改性Y分子筛加氢裂化催化剂耐氮性能的研究

采用水热处理法制备了两种改性Y型分子筛NTY和USY，并用含吡啶正庚烷和甲苯为模型化合物，对引入这两种分子筛制备的加氢裂化催化剂性能进行了考察，发现引入表面积大、二次孔多、结晶度高的NTY分子筛制备的加氢裂化催化剂，其耐氮性能明显优于USY分子筛制备的催化剂。     

Effect of steaming on the defect structure and acid catalysis of protonated zeolites

The catalytic properties of ultrastable Y (USY) are directly influenced by the zeolite destruction which occurs during formation of USY and during subsequent hydrothermal treatment. A new picture of the formation and evolution of mesopores during hydrothermal treatment has emerged from recent electron microscopy studies on hydrothermally dealuminated USY materials. Laboratory steam treatments give rise to an inhomogeneous distribution of mesopores, which occurs concomitantly with further zeolite dealumination. Such inhomogeneities are observed among different USY grains as well as within single grains. In regions with high defect concentration, mesopores “coalesce” to form channels and cracks which, upon extended hydrothermal treatment, ultimately define the boundaries of fractured crystallite fragments. The predominant fate of aluminum ejected from lattice sites appears to be closely associated with dark bands which often decorate these newly formed fracture boundaries. High-silica Y materials, having little or no nonframework Al, exhibit poor catalytic activity. The results of recent studies provide compelling evidence that the critical nonframework Al species are (1) highly dispersed, and (2) quite possibly exist as cationic species in the small cages of dealuminated H-Y. Investigations of Lewis acidity in mildly dealuminated zeolites indicate that the origin of the high catalytic activity is a synergistic interaction between Brønsted (framework) and highly dispersed Lewis (nonframework) acid sites. The enhanced cracking, isomerization activity associated with the presence of highly dispersed nonframework Al species is not reflected in direct measures of solid acidity, as, for example, by calorimetry, or by NMR spectroscopy. The enhanced activity of mildly steamed protonated zeolites is not due to an increase in acidity of the bridging hydroxyl or Brønsted sites.     

Enhanced triisopropylbenzene cracking and suppressed coking on tailored composite of Y-zeolite/amorphous silica–alumina catalyst

Catalytic composites of Y-zeolite-amorphous silica–alumina (ASA) were prepared by four different methods to enhance pre-cracking and cracking of triisopropylbenzene (TIPB). TIPB cracking on composite catalysts were compared with a conventionally prepared catalyst. The samples were characterized by FESEM, XRD, N₂-adsorption and NH₃-TPD. The catalysts performance was evaluated by triisopropylbenzene cracking at 350 ̊C in a fixed bed reactor. The coke content of the catalysts was measured by TPO. Compared to the conventional catalyst, significantly deeper cracking to benzene of about 117% higher, up to 62% lower amount of coke, and lower deactivation rate are observed for the composite catalysts.     

Application of Novel Zeolite Y Nanoparticles in Catalytic Cracking Reactions

The cracking activity of a fluid catalytic cracking (FCC) catalyst containing novel zeolite Y nanoparticles fabricated using mesoporous silica (average particle size of 150 nm) was examined and compared with the performance of other catalysts. The activity experiments were carried out in a fluidized bench-scale batch riser simulator reactor. The bulky probing compound of 1,3,5-triisopropylbenzene (TIPB) was cracked to lighter compounds over a catalyst containing 25% of the developed zeolite. The synthesized sodium-type zeolite nanoparticles were subjected to two cycles of ion-exchange treatment using ammonium sulfate and lanthanum chloride and then to calcination. To investigate the effects of particle size on the activity, three additional catalysts were prepared with the mean particle size of the supported zeolites ranging from 450 to 1800 nm. The preparation of the FCC catalysts was conducted by mixing the highly aqueous dispersed zeolite Y nanoparticles with colloidal silica–alumina as a matrix and silica sol as a binder. The results of the catalytic cracking of TIPB demonstrated the significant effect of the size reduction of the synthesized zeolite Y nanoparticles on the catalytic performance of the catalyst. The FCC catalyst that contained zeolite Y nanoparticles (150 nm) showed superior conversion and selectivity percentages for the main products. The results of this study have a direct implication on the preparation of colloidal catalysts containing zeolite Y nanoparticles, which form stable emulsion with petroleum products. These emulsions can be utilized for slurry and ebullated bed reactors in heavy oil upgrading applications.     

气相低浓度甲苯在超稳Y分子筛的吸附-脱附性能

为提高Y分子筛对可挥发性有机废气的选择性吸附能力,采用高温水热处理技术对NaY分子筛进行骨架脱铝制备超稳Y分子筛(USY),并在固定床反应器中考察了USY在水汽存在下动态吸附低浓度甲苯的性能。结果表明,随着USY分子筛骨架Si/Al比的增加,虽然其微孔孔体积和比表面积发生了下降,但形成了较多的中孔结构。并且骨架硅含量增加后,USY对非极性的甲苯分子选择性吸附能力明显增加,当Si/Al为22左右,在相对湿度50%下,单位面积甲苯吸附量要比水吸附量大5.6倍。热重脱附研究表明,经过改性后,甲苯脱附温度可从NaY的300℃下降到超稳Y分子筛的160℃,具有优良的热再生性能。     

Catalyst design and development for upgrading aromatic hydrocarbons

Background and strategy of catalyst development for upgrading aromatic hydrocarbons are intensively discussed. Originally prepared catalysts (hydrogenation and hydrocracking catalysts) were used for accelerated aging tests. Though each catalyst showed superior catalytic performance as compared to commercially available catalysts, a severe deactivation was observed on the hydrocracking (HC) catalysts. A new type of HC catalyst was designed and prepared, based on the understanding of catalyst deactivation. High silica NaY zeolites were synthesized using crown-ether. USY zeolites were then prepared by ion exchange, steaming and calcining. Surface properties and catalytic functions of well-crystallized USY zeolites were investigated to develop practical HC catalysts. The Ni–W catalyst prepared using the newly prepared USY zeolite showed a considerable improvement in the HC activity.     

Hydroisomerization of n-Heptane Over Cr Promoted Pt-bearing H3PW12O40 Catalysts Supported on Dealuminated USY Zeolite

The Pt-bearing H₃PW₁₂O₄₀ (PW) catalysts, promoted by Cr or La, supported on dealuminated USY zeolite were prepared and their catalytic activities were evaluated in the hydroisomerization of n-heptane with an atmospheric fixed-bed reactor. The catalysts were characterized by XRD, BET, IR and H₂-chemisorption. The results showed that the dealuminated USY support retained the Y zeolite structure and the PW well kept its Keggin structure in the supported PW catalysts and the doping of Cr or La into the catalysts enhanced the dispersion of Pt on the catalyst surface. The Pt-bearing PW catalysts doped with Cr or La, especially Cr, exhibited much higher catalytic activity and selectivity than the catalysts without dopants. Both the conversion and selectivity were discussed in relation with physicochemical properties of catalysts.     

Enhanced hydrocarbon cracking activity of Y zeolites

It has been known for a long time that faujasite zeolites that have been steamdealuminated to form USY zeolite are much more active than the unsteamed parent material for hydrocarbon cracking. A popular model to explain this phenomenon is the generation of active sites of unusually high activity. In this paper, a brief review of recent advances towards understanding this phenomenon is presented. Evidence suggests that steaming does not generate sites of new chemical or catalytic properties for cracking. An alternate model is summarized that incorporates a change in the dominant cracking reaction mechanism as a function of conversion, and raises the possibility that the rates of bimolecular and oligomeric cracking are influenced by pore diffusion.     

超稳Y分子筛脱铝改性的研究进展

超稳Y分子筛(USY)在石油化工催化领域应用广泛,尤其是作为加氢裂化和异构化反应的催化剂。随着工业化的发展,超稳Y分子筛逐渐满足不了催化剂的要求,达不到生产目的,而脱铝的超稳Y分子筛(DUSY)作为催化剂载体或活性组分的效果比母体USY分子筛要好,因此对脱铝改性的USY分子筛的研究引起关注。综述超稳Y分子筛的制备与脱铝改性方法的研究进展,改性方法包括水热法、化学法和水热-化学法,重点介绍化学脱铝改性对超稳Y分子筛的性质影响,展望超稳Y分子筛脱铝改性的发展方向。     

Dealumination of Y zeolite through an economic and eco-friendly defect-engineering strategy

A sustainable defect-engineering strategy for the dealumination of Y zeolite is described. This strategy includes the green synthesis of a well-crystallized Y zeolite with point defects arising from the incorporation of Fe atoms by using Fe-containing perlite and the subsequent preparation of ultra-stable Y (USY) zeolite by efficient steaming dealumination. The systematic characterizations verify that Fe atoms originally existing in the perlite are incorporated into the as-synthesized Y zeolite and function as point defects, leading to the distortion of framework Al. The step-by-step investigation of dealumination process shows that vacancies are formed by the extraction of framework Fe in ammonium exchange, and the framework dealumination is promoted under the combined effect of the distorted framework Al and the formed vacancies during steaming treatment. The resulting USY zeolite owns excellent features in (hydro)thermal stability, pore structure and acid property, and exhibits outstanding catalytic performance in the cracking of n-octane and 1,3,5-triisopropylbenzene.     

Role of zeolite non-framework aluminium in catalytic cracking

Catalytic cracking catalysts containing hydrothermally stabilized, acid treated (USE) Y zeolites were prepared and tested for the conversion of West Texas Heavy Gas Oil. The cracking catalyst zeolite contents were equivalent; however, the amounts of zeolite non-framework aluminium were decreased from catalyst to catalyst. Steam deactivated cracking catalyst activity was highest when catalyst zeolite non-framework aluminium content was highest, as was the selectivity to gasoline. Zeolites which have low amounts of non-framework aluminium also have maximum free mesopore volumes. Cracking catalysts prepared from such low-aluminium zeolites are not active for heavy oil cracking and high boiling hydrocarbons plug the mesopores causing high coke yields.     

Evolution of the deactivation mode and nature of coke of HZSM-5 and USY zeolites in the catalytic cracking of low-density polyethylene during successive cracking runs

The coke deposited in the HZSM-5 zeolite at higher coke levels causes a more important pore blockage than the coke deposited in the HZSM-5 zeolite at low coke content. On the other hand, it would appear that there is an important deactivation mode change in the USY coked zeolites during the cracking runs and when the coke level in the catalyst increases an important pore blockage is observed. In the HZSM-5 zeolite, it seems that the formation of insoluble coke during the several polymer cracking runs, as well as the possible location in the external surface could be responsible for the important pore blockage observed in this zeolite. In the USY coked zeolites, the study of the nature of the soluble coke suggests that the pyrene compounds and their evolution to insoluble coke could probably be responsible for the important pore blockage observed after the second cracking run.     

Studies on acidity,activity and coke deactivation of ZSM-5 during n-heptane aromatization

In order to understand the effects of acidity and acid strength distribution on the nature of coke formed over ZSM-5 zeolite in n-heptane aromatization reaction, a series of ZSM-5 samples dealuminated to different degrees are prepared. Microcalorimetric ammonia adsorption studies indicated the presence of very strong acid sites (ΔH>140 kJ/mol) in the catalysts steamed at 400 and 500°C. ¹³C CP/MAS NMR along with dipolar dephasing is used to estimate the fraction of aromatic carbon and variation in aliphatic components with change in acidity of the ZSM-5 zeolites. Maximum selectivity to aromatics in n-heptane conversion is observed in the case of partly dealuminated ZSM-5 catalyst, whereas the aromatic nature of the coke is continuously decreased with steaming temperature, i.e. dealumination.     

Influence of the final “ageing” temperature on the regeneration behaviour and location of the coke obtained in the HZSM-5 and USY zeolites during the LDPE cracking

In this work, the influence of the “ageing” temperature on the location and regeneration behaviour of the coke obtained in the cracking of LDPE in the presence of HZSM-5 and USY zeolites is studied. The coke content in the zeolites is influenced by the thermal treatment, and for both zeolites studied, the higher the final cracking temperature the lower the coke content. The nitrogen adsorption isotherms have shown the different deactivation mechanisms, related to the possible different locations of the coke on each zeolite and the influence of the final cracking temperature on these parameters. The regeneration study of the coked zeolites has shown that the coke combustion process strongly depends on the insoluble content of the coke (i.e., of the presence of bulky polyaromatic compounds) and of the zeolite framework.     

A novel method for enhancing on-stream stability of fluid catalytic cracking (FCC) gasoline hydro-upgrading catalyst: Post-treatment of HZSM-5 zeolite by combined steaming and citric acid leaching

This article describes a novel modification method consisting of steaming and subsequent citric acid leaching to finely tune acidity and pore structure of HZSM-5 zeolite and thereby to enhance the on-stream stability of the zeolite derived fluid catalytic cracking (FCC) gasoline hydro-upgrading catalyst. A series of dealuminated HZSM-5 zeolites and their derived catalysts were prepared and characterized by X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), ²⁷Al MAS NMR, nitrogen adsorption, temperature programmed desorption of ammonium (NH₃-TPD) and infrared (IR) spectroscopy of chemisorbed pyridine. The results showed that the citric acid leaching could preferentially remove the extra-framework Al (EFAl) species formed by steaming treatment and thus reopen the EFAl-blocked pore channels of the steamed zeolite. The steaming treatment at a suitable temperature and subsequent citric acid leaching not only decreased the strength of acid sites to a desirable degree but also increased the ratio of medium and strong Lewis acidity to medium and strong Brönsted acidity, both of which conferred the resulting catalyst with superior selectivity to aromatics, good hydroisomerization activity and gasoline research octane number (RON) preservability, as well as enhanced on-stream stability. The results fully demonstrated that the treatments by steaming and followed citric acid leaching can serve as an important method for adjusting the physicochemical properties of HZSM-5 zeolite.     

Hydro-conversion of 1-methyl naphthalene into (alkyl)benzenes over alumina-coated USY zeolite-supported NiMoS catalysts

Hydro-conversion reactions were carried out at 360 °C under 5 MPa of H₂ pressure to study ring opening reactions of 1-methyl naphthalene using NiMoS supported on γ-alumina and alumina-coated/mixed USY zeolites. The catalysts were characterized using N₂ BET, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), pyridine FT-IR, and high-resolution transmission electron microscopy (HR-TEM) to study the influence of morphological and acidic properties on hydrogenation (HYD) and hydrocracking (HC) reactions. NMACZ-2 (NiMoS supported on the minimum amount of alumina-coated USY zeolite) showed enhanced reactivity for HC and produced (alkyl)benzenes with the highest yield, of ca. 80%. By-products were tetralin, decalin and cyclo-paraffin species. The tetralin species produced using NMACZ-2 moved into the alumina-coated USY zeolite support before undergoing HYD to produce decalin species, which were rapidly and selectively hydro-cracked into (alkyl)benzenes. A large amount of decalin was produced through the HYD of tetralin without significant cracking, possibly due to the weak acid character of γ-alumina. Bulk phase Mo oxide species on NMAZ (physical mixture of alumina and USY zeolite), as well as deactivation of the catalysts due to coke formation over the naked zeolite surface, inhibited the ring opening of tetralin, decreasing the yield of (alkyl)benzene. Various morphologies, such as the MoS₂ structure and acidic characteristics of the catalysts, were crucial factors affecting the HC reactivity of 1-methyl naphthalene.     

Polymerisation of styrene using Y, USY and β zeolites as catalysts

The homopolymerisation of styrene is studied in the presence of Y, USY and beta zeolites. High molecular weight polymers, in the range 0.7 × 10⁶–1 × 10⁶, are obtained in good yields. The activity of zeolite beta is only slightly increased by calcination of the as-synthesised material, pointing to an important role of the zeolite outer surface. The influence of the catalyst acidity upon the polymer molecular weight is evaluated by the use of dealuminated zeolites. This revised version was published online in July 2006 with corrections to the Cover Date.     

Propane Reactions over Faujasite Structure Zeolites Type-X and USY: Effect of Zeolite Silica over Alumina Ratio, Strength of Acidity and Kind of Exchanged Metal Ion

In this work we prepared various zeolite-X and USY samples partially exchanged with copper, iron and platinum. These samples were characterized by XRD, Chemical Analysis, SEM-EDS, N₂-adsorption–desorption, ammonia-TPD, and tested as catalysts in high temperature (400 and 550 °C) propane transformation. The obtained results revealed the strong effect of Si/Al ratio in faujasite zeolite structure, the number and strength of acid sites and of the presence of different metal ions in countered ion sites, on the catalytic activity and selectivity of zeolite-X and USY. The highest propane dehydrogenation activity was achieved with the platinum-exchanged X zeolite (∼11.2% propylene yield, ∼31% selectivity). On the contrary USY zeolites showed high cracking capability and relatively low dehydrogenation activity excepting the platinum-exchanged sample which yielded notably high aromatization products.     

Comparison of protonated zeolites with various dimensionalities for the liquid phase alkylation of i-butane with 2-butene

This study focused on the effects of structure on the catalytic performance of various three-, two-, and one-dimensional zeolites. The alkylation of isobutane with 2-butene was carried out under both mild and severe conditions with respect to the feed flow rate. It was observed that zeolite beta outperformed the other zeolites, exhibiting high olefin conversion and alkylate selectivity. For the olefin WHSV used in this work, LTL and USY deactivated rapidly. It is proposed that their fast deactivation was a result of the periodic expansions of their respective pore structures. In contrast to the behavior of other zeolites, the C₈ selectivities almost remained high and constant over LTL. The one-dimensional ZSM-12 was found to outperform in terms of activity many of the samples in this study because of its unique pore structure. A study of the carbonaceous material formed inside the zeolites pores discovered that their composition also depended on the zeolite pore structure. The results of this study indicate that the ability of certain zeolites to inhibit the formation of coke precursors because of their particular pore structures is an important parameter.     

Activity of different zeolite-supported Ni catalysts for methane reforming with carbon dioxide

The catalytic performance of Ni based on various types of zeolites (zeolite A, zeolite X, zeolite Y, and ZSM-5) prepared by incipient wetness impregnation has been investigated for the catalytic carbon dioxide reforming of methane into synthesis gas at 700 °C, at atmospheric pressure, and at a CH₄/CO₂ ratio of 1. It was found that Ni/zeolite Y showed better catalytic performance than the other types of studied zeolites. In addition, the stability of the Ni/zeolite Y was greatly superior to that of the other catalysts. A weight of Ni loading at 7 wt.% showed the best catalytic activity on each zeolite support; however, the 7% Ni catalysts produced a higher amount of coke than that of two other Ni loadings, 3 and 5%.