Microcalorimetric and FTIR Study of the Adsorption of Carbon Dioxide on Alkali-Metal Exchanged FER Zeolites

Adsorption of CO₂ on alkali-metal exchanged (Li⁺, Na⁺, K⁺) FER zeolites was investigated by means of microcalorimetry and FTIR spectroscopy. The adsorption enthalpies strongly depend on coverage for all investigated materials and they are also influenced by concentration of Al in the framework. Especially, samples of Na- and K-FER with lower Si/Al ratio (8.6) exhibited substantially larger initial interaction energy than samples with Si/Al 27.5. Differences in zero-coverage adsorption energy of zeolites with different cation concentration (Si/Al ratio) are 9 and 7.2 kJ/mol for Na- and K-FER zeolites respectively. This phenomenon is attributed to formation of bridged CO₂ adsorption complexes formed between two cations, which are characterized by IR absorption band of ν₃ stretching vibration mode at 2370 and 2357 cm^?1 for Na- and K-FER respectively.     

碱改性介-微孔HZSM-5分子筛催化乙醇脱水制乙烯性能

对两种不同硅铝比的HZSM-5分子筛进行碱处理,制备介-微孔复合HZSM-5分子筛,研究乙醇脱水制乙烯的催化性能,并考察碱溶液浓度和处理温度对HZSM-5分子筛孔结构和表面酸性的影响。结果表明,适宜的碱处理条件有利于分子筛发生骨架脱硅和脱铝,从而形成介孔。碱处理对硅铝比低的HZSM-5分子筛酸性质影响明显,而硅铝比高的HZSM-5分子筛在碱处理过程中酸性质变化不明显,更易发生脱硅和脱铝而形成更多介孔。碱改性介-微孔HZSM-5分子筛催化剂使乙醇脱水制乙烯催化性能得到改善,尤其低温催化活性提高,这主要归功于碱处理中介孔的形成和表面酸性的调变。     

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。     

沸石的碱溶液处理改性

与沸石的酸处理脱铝改性相类似，沸石的碱溶液处理也是一种沸石改性的方法。通过优先提取沸石中的硅物种，沸石的碱溶液处理改性能降低沸石的硅铝比，从而改变与沸石硅铝比相关的性能，如阳离子交换能力和催化活性。此外，采用低浓度的碱液处理沸石还可以制造出孔径规整的介孔，而不会改变沸石的微孔结构，还可以将碱金属阳离子引入到沸石中，从而得到固体碱沸石催化剂。因此，详细研究沸石的碱溶液处理改性，将为人们提供更多的沸石后处理改性的选择。     

正丁烷及丁烯-1在不同硅铝比ZSM-5分子筛上吸附的实验与模型

Four ZSM-5 zeolite catalysts with different Si/Al ratios for the catalytic cracking of C4 fractions to produce ethylene and propylene were prepared in this study.First,the adsorption isotherms of pure n-butane and butene-1 and their mixtures on these catalysts at 300K and p=0—100kPa were measured using the intelligent gravimetric analyzer.The experimental results indicate that the presence of Al can significantly affect the adsorption of butene-1 than that of n-butane on ZSM-5 zeolites.Then,the double Langmuir（DL）model was applied to study the pure gas adsorption on ZSM-5 zeolites for pure n-butane and butene-1.By combining the DL model with the ideal adsorbed solution theory（IAST）,the IAST-DL model was applied to model the butene-1（1）/n-butane（2）binary mixture adsorption on ZSM-5 zeolites with different Si/Al ratios.The calculated results are in good agreement with the experimental data,indicating that the IAST-DL model is effective for the present systems.Finally,the adsorption over a wide range of variables was predicted at low pressure and 300K by the model proposed.It is found that the selectivity of butene-1 over n-butane increases linearly with the decrease of Si/Al ratio.A correlation between the selectivity and Si/Al ratio of the sample was proposed at 300K and p=0.08MPa.     

Promoting Xylene Production in Benzene Methylation using Hierarchically Porous ZSM-5 Derived from a Modified Dry-gel Route

Methylation of benzene is an alternative low-cost route to produce xylenes, but selectivity to xylene remains low over conventional zeolitic catalysts. In this work, a combined dry-gel-conversion and s...     

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.     

沸石的碱处理溶解

晶体的溶解与晶体的生长存在着密切的联系，详细研究沸石晶体的溶解行为将有助于更好的理解沸石晶体的生长机理。鉴于目前对沸石晶体的碱处理溶解行为的研究尚处于初始阶段，所以从沸石碱溶解的几点关键内容出发，如沸石的硅铝比对沸石碱处理的影响，焙烧“活化”后沸石的碱处理溶解行为的变化，沸石与其无定形前驱物的溶解性差异以及沸石的溶解机理和溶解动力学方程方面，综述了有关沸石碱处理溶解研究方面的最新动态。     

Fractal Extra-Framework Species in De-aluminated LaY Zeolites and Their Catalytic Activity

Lanthanum-containing Y (LaY) zeolites were prepared by ionic exchange from NaY parent zeolite. The LaY zeolites were de-aluminated by steaming. De-aluminated zeolites presented different Si/Al ratio. The physicochemical properties of these catalysts were characterized by X-ray diffraction, pyridine and xenon adsorption, infrared spectroscopy and ²⁹Si, ²⁷Al, ¹²⁹Xe, ¹³⁹La solid-state nuclear magnetic resonance spectroscopy. Furthermore, a fractal geometry approach was adopted to describe the evolution in the texture as a consequence of de-alumination. The catalytic properties of materials were evaluated in the n-hexane cracking reaction. The catalyst with the highest catalytic activity was the zeolite highest de-aluminated (Si/Al ratio of 3.7). Such performance was attributed on the one hand, to active extra-framework aluminum species hosted in the large cavities of zeolites and, on the other hand to redistribution of lanthanum species into the zeolite as a consequence of de-alumination.     

Xylene Isomerization in the Liquid Phase Using Large‐Pore Zeolites

Three large‐pore zeolites, Beta with Si/Al ratios of 25 and 35 and Mordenite with an Si/Al ratio of 30, were studied in the conversion of o‐xylene at 493 K. Maximum conversion was achieved by the catalyst with the highest Si/Al ratio due to faster diffusion of the isomer inside the zeolite channels because of the lower acidity of the solid even with larger crystal size. A kinetic study was then carried out over this catalyst between 473 and 513 K in a batch reactor in the liquid phase. The activation energies obtained do not indicate the presence of diffusional constraints towards any isomer. Finally, the kinetic model obtained was simulated in a fixed‐bed reactor and compared to ZSM‐5 in the temperature range from 493 to 533 K. An increment in p‐xylene production of 20 % on average was obtained.     

TUN, IMF and -SVR Zeolites; Synthesis, Properties and Acidity

The effect of synthesis conditions on the preparation and properties of three novel zeolites TUN, IMF, and -SVR was investigated and compared with MFI. X-ray powder diffraction, infrared spectroscopy, chemical analysis, sorption measurements, and scanning electron microscopy were employed to characterize the textural and chemical properties of these zeolites. FTIR spectroscopy in combination with pyridine as probe molecule was used to describe the type, concentration and acid strength of these zeolites. Zeolite -SVR was synthesized with Si/Al ratios higher than 100 in contrast with TUN and IMF having Si/Al ratios about 20–30, respectively. TUN, MFI and IMF zeolites exhibit similar concentrations of Brønsted and Lewis acid sites and also similar acid strength of Brønsted sites. In contrast, the presence of one vacancy/unit cell in the case of -SVR zeolite substantially changes its acidic properties. Generally, zeolites TUN and IMF exhibit similar acidic properties in terms of acid strength and Brønsted to Lewis acid site ratio like MFI and due to their slightly larger pores higher activities in catalytic reactions are expected.     

ZSM-5分子筛形貌及硅铝比对甲缩醛气相羰基化反应性能的影响

通过调控合成方式、改变原料比例,制备纳米棒状、纳米球状、椭球状、圆柱状及棋子状等不同形貌及硅铝比的ZSM-5分子筛,并对其催化甲缩醛气相羰基化反应性能进行详细考察。在110℃、0.6 MPa、CO与甲缩醛流速分别为100 mL·min-1和0.035 mL·min-1条件下,硅铝物质的量比为30的棋子形ZSM-5分子筛表现出最佳的催化活性,甲缩醛转化率达31.9%,目标产物甲氧基乙酸甲脂选择性为21.4%。通过XRD、SEM、XRF、Py-FTIR、NH 3-TPD以及27 Al MAS NMR等对合成的分子筛进行详细表征,发现调控分子筛形貌及硅铝物质的量比可改变ZSM-5分子筛的酸性特征,并改变分子筛骨架中活性铝物种分布。适量的中强B酸酸位及分子筛交叉孔道内较高比例的活性铝物种分布可能是硅铝物质的量比30的棋子形ZSM-5分子筛表现出较好催化活性的原因。     

Pozzolanic reactions of common natural zeolites with lime and parameters affecting their reactivity

The pozzolanic reaction between portlandite and different types of nearly pure natural zeolites was studied. Analcime, phillipsite, chabazite, erionite, mordenite and clinoptilolite-rich tuffs were mixed with portlandite and water (1:1:2 by weight), and the progress of the pozzolanic reaction was quantitatively determined by thermogravimetrical analyses from 3 to 180 days.A thorough characterization of the raw materials was performed by quantitative XRD, XRF, SEM-EDX, BET specific surface area measurements, grain-size analyses, FTIR and Cation Exchange Capacity measurements. The difference in reactivity of the samples containing zeolites with varying Si/Al ratios, as well as between clinoptilolite-rich samples exchanged with different cations or ground to different grain sizes was assessed.The results indicate that the external surface area only influences the short-term reactivity, whereas the cation content has an effect on both the long- and short-term reactivity. The early reactivity of the unexchanged samples can be explained by these two parameters, but their long-term reactivity is mainly related to the Si/Al ratio of the zeolites. Samples with zeolites rich in Si react faster then their Al-rich counterparts.     

Statistical analysis of Al distributions and metal ion pairing probabilities in zeolites

The distributions of Al tetrahedral sites are studied as a function of Si : Al ratio (from 11 to 95) in three zeolites: ZSM-5, ferrierite, and mordenite. Al configurations obeying Loewenstein’s rule are generated by a Monte Carlo procedure and analyzed in terms of accessibility to specific channels. The distribution of pairs of Al sites accessible to the same channel segregates into distinct nearest-neighbor and ring-bridging types. Such pairs provide favorable binding environments for extraframework MO_xM²⁺ cations in the metal-ion-exchanged forms of the zeolites. In all three zeolites, the probability of a given Al site having at least one suitable partner for pairing within 8.5 Å is close to unity for typical Si : Al ratios. The probability at shorter distances is more sensitive to the zeolite structure, reflecting the larger number of highly puckered five- and six-membered rings in ZSM-5. This sensitivity, and its implications for CuO_xCu²⁺ formation in the three Cu-exchanged forms, may explain why Cu-ZSM-5 is the most active of the three for catalytically decomposing NO.     

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.     

The effect of hierarchical single-crystal ZSM-5 zeolites with different Si/Al ratios on its pore structure and catalytic performance

Hierarchical single-crystal ZSM-5 zeolites with different Si/Al ratios(Hier-ZSM-5-x,where x=50,100,150 and 200)were synthesized using an ordered mesoporous carbon-silica composite as hard template.Hier-ZSM-5-x exhibits improved mass transport properties,excellent mechanical and hydrothermal stability,and higher catalytic activity than commercial bulk zeolites in the benzyl alcohol self-etherification reaction.Results show that a decrease in the Si/Al ratio in hierarchical single-crystal ZSM-5 zeolites leads to a significant increase in the acidity and the density of micropores,which increases the final catalytic conversion.The effect of porous hierarchy on the diffusion of active sites and the final catalytic activity was also studied by comparing the catalytic conversion after selectively designed poisoned acid sites.These poisoned Hier-ZSM-5-x shows much higher catalytic conversion than the poisoned commercial ZSM-5 zeolite,which indicates that the numerous intracrystalline mesopores significantly reduce the diffusion path of the reactant,leading to the faster diffusion inside the zeolite to contact with the acid sites in the micropores predominating in ZSM-5 zeolites.This study can be extended to develop a series of hierarchical single-crystal zeolites with expected catalytic performance.     

High-temperature adsorption of n-alkanes on ZSM-5 zeolites: influence of the Si/Al ratio and the synthesis method on the low-coverage adsorption properties

The influence of the composition and synthesis method on the low-coverage adsorption properties of C₅–C₉ n-alkanes on ZSM-5 zeolites was studied using the pulse chromatographic technique at temperatures between 200 and 400 °C. Experiments were performed with materials having Si/Al ratios between 12 and 400, synthesized with and without an organic template. For all ZSM-5 samples, the Henry adsorption constants increase exponentially with the carbon number, while zero-coverage adsorption enthalpies increase in a linear way. With decreasing Al content, the Henry constants and adsorption enthalpies decrease. An increase in adsorption enthalpy of 10.1 kJ/mol per added –CH₂– group is observed for an Si/Al ratio of 400, while an increase of 12.1 kJ/mol is found for an Si/Al ratio of 15. The contribution to the adsorption entropy per carbon atom depends on the ZSM-5 composition and varies between 11.2 and 14.4 J/(mol K). A significant effect of the synthesis method on the Henry constants, adsorption enthalpies and entropies is observed. All ZSM-5 samples synthesized using organic templates show the same unique relationship between adsorption enthalpy and entropy, different from that of zeolites synthesized without organic template.     

碱处理制备介孔-微孔沸石分子筛的影响因素及其应用研究进展

综述了碱处理制备介孔-微孔沸石分子筛的影响因素,包括碱处理条件、沸石分子筛硅铝比和模板剂对碱处理脱硅形成介孔的影响。评述了碱处理所制备介孔-微孔沸石分子筛在应用方面所取得的进展,重点介绍了它们在烷基化、异构化、裂化和醇烃化等催化反应中的应用。通过碱处理引入介孔可极大地缩短分子在沸石微孔道中的扩散距离,从而增强表观催化反应活性及提高催化剂的稳定性。提出了今后研究的重点为：阐明碱处理引入介孔的形成机理和碱处理对分子筛骨架结构、酸性的影响,拓展碱处理制备介孔-微孔沸石分子筛的应用 范围。     

Effects of the Nitridation of Y and USY Zeolites on their Catalytic Activity for the Base Catalyzed Knoevenagel Condensation

This contribution reports on the preparation, physicochemical characterization and catalytic performances of nitrided zeolites in the Knoevenagel condensation reaction. These basic materials were prepared by subjecting one Y zeolite (Si/Al ratio of 2.6) and two ultrastable Y zeolites (Si/Al ratio of 13 and 37) to nitridation, i.e., treatment with ammonia at high temperature. Both the amount and the chemical nature of incorporated nitrogen species were controlled by the nitridation temperature. Namely, an increase of the temperature induces an increase of the nitrogen content and the appearance of nitrogenous species in the following order of increasing temperature: NH₄ ⁺, adsorbed NH₃, –NH₂, >NH and >N–. The nitridation occurred practically in the same manner whatever the Si/Al ratio of the starting material. However, from a catalytic point of view different behavior was observed. No direct correlation was found with the nitrogen content of the samples. Nitrided zeolites were found to exhibit catalytic activity as long as the zeolitic framework was maintained.     

用于高湿度废气中甲苯吸附净化的疏水型ZSM-5分子筛的合成及其吸附性能研究

采用水热原位法合成了不同硅铝比的ZSM-5分子筛，研究了硅铝比对ZSM-5分子筛结构和疏水性的影响。以典型的挥发性有机物甲苯为对象，在动态吸附实验装置上评价了ZSM-5分子筛吸附有机物的性能，并拟合了甲苯在疏水ZSM-5上的吸附等温线方程。结果表明，高硅铝比ZSM-5具有良好的疏水性，其静态水吸附容量为0.014 g·g^-1，在高湿度条件下，甲苯浓度为1800 mg·m^-3，GHSV为25000 ml·h^-1·g^-1，温度为35℃，甲苯穿透吸附容量为0.041 g·g^-1，甲苯饱和吸附容量为0.075 g·g^-1。吸附等温线的拟合显示，甲苯在疏水ZSM-5分子筛上的吸附符合Langmuir-Freundlich复合模型。