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1.
The aim of this work is to find out how platinum supported over a gallosilicate of the MFI type influences the removal of Ga from the framework and affects the properties of the Pt/H[Ga]ZSM5 catalysts. In this regard, a gallosilicate and an aluminosilicate of MFI structure, with a Si/M ratio ≈15 (M = Ga, Al) were synthesized and characterized by XRD, nitrogen physical adsorption at ?196 °C and chemical analysis by ICP-AES. Afterwards, they were used to prepare the following bifunctional catalysts: xPt/H[Ga]ZSM5 (x=0.10, 0.50 and 1.00 wt.% Pt) and 1.00%Pt/H[Al]ZSM5, which were characterized by ICP-AES, TEM, XPS, and the model reaction of toluene hydrogenation. The results found show dispersions within 50–80% for the supported platinum; the XPS analysis indicated a decrease in the Si/Ga ratio as a response to the increase of Pt content, suggesting a substantial influence of platinum on the migration of structural Ga toward the surface of the catalysts. This nonframework gallium remains oxidic and appears to strongly interact with Pt, which considerably affects the hydrogenating ability of these catalysts.  相似文献   

2.
Bifunctional monometallic Pt/H[Al]ZSM5, Sn/H[Al]ZSM5 and bimetallic Pt-Sn/H[Al]ZSM5 (tin atomic fraction, X Sn, of 0.46) catalysts were prepared and characterized by means of XPS, EPR, TEM and toluene hydrogenation. The species on their surface as well as the presence of an effect of the electronic and/or geometric type between Pt and Sn in the bimetallic catalyst, which would result in the existence of reduced tin species (Sn0 and/or Sn-Pt), were determined. These species were determined through XPS and would explain the decrease in the hydrogenating activity in the toluene hydrogenation reaction.  相似文献   

3.
《Fuel》2006,85(14-15):2202-2212
MCM-41, is one of the latest members of the mesoporous family of materials. They possess a hexagonal array of uniform mesopores (1.4–10 nm), high surface areas (>1000 m2/g) and moderate acidity. Due to these properties the MCM-41 materials are currently under study in a variety of processes as catalysts or catalyst supports. The objective of this study was to evaluate different types of MCM-41 materials as potential catalysts in the catalytic biomass pyrolysis process. We expected that the very high pore size and the mild acidity of these materials could be beneficial to reformulate the high molecular weight primary molecules from biomass pyrolysis producing useful chemical (and especially phenolic compounds) and lighter bio-oil with less heavy molecules. Three different samples of Al-MCM-41 materials (with different Si/Al ratio) and three metal containing mesoporous samples (Cu–Al-MCM-41, Fe–Al-MCM-41 and Zn–Al-MCM-41) have been synthesised, characterized and tested as catalysts in the biomass catalytic pyrolysis process using a fixed bed pyrolysis combined with a fixed catalytic reactor and two different types of biomass feeds. Compared to conventional (non-catalytic) pyrolysis, it was found that the presence of the MCM-41 material alters significantly the quality of the pyrolysis products. All catalysts were found to increase the amount of phenolic compounds, which are very important in the chemical (adhesives) industry. A low Si/Al ratio was found to have a positive effect on product yields and composition. Fe–Al-MCM-41 and Cu–Al-MCM-41 are the best metal-containing catalysts in terms of phenols production. The presence of the Al-MCM-41 material was also found to decrease the fraction of undesirable oxygenated compounds in the bio-oil produced, which is an indication that the bio-oil produced is more stable.  相似文献   

4.
Seon-Ki Song  Yuhong Wang  Son-Ki Ihm   《Catalysis Today》2006,111(3-4):194-198
A series of Al-MCM-41 modified with 1–7% lanthanum were used as supports to prepare the Mo/La–Al-MCM-41 catalysts containing 10 wt.% molybdenum. The supports and catalysts were characterized with XRD, BET, XPS, TPD, TEM and SEM, and their catalytic activities were tested for thiophene hydrodesulfurization. The La addition did not cause any significant collapse of the structure and morphology of Al-MCM-41 samples, and increased the acidity of Al-MCM-41 samples. The Mo/La–Al-MCM-41 catalysts showed higher thiophene HDS activity than non-modified catalysts. The La-modified catalysts showed an enhanced butene selectivity but a decreased tetrahydrothiophene selectivity, indicating that the La–Al-MCM-41 supports contained a larger amount of acid sites.  相似文献   

5.
用SO24-物质的量相同的H2SO4和Al2(SO4)3分别对Al-MCM-41进行改性,得到样品SO42-/Al-MCM-41和Al/SO24-/Al-MCM-41。采用X射线多晶衍射(XRD)、红外光谱(FTIR)、N2吸附-脱附和NH3程序升温脱附(NH3-TPD)等测试技术对样品进行表征。分别用H2SO4、MCM-41、Al-MCM-41、SO42-/Al-MCM-41和Al/SO24-/Al-MCM-41催化合成丙酸香叶酯,比较了它们的催化性能。结果表明,H2SO4和Al2(SO4)3改性对Al-MCM-41中孔分子筛结构影响不明显,都可提高其酸性,改性后中孔分子筛的骨架仍保持着六方介孔结构,孔径、孔容和比表面积有所降低,但用Al2(SO4)3改性的分子筛酸性和催化性能更强;SO42-/Al-MCM-41的酸催化活性主要源于SO42-与分子筛表面硅羟基作用形成的双齿螯合配位结构,而Al/SO42-/Al-MCM-41的酸催化活性一方面来自SO24-与分子筛表面硅羟基作用形成的双齿螯合配位结构,另一方面,也来自与分子筛骨架接枝的铝,使其产生了更多的Brnsted酸中心。  相似文献   

6.
Al-MCM-41 supported ceria samples of various cerium content (0.2, 0.3, 0.5, 0.8 and 3.0 wt.%) were prepared by impregnation and are characterized by BET, XRD, UV–VIS DRS, XPS and ESR techniques. At lower cerium contents the DRS clearly shows a blue shift of 50 nm in the absorbtion edge of CeO2 indicating the size quantization and high dispersion of cerium particles. The XPS analyses of Ce–Al-MCM-41 samples revealed the interaction of cerium with Al-MCM-41 in Ce3+ state and at higher loadings in Ce3+/4+ states. ESR studies also further substantiated this observation. These catalysts when subjected to photo degradation activity of phenol, 0.3 wt.% Ce–Al-MCM-41 is showing maximum degradation among all the catalysts tested. The present study highlights that cerium at lower loadings is in +3 oxidation state and is dispersed highly showing good photocatalytic activity in comparison with pure ceria.  相似文献   

7.
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.  相似文献   

8.
利用下行床连续热解实验装置,采用催化剂原位填充方式考察了三种孔道结构,不同酸量的酸性催化剂HZSM-5、Al-MCM-41、USY和一种碱性催化剂铝酸钙(Ca-Al)及酸碱催化剂的不同组合方式对挥发分转化行为的影响。结果表明,Al-MCM-41因具有适宜酸性及较大的比表面积和丰富的介孔结构,降低了焦油中重质组分含量,增加了轻质组分含量,在降低积炭和减少焦油损失方面优于酸性较强的HZSM-5和USY催化剂。Ca-Al促进烃类物质脱氢产生富氢小分子,抑制了大分子物质的缩聚,显著降低了积炭产率。结合酸碱催化剂对热解挥发分各自作用的优势,将其进行不同方式的组合,探究了在组合催化剂作用后热解挥发分产物的组成和产率变化情况,结果显示热解挥发分先通过具有脱氢性能的Ca-Al、然后再通过裂解作用适中的Al-MCM-41的Ca-Al/Al催化剂组合,表现出较强的调控挥发分组分间转化行为的能力,有效地降低了积炭的产率。  相似文献   

9.
The Fe‐Mo/ZSM‐5 catalysts were prepared by an impregnation method. A comparison of the catalytic activity for the reduction of NOx with ammonia over Fe‐Mo/ZSM‐5, Fe‐ZSM‐5 and Mo/ZSM‐5 catalysts was carried out. Also, the effects of the conditions used for calcination as well as of the Fe/Mo ratio on the catalytic performance of Fe‐Mo/ZSM‐5 catalysts were studied. It was found that Fe‐Mo/ZSM‐5 is more active than Fe‐ZSM‐5 and Mo/ZSM‐5 separately. Fe‐Mo/ZSM‐5 exhibited the best performance for SCR reaction with a Fe/Mo ratio of 1.5 and yielded the highest NOx conversion of 96 % at a temperature of 430 °C. The results also showed that the performance of Fe‐Mo/ZSM‐5 is sensitive to the conditions used during calcination. The bulk phase and surface composition of the Fe‐Mo/ZSM‐5 catalysts were determined by XRD, BET, and XPS techniques, respectively. The results revealed that the surface Mo percentage is the largest when the Fe/Mo ratio is 1.5, which may be related to its higher activity for catalytic reduction of NOx. XRD results indicate that the best catalytic performance of the Fe/Mo = 1.5 sample results from a strong interaction among Fe, Mo and HZSM‐5. In addition, it can be tentatively presumed that the surface nitrous species from the calcinations play an important role in SCR of NOx over Fe‐Mo/ZSM‐5 catalysts.  相似文献   

10.
The mesoporous molecular sieves Al-MCM-41 with Si/Al ratio equal to 16, was synthesized under hydrothermal conditions using cetyltrimethylammonium bromide (CTMA+Br) as surfactant. The same ratio of Al-MCM-41 materials was impregnated using sulfuric acid, the materials as sulfated Al-MCM-41 (SO42−/Al-MCM-41). The mesoporous materials viz Al-MCM-41 and SO42−/Al-MCM-41 were characterized using several techniques e.g. ICP-AES, Nephelometer, XRD, FT-IR, TG/DTA, N2-adsorption, solid-state-NMR, SEM and TPD-pyridine. ICP-AES studies indicated the presence of Al in the mesoporous materials. Nephelometer studies indicated the SO42− presence of the SO42−/Al-MCM-41. XRD studies indicated that the calcined materials of Al-MCM-41 and SO42−/Al-MCM-41 had the standard MCM-41 structure. The surface area, pore diameter, pore volume and wall thickness of the mesoporous materials were calculated by BET and BJH equations, respectively. Crystallinity, surface area, pore diameter and pore volume of SO42−/Al-MCM-41 decreased except wall thickness and the expelling aluminum from the Al-MCM-41 framework increased the Lewis acidity. FT-IR studies indicated that Al-ions were incorporated in the hexagonal mesoporous structure of Al-MCM-41 and sulfuric acid was impregnated into hexagonal Al-MCM-41 materials. The thermal stability of as-synthesized Al-MCM-41 materials and SO42−/Al-MCM-41 materials were studied using TG/DTA. The environments of the Al-ions coordinated in the silica matrix were determined by 27Al-MAS-NMR. The morphology of Al-MCM-41 and SO42−/Al-MCM-41 was determined by SEM. The total acidity of Al-MCM-41 and SO42−/Al-MCM-41 materials was determined by TPD-pyridine. The catalytic results were compared with those obtained by using sulfuric acid, amorphous silica–alumina, H-β, USY and H-ZSM-5 zeolites. The SO42−/Al-MCM-41 catalyst exclusively forms the product of dypnone from self-condensation of acetophenone molecules due to higher number of Lewis acid sites and has much higher yields than other catalysts except USY.  相似文献   

11.
以硅酸钠为硅源、硫酸铝为铝源、十六烷基三甲基溴化铵(CTAB)作模板剂,采用共沸蒸馏与超声波分散技术相结合的方法制备了介孔分子筛Al-MCM-41。以Al-MCM-41为载体、硝酸镍和磷酸氢二氨为原料,采用超声波振荡、程序升温还原法制备了Ni2P/Al-MCM-41催化剂,并对Al-MCM-41和Ni2P/Al-MCM-41进行了傅里叶变换红外光谱、比表面积测定、X射线衍射、扫描电镜表征。考察了Ni2P/Al-MCM-41催化剂对噻吩加氢脱硫的催化性能。结果表明:采用超声波制得的Al-MCM-41其比表面积、孔容和孔径明显高于常规搅拌制得的Al-MCM-41,共沸蒸馏制得的Al-MCM-41其比表面积、孔容和孔径高于未共沸蒸馏的Al-MCM-41;在反应时间为5 h、548 K、3.5 MPa条件下,Ni2P/Al-MCM-41催化剂对噻吩加氢脱硫的转化率接近100%。  相似文献   

12.
Selective liquid-phase t-butylation of p-cresol with t-butyl alcohol (t-BuOH) to produce 2-t-butyl-p-cresol (TBC) has been conducted over Al-MCM-41 catalysts with different Si/Al ratios. The effects of various reaction parameters such as temperature, reaction time and nt-BuOH:np-cresol ratio on the conversion of p-cresol and the selectivity of TBC have been systematically investigated as well. When the Si/Al ratio of Al-MCM-41 catalysts is increased from 21 to 104 (respectively yielding Al-MCM-41(21), Al-MCM-41(42), Al-MCM-41(62), Al-MCM-41(83) and Al-MCM-41(104)), both the conversion of p-cresol and the yield and selectivity of TBC decrease due to the decrease of the number of Brønsted acid sites of the Al-MCM-41 catalysts. Al-MCM-41(21) catalyst is found to give the highest conversion of p-cresol (88.2%) and the highest selectivity of TBC (90.40%) under the optimal nt-BuOH:np-cresol mole ratio of 2:1, the optimal reaction temperature of 90 °C and the optimal reaction time of 2 h. Furthermore, Al-MCM-41(21) can be recycled up to at least four times without losing its catalytic performance for butylation reaction.  相似文献   

13.
Supported Pd catalysts were prepared by direct hydrothermal (DHT) or template-ion exchange (TIE) method on Al-substituted MCM-41 as the support and tested in the hydrodechlorination of aryl chlorides such as 4-chloroanisole in liquid phase, together with impregnated Pd catalysts as references. When Pd was loaded on Al-MCM-41 with the Si/Al ratio of 150 by the TIE method, the catalyst showed the highest activity among the Pd catalysts prepared. PdO originally formed on the catalyst surface was in situ reduced to Pd metal during the reaction as the active form for the dechlorination. The activities of the supported Pd catalysts well correlated with the Pd dispersion on the TIE or impregnated Pd catalysts, whereas the DHT catalysts showed relatively high activities independently on the Pd dispersions. It was confirmed that the dechlorination proceeded by a heterogeneous mechanism catalyzed by Pd metal particles sized less than 10 nm on the surface of the catalyst. Al substitution for Si on MCM-41 was effective for the loading of Pd metal with the high dispersion, none the less Pd was located on the surface of the TIE catalyst particles and no significant effect of mesoporous structure on the reaction was observed. Methanol was the most profitable as the solvent among the various solvents tested. Various types of arylchlorides bearing hydroxy, methoxy, methyl, nitro and phenylcarbonyl group at the p-position were efficiently dechlorinated over Pd–Al-MCM-41 catalyst at 40 °C. Electrophilic attack of arylchloride was proposed as the rate determining step, where ionic mechanism positively worked and electron-releasing substituents increased the catalytic activity.  相似文献   

14.
《工业催化》2006,14(1):51-55
报道了一种新的微波固相法制备Mn(Salen)/Al-MCM-41催化剂的方法,并与常规制备方法进行了比较。对微波固相法制备的催化剂进行了一系列的表征,表征结果表明,微波固相方法和常规方法均能成功地将Mn(Salen)络合物固载于介孔Al-MCM-41分子筛中,且在原料的量相同的情况下,红外光谱显示微波固相法具有更强的吸收峰。比较了不同方法制备的催化剂在苯乙烯环氧化反应中的催化性能,发现微波固相法制备的Mn(salen)/Al-MCM-41-IP催化剂具有较高的催化活性和最好的环氧化物选择性。还考察了催化剂性能与制备过程中的微波辐射时间的关系。进行了催化剂的重复使用的实验,使用三次后,转化率达到59.4%,选择性可达78.3%。  相似文献   

15.
以十六烷基三甲基溴化铵(CTAB)为模板剂,正硅酸乙酯(TEOS)为硅源,乙二胺为碱性介质,当n(TEOS)∶n(NaAlO2)(或LaCl3)∶n(CTAB)∶n(H2NCH2CH2NH2)∶n(H2O)=1∶X∶0 12(或0 14)∶3 5(或8 0)∶130,其中X=0 1,0 05,0 033时,水热法合成了硅铝(硅镧)摩尔比为10、20和30的Al MCM 41和La MCM 41介孔分子筛。通过XRD、IR、NH3 TPD吸附脱附、BET及CCl4吸附等方法对分子筛的晶体结构和表面物性进行了研究,结果表明,合成的分子筛具有典型的六方介孔结构特征。将Al MCM 41和La MCM 41分子筛分别用于催化乙氧基化反应,研究结果表明,Al MCM 41的催化活性高于La MCM 41,当Al MCM 41用量为正辛醇质量的3%,反应温度为120℃,反应压力0 2MPa,n(正辛醇)∶n(环氧乙烷)=1∶2时,正辛醇聚氧乙烯醚产品的收率达85%。  相似文献   

16.
Pure SiO2 having a MCM-41 structure was modified by the introduction of 1 mmol/g of Al, Zr, W, B, or P. The parent silica and the modified materials were used to support a dispersed cupric oxide. The distribution, properties and thermal stability of the catalytic Cu2+-active sites were examined by ESR and IR spectroscopy and by measuring the activity in a test reaction of ethane oxidation. Modification of the parent silica MCM-41 influences drastically the stabilization of isolated Cu2+-species. Al-MCM-41 provides the most disperse (70–80%) and thermally stable state of the cupric phase. However, no simple correlation exists between the total number of surface Cu2+-sites and the catalytic activity. The specific catalytic activity (per one Cu2+-active site accessible to the reactants) depends strongly on the structure of the localized site. Isolated Cu2+-sites grafted to Al-MCM-41 show relatively high activity for the sample calcined at 520 °C. Thermal treatment at 650–750 °C causes a sharp loss of specific Cu2+ catalytic activity of Cu/Al-MCM-41 (as is also the case with CuH-ZSM-5). The less disperse cupric phase in non-modified MCM-41 demonstrates a higher specific catalytic activity.  相似文献   

17.
Al-MCM-41, Fe,Al-MCM-41 and Zn,Al-MCM-41 materials with different silicon to metal ratios were synthesized hydrothermally and characterized by XRD, BET, FT-IR, Acidity measurement by pyridine adsorbed FT-IR spectroscopy, 29Si and 27Al MAS NMR and ESR techniques. The orderly arrangement of mesoporous materials was clearly revealed from the XRD patterns. 29Si and 27Al MAS NMR established the co-ordination environment of silicon and aluminium. Electron paramagnetic resonance (EPR) study confirmed the co-ordination environment of Fe in Fe,Al-MCM-41 framework. The catalytic activity of these materials was evaluated in the vapour phase alkylation and acylation of ethylbenzene with ethyl acetate in the temperature range between 250 and 400 °C. The products were found to be 1,3-diethylbenzene (1,3-DEB), 1,4-diethylbenzene (1,4-DEB), 1,2-diethylbenzene (1,2-DEB), 4-ethylacetophenone (4-EAP) and acetophenone (AP). The reaction products revealed that activation of ethyl acetate is a convenient route for both alkylation and acylation reactions. The order of the catalysts activity for the reaction is found to be Fe,Al-MCM-41 (50) > Fe,Al-MCM-41 (100) > Zn,Al-MCM-41 (50) > Zn,Al-MCM-41 (100) > Al-MCM-41 (50) > Al-MCM-41 (100). In addition to the density of acid sites, the strength of acid sites is also important for this reaction. The effects of temperature, feed ratio, WHSV and time on stream were also examined and the results are discussed.  相似文献   

18.
The potential application of hybrid ZSM-5/Al-MCM-41 zeolitic-mesostructured materials as supports of metallocene polymerization catalysts has been investigated and compared with the behaviour of standard mesoporous Al-MCM-41 and microporous ZSM-5 samples. Hybrid zeolitic-mesostructured solids were prepared from zeolite seeds obtained with different Si/Al molar ratios (15, 30 and 60), which were assembled around cetyltrimethylammonium bromide (CTAB) micelles to obtain hybrid materials having a combination of both zeolitic and mesostructured features. (nBuCp)2ZrCl2/MAO catalytic system was impregnated onto the above mentioned solid supports and tested in ethylene polymerization at 70 °C and 5 bar of ethylene pressure. Supports and heterogeneous catalysts were characterized by X-ray powder diffraction, nitrogen adsorption-desorption isotherms at 77 K, transmission electron microscopy, 27Al-MAS-NMR, ICP-atomic emission spectroscopy and UV-vis spectroscopy.Catalysts supported over hybrid ZSM-5/Al-MCM-41 (Si/Al = 30-60) exhibited the best catalytic activity followed by those supported on Al-MCM-41 (Si/Al = 30-60). However, catalyst supported on ZSM-5 gave lower polymerization activity because of its microporous structure with narrower pores and lower textural properties than hybrid and mesoporous materials.Although higher acid site population shown by hybrid materials could contribute to the stabilization of the metallocene system on the support, in this case their better catalytic performance is mainly ascribed to the larger textural properties.  相似文献   

19.
《Fuel》2005,84(12-13):1494-1502
Al-MCM-41 type mesoporous catalysts were used for converting the pyrolysis vapours of spruce wood in order to obtain better bio-oil properties. Four Al-MCM-41 type catalysts with a Si/Al ratio of 20 were tested. The catalytic properties of Al-MCM-41 catalyst were modified by pore enlargement that allows the processing of larger molecules and by introduction of Cu cations into the structure.Spruce wood pyrolysis at 500 °C was performed and the products were analysed with the help of on-line pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). In addition, thermogravimetry/mass spectrometry (TG/MS) experiments were applied for monitoring the product evolution under slow heating conditions (20 °C/min) from 50 to 800 °C.Levoglucosan is completely eliminated, while acetic acid, furfural and furanes become quite important among cellulose pyrolysis products over the unmodified Al-MCM-41 catalyst. The dominance of phenolic compounds of higher molecular mass is strongly cut back among the lignin products. Both the increase of the yield of acetic acid and furan and the decrease of large methoxyphenols are repressed to some extent over catalysts with enlarged pores. The Cu modified catalyst performed similarly to the catalyst with enlarged pore size in converting the pyrolysis vapours of wood, although its pore size was similar to the unmodified Al-MCM-41.  相似文献   

20.
Fe loaded Al-MCM-41, (Si/Al = 25, 50, 75 and 100) catalysts were synthesized by hydrothermal method and characterized by the XRD, BET (surface area), FT-IR, and UV- vis and Mössbauer techniques. The liquid phase hydroxylation of phenol with hydrogen peroxide was studied and exclusive formation of dihydroxybenzene was observed. The phenol conversion was found to be almost same at various reaction temperatures viz 40, 60 and 80 °C, but at room temperature only about 30% conversion was recorded. The activity followed the order Fe/Al-MCM-41 (25) > Fe/Al-MCM-41(50) > Fe/Al-MCM-41 (75) > Fe/Al-MCM-41 (100) which was also the order of acidity. Effects of Fe content in Fe/Al-MCM-41 catalysts, solvent, phenol/H2O2 mole ratio on phenol conversion was examined. The reaction was also carried out over 10% iron loaded mordenite and the results are compared.  相似文献   

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