首页 | 官方网站   微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 383 毫秒
1.
《Catalysis communications》2001,2(10):323-327
Hydrogenation of (E)-2-hexenal was carried out in a liquid phase using Co-based bimetallic catalysts (M–Co/Al2O3, M=Pd, Pt, Ru, Rh, Sn, Fe, or Cu). Pd–Co/Al2O3 showed the highest activity among the catalysts tested and catalyzed the hydrogenation of CC bond predominantly to produce hexanal and 1-hexanol. Pt–Co/Al2O3 was more active than monometallic Co/Al2O3 for the hydrogenation of CO bond. The excellent result, 92% selectivity to (E)-2-hexen-1-ol formation at 90% conversion, was obtained by the hydrogenation over Pt–Co/Al2O3 bimetallic catalyst. No improved activities were observed for the other bimetallic catalysts.  相似文献   

2.
《Applied Catalysis A: General》2001,205(1-2):129-146
The effect of combining 0.35 wt.% Pt with 0.35 wt.% of either Ir, Rh, Re or U on γ-Al2O3 support was investigated for the hydroconversion of n-pentane and n-hexane in a pulsed micro-reactor system at a temperature range of 300–500°C, except for Rh/Al2O3 (150–500°C). The dispersion of the metals in the catalysts under study was determined by H2 chemisorption. The effect of chlorine addition between 1.0 and 6.0 wt.% was investigated and a content of 3.0 wt.% Cl being of optimum promotion. Highest activities for hydroisomerization, hydrocracking and hydrogenolysis were exhibited by Pt, Ir and Rh/Al2O3 catalysts, respectively, whether the catalysts were Cl-free or containing 3% Cl. However, Re and U catalysts were inactive. Maximum hydroisomerization selectivities using chlorinated bimetallic catalysts could be arranged in the following order: PtU/Al2O3>PtRe/Al2O3>PtIr/Al2O3>PtRh/Al2O3. However, PtRh/Al2O3, before and after chlorination, was the most active catalyst for hydrogenolysis. The apparent reaction rate constants as well as the apparent activation energies (Ea) for the hydroconversion of n-pentane and n-hexane were calculated and the compensation effect relationship between Ea and logarithm of the pre-exponential factor was estimated. n-hexane reaction on PtRh/Al2O3 catalysts deviates from this relationship for mechanistic variation.  相似文献   

3.
Influence of thermal pretreatments (under N2, air or H2 gas atmosphere at 500 °C or 700 °C) has been investigated for the Pd/Al2O3 and Pd/Carbon catalysts in terms of its effect on their Pd particle size and performance in the H2-to-H2O2 oxidation and H2O2 destruction (by decomposition and/or hydrogenation) reactions in aqueous acidic medium containing Br promoter. The influence on the net H2O2 formation is found to depend strongly upon the catalyst support due to support–Pd cluster interactions. For both the catalysts, the thermal treatments (except in air) caused a large increase in their Pd particle size. The increase in Pd particle size caused an increase in the H2O2 formation activity of Pd/Al2O3 but a decrease in the H2O2 formation activity of Pd/C.  相似文献   

4.
The oxidized and weakly reducible perovskite oxide YBa2Cu3O7 − x (YBCO) has been prepared as a catalyst, supported on γ‐Al2O3. It was further modified by (i) impregnation with Ru and Pd and (ii) cobalt incorporation via co‐precipitation. All the catalysts were either 20% (w/w) YBCO/γ‐Al2O3 or 2% (w/w) Ru, Pd or Co/20% (w/w) YBCO/γ‐Al2O3. The catalysts were characterized using temperature programmed reduction (TPR), surface area measurements and X‐ray diffraction (XRD) studies before and after various treatments. They were studied as catalysts in the pressure range 20–50 atmospheres and in the temperature range 523–573 K in an autoclave equipped with a spinning basket catalyst container. The Pd‐, Ru‐ and Co‐modified catalysts gave predominantly methanation products, along with some C2–C4 hydrocarbons. However the YBCO/γ‐Al2O3 catalyst exhibited significant methanol selectivity at 50 atmospheres and at 523 K X‐ray diffraction studies revealed the presence of Cu(0), Cu(I) and Cu(II) after reduction and the species Cu(0) and Cu(I) are probably essential to CH3OH production. © 2000 Society of Chemical Industry  相似文献   

5.
Hydrogenation of 4‐chloro‐2‐nitrophenol (CNP) was carried out at moderate hydrogen pressures, 7–28 atm, and temperatures in the range 298–313 K using Pt/carbon and Pd/γ‐Al2O3 as catalysts in a stirred pressure reactor. Hydrogenation of CNP under the above conditions gave 4‐chloro‐2‐aminophenol (CAP). Dechlorination to form 2‐aminophenol and 2‐nitrophenol is observed when hydrogenation of CNP is carried out above 338 K, particularly with Pd/γ‐Al2O3 catalyst. Among the catalysts tested, 1%Pt/C was found to be an effective catalyst for the hydrogenation of CNP to form CAP, exclusively. To confirm the absence of gas–liquid mass transfer effects on the reaction, the effect of stirring speed (200–1000 rpm) and catalyst loading (0.02–0.16 g) on the initial reaction rate at maximum temperature 310 K and substrate concentration (0.25 mole) were thoroughly studied. The kinetics of hydrogenation of CNP carried out using 1%Pt/C indicated that the initial rates of hydrogenation had first order dependence with respect to substrate, catalyst and hydrogen pressure in the range of concentrations varied. From the Arrhenius plot of ln rate vs 1000/T, an apparent activation energy of 22 kJ mol?1 was estimated. © 2001 Society of Chemical Industry  相似文献   

6.
Aiming at enhancing H2 production in water gas shift (WGS) for fuel cell application, a small amount of oxygen was added to WGS reaction toward oxygen-enhanced water gas shift (OWGS) on ceria-supported bimetallic Pd–Cu and Pt–Cu catalysts. Both CO conversion and H2 yield were found to increase by the oxygen addition. The remarkable enhancement of H2 production by O2 addition in short contact time was attributed to the enhanced shift reaction, rather than the oxidation of CO on catalyst surface. The strong dependence of H2 production rate on CO concentration in OWGS kinetic study suggested O2 lowers the CO surface coverage. It was proposed that O2 breaks down the domain structure of chemisorbed CO into smaller domains to increase the chance for coreactant (H2O) to participate in the reaction and the heat of exothermic surface reaction helping to enhance WGS kinetics. Pt–Cu and Pd–Cu bimetallic catalysts were found to be superior to monometallic catalysts for both CO conversion and H2 production for OWGS at 300 °C or lower, while the superiority of bimetallic catalysts was not as pronounced in WGS. These catalytic properties were correlated with the structure of the bimetallic catalysts. EXAFS spectra indicated that Cu forms alloys with Pt and with Pd. TPR demonstrated the strong interaction between the two metals causing the reduction temperature of Cu to decrease upon Pd or Pt addition. The transient pulse desorption rate of CO2 from Pd–Cu supported on CeO2 is faster than that of Pd, suggesting the presence of Cu in Pd–Cu facilitate CO2 desorption from Pd catalyst. The oxygen storage capacity (OSC) of CeO2 in the bimetallic catalysts indicates that Cu is much less pyrophoric in the bimetallic catalysts due to lower O2 uptake compared to monometallic Cu. These significant changes in structure and electronic properties of the bimetallic catalysts are the result of highly dispersed Pt or Pd in the Cu nanoparticles.  相似文献   

7.
We investigated the influence of the calcination temperature on the structural properties of Al2O3 and how the resultant Al2O3 support affects the characteristics of Pd/Al2O3 catalysts. Al2O3 pretreated at different calcination temperatures ranging from 500 °C to 1,150 °C, was used as catalyst supports. The Pd/Al2O3 catalysts were prepared by a deposition-precipitation method using a pH 7.5 precursor solution. Characterization of the prepared Pd/Al2O3 catalysts was performed by X-ray diffraction (XRD), N2-physisorption, CO2-temperature programmed desorption (TPD), CO-chemisorption, and field emission-transmission electron microscopic (FE-TEM) analyses. The CO-chemisorption results showed that the Pd catalyst with the Al2O3 support calcined at 900 °C, Pd/Al2O3 (900), had the highest and most uniformly dispersed Pd particles, with a Pd dispersion of 29.8%. The results suggest that the particle size and distribution of Pd are related to the phase transition of Al2O3 and the ratio of isolated tetrahedral to condensed octahedral coordination sites (i.e., functional groups), where the tetrahedral sites coordinate more favorably with Pd.  相似文献   

8.
This paper reports on notable promotion of C2 + hydrocarbons formation from CO2 hydrogenation induced by combining Fe and a small amount of selected transition metals. Al2O3-supported bimetallic Fe–M (M = Co, Ni, Cu, Pd) catalysts as well as the corresponding monometallic catalysts were prepared, and examined for CO2 hydrogenation at 573 K and 1.1 MPa. Among the monometallic catalysts, C2 + hydrocarbons were obtained only with Fe catalyst, while Co and Ni catalysts yielded higher CH4 selectively than other catalysts. The combination of Fe and Cu or Pd led to significant bimetallic promotion of C2 + hydrocarbons formation from CO2 hydrogenation, in addition to Fe–Co formulation discovered in our previous work. CO2 conversion on Ni catalyst nearly reached equilibrium for CO2 methanation which makes this catalyst suitable for making synthetic natural gas. Fe–Ni bimetallic catalyst was also capable of catalyzing CO2 hydrogenation to C2 + hydrocarbons, but with much lower Ni/(Ni+Fe) atomic ratio compared to other bimetallic catalysts. The addition of a small amount of K to these bimetallic catalysts further enhanced CO2 hydrogenation activity to C2 + hydrocarbons. K-promoted Fe–Co and Fe–Cu catalysts showed better performance for synthesizing C2 + hydrocarbons than Fe/K/Al2O3 catalyst which has been known as a promising catalyst so far.  相似文献   

9.
The effect of noble metal addition on the catalytic properties of Co/Al2O3 was evaluated for the steam reforming of methane. Co/Al2O3 catalysts were prepared with addition of different noble metals (Pt, Pd, Ru and Ir 0.3 wt.%) by a wetness impregnation method and characterized by UV–vis spectroscopy, temperature programmed reduction (TPR) and temperature programmed oxidation (TPO) of the reduced catalysts. The UV–vis spectra of the samples indicate that, most likely, large amounts of the supported cobalt form Co species in which cobalt is in octahedral and tetrahedral symmetries. No peaks assigned to cobalt species from aluminate were found for the promoted and unpromoted cobalt catalysts. TPO analyses showed that the addition of the noble metals on the Co/Al2O3 catalyst leads to a more stable metallic state and less susceptible to the deactivation process during the reforming reaction. The Co/Al2O3 promoted with Pt showed higher stability and selectivity for H2production during the methane steam reforming.  相似文献   

10.
The influence of Pd on a Co–Pd/γ‐Al2O3 heavy oil upgrading catalyst is investigated using different physicochemical and reactive Characterization techniques. Nitrogen adsorption isotherm analysis shows that the specific surface area and porosity of the support alumina is significantly decreased due to the blockage of the pores by the loaded cobalt species. The estimated activation energy of NH3 desorption is found to be less for Co–Pd/γ‐Al2O3 sample, which confirms improved acidity due to Pd. TPR experiments show that the reducibility of the catalyst is significantly improved with the presence of Pd. Higher metal dispersion and hydrogen spillover effects are the main reasons for the enhanced reducibility of the Pd promoted catalyst as revealed by the H2‐pulse chemisorptions study. When evaluated using VGO as feed stock, the Co–Pd/γ‐Al2O3 displayed superiority both in hydrodesulphurisation (HDS) and hydrocracking (HC) activities as compared to the unpromoted Co/γ‐Al2O3 catalyst. The coke deposition on the spent catalyst is also found to be low due to the Pd promotional effects. This is an encouraging result, given that higher hydrogenation activity of the catalyst can be achieved without compromising the cracking activity and sustained activity of the catalyst.  相似文献   

11.
Present-day three-way catalysts operate in contact with exhaust gases whose temperature is as high as >1000°C, so the problem of developing thermally stable catalytic compositions is still topical. A series of Al2O3-Ce0.75Zr0.25O2 composites containing 0, 10, 25, and 50 wt % Al2O3 has been synthesized by direct precipitation. The as-prepared composites and those calcined in air at 1000 and 1100°C have been characterized by BET, X-ray diffraction, transmission electron microscopy, and temperature-programmed reduction methods. The composites aged at 1050°C in a 2% O2 + 10% H2O + 88% N2 atmosphere have been used to prepare monolith catalysts, and the oxygen storage capacity (OSC) of the latter has been measured using a gas analysis setup. As the proportion of Al2O3 in the composite is raised, the mixing uniformity and degree of dispersion of Ce x Zr1?x O2?δ particles increase, their chemical composition becomes homogeneous, and the amount of cerium involved in oxidation and reduction increases. The composite containing 50 wt % Al2O3 is a mixture of Ce x Zr1?x O2?δ and Al2O3 crystallites, whose size is practically unaffected by calcination. The (Pt/Al2O3 + Al2O3-Ce0.75Zr0.25O2) based on this composite has the highest OSC and is the most active. For this reason, full-scale testing of this catalyst is recommended.  相似文献   

12.
A series of Pd/γ-Al2O3 catalysts was prepared from [Pd(hfac)2] (hfac = hexafluoroacetylacetonate) in liquid carbon dioxide using the method reported by Kim et al. [Chem Mater 18:4710 (2006)]. The catalysts were characterized using CO pulse chemisorption, diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray absorption fine structure (XAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS), and electron microscopy. The catalysts were reduced initially in the high-pressure CO2 reaction cell using H2 at 75 °C. Samples were removed, stored in a desiccator, and re-reduced in situ at 250 °C prior to pulse chemisorption, DRIFTS and XAFS. CO pulse chemisorption evidenced that the Pd dispersion decreased from 55% to 5% as the Pd loading increased from 0.58 to 3.94 wt.%. The as-prepared 0.58 and 1.77 wt.% Pd/γ-Al2O3 catalysts (after air exposure) contained oxidized Pd species that were converted after in situ reduction to supported Pd particles. The average Pd particle sizes of these two catalysts (16 and 23 Å, respectively) estimated from the first-shell Pd–Pd coordination numbers are in good agreement with the CO chemisorption results. DRIFTS evidenced a prevalence of weakly bound linear CO (νCO = 2083 cm?1) adsorbed on the 0.58 wt.% Pd catalyst. A 2.95 wt% Pd catalyst (49 Å average particle size) also exhibited a strong linear CO band (νCO = 2093 cm?1). In contrast, CO chemisorption on a commercial 1 wt.% Pd/Al2O3 catalyst (37 Å average particle size) gave predominantly 2-fold bridging CO species. We infer that the supported Pd particles prepared from [Pd(hfac)2] are rougher on the atomic scale (with a higher percentage of edge and corner atoms) than equivalently sized particles in conventionally prepared Pd/γ-Al2O3 catalysts.  相似文献   

13.
Silica‐alumina (SiO2‐Al2O3)‐supported palladium catalysts prepared by adsorption of the tetrachloropalladate anion (PdCl42−) followed by calcination and reduction with either hexanol or hydrogen were studied for the aerobic oxidation of alcohols. The mean size of the Pd particles over the SiO2‐Al2O3 support was found to depend on the Si/Al ratio, and a decrease in the Si/Al ratio resulted in a decrease in the mean size of the Pd nanoparticles. By changing the Si/Al ratio, we obtained supported Pd nanoparticles with mean sizes ranging from 2.2 to 10 nm. The interaction between the Pd precursor and the support was proposed to play a key role in tuning the mean size of the Pd nanoparticles. The Pd/SiO2‐Al2O3 catalyst with an appropriate mean size of Pd particles could catalyze the aerobic oxidation of various alcohols to the corresponding carbonyl compounds, and this catalyst was particularly efficient for the solvent‐free conversion of benzyl alcohol. The intrinsic turnover frequency per surface Pd atom depended significantly on the mean size of Pd particles and showed a maximum at a medium mean size (3.6–4.3 nm), revealing that the aerobic oxidation of benzyl alcohol catalyzed by the supported Pd nanoparticles was structure‐sensitive.  相似文献   

14.
Water gas shift reaction on supported noble metal catalysts is an essential process for upgrading hydrogen source industrially. Here a series of Pd/FeOx catalysts were detected for this reaction with Pd/Al2O3 as reference. It was found that Pd/FeOx exhibited higher CO conversion than Pd/Al2O3 with a good stability even in the presence of CO2 and H2. Along the loading decreasing, the turnover frequency of exposed Pd atoms increased with the dispersion from subnanometer (~1 nm) to single atoms. Various characterizations suggested that Pd single atoms greatly enhanced the reducibility of FeOx and facilitated the formation of oxygen vacancies, which served as sites to promote the dissociation of H2O to form H2 and atomic O. The atomic O was ready to react with the linear adsorbed CO species on Pd single‐atom sites through a redox mechanism, which resulted in low activation energy of ~30 kJ mol?1. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4022–4031, 2017  相似文献   

15.
Monometallic and bimetallic catalysts (Pt, Ni, and Pt‐Ni) with single support (Al2O3, TiO2) and composite support (CeO2/Al2O3, CeO2/TiO2) were prepared and tested for water‐gas shift reaction in a tubular quartz reactor. Syngas and steam with different steam‐to‐carbon ratios served as feedstock. The operating pressure was fixed while the reaction temperature was varied. The measured results indicated that the monometallic Ni/Al2O3 catalyst exhibits the lowest CO conversion and H2 yield as compared with other catalysts. About the same CO conversion can be obtained from Pt and Pt‐Ni catalysts with single or composite support. However, higher H2 yield can be achieved from the TiO2‐supported catalyst compared with those supported by Al2O3. The experimental data also indicated that good thermal stability can be reached for the Pt‐based catalysts studied.  相似文献   

16.
A study of nitrous oxide (N2O) reduction with methane (CH4) and propene (C3H6) in the presence of oxygen (5%) over Ag/Al2O3, Rh/Al2O3 and Ag–Rh/Al2O3 catalysts, with Ag and Rh loadings of 5 wt% and 0.05 wt% respectively, has been performed. From the results, it was observed that the Ag–Rh bimetallic catalyst was the most active for both nitrous oxide removal (more than 95%) and hydrocarbon oxidation. This high activity seems to be connected with a synergistic effect between Ag and Rh. The findings from X‐ray diffraction and X‐ray photoelectron spectroscopy studies showed also, that there were no strong interactions (eg alloying) between Ag and Rh. Copyright © 2005 Society of Chemical Industry  相似文献   

17.
The sulfur tolerance (i.e., degree of sulfidation) of Pd and Pt in sulfided bimetallic Pd–Pt catalysts (Pd : Pt mole ratio of 4 : 1) supported on USY (ultrastable Y) zeolites (SiO2/Al2O3 = 10.7, 48, and 310) was investigated using an extended X‐ray absorption fine structure (EXAFS) method. The sulfidation of the catalysts was done in a 1000 ppm H2S–2% H2/N2 stream at 573 K for 0.5 h. In the Fourier transforms of Pd K‐edge and Pt LIII‐edge EXAFS spectra, both of the peaks due to metallic Pd and to metallic Pt for the Pd–Pt/USY (SiO2/Al2O3 = 10.7) catalyst remained most after sulfidation. Further, the results of the Fourier transforms confirmed that the sulfur tolerance of both Pd and Pt decreased with increasing SiO2/Al2O3 ratio, suggesting that Pd and Pt become sulfur‐tolerant when Pd–Pt bimetallic particles are supported on highly acidic USY zeolite. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

18.
The effect of CeO2 loading on the surface properties and catalytic behaviors of CeO2–Al2O3-supported Pd catalysts was studied in the process of steam reforming of methane. The catalysts were characterized by SBET, X-ray diffraction (XRD), temperature-programmed reduction (TPR), UV–vis diffuse reflectance spectroscopy (DRS) and Fourier transform infrared spectroscopy (FTIR). The XRD measurements indicated that palladium particles on the surface of fresh and reduced catalysts are well dispersed. TPR experiments revealed a heterogeneous distribution of PdO species over CeO2–Al2O3 supports; one fraction of large particles, reducible at room temperature, another fraction interacting with CeO2 and Al2O3, reducible at higher temperatures of 347 and 423 K, respectively. The PdO species reducible at room temperature showed lower CO adsorption relative to the PdO species reducible at high temperature. In contrast to Pd/Al2O3, the FTIR results revealed that CeO2-containing catalyst with CeO2 loading ≥12 wt.% show lower ratio (LF/HF) between the intensity of the CO bands in the bridging mode at low frequency (LF) and the linear mode at high frequency (HF). This ratio was constant with increasing the temperature of reduction. The FTIR spectra and the measurement of Pd dispersion suggested that Pd surface becomes partially covered with ceria at all temperature of reduction and with increasing ceria loading in Pd/CeO2–Al2O3 catalysts. Although the PdO/Al2O3 showed higher Pd dispersion compared to that of CeO2-containing catalysts, the addition of ceria resulted in an increase of the turnover rate and specific rate to steam reforming of methane. The CH4 turnover rate of Pd/CeO2–Al2O3 catalysts with ceria loading ≥12 wt.% was around four orders of magnitude higher compared to that of Pd/Al2O3 catalyst. The increase of the activity of the catalysts was attributed to various effects of CeO2 such as: (i) change of superficial Pd structure with blocking of Pd sites; (ii) the jumping of oxygen (O*) from ceria to Pd surface, which can decrease the carbon formation on Pd surface. Considering that these effects of CeO2 are opposite to changes of the reaction rate, the increase of specific reaction rate with enhancing the ceria loading suggests that net effect results in the increase of the accessibility of CH4 to metal active sites.  相似文献   

19.
Hydrogen production by partial oxidation and steam reforming (POSR) of n‐octane was investigated over alumina‐supported Ni and Ni‐Pd catalysts. It showed that Ni‐Pd/Al2O3 had higher activity and hydrogen selectivity than the nickel catalyst under the experimental conditions, which indicated Ni‐Pd/Al2O3 could be an effective catalyst for the production of hydrogen from hydrocarbons.  相似文献   

20.
《Catalysis communications》2007,8(8):1287-1292
The catalytic methane combustion was investigated over alumina-supported monometallic and bimetallic palladium and manganese oxide catalysts. The catalytic activity of these systems showed that palladium incorporation on MnOx/Al2O3 catalyst leads to an enhancement in methane combustion. The higher catalytic activity of the PdMn/Al2O3 catalysts is related to a greater mobility of lattice oxygen in manganese oxide in the presence of palladium. These bimetallic catalysts also showed a significant improvement in catalysts stability with respect the monometallic ones. Surface analysis of the used catalysts revealed less amount of coke and Mn/Al and Pd/Al atomic ratios almost unchanged, which is indication of absence of active phase sintering.  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-23

京公网安备 11010802026262号