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1.
NiSO4/Al2O3 and NiO/Al2O3 catalyst precursors were formed by calcination of NiSO4·6H2O/Al2O3 at 500 and 800 °C, respectively. The catalyst precursor was reduced under H2 and N2 and then reacted under C2H2, H2 and N2 at 650 °C. Coiled carbon fibres were formed in fixed- and fluidised-bed reactors using the NiSO4/Al2O3 catalyst precursor. Thermodynamic modelling using an infinite equilibrium stage construction predicted complete reduction of NiSO4 to Ni and simultaneous H2S formation occurs in both fixed- and fluidised-bed systems. XRD measurements confirmed that Ni was the only catalytically active crystalline species present at concentrations >0.5 wt.% (XRD detection limit) post-reduction, however XRF and XPS measurements additionally detected the presence of small quantities (<0.9 wt.% S) of S species. S is adsorbed onto the Ni surfaces during reduction when H2S is released and dissociates on the Ni surface. Non-coiled carbon fibres produced on the Ni/Al2O3 catalyst formed from the NiO/Al2O3 precursor demonstrated that modification of Ni/Al2O3 with S is required for coiled carbon fibre synthesis.  相似文献   

2.
This work investigates the improvement of Ni/Al2O3 catalyst stability by ZrO2 addition for H2 gas production from CH4/CO2 reforming reactions. The initial effect of Ni addition was followed by the effect of increasing operating temperature to 500–700 °C as well as the effect of ZrO2 loading and the promoted catalyst preparation methods by using a feed gas mixture at a CH4:CO2 ratio of 1:1.25. The experimental results showed that a high reaction temperature of 700 °C was favored by an endothermic dry reforming reaction. In this reaction the deactivation of Ni/Al2O3 was mainly due to coke deposition. This deactivation was evidently inhibited by ZrO2, as it enhances dissociation of CO2 forming oxygen intermediates near the contact between ZrO2 and nickel where the deposited coke is gasified afterwards. The texture of the catalyst or BET surface area was affected by the catalyst preparation method. The change of the catalyst texture resulted from the formation of ZrO2–Al2O3 composite and the plugging of Al2O3 pore by ZrO2. The 15% Ni/10% ZrO2/Al2O3 co-impregnated catalyst showed a higher BET surface area and catalytic activity than the sequentially impregnated catalyst whereas coke inhibition capability of the promoted catalysts prepared by either method was comparable. Further study on long-term catalyst stability should be made.  相似文献   

3.
In this investigation, a comparative study for a NO X storage catalytic system was performed focusing on the parameters that affect the reduction by using different reductants (H2, CO, C3H6 and C3H8) and different temperatures (350, 250 and 150 °C), for a Pt/BaO/Al2O3 catalyst. Transient experiments show that H2 and CO are highly efficient reductants compared to C3H6 which is somewhat less efficient. H2 shows a significant reduction effect at relatively low temperature (150 °C) but with a low storage capacity. We find that C3H8does not show any NO X reduction ability for NO X stored in Pt/BaO/Al2O3 at any of the temperatures. The formation of ammonia and nitrous oxide is also discussed.  相似文献   

4.
Ethanol reforming and partial oxidation were studied on Cu/Nb2O5 and Ni/Al2O3 catalysts. Compared to the Ni/Al2O3 catalyst, the Cu/Nb2O5 catalyst presents conversion as high as Ni/Al2O3 catalyst, however, for the same level of formation of hydrogen it occurs at much lower temperature on the Cu/Nb2O5 catalyst, 200 °C lower than for the Ni/Al2O3 catalyst, with remarkable little formation of CO, which can be attributed to the strong interaction between copper and niobia. Temperature-programmed desorption (TPD-ethanol) and surface reactions (TPSR) of partial oxidation of ethanol showed formation of ethylene, acetaldehyde, ethane and mainly H2 and CO2 besides little methane. DRIFTS results are in accordance with TPD analysis and the formation of acetate species at room temperature suggests reactivity of the surface and its oxidative dehydrogenation capacity. The adsorption of ethanol gives rise to ethoxide species, which form acetate and acetaldehyde that can be oxidized to CO2 via carbonate. A comparison with reported results for Cu/Al2O3 this catalyst is promising, yielding high level of H2 with little CO production during reforming and partial oxidation reaction. The maximum H2 formation for the partial oxidation of ethanol was 41% at ratio (O2/Et) 0.8, increasing to 50% at ratio 1.5. The H2/CO is around 10 for the partial oxidation and 7 for steam reforming, which is excellent, compared to the Ni/Al2O3 catalyst with a factor 4–8 lower.  相似文献   

5.
The Fe2O3/Al2O3 catalyst was studied to selectively synthesize mixed alcohols from syngas in a continuously stirred slurry reactor with the oxygenated solvent Polyethylene Glycol-400 (PEG-400). The selectivity of mixed alcohols in the products reached as high as 95 wt.% and the C2+ alcohols (mainly ethanol) was more than 40 wt.% in the total alcohol products at the reaction conditions of 250 °C, 3.0 MPa, H2/CO = 2 and space velocity = 360 ml/gcat h. The hydrogen temperature programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS) measurements of the catalyst confirmed that the FeO phase was responsible for the high selectivity to mixed alcohols in the process. And the oxygenated solvent PEG-400 was also necessary for the selective synthesis of mixed alcohols in the reaction system.  相似文献   

6.
Ni modified K2CO3/MoS2 catalyst was prepared and the performance of higher alcohol synthesis catalyst was investigated under the conditions: T = 280–340 °C, H2/CO (molar radio) = 2.0, GHSV = 3000 h 1, and P = 10.0 MPa. Compared with conventional K2CO3/MoS2 catalyst, Ni/K2CO3/MoS2 catalyst showed higher activity and higher selectivity to C2+OH. The optimum temperature range was 320–340 °C and the maximum space-time yield (STY) of alcohol 0.30 g/ml h was obtained at 320 °C. The selectivity to hydrocarbons over Ni/K2CO3/MoS2 was higher, however, it was close to that of K2CO3/MoS2 catalyst as the temperature increased. The results indicated that nickel was an efficient promoter to improve the activity and selectivity of K2CO3/MoS2 catalyst.  相似文献   

7.
The steam reforming of liquefied petroleum gas (LPG) over Ni- and Rh-based catalysts supported on Gd-CeO2 (CGO) and Al2O3 was studied at 750-900 °C. The order of activity was found to be Rh/CGO > Ni/CGO ∼ Rh/Al2O3 > Ni/Al2O3; we indicated that the comparable activity of Ni/CGO to precious metal Rh/Al2O3 is due to the occurring of gas-solid reactions between hydrocarbons and lattice oxygen () on CGO surface along with the reaction taking place on the active site of Ni, which helps preventing the carbon deposition and promoting the steam reforming of LPG.The effects of O2 (as oxidative steam reforming) and H2 adding were further studied over Ni/CGO and Ni/Al2O3. It was found that the additional of these compounds significantly reduced the amount of carbon deposition and promoted the conversion of hydrocarbons (i.e., LPG as well as CH4, C2H4 and C2H6 occurred from the thermal decomposition of LPG) to CO and H2. Nevertheless, the addition of too high O2 oppositely decreased H2 yield due to the oxidizing of Ni particle and the possible combusting of H2 generated from the reaction, while the addition of too high H2 also negatively affect the catalyst activity due to the occurring of catalyst active site competition and the inhibition of gas-solid reactions between the gaseous hydrocarbon compounds and on the surface of CGO (for the case of Ni/CGO).  相似文献   

8.
O.C. Carneiro  R.T.K. Baker 《Carbon》2005,43(11):2389-2396
The growth of carbon nanofibers from Fe-Cu catalyzed decomposition of CO/C2H4/H2 mixtures at temperatures over the range 500-650 °C has been investigated. Based on analysis of the gas phase and solid products it is apparent that co-adsorption of CO and C2H4 induces major perturbations in the surfaces of the bimetallic catalyst particles. These features are reflected in an increase in the yield of solid carbon and subtle changes in the structural characteristics of the carbon nanofibers. Optimum performance with respect to the yield of carbon nanofibers is found for iron-rich particles treated in CO/C2H4/H2 (1:3:1) at 600 °C. Deactivation of the catalyst is observed to occur with high Cu concentrations and at reaction temperatures in excess of 600 °C. It is suggested that under these conditions the surface of the particles in contact with the reactant gas mixture become enriched in Cu, which does not possess the ability to dissociatively chemisorb either CO or C2H4.  相似文献   

9.
In this study, various Cu-based spinel compounds, i.e., CuFe2O4, CuMn2O4, CuAl2O4 and CuLa2O4, were fabricated by a solid-state reaction method. Reduction behaviors and morphological changes of these materials have been characterized by H2 temperature-programmed reduction (H2-TPR), X-ray diffraction (XRD), Scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Moreover, the catalytic properties for steam reforming of methanol (SRM) of these Cu-based spinel compounds were investigated. H2-TPR results indicated that the reducibility of Cu-based spinel compounds was strongly dependent on the B-site component while the CuFe2O4 catalyst revealed the lowest reduction temperature (190 °C), followed respectively by CuAl2O4 (267 °C), CuMn2O4 (270 °C), and CuLa2O4 (326 °C). The reduced CuAl2O4 catalyst demonstrated the best performance in terms of catalytic activity. Based on the SEM and XRD results, pulverization of the CuAl2O4 particles due to gas evolution and a high concentration of nanosized Cu particles (≈50.9 nm) precipitated on the surfaces of the Al2O3 support were observed after reduction at 360 °C in H2. The BET surface area of the CuAl2O4 catalyst escalated from 5.5 to 13.2 m2/g. Reduction of Cu-based spinel ferrites appear to be a potential synthesis route for preparing a catalyst with high catalytic activity and thermal stability. The catalytic performance of these copper-oxide composites was superior to those of conventional copper catalysts.  相似文献   

10.
NiSO4/Al2O3 was reacted with H2 and C2H2 in a fluidised-bed reactor at 650 °C to form Ni/Al2O3 and H2S. The Ni catalyst became coated with a moderately graphitised (0.6 ID/IG ratio) carbonaceous product containing twisted carbon fibres, 200-500 nm in diameter and up to 27 μm in length. The fibres are comprised of four intertwined helical strands and are a unique carbon morphology. Their growth pattern and surface morphology is attributed to differing carbon extrusion speeds from the faces of the polycrystalline Ni catalyst particles that have been modified by H2S.  相似文献   

11.
Newly synthesized nickel calcium aluminum catalysts (Ni/Ca12Al14O33) were tested in a fixed bed reactor for biomass tar steam reforming, toluene as tar destruction model compound. Four catalysts (Ni/Ca12Al14O33) were prepared with Ni loading amount from 1, 3, 5 to 7 wt%, even 1% loading catalyst also showed excellent performance. Catalysts aged experiments in the absence (60 h on stream) and presence of H2S were characterized by BET, X-ray diffraction (XRD), and Raman spectra. It was observed that Ni/Ca12Al14O33 showed excellent sustainability against coke formation due to the “free oxygen” in the catalysts. It also exhibited higher H2S-poisoning resistance property compared to the commercial catalysts Ni/Al2O3 (5%) and Ni/CaO0.5/MgO0.5. Raman spectra revealed that “free oxygen O2 and O22−” in the structure of the catalysts could be substituted by sulfur then protected Ni poisoning on some degree, but reactivation experiments by O2 flowing showed that the sulfide Ni/Ca12Al14O33 was difficult to completely restore, incorporation of sulfur in the structure only partly regain by O2. The kinetic model proposes, as generally accepted, a first-order reaction for toluene with activation energy of 82.06 kJ mol−1 was coincident with the literature data. The Ni/Ca12Al14O33 catalyst was effective and relative cheap, which may be lead to reduction in the cost of hot gas cleaning process.  相似文献   

12.
We discuss growth of high-quality carbon nanotube (CNT) films on bare and microstructured silicon substrates by atmospheric pressure thermal chemical vapor deposition (CVD), from a Mo/Fe/Al2O3 catalyst film deposited by entirely electron beam evaporation. High-density films having a tangled morphology and a Raman G/D ratio of at least 20 are grown over a temperature range of 750-900 °C. H2 is necessary for CNT growth from this catalyst in a CH4 environment, and at 875 °C the highest yield is obtained from a mixture of 10%/90% H2/CH4. We demonstrate for the first time that physical deposition of the catalyst film enables growth of uniform and conformal CNT films on a variety of silicon microstructures, including vertical sidewalls fabricated by reactive ion etching and angled surfaces fabricated by anisotropic wet etching. Our results confirm that adding Mo to Fe promotes high-yield SWNT growth in H2/CH4; however, Mo/Fe/Al2O3 gives poor-quality multi-walled CNTs (MWNTs) in H2/C2H4. An exceptional yield of vertically-aligned MWNTs grows from only Fe/Al2O3 in H2/C2H4. These results emphasize the synergy between the catalyst and gas activity in determining the morphology, yield, and quality of CNTs grown by CVD, and enable direct growth of CNT films in micromachined systems for a variety of applications.  相似文献   

13.
Ni/Al2O3 with the doping of CeO2 was found to have useful activity to reform ethane and propane with steam under Solid Oxide Fuel Cells (SOFCs) conditions, 700-900 °C. CeO2-doped Ni/Al2O3 with 14% ceria doping content showed the best reforming activity among those with the ceria content between 0 and 20%. The amount of carbon formation decreased with increasing Ce content. However, Ni was easily oxidized when more than 16% of ceria was doped. Compared to conventional Ni/Al2O3, 14%CeO2-doped Ni/Al2O3 provides significantly higher reforming reactivity and resistance toward carbon deposition. These enhancements are mainly due to the influence of the redox properties of doped ceria. Regarding the temperature programmed reduction experiments (TPR-1), the redox properties and the oxygen storage capacity (OSC) for the catalysts increased with increasing Ce doping content. In addition, it was also proven in the present work that the redox of these catalysts are reversible, according to the temperature programmed oxidation (TPO) and the second time temperature programmed reduction (TPR-2) results.During the reforming process, in addition to the reactions on Ni surface, the gas-solid reactions between the gaseous components presented in the system (C2H6, C3H8, C2H4, CH4, CO2, CO, H2O, and H2) and the lattice oxygen (Ox) on ceria surface also take place. The reactions of adsorbed surface hydrocarbons with the lattice oxygen (Ox) on ceria surface (CnHm+OxnCO+m/2(H2)+Oxn) can prevent the formation of carbon species on Ni surface from hydrocarbons decomposition reaction (CnHmnC+m/2H2). Moreover, the formation of carbon via Boudard reaction (2CO⇔CO2+C) is also reduced by the gas-solid reaction of carbon monoxide (produced from steam reforming) with the lattice oxygen (CO+Ox⇔CO2+Ox−1).  相似文献   

14.
In this work, the microwave-assisted CO2 reforming of CH4 over mixtures of carbonaceous materials and an in-lab prepared Ni/Al2O3 was studied. Ni/Al2O3 is not heated by microwave radiation, and for this reason, microwave receptors, such as carbonaceous materials, must be mixed with this catalyst. In order to evaluate the role of the carbonaceous component of the blend, two different carbonaceous materials were used: an activated carbon, FY5, and a metallurgical coke, CQ. The carbonaceous component acted not only as microwave receptor but also as catalyst and, consequently, it influenced the catalytic activity of the mixture. FY5 + Ni/Al2O3 was found to be a better catalyst than CQ + Ni/Al2O3, since FY5 on its own showed a better catalytic activity than CQ. Ni/FY5, which consists of Ni impregnated directly onto the microwave receptor, was also evaluated as a catalyst. It was found that the catalytic activity of the mixture FY5 + Ni/Al2O3 was better than that of Ni/FY5. Finally, the influence of the heating device on the catalytic activity of FY5 + Ni/Al2O3 was studied. Conversions over FY5 + Ni/Al2O3 and microwave heating were found to be similar to conversions over Ni/Al2O3 and conventional heating.  相似文献   

15.
The CH4-CO2 reforming was investigated in a fluidized bed reactor using nano-sized aerogel Ni/Al2O3 catalysts, which were prepared via a sol–gel method combined with a supercritical drying process. The catalysts were characterized with BET, XRD, H2-TPR and H2-TPD techniques. Compared with the impregnation catalyst, aerogel catalysts exhibited higher specific surface areas, lower bulk density, smaller Ni particle sizes, stronger metal-support interaction and higher Ni dispersion degrees. All tested aerogel catalysts showed better catalytic activities and stability than the impregnation catalyst. Their catalytic stability tested during 48 h reforming was dependent on their Ni loadings. Characterizations of spent catalysts indicated that only limited graphitic carbon formed on the aerogel catalyst, while massive graphitic carbon with filamentous morphology was observed for the impregnation catalyst, leading to significant catalytic activity degradation. An aerogel catalyst containing 10% Ni showed the best catalytic stability and the lowest rate of carbon deposition among the aerogel catalysts due to its small Ni particle size and strong metal-support interaction.  相似文献   

16.
Non conventional nickel (1%) and nickel (1%)-copper (0.2%-0.75%) catalysts supported on silica have been prepared by aqueous hydrazine reduction of nickel acetate at 70 °C. They were characterized by TEM, H2-adsorption, H2-TPD and tested in the gas phase hydrogenation of benzene at atmospheric pressure in the temperature range 75 °C-230 °C. The obtained results show that nickel is in a whisker-like shape or as a film of low density for the Ni/SiO2 and Ni-Cu/SiO2 catalysts respectively. Copper is in the shape of facetted particles in the mono or bimetallic systems with a mean particle size varying from 25 to 100 nm. The presence of copper decreased the nickel phase dispersion as well as the conversion whereas it increased carbon deposit in benzene hydrogenation. The results obtained are ascribed to nickel phase shape changes and Ni-Cu interactions. A kinetic reaction mechanism model is proposed. The comparative study of a pair of classical/non-classical Ni/SiO2 catalysts showed much higher surface and catalytic properties of the hydrazine catalyst.  相似文献   

17.
A new process to integrate coal pyrolysis with CO2 reforming of methane over Ni/MgO catalyst was put forward for improving tar yield. And several Chinese coals were used to confirm the validity of the process. The experiments were performed in an atmospheric fixed-bed reactor containing upper catalyst layer and lower coal layer to investigate the effect of pyrolysis temperature, coal properties, Ni loading and reduction temperature of Ni/MgO catalysts on tar, water and char yields and CH4 conversion at fixed conditions of 400 ml/min CH4 flow rate, 1:1 CH4/CO2 ratio, 30 min holding time. The results indicated that higher tar yield can be obtained in the pyrolysis of all four coals investigated when coal pyrolysis was integrated with CO2 reforming of methane. For PS coal, the tar, water and char yield is 33.5, 25.8 and 69.5 wt.%, respectively and the CH4 conversion is 16.8%, at the pyrolysis temperature of 750 °C over 10 wt.% Ni/MgO catalyst reduced at 850 °C. The tar yield is 1.6 and 1.8 times as that in coal pyrolysis under H2 and N2, respectively.  相似文献   

18.
Gang Wang  Yuqing Zha  Tong Ding 《Fuel》2010,89(9):2244-95
A series of high-temperature close coupled catalysts Pd/Ce-Zr-M/Al2O3 (M = Y, Ca or Ba) were prepared by ultrasonic-assisted successive impregnation. The catalysts were subjected to a series of characterization measurements. The results of activity evaluation show that Y is the best promoter for propane total oxidation, especially at the calcination temperature of 1100 °C. It is interesting that although the BET specific surface areas and the dispersion of Pd species decrease, the Y-promoted catalyst calcined at 1100 °C shows higher catalytic activity than the corresponding one calcined at 900 °C and better sulfur-resisting performance. The results of TEM, TPHD and CO chemisorption indicate that Y can remarkably increase the dispersion of Pd species. However, the dispersion is hard to be connected with the activity increase as the calcination temperature is elevated from 900 to 1100 °C. The change of active phases and the interaction between Pd species and the supports may account for the activity enhancement. Combined with XRD, H2-TPR and O2-TPD results, it is deduced that the coexistence of metallic Pd and PdO species in the catalysts calcined at 1100 °C may be also favorable to C3H8 oxidation. In a word, Pd/Ce-Zr-Y/Al2O3 is indeed a promising high-temperature close coupled catalyst applicable to high temperature.  相似文献   

19.
The Se(VI)-analogues of ettringite and monosulfate, selenate-AFt (3CaO·Al2O3·3CaSeO4·37.5H2O), and selenate-AFm (3CaO·Al2O3·CaSeO4·xH2O) were synthesised and characterised by bulk chemical analysis and X-ray diffraction. Their solubility products were determined from a series of batch and resuspension experiments conducted at 25 °C. For selenate-AFt suspensions, the pH varied between 11.37 and 11.61, and a solubility product, log Kso=61.29±0.60 (I=0 M), was determined for the reaction 3CaO·Al2O3·3CaSeO4·37.5H2O+12 H+⇔6Ca2++2Al3++3SeO42−+43.5H2O. Selenate-AFm synthesis resulted in the uptake of Na, which was leached during equilibration and resuspension. For the pH range of 11.75 to 11.90, a solubility product, log Kso=73.40±0.22 (I=0 M), was determined for the reaction 3CaO·Al2O3·CaSeO4·xH2O+12 H+⇔4Ca2++2Al3++SeO42−+(x+6)H2O. Thermodynamic modelling suggested that both selenate-AFt and selenate-AFm are stable in the cementitious matrix; and that in a cement limited in sulfate, selenate concentration may be limited by selenate-AFm to below the millimolar range above pH 12.  相似文献   

20.
The modification of Ni/CeO2/Al2O3 with Pt can make the activation by H2 reduction unnecessary, and this indicates that the Pt/Ni/CeO2/Al2O3 catalyst can be activated automatically by the compounds contained in tar. This can be explained by the enhancement of the Ni reducibility by the addition of Pt. The results of the temperature programmed reduction with H2 also support this enhancement. Furthermore, the addition of 0.1% Pt to Ni/CeO2/Al2O3 (4 wt% Ni, 30 wt% CeO2) enhanced the performance in the steam gasification of biomass, compared to Ni/Al2O3 and Ni/CeO2/Al2O3 in terms of low tar yield and high gas yield. This can be related to the Pt–Ni alloy formation indicated by the extended X-ray absorption fine structure analysis.  相似文献   

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