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1.
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   

2.
Dry reforming of methane was studied over Ni catalysts supported on γAl2O3, CeO2, ZrO2 and MgAl2O4 (670 °C, 1.5 bar, 16–20 l CH4 mlcatalyst−1 h−1). It is shown that MgAl2O4 supported Ni catalysts promoted with both CeO2 and ZrO2 are promising catalysts for dry reforming of methane with carbon dioxide. Within a certain composition range, the simultaneous promotion with CeO2 and ZrO2 has great influence on the amount of coke and the catalyst service time. XRD analyses indicate that formation of crystalline CexZr1−xO2 mixed oxide phases occurs on double promotion. In particular, incorporation of low amounts of Zr in the CeO2 fluorite structure provides stable dry reforming catalysis. As shown with TPR, promotion leads to a higher reduced state of Ni. SEM, XRD and TPR analyses demonstrate that highly dispersed, doubly promoted Ni catalysts with a strong metal-support interaction are essential for stable dry reforming and suppression of the formation of carbon filaments.  相似文献   

3.
Alumina (Al2O3) and alumina-yttria stabilized zirconia (YSZ) composites containing 3 and 5 mass% ceria (CeO2) were prepared by spark plasma sintering (SPS) at temperatures of 1350-1400 °C for 300 s under a pressure of 40 MPa. Densification, microstructure and mechanical properties of the Al2O3 based composites were investigated. Fully dense composites with a relative density of approximately 99% were obtained. The grain growth of alumina was inhibited significantly by the addition of 10 vol% zirconia, and formation of elongated CeAl11O18 grains was observed in the ceria containing composites sintered at 1400 °C. Al2O3-YSZ composites without CeO2 had higher hardness than monolithic Al2O3 sintered body and the hardness of Al2O3-YSZ composites decreased from 20.3 GPa to 18.5 GPa when the content of ZrO2 increased from 10 to 30 vol%. The fracture toughness of Al2O3 increased from 2.8 MPa m1/2 to 5.6 MPa m1/2 with the addition of 10 vol% YSZ, and further addition resulted in higher fracture toughness values. The highest value of fracture toughness, 6.2 MPa m1/2, was achieved with the addition of 30 vol% YSZ.  相似文献   

4.
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   

5.
Preparation of the (Ti1−xNbx)2AlC solid solution (formed from the Mn+1AXn or MAX carbides, where n = 1, 2, or 3, M is an early transition metal, A is an A-group element, and X is C) with x = 0.2-0.8 was investigated by self-propagating high-temperature synthesis (SHS). Nearly single-phase (Ti,Nb)2AlC was produced through direct combustion of constituent elements. Due to the decrease of reaction exothermicity, the combustion temperature and reaction front velocity decreased with increasing Nb content of (Ti1−xNbx)2AlC formed from the elemental powder compacts. In addition, the samples composed of Ti, Al, Nb2O5, and Al4C3 were adopted for the in situ formation of Al2O3-added (Ti,Nb)2AlC. The SHS process of the Nb2O5/Al4C3-containing sample involved aluminothermic reduction of Nb2O5, which not only enhanced the reaction exothermicity but also facilitated the evolution of (Ti,Nb)2AlC. Based upon the XRD analysis, two intermediates, TiC and Nb2Al, were detected in the (Ti,Nb)2AlC/Al2O3 composite and their amounts were reduced by increasing the extent of thermite reduction involved in the SHS process. The laminated microstructure characteristic of the MAX carbide was observed for both monolithic and Al2O3-added (Ti,Nb)2AlC solid solutions synthesized in this study.  相似文献   

6.
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   

7.
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   

8.
In the CaO-SiO2-Al2O3-Fe2O3 pseudoquaternary system, the solid solutions of Ca2(AlxFe1−x)2O5, with x<0.7 (ferrite), Ca2SiO4 (belite), Ca3Al2O6 (C3A) and Ca12Al14O33 (C12A7), were crystallized out of a complete melt during cooling at 8.3 °C/min. Upon cooling to 1370 °C, both the crystals of ferrite with x=0.41 and belite would start to nucleate from the melt. During further cooling, the x value of the precipitating ferrite would progressively increase and eventually approach 0.7. At ambient temperature, the ferrite crystals had a zonal structure, the x value of which successively increased from the cores toward the rims. The value of 0.45 was confirmed for the cores by EPMA. The chemical formula of the rims was determined to be Ca2.03[Al1.27Fe0.68Si0.02]Σ1.97O5 (x=0.65). As the crystallization of ferrite and belite proceeded, the coexisting melt would become progressively enriched in the aluminate components. After the termination of the ferrite crystallization, the C3A and belite would immediately crystallize out of the melt, followed by the nucleation of C12A7. The C12A7 accommodated about 2.1 mass% Fe2O3 in the chemical formula Ca12.03[Al13.61Fe0.37]Σ13.98O33, being free from the other foreign oxides (SiO2 and P2O5).  相似文献   

9.
An Al2O3-ZrO2 support was prepared by grafting a zirconium precursor onto the surface of commercial γ-Al2O3. A physical mixture of Al2O3-ZrO2 was also prepared for the purpose of comparison. Ni/Al2O3-ZrO2 catalysts were then prepared by an impregnation method, and were applied to the hydrogen production by steam reforming of liquefied natural gas (LNG). The effect ZrO2 and preparation method of Al2O3-ZrO2 on the performance of supported nickel catalysts in the steam reforming of LNG was investigated. The Al2O3-ZrO2 prepared by a grafting method was more efficient as a support for nickel catalyst than the physical mixture of Al2O3-ZrO2 in the hydrogen production by steam reforming of LNG. The well-developed tetragonal phase of ZrO2 and the high dispersion of ZrO2 on the surface of γ-Al2O3 were responsible for the enhanced catalytic performance of Ni/Al2O3-ZrO2 prepared by way of a grafting method.  相似文献   

10.
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   

11.
Oxygen storage capacity (OSC) of CeO2–ZrO2 solid solution, CexZr(1−x)O4, is one of the most contributing factors to control the performance of an automotive catalyst. To improve the OSC, heat treatments were employed on a nanoscaled composite of Al2O3 and CeZrO4 (ACZ). Reductive treatments from 700 to 1000 °C significantly improved the complete oxygen storage capacity (OSC-c) of ACZ. In particular, the OSC-c measured at 300 °C reached the theoretical maximum with a sufficient specific surface area (SSA) (35 m2/g) after reductive treatment at 1000 °C. The introduced Al2O3 facilitated the regular rearrangement of Ce and Zr ions in CeZrO4 as well as helped in maintaining the sufficient SSA. Reductive treatments also enhanced the oxygen release rate (OSC-r); however, the OSC-r variation against the evaluation temperature and the reduction temperature differed from that of OSC-c. OSC-r measured below 200 °C reached its maximum against the reduction temperature at 800 °C, while those evaluated at 300 °C increased with the reduction temperature in the same manner as OSC-c.  相似文献   

12.
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   

13.
Lifeng Zhang 《Fuel》2009,88(3):511-24
Nickel-based catalysts supported on Al2O3 · SiO2 were prepared with modification of the second metal involving La, Co, Cu, Zr or Y, of which the catalytic behaviors were assessed in the ethanol steam reforming reaction. Activity test indicated that addition of La resulted in higher selectivity of hydrogen and lower selectivity of carbon monoxide, compared with Co-doped nickel catalyst. Influences of lanthanum amounts on catalytic performance were studied over 30NixLa/Al2O3 · SiO2 (x = 5, 10, 15), and characterizations by XRD, TPR and XPS indicated that low amount of lanthanum additives (5%) was superior to inhibit the crystal growth of nickel as well as beneficial to the reduction of nickel oxide. Finally 100 h test for the optimal catalyst 30Ni5La/Al2O3 · SiO2 indicated its good long-term stability to provide high hydrogen selectivity and low carbon monoxide formation, as well as good resistance to coke deposition at low temperature.  相似文献   

14.
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   

15.
Mayenite (Ca12Al14O33 or 12CaO.7Al2O3) was previously developed and applied as Ni support for biomass tar steam reforming in the absence and presence of H2S by our group because of its high oxygen restoring property in the structure [C. Li et al., Appl. Catal., B. 2008]. In this study, catalyst Ni/mayenite (mayenite as support) was prepared by impregnation method with nickel nitrate hexahydrate. Experiments were tested in a fixed-bed reactor, toluene as a tar model compound. The influence of the catalyst preparation and operating parameters (reaction temperature, steam to carbon ratio and space time) on catalyst activity and products selectivity were studied, and a long-time evaluation (more than 76 h) also exhibited excellent resistance to coking. These results were compared to these obtained by commercial-like catalysts: Ni/CaOx/MgO1−x and our previous NiO/mayenite, showing that Ni/mayenite exhibited excellent property for biomass tar reforming, with higher H2 yield than that of Ni/CaOx/MgO1−x, and higher CO selectivity than that of NiO/mayenite. For kinetic model, the first order reaction used for toluene with activation energy of 80.24 kJ.mol− 1 was coincident with literature data.  相似文献   

16.
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   

17.
The deposition of coke from methane on a Ni/MgAl2O4 catalyst   总被引:1,自引:0,他引:1  
Jianjun Guo  Hui Lou 《Carbon》2007,45(6):1314-1321
Temperature-programmed reaction techniques and Raman spectroscopy were used to characterize coke species deposited on a 5% Ni/MgAl2O4 catalyst for dry reforming of methane. The CH4 temperature-programmed decomposition profiles showed that the ignited decomposition temperatures of CH4 increased from 273 to 378 °C when MgAl2O4 replaced the catalyst support γ-Al2O3. The temperature-programmed oxidation, temperature-programmed hydrogenation and temperature-programmed CO2 reaction profiles showed that there were three carbon species (i.e. Cα, Cβ and Cγ) on the catalyst surface. Raman spectroscopy showed that Cγ was graphite-like carbon species, which was responsible for catalyst deactivation. The Cγ species was the most inactive species toward H2 and O2, while it was unexpectedly more active toward CO2. The unique reactivity of CO2 with different coke specie could be ascribed to the carbonate, bidentate and formate species formation on MgAl2O4 surface. These surface species enhanced the oxidation of Cγ species and thus contributed to the high stability of Ni/MgAl2O4 catalyst.  相似文献   

18.
Pure and Ni-doped ZnO nanofibers were synthesized using the electrospinning method. The morphology, crystal structure and optical properties of the nanofibers were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy, respectively. It is found that Ni doping does not change the morphology and crystal structures of the nanofibers, and the ultraviolet emissions of ZnO nanofibers present red shift with increasing Ni doping concentration. C2H2 sensing properties of the sensors based on the nanofibers were investigated. The results show that the C2H2 sensing properties of ZnO nanofibers are effectively improved by Ni doping, and 5 at% Ni-doped ZnO nanofibers exhibit a maximum sensitivity to C2H2 gas.  相似文献   

19.
The effect of SO2 for the selective reduction of NO by C3H8 on Ag/Al2O3 was investigated in the presence of excess oxygen and water vapor. The NOx conversion decreased permanently even in the presence of a low concentration of SO2 (0.5–10 ppm) at <773 K. The increase in SO2 concentration resulted in a large decrease in NOx conversion at 773 K. However, when the reaction temperature was more than 823 K, the activity of Ag/Al2O3 remained constant even in the presence of 10 ppm of SO2. The sulfate species formed on the used Ag/Al2O3 were characterized by a temperature programmed desorption method. The sulfated species formed on silver should mainly decrease the deNOx activity on the Ag/Al2O3. The sulfated Ag/Al2O3 was appreciably regenerated by thermal treatment in the deNOx feed at 873 K. The moderate activity remains at 773 K in the presence of 1 ppm SO2 for long time by the heat treatment at every 20 h intervals.  相似文献   

20.
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   

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