are investigated, demonstrating that n-hexane adsorption is a useful tool for characterizing the effective pore sizes and volumes of small pore zeolites.     

四乙基氢氧化铵改性对HMOR分子筛结构及二甲醚羰基化性能的影响

合成气经二甲醚（DME）羰基化合成乙酸甲酯（MA）,MA进一步加氢制备乙醇是一种新型高效的煤基合成气制备乙醇路线。采用温和的后处理方法改性DME羰基化分子筛,进一步提高DME羰基化效率,对其工业应用具有重要意义。本研究利用四乙基氢氧化铵（TEAOH）对HMOR分子筛改性处理,探讨了有机碱改性处理对HMOR分子筛的结构和DME羰基化催化性能的影响。研究发现,TEAOH浓度为0.3 mol/L时,HMOR分子筛介孔孔容增大约26%,外比表面积增大约10%,DME的转化率增幅达68%。TEAOH水解产生的OH^-能够温和脱除HMOR分子筛中的骨架硅,获得介-微多级孔结构,提高DME羰基化反应过程中的传质速率。此外,水解的TEA⁺在分子筛表面富集,抑制了OH^-的过度脱硅,保护分子筛基本骨架结构不被更深层次破坏。     

合成气直接催化转化制低碳烯烃研究进展

合成气直接催化转化制乙烯、丙烯等低碳烯烃因具有原料来源广泛、流程较短等优点,成为目前合成气催化转化和烯烃制备技术的一个重要发展方向。本文首先介绍了合成气经费托合成直接制备低碳烯烃的路线（FTO）,简单概括了铁基和钴基催化剂的研究进展以及催化反应机理。随后重点综述了近年来提出并发展的基于双功能催化体系的合成气直接制低碳烯烃路线（STO）,详细阐述了金属氧化物的组成、配比等以及分子筛的酸性、孔道等性质对反应性能的影响,同时讨论了双功能催化体系以乙烯酮或甲醇/二甲醚为关键中间体的催化反应机理。最后对双功能催化体系的研究方向和挑战进行了展望。     

Zeolite HNU-87: synthesis, characterization and catalytic properties in the shape-selective conversion of methylnaphthalenes

The synthesis of the high-silica zeolite NU-87 and its physicochemical characterization are reported. The catalytic properties of zeolite HNU-87 were investigated in the conversion of 1- and 2-methylnaphthalene. Both isomerization to the corresponding methylnaphthalene and transalkylation to naphthalene and dimethylnaphthalenes are observed. The influence of reaction temperature and the modified residence time on the product distributions is reported and discussed in terms of shape selectivity effects in the peculiar pore system of NU-87. For comparison, typical results obained with zeolite HMCM-22, which possesses a similar pore architecture, are also included. The results of methylnaphthalene conversion over HNU-87 are compared to those obtained in the alkylation of naphthalene with methanol on the same zeolite catalyst. This revised version was published online in July 2006 with corrections to the Cover Date.     

复合分子筛的发展现状

复合材料通过将几种单一材料性能上互相取长补短,产生良好的协同效应和催化性能,使其综合性能优于原组成材料。这种具有多重结构和叠加功能的分子筛可以避免单一孔结构的缺陷,多级孔道体系能同时提供尺寸不同的孔道,对解决传质等问题将会有很大帮助,而被广泛使用。通过合成方法、影响因素、表征技术和催化性能评价等几个方面详细地介绍了复合分子筛,并进行了展望。     

The Effect of Zeolite Structure on the Activity and Selectivity in p-Xylene Alkylation with Isopropyl Alcohol

The effect of zeolite architecture and channel dimensionality on p-xylene conversion and selectivity to 1-isopropyl-2,5-dimethyl-benzene was investigated in p-xylene alkylation with isopropyl alcohol over novel zeolites SSZ-33 and SSZ-35. Catalytic behavior of these zeolites was compared with those of zeolites Beta, mordenite, ZSM-11 and ZSM-5. It was found that p-xylene conversion increases with increasing pore size and connectivity of the channel system of individual zeolites with the exception of SSZ-35, which possesses a system of one-dimensional 10-ring channels that periodically open into wide, shallow cavities circumscribed by 18-rings. SSZ-35 exhibited the highest conversion among all zeolites at the reaction temperature of 150 °C and also the highest selectivity to 1-isopropyl-2,5-dimethyl-benzene. Molecular modeling confirmed the dimensions of the 18-ring cages are optimal for the formation of this alkylation product.     

Organosilane surfactant-assisted synthesis of mesoporous SSZ-39 zeolite with enhanced catalytic performance in the methanol-to-olefins reaction

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, N,N-dimethyl-N-(3-(trimethoxysilyl)propyl)octan-1-aminium chloride, as a mesopore template and N,N-dimethyl-cis-2,6-dimethylpiperidinium as a micropore template. The obtained zeolites were characterized by X-ray diffraction, N₂ sorption, scanning electron microscopy, temperature programmed desorption of ammonia, and magic angle spinning nuclear magnetic resonance of ²⁷Al. 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.     

Current Understanding of Cu-Exchanged Chabazite Molecular Sieves for Use as Commercial Diesel Engine DeNOx Catalysts

Selective catalytic reduction (SCR) of NO_x with ammonia using metal-exchanged molecular sieves with a chabazite structure has recently been commercialized on diesel vehicles. One of the commercialized catalysts, i.e., Cu-SSZ-13, has received much attention for both practical and fundamental studies. For the latter, the particularly well-defined structure of this zeolite is allowing long-standing issues of the catalytically active site for SCR in metal-exchanged zeolites to be addressed. In this review, recent progress is summarized with a focus on two areas. First, the technical significance of Cu-SSZ-13 as compared to other Cu ion-exchanged zeolites (e.g., Cu-ZSM-5 and Cu-beta) is highlighted. Specifically, the much enhanced hydrothermal stability for Cu-SSZ-13 compared to other zeolite catalysts is addressed via performance measurements and catalyst characterization using several techniques. The enhanced stability of Cu-SSZ-13 is rationalized in terms of the unique small pore structure of this zeolite catalyst. Second, the fundamentals of the catalytically active center; i.e., the chemical nature and locations within the SSZ-13 framework are presented with an emphasis on understanding structure–function relationships. For the SCR reaction, traditional kinetic studies are complicated by intra-crystalline diffusion limitations. However, a major side reaction, nonselective ammonia oxidation by oxygen, does not suffer from mass-transfer limitations at relatively low temperatures due to significantly lower reaction rates. This allows structure–function relationships that are rather well understood in terms of Cu ion locations and redox properties. Finally, some aspects of the SCR reaction mechanism are addressed on the basis of in situ spectroscopic studies.