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1.
One-pot synthesis of R-1-phenyethylacetate at 70°C was investigated using three different catalysts simultaneously, namely a bimetallic PdZn/Al2O3 as a hydrogenation catalyst, an immobilized lipase as an acylation catalyst and Ru/Al2O3 as a racemization catalyst. The most active bimetallic catalyst was PdZn/Al2O3 calcined at 300°C and reduced at 400°C, whereas the most selective although less active catalyst was the one being calcined and reduced at 500°C. The highest selectivity to R-1-phenylethyl acetate over this catalyst was 32 at 48% conversion. Ru/Al2O3 was confirmed to have a positive effect on the formation of the desired product, although it was not very active in the racemization during one-pot synthesis.  相似文献   

2.
One-pot synthesis of R-1-phenyethylacetate at 70°C was investigated using three different catalysts simultaneously, namely a bimetallic PdZn/Al2O3 as a hydrogenation catalyst, an immobilized lipase as an acylation catalyst and Ru/Al2O3 as a racemization catalyst. The most active bimetallic catalyst was PdZn/Al2O3 calcined at 300°C and reduced at 400°C, whereas the most selective although less active catalyst was the one being calcined and reduced at 500°C. The highest selectivity to R-1-phenylethyl acetate over this catalyst was 32 at 48% conversion. Ru/Al2O3 was confirmed to have a positive effect on the formation of the desired product, although it was not very active in the racemization during one-pot synthesis.  相似文献   

3.
The effect of thermal activation, sharp increase in the catalytic activity of the system MnO x -Al2O3 in reactions of deep oxidation of CO and hydrocarbons after calcination of the catalyst at 900–1000°C was discovered and investigated. With the use of X-ray phase analysis, X-ray electron spectroscopy, EXAFS, IR spectroscopy, electronic spectroscopy of diffuse reflections, electron microscopy etc. it was established that the effect of thermal activation is related to reversible phase transitions in the system at heating and cooling. On cooling from 1100°C to 650°C disperse particles of cubic spinel of composition Mn2.1 ? x · Al0.9 + x O4 are conserved on the corundum surface. On further cooling the spinel decomposes and finally the nanocristalline species of β-Mn3O*4 containing up to 15 at% of Al3+ form and govern the activity.The thermal activation effect was implemented in an industrial catalyst IK-12-40. Joint Stocks Co “KATALIZATOR” produced and supplied to customers hundreds of tons of this catalyst. The catalyst was awarded with a silver medal of the International exhibition EUREKA in Brussels (1995).  相似文献   

4.
The oxidative dehydrogenation of propane on a supported vanadium catalyst was studied (the support was a complex oxide system consisting of a ceria–zirconia solid solution deposited on γ-Al2O3 (CeZrO/γ-Al2O3)). A comparative analysis of the properties of the support and the catalyst prepared on its basis was performed. The support and catalyst were characterized by the BET method, scanning electron microscopy, X-ray diffraction analysis, and Raman spectroscopy. The catalytic properties of the catalyst and support were studied in propane oxidation at 450 and 500°C with pulse feeding of the reagent. The effect of propane on the support was found to improve the oxidative properties of the latter. This behavior of the support is related to the preparation procedure, which leads to the formation on its surface of the crystalline phase of the ceria–zirconia solid solution and amorphous ZrO2 and Al2O3 phases and/or their solid solution. Similar processes occur with the catalyst support during the oxidative dehydrogenation, giving rise to additional active centers (CeVO4).  相似文献   

5.
Highly monodispersed ruthenium nanoparticles were prepared via wet impregnation technique using RuCl3 · nH2O as a precursor. Ru nanoparticles were supported on Al2O3 to synthesize Ru nanocatalyst. The nanocatalyst was characterized by various techniques like XRD, SEM, TEM and BET analysis. The catalyst was used for hydrogenation of phenol under mild condition. The activity of the catalyst was checked by varying different parameters such as reaction temperature, time, H2 partial pressure, metal loading and catalyst amount. The catalyst was recovered from product and reused up to four times without significant loss in its catalytic activity. After a reaction time of 1 h, Ru/Al2O3 nanocatalyst showed high reactivity (82% conversion) and selectivity to cyclohexanone (67%) at 80°C and 20 bar hydrogen pressure.  相似文献   

6.
Hydrogen gas as a clear energy resource was found to be largely bubbled from a H2O/H2O2/MnWO4 system. MnWO4 powder was fabricated by an aqueous reaction method. The powder was characterized with X-ray diffraction (XRD), transmission electron microscope (TEM), and X-ray photoelectron spectrometry (XPS). The efficiency of the hydrogen generation increases with an increase in initial pH in the appropriate range, H2O2 proportion, MnWO4 proportion, and intensity of light resource. Calcining at 400 °C for 1 h can make the MnWO4 powder synthesized by an aqueous reaction more effective for H2 generation and more stable in higher initial pH. The MnWO4 catalyst shows a long-term stability for photocatalytic H2 generation. A mechanism was suggested for the hydrogen generation from the H2O/H2O2/MnWO4 system together with XPS analysis.  相似文献   

7.
A series of NiMoW/P-Al2O3 catalysts with different Mo/W ratios (sample containing Mo only, Mo/W = 2: 1, Mo/W = 1: 1, Mo/W = 1: 2, and sample containing W only; P2O5 content of the support 2.0 wt %) were synthesized. The precursors of the active phase were the heteropoly acids H3PMo12O40?nH2O and H3PW12O40?nH2O, and also nickel citrate. The sulfide phase in the samples was studied by high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy; the catalytic activity of the samples in dibenzothiophene hydrodesulfurization and naphthalene hydrogenation was determined. For the dibenzothiophene hydrogenolysis in the presence of quinoline and naphthalene (content in the model mixture, wt %: dibenzothiophene 0.3, naphthalene 1.5, and quinoline 0.5), kHDS for different samples is in the range 17.6–42.5 h–1 at 275°C and 24.6–45.9 h–1 at 300°C. For the naphthalene hydrogenation, kHYD varies from 0.79 to 1.89 h–1 at 275°C and from 0.91 to 3.78 h–1 at 300°C. The sample based on molybdenum showed the highest activity in hydrogenation and hydrodesulfurization.  相似文献   

8.
(1.2–8.3)%FeOх/Al2O3 monolith catalysts have been prepared by impregnating alumina with aqueous solutions of iron(III) nitrate and oxalate and have been tested in NH3 oxidation and in the selective decomposition of N2O in mixtures resulting from ammonia oxidation over a Pt–Rh gauze pack under conditions of nitric acid synthesis (800–900°C). In the case of the support calcined at 1200°C, the catalyst is dominated by bulk Fe2O3 particles localized on the Al2O3 surface. The activity of these samples in both reactions decreases with a decreasing active component content, thus limiting the potential of Fe2(C2O4)3 · 5H2O, an environmentally friendlier but poorly soluble compound, as a substitute for Fe(NO3)3 · 9H2O. Decreasing the support calcination temperature to 1000°C or below leads to the formation of a highly defective Fe–Al–O solid solution in the (1.2–2.7)%FeOх/Al2O3 catalysts. The surface layers of the solid solution are enriched with iron ions or stabilize ultrafine FeOх particles. The catalytic activity of these samples in both reactions is close to the activities measured for ~8%FeOх/Al2O3 samples prepared using iron nitrate.  相似文献   

9.
Trimetallic NiMoW/Al2O3 catalyst was prepared using mixed H4SiMo3W9O40 heteropoly acid of Keggin structure and nickel citrate. Bimetallic NiMo/Al2O3 and NiW/Al2O3 catalysts based on H4SiMo12O40 and H4SiW12O40, respectively, were synthesized as reference samples. The use of mixed H4SiMo3W9O40 heteropoly acid as an oxide precursor allows the tungsten sulfidation degree and the degree of promotion of active phase particles to be increased. The hydrodesulfurization activity is enhanced as compared to NiW/Al2O3 catalyst. The synergistic enhancement of the activity of the NiMo3W9/Al2O3 catalyst relative to the bimetallic analogs is probably caused by formation of new mixed promoted active sites for direct desulfurization.  相似文献   

10.
To enhance film conformality together with electrical property suitable for dynamic random access memory (DRAM) capacitor dielectric, the effects of oxidant and post heat treatment were investigated on aluminum and titanium oxide (Al2O3–TiO2) bilayer (ATO) thin film formed by atomic layer deposition method. For the conformal deposition of Al2O3 thin film, the O3 oxidant required a higher deposition temperature, more than 450 °C, while H2O or combined oxygen sources (H2O+O3) needed a wide range of deposition temperatures ranging from 250 to 450 °C. Conformal deposition of the TiO2 thin film was achieved at around 325 °C regardless of the oxidants. The charge storage capacitance, measured from the ATO bilayer (4 nm Al2O3 and 2 nm TiO2) deposited at 450 °C for Al2O3 and 325 °C for TiO2 with O3 oxidant on the phosphine-doped poly silicon trench, showed about 15% higher value than that of 5 nm Al2O3 single layer thin film without any increase of leakage current. To maintain the improved electrical property of the ATO bilayer for DRAM application, such as enhanced charge capacitance without increase of leakage current, upper electrode materials and post heat treatments after electrode formation must be selected carefully. Dedicated to Professor Su-Il Pyun on the occasion of his 65th birthday.  相似文献   

11.
Carbon dioxide reforming (CDR) of methane to synthesis gas over supported nickel catalysts has been reviewed. The present review mainly focuses on the advantage of ceria based nickel catalysts for the CDR of methane. Nickel catalysts supported on ceria–zirconia showed the highest activity for CDR than nickel supported on other oxides such as zirconia, ceria and alumina. The addition of zirconia to ceria enhances the catalytic activity as well as the catalyst stability. The catalytic performance also depends on the crystal structure of Ni–Ce–ZrO2. For example, nickel catalysts co-precipitated with Ce0.8Zr0.2O2 having cubic phase gave synthesis gas with CH4 conversion more than 97% at 800 °C and the activity was maintained for 100 h during the reaction. On the contrary, Ni–Ce–ZrO2 having tetragonal phase (Ce0.8Zr0.2O2) or mixed oxide phase (Ce0.5Zr0.5O2) deactivated during the reaction due to carbon formation. The enhanced catalytic performance of co-precipitated catalyst is attributed to a combination effect of nano-crystalline nature of cubic Ce0.8Zr0.2O2 support and the finely dispersed nano size NiO x crystallites, resulting in the intimate contact between Ni and Ce0.8Zr0.2O2 particles. The Ni/Ce–ZrO2/θ–Al2O3 also exhibited high catalytic activity during CDR with a synthesis gas conversion more than 97% at 800 °C without significant deactivation for more than 40 h. The high stability of the catalyst is mainly ascribed to the beneficial pre-coating of Ce–ZrO2 resulting in the existence of stable NiO x species, a strong interaction between Ni and the support, and an abundance of mobile oxygen species in itself. TPR results further confirmed that NiO x formation was more favorable than NiO or NiAl2O4 formation and further results suggested the existence of strong metal-support interaction (SMSI) between Ni and the support. Some of the important factors to optimize the CDR of methane such as reaction temperature, space velocity, feed CO2/CH4 ratio and H2O and/or O2 addition were also examined.  相似文献   

12.
The samples of the NiO/B2O3-Al2O3 system with NiO contents from 0.48 to 38.30 wt % were synthesized by the impregnation of borate-containing alumina (20 wt % B2O3). It was found that nickel oxide occurred in an X-ray amorphous state in the samples containing to 23.20 wt % NiO. At a NiO content of 4.86 wt % or higher, the support was blocked by the modifier to cause a decrease in the specific surface area from 234 to 176 m2/g and in the amount of acid sites from 409–424 to 333 μmol/g. An extremal character of the dependence of catalyst activity in ethylene oligomerization on NiO content was found with a maximum in the range of 4.86–9.31 wt %. Based on spectroscopic data, it was found that ethylene activation on the NiO/B2O3-Al2O3 catalyst can be associated with the presence of Ni2+ cations, which chemically interact with the support. The catalyst containing 4.86 wt % NiO at 200°C, a pressure of 4 MPa, and an ethylene supply rate of 1.1 h−1 provided almost complete ethylene conversion at the yield of liquid oligomerization products to 90.0 wt %; the total concentration of C8+ alkenes in these products was 89.0 wt %.  相似文献   

13.
This work is focused on the role of gold and Al3CrO6 support for physicochemical properties, and catalytic activity of supported nickel catalysts in partial oxidation of methane (POM). Catalysts, containing 5% Ni and 5% Ni-2% Au active phases dispersed on mono- (Al2O3, Cr2O3) and bi-oxide Al3CrO6 support, were investigated by TPR, BET and XRD methods, and the activity tests in POM reaction were carried out. Bimetallic Ni-Au catalysts dispersed on Al3CrO6 support remained highly stable and active. The amorphous binary oxide Al3CrO6 can stabilize considerable amount of Cr4+, Cr5+, and Cr6+ species in Ni-Au/Al3CrO6 catalyst network during its calcination in the air. Nickel supported on binary oxide Ni/Al3CrO6 can form Ni(III)CrO3 bi-oxide phase in reductive conditions. During TPR H2 reduction of Ni-Au/Al3CrO6 catalyst chromium(II) oxide Cr(II)O phase is observed. After POM reaction the existence of bimetallic Au-Ni alloy was experimentally confirmed on mono-oxide Al2O3 support surface, but its formation was not identified on bioxide Al3CrO6 support. Published in Russian in Kinetika i Kataliz, 2009, Vol. 50, No. 1, pp. 149–156. The article is published in the original. Based on a report at the VII Russ. Conf. on Mechanisms of Catalytic Reactions (with international participation), St. Petersburg, July 2–8, 2006.  相似文献   

14.
A series of Co-modified Ce0.5Zr0.5O2 catalysts with different concentrations of Co (mass %: 0, 2, 4, 6, 8, 10) was investigated for diesel soot combustion. Ce0.5Zr0.5O2 was prepared using the coprecipitation method and Co was loaded onto the oxide using the incipient wetness impregnation method. The activities of the catalysts were evaluated by thermogravimetric (TG) analysis and temperature-programmed oxidation (TPO) experiments. The results showed the soot combustion activities of the catalysts to be effectively improved by the addition of Co, 6 % Co/Ce0.5Zr0.5O2 and that the 8 % Co/Ce0.5Zr0.5O2 catalysts exhibited the best catalytic performance in terms of lower soot ignition temperature (Ti at 349°C) and maximal soot oxidation rate temperature (Tm at 358°C). The reasons for the improved activity were investigated by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), H2 temperature-programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). These results revealed that the presence of Co could lower the reduction temperature due to the synergistic effect between Co and Ce, thereby improving the activity of the catalysts in soot combustion. The 6 % Co catalyst exhibited the best catalytic performance, which could be attributed to the greater amounts of Co3+ and surface oxygen species on the catalyst.  相似文献   

15.
Global warming, fossil fuel depletion and fuel price increases have motivated scientists to search for methods for the storage and reduction of the amount of greenhouse gases, especially CO2. The hydrogenation process has been introduced as an emerging method of CO2 capture and convertion into value-added products. In this study, new types of catalysts are introduced for CO2 hydrogenation and are compared based on catalytic activity and product selectivity. The physical properties of the samples are specified using BET. Iron catalysts supported on γ-Al2O3 with different metal promoters (X = Ni, K, Mn, Cu) are prepared through the impregnation method. Moreover, Fe–Ni catalysts supported on HZSM5-Al2O3 and Ce–Al2O3 are synthesized. Samples are reduced by pure H2 and involved in hydrogenation reaction in a fixed bed reactor (H2/CO2 = 3, total pressure = 10 MPa, temperature = 523 K, GHSV = 2000, 1250 nml/min). All catalysts provide high conversion in hydrogenation reactions and the results illustrate that the selectivity of light hydrocarbons is higher than that of methane and CO. It is found that Ni has a promoting effect on the conversion fluctuations throughout the reaction with 66.13% conversion. Using combined supported catalysts leads to enhancing catalytic performance. When Fe–Ni/γ–Al2O3—HZSM5 is utilized, CO2 conversion is 81.66% and the stability of the Fe–Ni catalyst supported on Al2O3 and Ce–Al2O3 furthey improves.  相似文献   

16.
It was studied the influence of gold addition on physico-chemical properties and catalytic activity of bimetallic Ni-Au/Al2O3 catalyst in partial oxidation of methane (POM). The reduction behavior in hydrogen, XRD crystal structure, XPS spectra and POM catalytic activity were investigated. The reduction of Ni-Au catalyst is a prerequisite condition to catalyze POM reaction. The formation of Ni-Au alloy during high temperature reduction in hydrogen and also in the conditions of POM reaction was experimentally proved. The addition of gold to Ni/Al2O3 system improves catalyst stability and activity in POM reaction.  相似文献   

17.
Single-phase Ca3Al2O6 was prepared via polymeric precursor method. The influence of the reactants nature in the Ca3Al2O6 synthesis was investigated. For this purpose, citric acid and soluble salts of calcium (nitrate, chloride, carbonate) and aluminium (nitrate, chloride, acetate) were used as starting materials, in the presence and, respectively, in the absence of ethylene glycol. Ca3Al2O6 resulted as single-phase after annealing at 1050 °C for 1 h only starting from calcium nitrate or carbonate and aluminium nitrate or acetate as salts precursor for Ca2+ and Al3+ cations. The formation of Ca3Al2O6 is not conditioned by the ethylene glycol presence in these mixtures. Using calcium and aluminium chlorides, the phases present at 1050 °C are Ca12Al14O33 and unreacted CaO.  相似文献   

18.
We show a feasibility of preparing a highly homogeneous composite gel (CG) based on hydrolysis products of Al2O3-ZrO2 salts. The phase composition of a sample calcined at 1250°C for 2 h is as follows: α-Al2O3, t-ZrO2, and m-ZrO2 where the t-ZrO2/m-ZrO2 phase ratio ranges from 2.8 to 3.8 depending on gel preparation conditions. The investigative tools used are powder X-ray diffraction, differential thermal analysis (atmosphere: Ar), and IR spectroscopy.  相似文献   

19.
A H3PW12O40/ZrO2 catalyst for effective dimethyl carbonate (DMC) formation via methanol carbonation was prepared using the sol–gel method. X-ray photoelectron spectra showed that reactive and dominant (63%) W(VI) species, in WO3 or H2WO4, enhanced the catalytic performances of the supported ZrO2. The mesoporous structure of H3PW12O40/ZrO2 was identified by nitrogen adsorption–desorption isotherms. In particular, partial sintering of catalyst particles in the duration of methanol carbonation caused a decrease in the Brunauer–Emmett–Teller surface area of the catalyst from 39 to 19 m2/g. The strong acidity of H3PW12O40/ZrO2 was confirmed by the desorption peak observed at 415 °C in NH3 temperature-programmed desorption curve. At various reaction temperatures (T?=?110, 170, and 220 °C) and CO2/N2 volumetric flow rate ratios (CO2/N2?=?1/4, 1/7, and 1/9), the calculated catalytic performances showed that the optimal methanol conversion, DMC selectivity, and DMC yield were 4.45, 89.93, and 4.00%, respectively, when T?=?170 °C and CO2/N2?=?1/7. Furthermore, linear regression of the pseudo-first-order model and Arrhenius equation deduced the optimal rate constant (4.24?×?10?3 min?1) and activation energy (Ea?=?15.54 kJ/mol) at 170 °C with CO2/N2?=?1/7 which were favorable for DMC formation.  相似文献   

20.
Со-Мо/Al2O3 and Ni-W/Al2O3 catalysts were tested in hydrotreating of light cycle oil from catalytic cracking, of the straight-run gasoil, and of their mixture under typical hydrotreating conditions used in industry. The catalysts prepared using PMo12 and PW12 heteropoly acids exhibit high catalytic activity. The Со-Мо/Al2O3 catalyst is more active in hydrodesulfurization and hydrogenation of olefin and diene hydrocarbons, whereas the Ni-W/Al2O3 catalysts are more active in hydrogenation of mono- and polycyclic aromatic hydrocarbons. Comparison of the quality characteristics of the hydrogenizates obtained with the requirements of the technical regulations shows that the required levels of the sulfur content and cetane number of the hydrogenizates at practically accessible process parameters can be reached for mixtures of the straight-run gasoil and light cycle oil from catalytic cracking with high content of the latter component only when the process with the Со-Мо/Al2O3 system and Ni-W/Al2O3 catalysts is performed in two steps.  相似文献   

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