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1.
A series of Rh catalysts on various supports (Al2O3, MgAl2O4, ZrO2, and ZrO2–CeO2) have been applied to H2 production from the ethanol steam reforming reaction. In terms of ethanol conversion at low temperatures (below 450 °C) with 1wt% Rh catalysts, the activity decreases in the order: Rh/ZrO2–CeO2 > Rh/Al2O3 > Rh/MgAl2O4 > Rh/ZrO2. Support plays a very important role on product selectivity at low temperatures (below 450 °C). Acidic or basic supports favor ethanol dehydration, while ethanol dehydrogenation is favored over neutral supports at low temperatures. The Rh/ZrO2–CeO2 catalyst exhibits the highest CO2 selectivity up to 550 °C, which is due to the highest water gas shift (WGS) activity at low temperatures. Among the catalysts evaluated in this study, the 2wt% Rh/ZrO2–CeO2 catalyst exhibited the highest H2 yield at 450 °C, which is possibly due to the high oxygen storage capacity of ZrO2–CeO2 resulting in efficient transfer of mobile oxygen species from the H2O molecule to the reaction intermediate.  相似文献   

2.
The reaction of ethanol and water has been investigated over K doped 1% Pt/Al2O3 catalysts. The presence of K resulted at room temperature in upward shift of the IR band of CO formed in the ethanol adsorption. At higher temperature the presence of surface acetate species was also detected which, according to the TPD results decomposed above 600 K to form CH4 and CO2. The K destabilized these forms. In the catalytic reaction the H2 selectivities were similar and much higher over all promoted Pt/Al2O3 than on the pure catalyst. In this study it was proved that the K had a destabilizing effect onto the surface acetate groups and thus improved the steam reforming activity of 1% Pt/Al2O3.  相似文献   

3.
Hydrogen production from ethanol reforming was investigated on bimetallic PtNi catalysts supported on CeO2/Al2O3. Pt content was varied from 0.5 to 2.5 %. Physico-chemical characterization of the as-prepared and H2-reduced catalysts by TPR, XRD and XPS showed that Pt phase interacted with the Ni and Ce species present at the surface of the catalysts. This interaction leads to an enhancement of the reducibility of both Ni and Ce species. Loadings of Pt higher than 1.0 wt% improved the activity and stability of the Ni/CeO2–Al2O3 catalyst in ethanol steam reforming, in terms of lower formation of coke, C2 secondary products and a constant production of CO2 and H2. The amount and type of carbon deposited on the catalyst was analyzed by TG–TPO while the changes in crystalline phases after reaction were studied by XRD. It was found that for Pt contents higher than 1 wt% in the catalysts, a better contact between Pt and Ce species is achieved. This Pt–Ce interaction facilitates the dispersion of small particles of Pt and thereby improves the reducibility of both Ce and Ni components at low temperatures. In this type of catalysts, the cooperative effect between Pt0, Ni0 and reduced Ce phases leads to an improvement in the stability of the catalysts: Ni provides activity in C–C bond breakage, Pt particles enhance the hydrogenation of coke precursors (CxHy) formed in the reaction, and Ce increases the availability of oxygen at the surface and thereby further enhances the gasification of carbon precursors.  相似文献   

4.
The decomposition of ethanol has been investigated on Pt metals supported by carbon Norit of high surface area. The reaction starts above 450 K and approaches total conversion at 673–723 K. The major products are H2, CO and CH4. The selectivity of hydrogen formation on all metals supported by carbon Norit scattered around 30%, and almost ~40% of the hydrogen content of ethanol has been converted to gaseous hydrogen at the total conversion. The order of the efficiency of the metals based on the turnover frequencies is Ru > Pt > Ir > Rh > Pd. An advantageous feature of the Norit-supported Pt metals is that no deactivation occurred at 723 K in 10 h, which is in contrast to the behaviour of Pt/Al2O3. The high stability of the catalysts is attributed to the lack of reactive OH groups required for the formation of acetate poisoning the metals. Adding water to ethanol only slightly improved the production of hydrogen.  相似文献   

5.
The ethanol steam reforming has been investigated over supported cobalt catalysts at atmospheric pressure. About 12% cobalt was supported on Al2O3, SiO2 and TiO2, and a commercial Ni/Al2O3 catalyst (G90B) was included for comparative purposes. The selectivity was found to depend strongly on the support, especially at low and medium temperatures. The initial activity of the cobalt catalysts correlated well with the metal dispersion. Acetaldehyde was an important C-containing product at low temperatures, whereas at high temperatures CO, CO2 and CH4 dominated the product spectrum. A significant production of ethene was observed, especially on the alumina-supported catalysts. The results are in agreement with a mechanism involving acetaldehyde as an intermediate in the steam reforming. At high temperatures (>550 °C) the conversion was complete and the product distribution approaches the equilibrium. The H2 yield approached 5 moles H2/mole ethanol converted, which is close to the maximum according to thermodynamic calculations. The alumina-supported catalysts (both Co and Ni) showed acceptable deactivation rates, but high carbon formation.  相似文献   

6.
Steam reforming of ethanol was examined over Co/SrTiO3 with addition of another metal—Pt, Pd, Rh, Cr, Cu, or Fe—for promotion of the catalytic activity. Ethanol conversion and H2 yield were improved greatly by adding Fe or Rh at 823 K. Although Rh addition promoted CH4 formation, Fe addition enhanced steam reforming of ethanol selectively. A suitable amount of Fe loading was in the window of 0.33–1.3 mol%. A comparative study of the reaction over a catalyst supported on SiO2 was conducted, but no additional effect of Fe was observed on the Co/SiO2 catalyst. High activity of Fe/Co/SrTiO3 catalyst came from interaction among Fe, Co, and SrTiO3.  相似文献   

7.
Fe/Al2O3 catalysts with different Fe loadings (10-90 mol%) were prepared by hydrothermal method. Ethanol decomposition was studied over these Fe/Al2O3 catalysts at temperatures between 500 and 800 °C to produce hydrogen and multi-walled carbon nanotubes (MWCNTs) at the same time. The results showed that the catalytic activity and stability of Fe/Al2O3 depended strongly on the Fe loading and reaction temperature. The Fe(30 mol%)/Al2O3 and Fe(40 mol%)/Al2O3 were both the effective catalyst for ethanol decomposition into hydrogen and MWCNTs at 600 °C. Several reaction pathways were proposed to explain ethanol decomposition to produce hydrogen and carbon (including nanotube) at the same time.  相似文献   

8.
A platinum/alumina catalyst was sintered in oxygen and hydrogen atmospheres using two metal loadings of the catalyst: 0.3% Pt and 0.6% Pt. After sintering, the aromatization selectivity was investigated with the reforming of n‐heptane as the model reaction at a temperature of 500 °C and a pressure of 391.8 kPa. The primary products of n‐heptane reforming on the fresh platinum catalysts were methane and toluene, with subsequent conversion of benzene from toluene demethylation. To induce sintering, the catalysts were treated with oxygen at a flow rate of 60 mL min?1, pressure of 195.9 kPa and temperatures between 500 and 800 °C. The 0.3% Pt/Al2O3 catalyst exhibited enhanced aromatization selectivity at various sintering temperatures while the 0.6% Pt/Al2O3 catalyst was inherently hydrogenolytic. The fact that aromatization was absent on the 0.6% Pt/Al2O3 catalyst was attributed to the presence of surface structures with dimensionality between two and three as opposed to essentially 2‐D structures on the 0.3% Pt/Al2O3 catalyst surface. On the 0.3% Pt/Al2O3 catalyst, the reaction product ranged from only toluene at a 500 °C sintering temperature to predominantly cracked product at a sintering temperature of 650 °C and no reaction at 800 °C. For sintering at about 650 °C, subsequent conversion of n‐heptane was complete and dropped thereafter. The turnover number was observed to change from 0.07 to 2.26 s?1 as the dispersion changed from 0.33 to 0.09. The Koros–Nowark (K–N) test was used to check for the presence of internal diffusional incursions and Boudart's criterion was used for structural sensitivity determination. The K–N test indicated the absence of diffusional resistances while n‐heptane reforming was found to be structure sensitive on the Pt/Al2O3 catalyst. Copyright © 2006 Society of Chemical Industry  相似文献   

9.
The effects of Co loading and calcination temperatures on the catalytic activity of Co/Al2O3 for selective catalytic reduction (SCR) of NO with ethylene in excess oxygen were investigated. Co/Al2O3 showed high and low activities when calcined at high (800 °C) and low (350 °C) temperatures, respectively. The formation and dispersion of cobalt species for catalysts calcined at 350 and 800 °C as well as for Al2O3 were studied by XRD, UV–vis and FTIR spectra. Combined with DRIFTS results of ad-species and reaction experiments, it allowed us to correlate the catalytic activity with active sites of Co/Al2O3, and the catalytic functions of active cobalt species and support were clarified. Co3O4 species contributed to the oxidation of NO to various nitrates and of C2H4 to reactive formate species, even in the absence of O2, whereas the side reaction of ethylene combustion occurred simultaneously when excess oxygen was present. Tetrahedral Co2+ ions in CoAl2O4, which acted as the active sites, were responsible for the reaction between formate and nitrate species to form organic nitro compound.  相似文献   

10.
The catalytic activity of Pt/Al2O3 for the total oxidation of hydrocarbon mixture of n-decane and 1-methylnaphthalene was strongly dependent on the Pt dispersion. The maximum hydrocarbon oxidation activity was achieved for Pt/Al2O3 with Pt dispersion (DPt) of 0.39. On the other hand, the activity of Pt/ZrO2 monotonously decreased with decreasing Pt dispersion from 1.00 to 0.09. In situ FT-IR spectroscopy suggested that the presence of plural Pt species in metallic state with slight different electric state, which well catalyze the formation of acrylate species as an intermediate, is responsible for the high catalytic activity of Pt/Al2O3 with DPt = 0.39.  相似文献   

11.
Oxidation of toluene has been investigated over supported platinum as well as over a variety metal oxide (M x O y ) catalysts dispersed on high surface area γ-Al2O3. Catalysts were characterized with respect to their specific surface area (BET), metal dispersion (selective chemisorption of CO), phase composition and M x O y crystallite size (XRD) and reducibility (H2-TPR). Catalytic performance for the title reaction was investigated in the temperature range of 100–500 °C, using a feed composition consisting of 0.1% toluene in air. For Pt/M x O y catalysts, it has been found that catalytic performance depends on the nature of the support, with Pt/CeO2 being the most active catalyst at low temperatures. The intrinsic reaction rate per surface platinum atom does not depend on Pt loading (0.5–5 wt%), at least for Pt/Al2O3. Reducible metal oxides, such as ceria, are active for the title reaction and catalytic performance is improved significantly with increase of specific surface area (SSA). However, the intrinsic reaction rate per unit surface area is invariant with SSA. Dispersion of M x O y on high surface area inert supports, such as Al2O3, results in materials with relatively high catalytic activity, which seems to correlate well with the reducibility of metal oxides. Catalytic performance of M x O y /Al2O3 catalysts can be optimized by proper selection of M x O y loading. Best performing catalysts of this series include 60% MnO, 90% CeO2 and 5% CuO on Al2O3 which, under the present experimental conditions, are able to completely convert toluene toward CO2 at temperatures lower than 350 °C. Dispersion of Pt on M x O y /Al2O3 catalysts improves significantly the catalytic performance of irreducible M x O y but does not alter appreciably the activity of reducible M x O y /Al2O3 catalysts.  相似文献   

12.
This work reports the enhancing effect of a highly cost effective and efficient metal, Fe, incorporation to Co or Ni based Mo/Al_2O_3 catalysts in the oxidative desulfurization(ODS) of dibenzothiophene(DBT) using H_2O_2 and formic acid as oxidants. The influence of operating parameters i.e. reaction time, catalyst dose, reaction temperature and oxidant amount on oxidation process was investigated. Results revealed that 99% DBT conversion was achieved at 60 °C and 150 min reaction time over Fe–Ni–Mo/Al_2O_3. Fe tremendously enhanced the ODS activity of Co or Ni based Mo/Al_2O_3 catalysts following the activity order: Fe–Ni–Mo/Al_2O_3 NFe–Co–Mo/Al_2O_3 NNi–Mo/Al_2O_3 NCo–Mo/Al_2O_3, while H_2O_2 exhibited higher oxidation activity than formic acid over all catalyst systems. Insight about the surface morphology and textural properties of fresh and spent catalysts were achieved using scanning electron microscopy(SEM), X-ray diffraction(XRD), energy dispersive X-ray(EDX)analysis, Atomic Absorption Spectroscopy(AAS) and BET surface area analysis, which helped in the interpretation of experimental data. The present study can be deemed as an effective approach on industrial level for ODS of fuel oils crediting to its high efficiency, low process/catalyst cost, safety and mild operating condition.  相似文献   

13.
Dendrimer encapsulated Pt nanoparticles were prepared by using hydroxyl terminated generation four (G4OH) PAMAM dendrimers (DEN) as the templating agents. The encapsulated Pt nanoparticles were dispersed on γ-Al2O3 at room temperature by impregnation. Pt/Al2O3 (DEN) catalysts were then subjected to thermal treatments in oxidizing and reducing atmospheres at different temperatures. These catalysts were characterized by Transmission Electron microscopy (TEM) and In situ Fourier-Transform Infrared (FTIR) spectroscopy. The TEM analysis of the as synthesized catalysts revealed that the Pt nanoparticles were found to be 2–4 nm in size. It is observed that the Pt particle size in 0.5% Pt/Al2O3 (DEN) catalyst increased upon thermal decomposition of the dendrimer. The in situ FTIR results suggested that the presence of oxygen and the Pt nanoparticles in the Pt-dendrimer nanocomposite accelerate the dendrimer decomposition at low temperatures. All the catalysts were tested for the reduction of NO x with CH4 in the temperature range of 250–500 °C. NO x reduction efficiency of Pt/Al2O3 (DEN) catalysts were compared with the Pt/Al2O3 (CON; conventional) catalyst. The conversion of NO x was started from the low temperatures over Pt/Al2O3 (DEN) catalysts. The high selectivity of NO x to N2 of 74% was obtained over 0.5% Pt/Al2O3 (DEN) catalyst at low temperatures around 350 °C.  相似文献   

14.
The catalytic oxidation of toluene, chosen as VOC probe molecule, was investigated over Co3O4, CeO2 and over Co3O4–CeO2 mixed oxides and compared with the catalytic behavior of a conventional Pt(1 wt%)/Al2O3 catalyst. Complete toluene oxidation to carbon dioxide and water was achieved over all the investigated systems at temperatures below 500 °C. The most efficient catalyst, Co3O4(30 wt%)–CeO2(70 wt%), showed full toluene conversion at 275 °C, comparing favorably with Pt/Al2O3 (100% toluene conversion at 225 °C).  相似文献   

15.
《Fuel》2007,86(7-8):1000-1007
Three bimetallic catalysts, consisting of platinum and a second metal supported on chlorinated alumina, i.e. Pt–Re/Al2O3, Pt–Sn/Al2O3, and Pt–Ge/Al2O3, have been used in the transformation of two α-olefins, 1-pentene and 1-hexene. Their conversion to internal and branched olefins is highly interesting for their use in reformulated gasolines and as intermediate chemicals. The catalysts characterization has been accomplished by different techniques, such as elemental and XRD analysis, N2 adsorption, TPD of ammonia and hydrogen chemisorption. Among the three catalysts, Pt–Sn/Al2O3 showed the highest hydrogenation activity, whereas Pt–Ge/Al2O3 was the less active towards the hydrogenation of the olefins, according to their H2 adsorption abilities. The bimetallic catalysts were compared to the monometallic one (Pt/Al2O3), as well as to the support. The catalyst and reaction conditions significantly influenced the products distribution. Hydrogenation was dominant at low temperatures (up to 350–400 °C) while skeletal isomerization and double bond shift prevailed at higher temperatures.  相似文献   

16.
Aqueous-phase reforming of 10 wt% ethylene glycol solutions was studied at temperatures of 483 and 498 K over Pt-black and Pt supported on TiO2, Al2O3, carbon, SiO2, SiO2-Al2O3, ZrO2, CeO2, and ZnO. High activity for the production of H2 by aqueous-phase reforming was observed over Pt-black and over Pt supported on TiO2, carbon, and Al2O3 (i.e., turnover frequencies near 8-15 min-1 at 498 K); moderate catalytic activity for the production of hydrogen is demonstrated by Pt supported on SiO2-Al2O3 and ZrO2 (turnover frequencies near 5 min-1); and lower catalytic activity is exhibited by Pt supported on CeO2, ZnO, and SiO2 (H2 turnover frequencies lower than about 2 min-1). Pt supported on Al2O3, and to a lesser extent ZrO2, exhibits high selectivity for production of H2 and CO2 from aqueous-phase reforming of ethylene glycol. In contrast, Pt supported on carbon, TiO2, SiO2-Al2O3 and Pt-black produce measurable amounts of gaseous alkanes and liquid-phase compounds that would lead to alkanes at higher conversions (e.g., ethanol, acetic acid, acetaldehyde). The total rate of formation of these byproducts is about 1-3 min-1 at 498 K. An important bifunctional route for the formation of liquid-phase alkane-precursor compounds over less selective catalysts involves dehydration reactions on the catalyst support (or in the aqueous reforming solution) followed by hydrogenation reactions on Pt.  相似文献   

17.
Catalytic hydrodesulfurization (HDS) of dibenzothiophene (DBT) was carried out in a temperature range of 320-?400 °C using in situ generated hydrogen via steam reforming of ethanol and the effect of some organic additives was studied for the first time. Four kinds of alumina-based catalysts, i.e. Co?-Mo/Al2O3, Ni-Mo/Al2O3 and their corresponding Pd promoted catalysts Pd-?Co-?Mo/Al2O3 and Pd-?Ni-?Mo/Al2O3, prepared through incipient impregnation method, were used for the desulfurization process. Catalytic activity was investigated in a batch autoclave reactor in the complete absence of external hydrogen gas. Experiments showed that organic additives like diethylene glycol (DEG), phenol, naphthalene, anthracene, o-xylene, tetralin, decalin and pyridine can affect the HDS activity of the catalysts in different ways, and only naphthalene is inhibitive for the catalytic activity towards HDS. The results showed that Ni-based catalysts are more active than Co-based ones while Pd shows a high promotion effect. DBT conversion of up to 97% was achieved with Pd-?Ni-?Mo/Al2O3 catalyst at 380 °C temperature and 13 h reaction time. Catalyst systems followed the HDS activity order of: Pd-?Ni-?Mo/Al2O3 > Ni-?Mo/Al2O3 > Pd-?Co-?Mo/Al2O3 > Co?-Mo/Al2O3 at all conditions. Qualitative analysis of the products stream was carried out using GC?-MS technique. The present HDS process using in situ generated hydrogen might be applied as an alternative approach for the catalytic HDS of DBT on industrial level due to its cost effectiveness, mild operating conditions and high activity of the catalysts.  相似文献   

18.
A series of Pt catalysts supported on Al2O3 (Pt/A), Al2O3-CeO2 (Pt/A-C), Al2O3-La2O3 (Pt/A-L) and Al2O3-La2O3-CeO2 (Pt/A-L-C) have been prepared and tested in the oxidative reforming of diesel surrogate with the aim of studying the influence of ceria and lanthana additives over the activity and stability toward hydrogen production for fuel cell application. Several characterization techniques, such as adsorption-desorption of N2, X-ray diffraction, X-ray photoelectron spectroscopy, temperature programmed reduction, H2 chemisorption, and thermogravimetric analysis, have been used to define textural, structural, and surface properties of catalysts and to establish relationships with their behaviour in reaction. This physicochemical characterization has shown that lanthana inhibits the formation of α phase in alumina support and decreases ceria dispersion. Activity results show a better performance of ceria-loaded catalysts, being the Pt/A-C sample the system that offers higher H2 yields after 8 h of reaction. The greater H2 production for ceria-loaded catalysts, particularly in the case of the system Pt/A-C, is attributed to the Pt-Ce interaction that may change the electronic properties and/or the dispersion of active metal phase. Also, the CeIII form of CeIV/CeIII redox pair enhances the adsorption of oxygen and water molecules, thus increasing the catalytic activity and also decreasing coke deposition over surface active Pt phases. Stability tests showed that catalysts in which Pt crystallites are deposited on the alumina substrate covered by a lanthana monolayer, give rise to an increase in stability toward H2 production.  相似文献   

19.
The dehydration of glucose into 5-hydroxymethylfurfural (HMF) was catalyzed by NKC-9 (a macroporous sulfonated polystyrene ion-exchange resin) combined with metal oxides (TiO2, ZrO2, Al2O3 calcined at different temperatures). In the combined catalytic system, Al2O3 calcined at 550°C exhibited excellent catalytic activity, when the dosage of NKC-9 was kept constant. Four parameters (catalyst dosage, reaction temperature, reaction time, and initial glucose amount) were optimized by employing response surface methodology (RSM), with HMF yield as the response parameter. The maximum HMF yield of 62.09% was obtained at catalyst 0.07 g, temperature 140°C, time 20 min, and glucose 0.01 g. The catalytic activity of the binary catalyst (NKC-9 and Al2O3) for the conversion of glucose into HMF did not show significant decrease after five-times uses at 140°C for 20 min.  相似文献   

20.
BACKGROUND: The metal dispersed over a support can be present as small crystallites with sizes less than 5 nm. The smaller crystallites favour aromatization while larger crystallites favour cracking/hydrogenolysis. Sintering results in the agglomerization of smaller metal crystallites. Correlation of size with aromatization selectivity was investigated. RESULTS: The primary products of n‐heptane reforming on fresh Pt were methane, toluene, and benzene, while on fresh Pt‐Re, the only product was methane. Both catalysts exhibited enhanced aromatization selectivity at different oxygen sintering temperatures. The reaction products ranged from only toluene at 500 °C sintering temperature to methane at a sintering temperature of 650 °C with no reaction at 800 °C for the Pt/Al2O3 catalyst. On Pt‐Re/Al2O3 catalyst, methane was the sole product at a sintering temperature of 500 °C while only toluene was produced at a sintering temperature of 800 °C. CONCLUSION: This is the first time that sintering has been used to facilitate aromatization of supported Pt and Pt‐Re catalysts. A superior selectivity behaviour associated with bi‐metallic Pt catalysts is established. It was found that no reaction occurred on Pt catalyst after sintering at 800 °C whereas sintering Pt‐Re at 800 °C promoted aromatization solely to toluene. Copyright © 2008 Society of Chemical Industry  相似文献   

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