新型择形分子筛MCM-68研究进展

分子筛材料的发展为择形催化的广泛应用提供了支撑,特别是ZSM-5分子筛的发明,促进了通过择形催化实现高选择性合成目的产物的工业应用,但ZSM-5主要针对小分子择形催化转化,在大分子择形催化转化上略显不足。研发大分子择形催化的新型分子筛,拓展择形催化工业应用成为材料界和工业催化领域的热点。综述了新型大分子择形催化分子筛MCM-68的研究进展,包括MCM-68的拓扑结构、合成方法和酸性能等。同时介绍了MCM-68在作为酸催化剂和择形催化剂方面的应用。MCM-68所具有的特殊孔道结构和强酸性等性能有望在重油加工和酸催化的精细化学品合成中应用。     

Theoretical and experimental study on the selectivity of dehydrogenation of α-limonene in ZSM-5 and zeolite-Y

Dehydrogenation of the natural terpene α-limonene to the industrially important p-cymene was studied over two zeolite-supported Pd catalysts, ZSM-5 and zeolite-Y. Reactor tests indicate that transalkylation of the p-cymene product can be avoided by employing the shape-selective properties of a medium-pore ZSM-5 catalyst. The diffusion properties of the three isomers of cymene were then calculated in the two zeolites using molecular mechanics. In case of ZSM-5, p-cymene was found to have the lowest barrier of the three isomers for diffusion through the straight, spherical channel of the zeolite. For zeolite-Y, differences in diffusivity for the three isomers were very small. Theory and experiments showed, in excellent agreement, that only ZSM-5 selectively produces p-cymene. This work shows that molecular mechanics is a powerful and reliable method for the screening of zeolites for performing shape-selective catalysis. This revised version was published online in July 2006 with corrections to the Cover Date.     

The Synthesis and Properties of Two Catalytically Important Zeolites

Abstract

With his discovery of stilbite in 1756, Cronstedt [1] recognized the existence of a new group of minerals consisting of hydrated “aluminosilicates” of the alkali and alkaline earth cations. While several members of the group may have similar or nearly identical compositions, each possesses its own, unique crystal structure. At present there are 35 known naturally occurring zeolites. The crystal structures have been determined for 27 and all but about 10 have been prepared synthetically. This paper will present the definition of zeolites and focus on the synthesis and physicochemical properties of two catalytically and commercially important synthetic zeolites, zeolite Y and zeolite ZSM-5.     

Synthesis of ZSM-5 zeolite from expanded perlite/kaolin and its catalytic performance for FCC naphtha aromatization

A hydrothermal synthesis method for ZSM-5 preparation was investigated by using expanded perlite (or kaolin) as the only alumina source. The ZSM-5 zeolites from the expanded perlite (or kaolin) have a distinctive pore systems which were a combination of a medium pore ZSM-5 zeolite and a large pore matrix perlite (or kaolin). The ZSM-5 zeolites from the expanded perlite (or kaolin) showed a better catalytic activity in the FCC naphtha aromatization reaction compared with ZSM-5 obtained by a ordinary method.     

Selective photooxidation reactions in zeolites X, Y and ZSM-5

The focus of this study is to develop photooxidation in zeolites as an environmentally benign alternative to conventional liquid phase oxidation of industrially important chemicals. Here we demonstrate that photooxidation in zeolites is a general technique and, therefore, synthetic strategies can be developed using the shape-selective and chemical properties of different zeolites. The photooxidation of toluene to benzaldehyde and propylene to acrolein were explored in three different zeolites - X, Y and ZSM-5. Photooxidation of toluene and propylene in zeolites other than Y has not hitherto been previously reported. This revised version was published online in July 2006 with corrections to the Cover Date.     

超重力预混+动态水热法制备ZSM-5分子筛——水热过程影响机制

ZSM-5分子筛作为一种重要的催化剂,被广泛应用于石油化工行业,其制备工艺一直是分子筛研究的热点。传统静态水热法制备ZSM-5分子筛存在产物粒度分布不均、晶化时间长等问题,本文提出开展超重力预混+动态水热法制备ZSM-5分子筛,考察了晶化过程中晶化方式、搅拌釜转速、晶化时间和晶化凝胶体积对ZSM-5分子筛粒径的影响规律,获得了较优的操作条件;并针对较优条件下制备的产品进行了系统表征。结果表明,相比于超重力预混+静态水热,动态水热更有利于合成粒径小且分布均匀、酸量大、比表面积大的多级孔ZSM-5分子筛,搅拌釜转速越大、晶化凝胶体积越小所制备的产品平均粒径越小,粒径分布越均匀。本文研究结果表明,水热过程参数对分子筛的粒径、结构和酸性具有重要影响。     

Exploring suitable ZSM-5/MCM-41 zeolites for catalytic cracking of n-dodecane: Effect of initial particle size and Si/Al ratio

In this study, various ZSM-5/MCM-41 micro/mesoporous zeolite composites have been prepared by alkalidesilication and surfactant-directed recrystallization of ZSM-5. The effects of particle size and Si/Al ratio of initial ZSM-5 zeolites on the structure and catalytic performance of ZSM-5/MCM-41 composites are studied. The results of XRD, TEM N₂-adsorption-desorption, NH₃-TPD and in situ FT-IR revealed that ordered hexagonal MCM-41 mesopores with 3-4 nm pore size were formed around ZSM-5 crystals, and the specific surface area and mesopore volume of composites increased with increasing the Si/Al ratio of initial ZSM-5. Catalytic cracking of n-dodecane (550 ℃, 4 MPa) showed that the ZSM-5/MCM-41 composites obtained from the high Si/Al ratio and nano-sized initial ZSM-5 zeolites exhibited superior catalytic performance, with the improvement higher than 87% in the catalytic activities and 21% in the deactivation rate compared with untreated zeolites. This could be ascribed to their suitable pore structure, which enhanced the diffusion of reactant molecules in pores of catalysts.     

烃分子动力学直径与分子筛择形催化性能的相关性

作为分子筛研究领域的一个热点,择形催化理论在工业上已经被研究了近60年。尽管在理论上很多研究还不够深入,但随着对催化反应类型、新型催化材料合成、分子筛结构测定、催化性能表征、催化反应作用机理等方面研究的深入,对择形催化反应的认识仍取得了令人欣慰的进步。本文在现有的研究基础上,对不同尺寸的烃分子在分子筛孔道内的吸附和扩散行为进行了总结,并对烃分子反应动力学直径与分子筛的择形相关性做了一定的探究。分析表明,烃分子的反应动力学直径与分子筛择形催化相关性存在一个适用规律区间,当其略小于或接近分子筛孔径时,分子筛的择形催化性能表现最好。此外,分子筛本身的拓扑结构等因素也会对分子筛催化性能造成影响。     

软模板法制备多级孔ZSM-5分子筛的研究进展

相比传统ZSM-5分子筛,多级孔ZSM-5分子筛具有空间位阻小、传质效率高、焦炭少等特点,近年来在分子筛领域应用广泛。多级孔分子筛通常可用后处理法和模板剂法制备,相比后处理法,模板剂法能更好地控制介孔的结构和孔道尺寸。概述了采用传统表面活性剂、两亲性的有机硅烷、双功能多季铵盐表面活性剂及高分子聚合物等软模板法合成多级孔ZSM-5分子筛的研究进展。分析不同软模板剂的特点和作用机理,阐述了合成后分子筛的结构特点及催化性能等。指出在今后的研究中,可以设计价格较低的新型功能化模板剂,优化合成过程,致力于在理解合成机理的前提下,寻找操作简单、绿色环保的合成路线,并将其推行到实际工业生产中。     

Sealing and reopening of micropores of mordenite and ZSM-5 by disilylbenzene compounds

Regularly-structured solid matrices are potent materials for regulating molecular permeation and diffusion. Zeolite materials bearing ordered micropores are very advantageous to control the diffusion of molecules. When some disilylbenzene compounds were grafted on mordenite and ZSM-5 zeolites, the penetrations of small molecules such as α-methylstyrene (AMS) and molecular nitrogen were prevented by the direct formation of the crosslinking with two grafting sites on the exterior surfaces of those zeolites. The dimerization reaction of α-methylstyrene effectively promoted by mordenite was not catalyzed by these grafted mordenite samples. No adsorptions of molecular nitrogen were observed in the grafted mordenite and ZSM-5 samples. When these grafted samples were calcined, both the catalytic activity for the dimerization and the permeation of molecular nitrogen were recovered. The reopening of the micropores of zeolites was also achieved by the treatment with HCl acidic solutions. Thus, the diffusion and the permeation of various small molecules can be perfectly and reversely controlled by the sealing and the reopening of the micropores of zeolites by the disilylbenzene compounds.     

提高多产丙烯性能的ZSM-5分子筛改性研究进展

催化裂化装置在多产丙烯方面扮演着重要的角色,ZSM-5分子筛由于具有特殊的孔道结构、活性较高以及择形催化等特点,是催化裂化多产丙烯主要催化剂。综述采用改性手段增强ZSM-5分子筛水热稳定性和引入介孔提高分子可及性研究进展,主要包括F改性,P改性,过渡金属及稀土掺杂等改性手段,以及物理化学法脱铝脱硅,软模板法和硬模板法修饰ZSM-5分子筛孔道。     

正丁烷和丁烯-1在不同Si/Al比ZSM-5分子筛上的吸附和扩散行为

以应用于烯烃催化裂解工艺中的具有独特择形性和酸性的ZSM-5分子筛为研究对象,采用重力分析仪在275, 288及300 K下对碳四烃(以正丁烷和丁烯-1为代表)在不同硅/铝比ZSM-5分子筛内的吸附和扩散行为进行了研究. 建立了正丁烷和丁烯-1在ZSM-5分子筛上的双朗格缪尔吸附模型. 同时,运用Fick扩散模型关联得到了正丁烷及丁烯-1在ZSM-5分子筛内的扩散系数. 结果表明,正丁烷及丁烯-1在ZSM-5分子筛内的扩散属于晶体扩散,二者的扩散系数在10-14 m2/s数量级,正丁烷的扩散速率大于丁烯-1. 正丁烷与丁烯-1在ZSM-5分子筛内的扩散速率均随温度的增加而增加,随着体系平衡压力的增加先增加后减小,而且二者的扩散系数随样品硅/铝比的增加而增加. 研究结果为碳四烃催化裂解工艺提供了相关的基础工程数据.     

C-radioisotope labeled methanol conversion over H- and Cs- modified ZSM-5, Beta zeolites and MCM-41 mesoporous molecular sieve

The Na–MCM-41 mesoporous molecular sieve, Na–ZSM-5 and Na–Beta zeolites have been modified by Cs- and H- using ion-exchange method and characterized by XRD, SEM and nitrogen adsorption. The conversion of methanol was studied over H- and Cs- modified ZSM-5, Beta zeolites and MCM-41 mesoporous molecular sieve. Methanol was in ¹¹C-radioisotope labeled form in-order to follow its conversion during the catalytic process, since the radioactivity method provides a very sensitive detection possibility to investigate the conversion of small amounts of methanol and some intermediates at different reaction times and temperatures. The understanding of reaction mechanism is important for side-chain methylation over Cs–zeolite catalysts by methanol, as they are more selective than other alkali exchanged zeolites (Li, Na and K). The reaction pathway of the transformation of methanol to hydrocarbons and aldehydes has been elaborated.     

以纯天然矿物为硅铝原料水热合成ZSM-5分子筛

以纯化硅藻土和热活化高岭土为硅铝原料,在水热条件下一步合成纯相ZSM-5分子筛。考察分子筛合成参数对产物的影响,得到合成ZSM-5分子筛的适宜条件:硅藻土与高岭土质量比32∶1,晶化温度170℃,晶化时间48 h,合成体系pH=13. 0。采用XRD、SEM及N2吸附-脱附等对样品进行表征。结果表明,最适宜条件下合成的ZSM-5分子筛晶型完整,具有与工业ZSM-5分子筛相似的六棱柱形貌以及相近的总比表面积和总孔容。     

The Synthesis and Properties of Two Catalytically Important Zeolites

With his discovery of stilbite in 1756, Cronstedt [1] recognized the existence of a new group of minerals consisting of hydrated “aluminosilicates” of the alkali and alkaline earth cations. While several members of the group may have similar or nearly identical compositions, each possesses its own, unique crystal structure. At present there are 35 known naturally occurring zeolites. The crystal structures have been determined for 27 and all but about 10 have been prepared synthetically. This paper will present the definition of zeolites and focus on the synthesis and physicochemical properties of two catalytically and commercially important synthetic zeolites, zeolite Y and zeolite ZSM-5.     

Effect of zeolite pore geometry on isomerization of n-butane

A comparative study of isomerization of n-butane over bifunctional catalysts based on zeolites with different pore geometry (ZSM-5 and mordenite) and with metal particles located inside and/or outside the zeolite main channel system has been carried out. 1,1,1,3,3,3-hexamethyldisilazane was used in order to obtain catalysts with external Brönsted acid sites poisoned. TPDA, FTIR, TPR and TEM techniques were used to characterize the catalysts. ZSM-5 catalysts were quite resistant to poisoning, mainly when metal sites were located inside the pore system. However, isomerization activity was virtually suppressed for the poisoned mordenite catalysts. It is proposed that the isomerization via C₈ formation cannot take place inside the one-dimensional pore system of mesopore-free mordenite catalysts, but this is not the case for isomerization on ZSM-5.     

Effect of Al content on the assembly of Al-MSU-S mesostructures: zeolite seed structure change from zeolite LZY to LTA with increasing Al content

Al-MSU-S mesoporous molecular sieve catalysts with Al contents ranging from 2.5 to 50 mol% have been prepared from “zeolite seed” solutions and C₁₆ TMABr templates. Hexagonal mesoporous structures are formed that exhibit significantly higher amounts of tetrahedrally coordinated Al than analogous Al-MCM-41 catalysts. The Al-MSU-S catalysts also possess smaller pores than corresponding Al-MCM-41 materials. Catalytic cumene cracking activity is very high over the low Al content materials (2.5 mol%), approaching that of zeolite ZSM-5, but the catalytic activity decreases with increasing Al. As the Al content is increased, the Al atoms remain tetrahedrally coordinated but become less accessible to the cumene reagent. This and knowledge of zeolite synthesis suggest the formation of zeolite seeds other than the large pore LZY, such as the small pore LTA structure.     

Synthesis, Characterization, and Catalytic Properties of Nu-1, FU-1, and Related Zeolites

The discovery of the striking catalytic properties of the Mobil zeolite ZSM-5 has been followed by a large and intensive research effort both in catalysis promoted by ZSM-5 and in the synthesis and properties of other highly siliceous zeolites. While the distinctions between ZSM-5 and some of the claimed new zeolites are barely perceptible (it would perhaps be invidious to name these zeolites), other new. highly-siliceous zeolites differ markedly from ZSM-5/ZSM-11 in structure and consequently in other properties as well. Zeolites Nu-1 and FU-1 have now been fairly well characterized in both physical and catalytic properties. Although their crystal structures have not yet been determined, it is clear that they are different from ZSM-5 (and indeed, any other published zeolite structure).     

劣质原油高效转化且增产低碳烯烃的择型分子筛研究进展

现有催化裂化多产低碳烯烃技术优先以石蜡基蜡油或常压渣油为原料油,原油重质化和高硫化限制了该技术的深入发展与推广应用。择型分子筛由于硅铝比及孔结构较为突出,具有适合重质油裂解的反应性能,得到广泛应用。为了更好的提高低碳烯烃的产率及选择性,对择型分子筛进行改性,通过调整分子筛的基础性质,使之成为优良的活性中心。重点介绍多种择型分子筛包括ZSM-5、β、SAPO-34、MCM-22等,并对其现有改性方法主要是以酸、碱改性及金属、非金属改性为主进行综述,并从其改性后的性能包括孔道结构优化、水热稳定性保留及裂化能力增强等方面阐述分子筛改性研究进展。     

Mathematical modelling of diffusion and reaction in blocked zeolite catalysts

A mathematical model for diffusion and reaction in blocked zeolites is developed which takes into account nonidealities arising from interaction between sorbed molecules as well as the effect of pore and surface blocking. The model combines a microscopic approach, in which expressions for chemical potential and diffusive fluxes are calculated within the lattice-gas framework, with the more traditional continuum approach which takes into account the effect of surface blocking. The effect of pore blocking on the diffusive fluxes in accounted for through an effective medium approximation. The effects of crystal size and blocking on the activity-selectivity characteristics of the crystal are illustrated through an example that is qualitatively similar to industrially important reactions such as alkylation of toluene in blocked ZSM-5 zeolite.