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。     

Effect of Si/Al ratio on performance of Pt–Sn-based catalyst supported on ZSM-5 zeolite for n-butane conversion to light olefins

The performance of Pt–Sn-based catalyst, supported on ZSM-5 of different Si/Al ratios were investigated for simultaneous dehydrogenation and cracking of n-butane to produce light olefins. The catalysts were characterized by number of physio-chemical techniques including XRF, TEM, IR spectra, NH₃-TPD and O₂-pulse analysis. Increase in Si/Al ratio of zeolite support ZSM-5 significantly increased light olefin's selectivity, while feed conversion decreases due to lower acidity of support. The results indicated that both the n-butane cracking and dehydrogenation activity to light olefin's over Pt–Sn/ZSM-5 samples with increasing Si/Al ratios greatly enhanced catalytic performance. The catalysts were deactivated with time-on-stream due to the formation of carbon-containing deposits. A coke deposition was significantly related to catalyst activity, while at higher Si/Al ratio catalyst the coke precursors were depressed. These results suggested that the Pt–Sn/ZSM-5 catalyst of Si/Al ratio 300 is superior in achieving high total olefins selectivity (above 90 wt.%). The Pt–Sn/ZSM-5 also demonstrates resistance towards hydrothermal treatment, as analyzed through the three successive reaction-regeneration cycles.     

Enhanced Stability of HZSM-5 Supported Ga2O3 Catalyst in Propane Dehydrogenation by Dealumination

Gallium oxide catalysts supported on HZSM-5 with different Si/Al ratios were characterized by pyridine adsorption FT-IR, model reactions and XPS studies. As the Si/Al ratio of the support HZSM-5 zeolite rises, the acidity of the supported catalysts decreases accordingly, which comes from two aspects: the loss of acid sites present on HZSM-5 support and the loss of the acid sites present on gallium oxides. The latter was caused by the change in the interaction between Ga₂O₃ and support. The initial activity in the propane dehydrogenation decreases with increasing Si/Al ratio while the stability increases. The enhanced stability is thought to be caused by the decrease of the acidity of the catalysts, resulting in the suppression of the side reactions, such as cracking and oligomerization.     

十氢萘在HY和Beta分子筛上加氢开环的研究

采用高温高压反应釜研究了十氢萘在低硅铝比HY分子筛[n(Si)/n(Al)=3.2]、Beta分子筛n(Si)/n(Al)=9.7]和双功能催化剂Pt-HY、Pt-Beta上的加氢开环反应,考察了分子筛孔道结构及酸性质、贵金属Pt及反应温度等因素对十氢萘转化率和产物选择性的影响。结果表明,十氢萘在Beta分子筛上的转化率较高,且有大量脱氢缩合产物（DHC）生成。Pt引入HY和Beta分子筛后,初始反应速率升高,十氢萘转化率增加,C₁₀产物中开环异构比增大,Beta分子筛上的脱氢缩合反应得到抑制。反应温度升高可以提高十氢萘在HY分子筛上的转化率,使得C₁₀产物选择性下降,而开环异构比（ROP/Iso）增大。     

Selective catalytic reduction of NO with propene over CuMFI zeolites: dependence on Si/Al ratio and copper loading

Selective catalytic reduction of nitrogen oxide by propene in an oxidising atmosphere was studied on several CuMFI catalysts with different Si/Al ratios (11 Si/Al 100) and different copper loadings (between 0 and 5.5 wt.-%). From the results it was observed that the influence of zeolite Si/Al ratio on CuMFI catalytic activity for NO SCR by propene is dependent on the catalyst copper loading. Furthermore, the effect of catalyst copper loading on catalytic performance depended on the catalyst Si/Al ratio. The results also demonstrated that CuMFI catalysts with different Si/Al ratios and copper loadings, but with the same Cu/Al ratio and, therefore, the same copper exchange level have similar catalytic activity profiles for NO SCR.

It was further observed that not all Cu cations exchanged into MFI catalysts have equivalent catalytic activity for NO SCR, which made the existence of different copper environments on CuMFI catalysts evident, isolated Cu²⁺ ions being the most active species for NO SCR by propene.

Moreover, the results showed an improvement of the CuMFI catalytic activity at low temperatures by increasing the catalyst copper exchange level and, consequently, decreasing the number of Brönsted acid sites, which can be performed either by increasing the zeolite Si/Al ratio or copper loading.     

Effect of metal/acid balance in Pt-loaded large pore zeolites on the hydroisomerization ofn-Hexane andn-heptane

Large-pore zeolites H-Beta, H-Mordenite and H-Omega were loaded with platinum and applied for the hydroisomerization of n-hexane andn-heptane. The catalytic activity of Pt-loaded zeolite showed good correlation with the effective acidity probed by pyridine rather than with the total acidity probed by ammonia when equal amounts of metal sites are present. The selectivity to multibranched isomers over three different catalysts was found dependent upon the conversion ofn-paraffin. At low conversion, the selectivity to multibranched isomers was higher over Pt-load-ed zeolites with high acid strength. At high conversion level, however, the selectivity was mainly governed by the metal/acid balance. On H-Mordenite and H-Omega, large amount of strong acid sites are located in the small pore or cage. In Pt/H-MOR, the metal/acid balance was poor because there was detrimental loss of metal sites caused by isolation of Pt in the side pockets of 8-MR and/or pore blockage of the linear 12-MR channel. Even though the acidity of H-Beta was very low compared to H-MOR and H-Omega, Pt/H-Beta yielded the best performance for the hydroisomerization ofn-paraffin because of better metal/acid balance in Pt/H-Beta.     

高温水蒸汽处理对HZSM-5分子筛催化甲醇制丙烯的影响

考察不同硅铝比的HZSM-5分子筛催化剂和经过高温水蒸汽处理后的HZSM-5分子筛催化剂在甲醇制丙烯反应中的催化性能,考察温度和空速对催化反应的影响。结果表明,随着HZSM-5分子筛硅铝比的增加,产物中丙烯选择性增大,可能是分子筛的酸性降低所致;经过高温水蒸汽处理后的HZSM-5分子筛表面酸性降低,提高了催化剂的催化性能。在反应温度450 ℃和空速1.0 h^-1条件下,600 ℃高温水蒸汽处理后的催化剂HT-600的丙烯选择性从改性前的26.8%提高到33.5%。     

Esterification of oleic acid in soybean oil on zeolite catalysts with different acidity

The catalytic activity of zeolites was studied in the esterification of oleic acid with methanol in soybean oil. The influences of acidity and pore structure of the zeolites were investigated in relation to conversion of the oleic acid on the zeolite catalysts. H⁺ ion exchanged ZSM-5 (HMFI) and mordenite (HMOR) zeolites conducted with different Si/Al ratio were employed to examine an influence of acidity in the reaction. Conversion of oleic acid was about 80% on HMOR zeolites and HMFI(25) zeolite. The conversion of oleic acid was improved as the amount of acid site increased. The amount of acid site of the zeolites affected significantly the catalytic activity in the esterification of oleic acid.     

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...     

Thermal-catalytic degradation kinetics of polypropylene over BEA, ZSM-5 and MOR zeolites

In this study, thermal degradation of additive-free polypropylene powder over different type of zeolite catalysts was investigated. BEA, ZSM-5 and MOR with different surface areas, pore structures, acidities and Si/Al molar ratios were used as solid catalysts for degradation of polypropylene (PP). Degradation rate of the PP over zeolites was studied by thermogravimetric analysis (TGA) employing four different heating rates and apparent activation energies of the processes were determined by the Kissinger equation. The catalytic activity of zeolites decreases as BEA > ZSM-5a (Si/Al = 12.5) > ZSM-5b (Si/Al = 25) > MOR depending on pore size and acidity of the catalysts. On the other hand, initial degradation is relatively faster over MOR and BEA than that over both ZSM-5 catalysts depending on the apparent activation energy. It can be concluded that acidity of the catalyst is the most important parameter in determining the activity for polymer degradation process as well as other structural parameters, such as pore structure and size.     

甲醇在水蒸汽处理改性ZSM-5分子筛上转化制丙烯

对硅铝物质的量比分别为20、80和220的ZSM-5分子筛进行水蒸汽处理改性,通过使用X射线衍射、吡啶红外吸附、N2吸附和透射电子显微镜等手段研究了水蒸汽改性对ZSM-5分子筛孔道结构的影响,并考察了改性后分子筛在甲醇转化制丙烯反应中的催化性能.结果表明,水蒸汽改性处理导致低硅ZSM-5酸性减弱,并使其出现大量介孔.在...     

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.     

Copper-exchanged mordenites as active catalysts for NO selective catalytic reduction by propene under oxidising conditions: Effect of Si/Al ratio, copper content and Brönsted acidity

CuMOR catalysts with different Si/Al ratios and copper contents, prepared from the acid and sodium forms, were studied in NO reduction with propene in the presence of excess oxygen. It was observed that the influence of zeolite Si/Al ratio on CuMOR catalytic activity for NO SCR by propene depends on the catalyst copper content, the reverse being also true. For mordenites prepared from the acid form, it was shown that the most active catalyst must have 60% of copper exchange, whereas for those prepared from the sodium form, the maximum catalytic activity is obtained for catalysts with 20% of copper exchange. Moreover, it was observed that at low copper-exchange levels, the catalyst prepared from the sodium form exhibits much higher activity than those prepared from the acid form. Although, when the copper-exchange level increases, the effect of zeolite form is less pronounced. Thus, it was indicated that Brönsted acidity does not promote the NO selective reduction by propene.     

固体酸对二氧化碳加氢合成二甲醚催化剂性能的影响

以Cu-ZnO-Al2O3催化剂作为甲醇合成组分,以不同固体酸作为脱水组分,制备了一系列CO2加氢合成二甲醚的复合催化剂。研究表明CO2的转化率与固体酸的酸性无关,而取决于Cu-ZnO-Al2O3催化剂上甲醇的合成速率;二甲醚的选择性取决于固体酸的酸量和酸强度,脱水速率与固体酸的中/强酸有关。HZSM-5分子筛作为复合催化剂脱水组分时,二甲醚的收率最高;硅铝比对CO2转化率无影响,但可显著地影响二甲醚选择性;低硅铝比的HZSM-5更适合作为CO2加氢合成二甲醚复合催化剂的脱水组分。     

Liquid-phase degradation of polyethylene wax over mordenite catalysts with different Si/Al molar ratios

The catalytic liquid-phase degradation of polyethylene wax into fuel oil was studied using mordenite catalysts with various Si/Al molar ratios prepared by dealumination. The total yield of gas and liquid products showed a volcano plot along the Si/Al molar ratio of mordenite. No significant change was observed in the composition of the liquid product for all catalysts used in this study. Fast deactivation was anticipated on the mordenite catalysts with low Si/Al molar ratios such as 5 and 10, due to pore blocking by the carbon deposited on the external surface of the zeolite. A high activity and a long catalyst life were obtained on the mordenite catalyst with a Si/Al molar ratio of 12.     

Acidity and catalytic activity of the mesoporous aluminosilicate molecular sieve MCM-41

The acidity and catalytic properties of aluminosilicate mesoporous molecular sieves with the MCM-41 structure and bulk Si/Al ratios in the 10–60 range have been investigated. The incorporation of 4-coordinate aluminium into the structure of MCM-41 generates both BrØnsted and Lewis acid sites in amounts increasing with the degree of incorporation. However, the BrØnsted/Lewis acid population ratio is independent of the content of aluminium. The number and strength of acid sites generated are comparable to those of a pillared acid-activated clay and lower than in zeolite H-Y with Si/Al=3.65. Aluminosilicate MCM-41 is a moderate catalyst for the conversion of cumene which proceeds predominantly via catalytic cracking to propene and benzene. The sample of MCM-41 with the highest content of framework aluminium (Si/Al=10) has the largest number of BrØnsted acid sites and exhibits highest catalytic activity.     

A Novel Radioisotope Method for Studying Catalytic Transformations over Alumina, H-ZSM-5 and H-Beta Zeolite Catalysts: Investigation of Conversion of 11C-Labeled Methanol to 11C-Labeled Dimethyl Ether and Hydrocarbons

A novel radiochemical method for investigating the catalytic transformations of the ¹¹C-radioisotope labeled methanol over H-ZSM-5 and H-Beta zeolite catalysts has been introduced. The catalysis process was monitored by gamma detectors and the ¹¹C-labeled products were analyzed by radio-gas chromatography. The medium pore H-ZSM-5 and H-Beta zeolite catalysts were synthesized and characterized using X-ray powder diffraction, scanning electron microscope, nitrogen adsorption, X-ray fluorescency and FTIR spectroscopy. The investigations of ¹¹C-labeled product distributions and reaction mechanism of the conversion of [¹¹C]methanol over H-ZSM-5 and H-Beta zeolite catalysts have been elaborated in terms of structure and acidity of the catalysts. In microreactors the effect of natural carbon compounds from environment can be a disturbing effect for the detection of inactive carbon products. Applied radio detection method eliminates these disturbing effects and detects only ¹¹C-labeled compounds during the whole catalytic process. In the study of the transformations of carbon compounds, besides the well known ¹⁴C tracer technique and ¹³C MAS NMR spectroscopy investigation, the ¹¹C-method is a new, more sensitive and simple one to monitor the transformation of the starting ¹¹C-labeled compound by radio detectors (gamma detector) and for analyzing the ¹¹C-labeled products by radio-gas chromatography.     

正己烷催化裂解制低碳烯烃：ZSM-5分子筛催化剂酸性的影响

在小型固定床装置上,以ZSM-5分子筛为催化剂,研究不同硅铝物质的量比对合成的ZSM-5分子筛织构性能以及酸性对正己烷催化裂解性能的影响。采用XRD、SEM、N₂吸附-脱附和NH_3-TPD等方法对不同硅铝物质的量比的ZSM-5分子筛进行表征,结果表明,硅铝物质的量比的改变对ZSM-5分子筛的形貌和结构没有影响;随着硅铝物质的量比的增加,分子筛的酸量减少,酸强度减弱,正己烷催化裂解活性逐渐降低。同时,随着酸量减少和酸强度减弱,高硅ZSM-5分子筛上氢转移反应得到明显抑制,丙烯选择性提高。     

Effect of Si/Al ratio and a secondary hydrothermal treatment on the properties of Al-MSU-SFAU

This work reexamines the preparation condition of Al-MSU-S_FAU, which is prepared with an assembly method from zeolite Y seed colloidal, and reveals the effect of Si/Al ratio and a secondary hydrothermal treatment on the property of the material, e.g. the texture, the hydrothermal stability, the acidity and the catalytic activity. With the specific condition for preparing Al-MSU-S_FAU, the samples with high Si/Al atomic ratios are uniform, but have no crystalline structure and low hydrothermal stability. The samples with Si/Al <5 contain a significant amount of micropores. However, they are also instable and are the mixtures of zeolite Y and mesoporous material. A secondary hydrothermal treatment destroys a part of the mesopores for all the samples irrespective of the Si/Al ratios but reforms the micropores, specifically improves the micropore volume and surface area for the sample with Si/Al = 5. This sample has the long expected micro/meso composite porous structure with higher hydrothermal stability and acidity.     

Carbon monoxide hydrogenation over Fe/HZSM-5 catalysts. Effect of SiO2/Al2O3 zeolite ratio

Iron catalysts supported on ZSM-5 zeolites of a wide range of silica-to-alumina ratios (29-) have been prepared and tested in carbon monoxide hydrogenation. The crystalline phases of the catalysts were characterized by X-ray diffraction and their acidity by infrared spectroscopy of adsorbed pyridine. The catalytic tests were conducted at 533 K, an overall pressure of 21 bar and a feed ratio CO/H₂ close to 1. It was found that the selectivity to light olefins (C₂–C₄) increases in parallel with the increase of the Si/Al ratio of the zeolite. This was explained in terms of the decrease in Brønsted acidity of the catalysts. As a consequence, very high olefin selectivities can be achieved by decreasing the number of strong acid sites in the zeolite structure, but at the expense of high oxygenate formation.