综述高岭土合成Y型分子筛研究进展,分别从原位合成、纳米分子筛、高硅分子筛和其他合成方法进行评述,并分析各种合成方法的优缺点。原位合成Y型分子筛是合成性质优良Y型分子筛的重要方法,相关研究不断深化成熟,以此方法合成特殊性能的Y型分子筛成功应用于催化裂化催化剂。合成具有特殊形态和结构组成的分子筛如小晶粒Y型分子筛、高硅Y型分子筛是近年来的研究热点。分别从优化合成条件、加入分散剂和使用微波加热法介绍小晶粒Y型分子筛合成研究进展。高硅Y型分子筛的合成主要分为直接合成和二次改性方法,直接合成法反应条件苛刻,存在原料浪费等问题;二次改性方法工艺流程长,易导致合成成本增加。重点讨论具有特种性能的特种Y型分子筛合成研究进展,对离子液体合成Y型分子筛、干胶转化合成Y型分子筛和高岭土合成复合分子筛等新方法进行综述,并结合其他先进的分子筛合成方法,指出Y型分子筛合成的研究方向和前景。

The research advance in synthesis of Y zeolite from kaolin were reviewed. The synthesis of Y zeolite with different methods such as in-situ synthesis of Y zeolite by kaolin microsphere,the synthesis of nanosized molecular sieves,the synthesis of high silica Y zeolite,and other methods were introduced. The analysis and comparison of various raw materials and different synthetic methods were given. Y zeolite synthesized by in-situ crystallization technique from kaolin clay was the most important method for obtaining excellent FCC catalysts. Recent progress in in-situ crystallizing technique was also reviewed. The research on synthesis of special Y zeolite with excellent performance ,especially the synthesis of nanosized and high silica Y zeolite,was focused on. The methods for preparing nanosized Y zeolites,such as optimizing synthesis conditions,adding dispersant agents and microwave synthesis,were described. Y zeolites with high molar ratio of silica to alumina was synthesize

以Beta分子筛为硅源通过水热合成法合成了SAPO-11/Beta复合分子筛,采用X射线衍射、N2物理吸脱附、扫描电镜、透视电镜-能谱分析、固体核磁及吡啶红外等方法对单分子筛、复合分子筛和机械混合分子筛的物化性质进行了表征.以正十二烷为模型化合物,在固定床反应器上考察了铂负载型分子筛催化剂的异构化性能.结果表明,复合分子筛的物理化学性质明显不同于单分子筛和机械混合分子筛,其呈现核壳结构,SAPO-11和Beta间存在化学作用,使得复合分子筛具有适宜的B酸分布.在正十二烷异构化反应中,复合分子筛催化剂的异构化性能优于单分子筛催化剂和机械混合分子筛催化剂,多支链异构体收率高.

The SAPO-11/Beta composite molecular sieve was synthesized by the hydrothermal method with zeolite Beta as the silicon source. The physicochemical properties of SAPO-11, Beta molecular sieve, the composite molecular sieve, and the mechanical mixture of SAPO-11 and Beta molecular sieve were characterized by X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy, transmission electron microscopy-energy dispersive spectroscopy, magic-angle spinning nuclear magnetic resonance, and pyridine adsorption infrared spectroscopy. In addition, the catalytic per-formance of platinum-loaded zeolite samples in the hydroisomerization of n-dodecane was investi-gated. The results indicate that the properties and catalytic performance of the composite molecular sieve were quite different from those of the pure zeolites and the mechanical mixture. Compared with the mechanical mixture, the combination of SAPO-11 and Beta by chemical bonds was more tightly bound in the composite

介绍了分子筛的作用和特点,总结了目前国内以粉煤灰为原料制备分子筛的种类,并介绍和比较了各种分子筛制备工艺。简述了近些年来分子筛制备工艺发展状况,指出各方法的优缺点。

T he types of domestic molecular sieves preparated using fly ash are introduced .Development status of molecular sieve preparation processes are discussed in the past years .T he advantages and disadvantages of these methods are pointed out .

采用液相离子交换法制备了NiY及NiY／Beta分子筛，利用智能重量分析仪测定了噻吩、苯在NiY、NiY／Beta分子筛上的吸附-脱附等温线，计算比较了噻吩、苯在分子筛上的扩散系数，同时使用固定床技术考查了改性后的分子筛对催化裂化汽油的吸附脱硫性能。结果表明，复合分子筛NiY／Beta仍然保持着较好的微孔结构，对噻吩的饱和吸附量大于苯的。而且噻吩在NiY／Beta分子筛上的相对扩散系数明显增大，而苯的扩散系数有所减少，这有利于噻吩在分子筛上的扩散过程，抑制了苯在分子筛上的吸附，从而提高了NiY／Beta复合分子筛对噻吩的选择性脱除能力。对于FCC汽油NiY／Beta复合分子筛也表现出更好的深度脱硫能力。

The adsorption-desorption isotherms of thiophene and benzene in the NiY and NiY/Beta zeolites ,prepared by liquid phase ion exchange ,have been investigated by an intelligent gravimetric analyzer (IGA) and the diffusion coefficients were also calculated .Properties of selective adsorptive desulfurization of FCC gasoline on the zeolites were evaluated by a fixed-bed adsorption experiment . The results show that the NiY/Beta zeolites remain the microporous structure . The saturated adsorption amount of thiophene is larger than that of benzene and so it is to the diffusion coefficients .The better diffusivity of thiophene inhibits the adsorption of benzene , resulting in the absorption desulfurization capability of the NiY/Beta zeolites improved .

利用频率响应技术考察了噻吩在NaY分子筛和两种分别采用液相和固相离子交换法制得的CeY分子筛上的吸附、扩散行为,并与TG/DTG曲线和吡啶红外等技术相结合来分析噻吩在分子筛上的吸附扩散机理。结果表明,L-CeY分子筛含有强B酸和弱L酸,S-CeY分子筛含有弱L酸和少量弱B酸。噻吩在S-CeY及NaY分子筛上只存在一种吸附过程,吸附作用相对较弱。而噻吩在L-CeY分子筛上存在两种不同的吸附过程,吸附作用相对较强,其吸附作用模式是与L-CeY分子筛上不同酸性位作用的结果。

Adsorption behavior of thiophene in NaY and CeY zeolites prepared by liquid phase ion exchange and solid state ion exchange methods by using the frequency response method ,combined with the TG/DTG curves and Py-FTIR technique to analyze the the adsorption and diffusion mechanism of thiophene on these zeolites .The results indicate that L-CeY zeolites contain the strong B acid and weak L acid sites ,while the S-CeY zeolites contain the weak L acid and a small amount of weak B acid sites .Only one weak adsorption process of thiophene can be observed for the S-CeY and NaY zeolites .Two different adsorption processes can be formed in L-CeY zeolites ,and the different interactions can be attributed to the different acid sites .