首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 15 毫秒
1.
The influence of aging environment of model diesel oxidation catalyst Pt/Al2O3 on the NO oxidation activity is studied. The fresh catalyst Pt/Al/F (calcined in air at 500 °C) is aged with or without phosphorus (P) poisoning (7.5 wt%) at 800 °C either in air (P/Pt/Al/O or Pt/Al/O) or in simulated diesel exhaust (P/Pt/Al/R or Pt/Al/R). Catalyst aged under diesel exhaust environment (Pt/Al/R) surprisingly presents the best NO oxidation activity under excess of O2 followed by the fresh (Pt/Al/F) and thermally aged (Pt/Al/O) catalysts. The activity difference between the catalysts is quite large, especially between Pt/Al/R and Pt/Al/O that are aged at the same temperatures but under different environments suggesting the importance of the aging environment for the catalytic activity. The NO oxidation activity of P poisoned catalysts P/Pt/Al/R and P/Pt/Al/O is minute as compared to their P free counter parts indicating that chemical aging is more detrimental for catalytic efficiency than thermal aging.  相似文献   

2.
The catalytic behavior of a Keggin type potassium dodecatungstocobaltate (II) salt supported on ZSM-5 zeolite for wet peroxide oxidation of 2-(methylthio)benzothiazole, as a model organic sulfide, was thoroughly studied. Microporous ZSM-5 zeolite was obtained by the hydrothermal crystallization method. The Keggin salt was incorporated in the MFI zeolite matrix by the wet impregnation method followed by calcination at 350 °C. Catalysts were further characterized by X ray diffraction, UV–Vis diffuse reflectance spectroscopy and scanning electron microscopy-EDAX techniques. Supported and bulk Keggin dodecatungstocobaltate (II) were compared with pure H-ZSM-5 zeolite as catalysts for the sulfide oxidation. When the reaction was not catalyzed, just a 9 mol% of sulfide conversion was obtained. Reaction parameters, such as nature of the solvent, hydrogen peroxide concentration, reaction time, catalyst mass, substrate initial concentration and reaction temperature, were evaluated to reach the optimum reaction conditions, considering substrate conversion and sulfoxide and sulfone selectivities. Catalyst stability in several oxidation cycles was also examined.  相似文献   

3.
Intrinsic catalytic activities (TOF values) in CH4 complete oxidation under lean conditions were estimated as a function of Pt and Pd particle sizes (dm) for two series of Pt/Al2O3 and Pd/Al2O3 catalysts. Comparison of TOF ~ f(dm) relationships revealed significant difference between Pt and Pd catalysts. For Pt catalyst TOF showed tendency to increase by 2–3 times with increasing particle size from 1 to ca 3 nm and remained constant, when Pt particles became larger than 3 nm. On the other hand, for Pd catalyst TOF increased almost linearly when particle size grew from 1 to 20 nm. These different tendencies were attributed to the different mechanisms of CH4 oxidation over Pt and Pd catalysts: Langmuir–Hinshelwood and Mars-Van Krevelen respectively.  相似文献   

4.
The commercial potential for a given catalytic process may be influenced by requirements on metal loading, in particular where noble metals are used. In an effort to substantially decrease the amount of catalyst material used for methane activation and catalytic partial oxidation (CPO), the effect of 0.005 wt% noble metal (Rh, Ru, Pd or Pt) on 0.5 wt% Ni/γ-Al2O 3 catalysts have been studied at temperatures below 1,173 K and 1 atm. The successful catalysts were activated directly by in situ reduction, without a calcination step, to promote formation of a highly dispersed (supported) metal phase from nitrate precursors. The obtained metal particles were not observable by XRD (size <  2–3 nm). This activation procedure had a decisive effect on catalyst activity, as compared to a catalyst which was calcined ex situ before in situ reduction. Adding a noble metal caused a significant drop in the ignition temperature during temperature programmed catalytic partial oxidation (TPCPO). The ignition temperature for partial oxidation coincides well with the temperature for methane dissociation, and is likely correlated to the reducibility of the noble metal oxide. Methane partial oxidation over 0.5 wt% Ni catalysts, both with and without promoter, yielded high selectivity to synthesis gas (>93%) and stable performance for continued operation, but synthesis gas production at temperatures below 1,073 K required a promoter when the catalyst was ignited by TPCPO. Ignition of the CPO reactions by introducing the feed at a high furnace temperature (1,073 K) also enabled formation of synthesis gas, but the reaction was then less stable than obtained with the TPCPO procedure. A dual bed concept attempted to beneficially use the activation and combustion properties of the noble metal followed by the reforming properties of Ni. However, it was concluded that co-impregnated catalysts yielded as high, or even higher conversion of methane and selectivity to synthesis gas.  相似文献   

5.
Palladium catalysts supported on α-Si3N4 were prepared by impregnation with Pd(II)-acetate dissolved either in toluene or in water. The mean metal particle size of ~0.5 wt% Pd catalysts was similar (~5 nm) and independent of the way of preparation. Nevertheless, the two catalysts present very different chemisorption behaviour chemisorptive and catalytic properties. Fourier transformed infrared (FTIR) spectra of adsorbed CO at different temperatures (ranging from room temperature to 300 °C) show a very different behaviour for both catalysts. While the CO adsorption states on the Pd/α-Si3N4 prepared in toluene are very similar to those generally measured for silica and/or alumina supported palladium catalysts, CO chemisorbs less strongly on Pd/α-Si3N4 prepared in water and on different adsorption sites. The Pd/α-Si3N4 catalyst obtained by aqueous impregnation is much less efficient for the methane total oxidation. It is less active and less stable: it deactivates strongly after 3 h on stream at 650 °C. The two catalysts present about the same activity for the 1,3-butadiene hydrogenation after stabilisation at 20 °C. But, the catalyst prepared in water shows a much better selectivity to butenes. The results are discussed in terms of the possible migration of silicon atoms from the silicon nitride support to the surface of the palladium particles, when the catalyst is prepared in water. This is not the case when prepared in an organic solvent.  相似文献   

6.
Foxtail millet husk has been used as a new source of silica for preparing copper catalysts via a sol–gel technique. X-Ray diffraction shows that silica is amorphous in the ash and catalyst I while in catalyst II it crystallizes to one of its polymorphs, β-cristobalite. Scanning electron micrographs show the particles to be well dispersed in the case of ash, but irregular and agglomerated in catalyst I and II. Transmission electron microscopy confirmed that catalyst II is a nano-composite. X-Ray fluorescence detected that the ash contains 98 % silica. The basic unit, SiO4 tethedra present in the prepared materials was discovered using IR spectroscopy. ESR observed the presence of Cu(II) in both catalyst. X-Ray photoelectron spectroscopy asserted the presence of only Cu(II) in catalyst I and both Cu(0) and Cu(II) in catalyst II. The prepared materials were utilized as catalyst in the oxidation of some tertiary amines to N-oxides, with molecular oxygen as the oxidant in methanol, under ambient conditions of temperature and pressure. The reaction was monitored online. Catalyst I shows better reactivity than II towards the oxidation reaction. High performance liquid chromatography was used to analyse the oxidation products.  相似文献   

7.
BACKGROUND: The effect of Pd loading, xylene concentration and GHSV on xylene oxidation was tested over Pd/CeO2(30%)‐clinoptilolite nanocatalysts at low temperatures. The catalysts were prepared by acid treatment of clinoptilolite, followed by the incipient wetness method of synthesized ceria and modified clinoptilolite in PdCl2 solution. The synthesized nanocatalysts were characterized by XRD, FESEM, EDAX, TEM, BET, FTIR and TG‐DTG analysis. RESULTS: The XRD patterns confirmed the formation of crystalline ceria with an average crystallite size of 11.8 nm. FESEM images showed nanostructures in cavities of natural zeolite, brought about by ceria incorporation and acid activation. TEM analysis showed high dispersion of Pd with a size distribution between 6.6 and 36.7 nm. The quantitative analysis showed that the specific surface area of Pd(1%)/CeO2(30%)‐clinoptilolite was 77 m2 g?1. The results showed that Pd(1%)/CeO2(30%)‐clinoptilolite is the most appropriate catalyst, with the conversion more than 90% at 275 °C. CONCLUSIONS: Experimental results established effective performance and durability for the catalysts. As a result, clinoptilolite modification and ceria incorporation significantly altered the samples' morphology at nanoscale, improving the structure of composites and distribution of noble metals. A reaction path was suggested based on the adsorption‐migration of species to reveal the mechanism of p‐xylene oxidation over nanocatalysts. © 2012 Society of Chemical Industry  相似文献   

8.
Silver modified (5 and 2 wt% loading) mesoporous molecular sieves (H-MCM-41, with Si/Al ratio 20, 40 and 50) and silica were synthesized by incipient wetness impregnation and ion-exchange methods. The obtained catalysts were characterized by different techniques (ICP, XRD, XRF, SEM, FTIR and nitrogen physisorption) and they were tested in heterogeneous catalytic decomposition of ozone and oxidation reactions involving ozone at ambient temperature. All the mesoporous catalysts have very high catalytic activities towards ozone decomposition at room temperature and they do not reveal any deactivation with the time on stream. The activities of the catalysts are enhanced upon increasing the amount of supported silver, decreasing the support acidity and modifying the catalyst with some additional metal having basic properties, such as Ce. The most active catalyst in the reaction of ozone decomposition—5Ag-H-MCM-41-50, shows also high activity at ambient temperature in the oxidation of CO and iso-propanol with ozone.  相似文献   

9.
Formation of carbon nanofibers (CNFs) and carbon nanotubes (CNTs) through the decomposition of ethylene at 973 K was achieved using various metal catalysts covered with silica layers. CNFs of various diameters were formed by ethylene decomposition over a Co metal catalyst supported on the outer surface of the silica. In contrast, silica-coated Co catalysts formed CNTs with uniform diameters by ethylene decomposition. Silica-coated Ni/SiO2 and Pt/carbon black also formed CNTs with uniform diameters, while CNFs and CNTs with various diameters were formed over Ni/SiO2 and Pt/carbon black without a silica coating. These results indicate that silica layers that envelop metal particles prevent sintering of the metal particles during ethylene decomposition. This results in the preferential formation of CNTs with a uniform diameter.  相似文献   

10.
Gold nano-particles confined in the walls of mesoporous silica (GMS) catalysts were successfully prepared by a novel and simple technique utilizing thioether functional groups in the walls of mesoporous silica to anchor HAuCl4. Calcination of the materials removed organic moieties and reduced the gold salt to gold nano-particles. In this procedure, the thioether groups were introduced into the silica wall via a co-condensation of tetraethyl orthosilicate (TEOS) with 1,4-bis(triethoxysily)propane tetrasulfide. These gold containing mesoporous catalysts have unusually high surface area and pore volume. The catalysts were evaluated for the solvent free liquid phase oxidation of benzyl alcohol by molecular oxygen. High selectivity to benzaldehyde was obtained under the reaction conditions of 403 K, 15 atm and 5 h in an autoclave. The 1.5% GMS catalyst was also evaluated for oxidation of alcohols using toluene as solvent under flowing oxygen at atmospheric pressure at 353 K in a two-necked flask. Under these conditions the conversion of benzyl alcohol reached 100% after 2 h and it was demonstrated that the catalyst can be recycled three times without significant loss of activity.  相似文献   

11.
Direct formic acid fuel cells (DFAFC) currently employ either Pt-based or Pd-based anode catalysts for oxidation of formic acid. However, improvements are needed in either the activity of Pt-based catalysts or the stability of Pd-based catalysts. In this study, a number of carbon-supported Pt-based and Pd-based catalysts, were prepared by co-depositing PdM (M = Bi, Mo, or V) on Vulcan® XC-72 carbon black, or depositing another metal (Pb or Sn) on a Pt/C catalyst. These catalysts were systematically evaluated and compared with commercial Pd/C, PtRu/C, and Pt/C catalysts in a multi-anode DFAFC. The PtPb/C and PtSn/C catalysts were found to show significantly higher activities than the commercial Pt/C catalyst, while the PdBi/C provided higher stability than the commercial Pd/C catalyst.  相似文献   

12.
Vanadium(V) oxide catalysts for the selective oxidation of hydrogen sulfide to sulfur on a nonporous glass-fiber support with a surface layer of a porous secondary support (SiO2) are studied. The catalysts are obtained by means of pulsed surface thermosynthesis. Such catalysts are shown to have high activity and acceptable selectivity in the industrially important region of temperatures below 200°C. A glass-fiber catalyst containing vanadium oxide (10.3 wt % of vanadium) in particular ensures the complete conversion of H2S at a temperature of 175°C and a reaction mixture hourly space velocity (RMHSV) of 1 cm3/(gcat s) with a sulfur yield of 67%; this is at least 1.35 times higher than for the traditional iron oxide catalyst. Using a structured glass-fiber woven support effectively minimizes diffusion resistance and greatly simplifies the scaleup of processes based on such catalysts. Such catalysts can be used for the cleansing of tail gases from Claus units and in other processes based on the selective oxidation of H2S.  相似文献   

13.
A titanium-polyoxometalate with a µ-hydroxo dimeric structure [(PW11O39Ti)2OH]7? ((PW11Ti)2OH) was used efficiently for the desulfurization of a model diesel containing a mixture of various refractory sulfur compounds present in real fuels. The catalytic performance of the µ-hydroxo dimeric compound was compared in its homogeneous form and also when immobilized in the trimethylammonium-functionalized SBA-15 ((PW11Ti)2OH@TM-SBA-15). An optimization study was performed using the homogeneous and heterogeneous catalysts to obtain high catalytic efficiency, sustainability and cost-effectiveness of the system. Different optimized conditions were found using the homogeneous and heterogeneous catalysts. Lower amounts of solvent extraction (MeCN, 175 µL), catalyst (0.5 µmol of active center) and oxidant (50 µL) were used to produce sulfur-free model diesel after 2 h at 70?°C, using the heterogeneous (PW11Ti)2OH@TM-SBA-15 catalyst. On the other hand, complete desulfurization was achieved with homogeneous (PW11Ti)2OH catalyst after only 40 min, although higher amounts of MeCN (750 µL), catalyst (1.5 µmol) and oxidant (75 µL) were used. Both systems combined liquid–liquid extraction and catalytic oxidation. Using the heterogeneous catalyst, adsorption of oxidized-sulfur compound was also observed. Both homogeneous and heterogeneous desulfurization systems presented a high capacity to be reused/recycled for consecutive desulfurization cycles.  相似文献   

14.
Iron-containing catalysts supported on mesoporous silica samples that differ in the methods of their preparation (commercial KSS silica gel, MSM-41 mesoporous silicalite, and silica gels obtained under laboratory conditions by means of spray drying and drying in supercritical СО2) are synthesized. Their porous structure is studied via low-temperature nitrogen adsorption. Their catalytic activity and stability in the oxidation of carmoisine (an anionic dye) with a 3% hydrogen peroxide solution in water at 60°C and рН 3 are compared. The initial carmoisine and catalyst concentrations in solution are 20 mg/L and 3 g/L, respectively, and the molar Н2О2/carmoisine ratio is 459/1. The KSS-based catalyst demonstrates the highest activity and stability with respect to the outwashing of an active component into a solution: the conversion of carmoisine on this catalyst is as high as 99% for 30 min, while the concentration of iron ions in solution (0.27 mg/L) does not exceed the maximum allowable concentration. After the support is preimpregnated with aluminum, the degree of iron outwashing into a solution is more than halved. The synthesized catalysts are of interest with regard to the purification of waste water containing organic admixtures.  相似文献   

15.
Cobalt silicate formation reduces the activity of the catalyst in Fischer–Tropsch synthesis (FTS). In this article, the effects of calcination temperature and support surface area on the formation of cobalt silicate are explored. FTS catalysts were prepared by incipient wetness impregnation of cobalt nitrate precursor into various silica supports. Deionized water was used as preparation medium. The properties of catalysts were characterized at different stages using FTIR, XRD and BET techniques. FTIR-ATR analysis of the synthesized catalyst samples before and after 48 h reaction identified cobalt species formed during the impregnation/calcination stage and after the reduction/reaction stage. It was found that in the reduction/reaction stage, metal-support interaction (MSI) added to the formation of irreducible cobalt silicate phase. Co/silica catalysts with lower surface area (300 m2/g) exhibited higher C5+ selectivity which can be attributed to less MSI and higher reducibility and dispersion. The prepared catalysts with different drying and calcination temperatures were also compared. Catalysts dried and calcined at lower temperatures exhibited higher activity and lower cobalt silicate formation. The catalyst sample calcined at 573 K showed the highest CO conversion and the lowest CH4 selectivity.  相似文献   

16.
Catalytic wet oxidation has become one of the best options for mineralization of dyes in water. In this work, mineralization of methylene blue in water was tried by using raw and acid-treated (0.50, 0.75, and 1.00 N H2SO4) MnO2 as oxidation catalysts. Fourier transform infrared, scanning electron microscopy, surface area and cation exchange capacity measurements were used to characterize the catalysts. The acid-treated materials showed large increases in surface area while changes in other surface characteristics were moderate in nature. The oxidative destruction of the dye was possible at near room temperature and the process was optimized with respect to interaction time, dye concentration, catalyst loading, pH of the medium, and temperature. The dye (1.0 mg/L) was oxidized to the extents of 88.5%, 96.5%, 96.8%, and 97.7% with corresponding chemical oxygen demand (COD) reduction of 64.7%, 86.4%, 87.2%, and 88.2% by raw MnO2, 0.50, 0.75, and 1.00 N acid-treated MnO2(catalyst loading 2.5 g/L), respectively. The reduction in COD indicated oxidation of the dye to simpler organic compounds achieving mineralization to a large extent. The oxidation followed first-order kinetics and the catalysts could be used up to six repeated runs without much change in activity. Analysis of the intermediate products of oxidation helped in proposing the potential pathways for oxidative conversion of methylene blue.  相似文献   

17.
A series of silica supported Mn–Ce composite oxides with different Mn/Ce molar ratios were obtained by a simple and environment-friendly oxalate route. The physical and chemical properties were characterized by TG, BET, SEM, TEM, XPS and TPR analysis. All catalysts showed excellent activity towards deep oxidation of benzene. The effects of Mn/Ce ratio, calcination temperature on the structure and catalytic activity of catalysts were investigated. Catalyst from nitrate precursor was also characterized to compare the influence of different precursors. The 6Mn4Ce sample from oxalate route sintered at 400?°C showed the maximum reaction rate of 0.50 mmol gcat?1h?1; T90 of the catalyst is 216?°C. The catalytic activity is related to surface area, pore size distribution, surface elemental species, particle size distribution and low temperature reducibility which may derived from synergistic effect between manganese and cerium oxide. Compared with nitrate precursors, catalyst from oxalate route can be more finely dispersed on the pores of silica without damaging the pore structure of support. The role of silica is not only a support, but also an in situ reaction site for precursor’s decomposition, which ensure the finely distribution of active components. In addition, the best catalyst showed good stability with prolonged time on stream.  相似文献   

18.
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.  相似文献   

19.
Vanadium phosphorous oxide (VPO) catalyst was prepared using dihydrate method and tested for the potential use in selective oxidation of n-butane to maleic anhydride. The catalysts were doped by La, Ce and combined components Ce + Co and Ce + Bi through impregnation. The effect of promoters on catalyst morphology and the development of acid and redox sites were studied through XRD, BET, SEM, H2-TPR and TPRn reaction of n-butane/He. Addition of rare-earth element to VPO formulation and drying of catalyst precursor by microwave irradiation increased the fall width at half maximum (FWHM) and reduced the crystallite size of the Vanadyl hydrogen phosphate hemihydrate (VOHPO4 · 1/2 H2O, VHP) precursor phase and thus led to the production of final catalysts with larger surface area. The Ce doped VPO catalyst which, assisted by the microwave heating method, exhibited the highest surface area. Moreover, the addition of promoters significantly increased catalyst activity and selectivity as compared to undoped VPO catalyst in the oxidation reaction of n-butane. The H2-TPR and TPRn reaction profiles showed that the highest amount of active oxygen species, i.e., the V4+–O? pair, was removed from the bimetallic (Ce + Bi) promoted catalyst. This pair is responsible for n-butane activation. Furthermore, based on catalytic test results, it was demonstrated that the catalyst promoted with Ce and Bi (VPOD1) was the most active and selective catalyst among the produced catalysts with 52% reaction yield. This suggests that the rare earth metal promoted vanadium phosphate catalyst is a promising method to improve the catalytic properties of VPO for the partial oxidation of n-butane to maleic anhydride.  相似文献   

20.
The systems based on granular mesoporous nanofibrous carbonaceous (NFC) materials synthesized by decomposition of hydrocarbons over nickel-containing catalysts are promising catalysts for selective oxidation of hydrogen sulfide. Sample series of nanofibrous carbon with three main types of their fiber structures and different contents of metal catalysts inherited from the catalysts for their synthesis were studied in this reaction. The correlation between NFC structure and its activity and selectivity in hydrogen sulfide oxidation was determined. The metal inherited from the initial catalysts for the synthesis of NFC influences the activity and selectivity of the resulting carbon catalysts. A particular influence is observed in the case of the catalyst withdrawn from the synthesis reactor at the stage of stationary operation of the metal catalyst (low specific carbon yields per unit weight of the catalyst). The presence of the metal phase results in an increase in the carbon catalyst activity and in a decrease in the selectivity to sulfur. NFC samples with the highest activity and selectivity are nanotubes and those with graphite planes perpendicular to the axis of the fibers. Carbon nanotubes have high selectivity, while samples obtained on copper–nickel catalysts also possess high activity. The promising NFC catalysts provide high conversion and selectivity (almost independent of the molar oxygen/hydrogen sulfide ratio) when a large excess of oxygen is contained in the reaction mixture.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号